Ball-Milling in Liquid Media

Progress in Materials Science 50 (2005) 192
www.elsevier.com/locate/pmatsci
Ball-milling in liquid media

Applications to the preparation of anodic
materials for lithium-ion batteries
Raphael Janot, Daniel Guerard
Laboratoire de Chimie du Solide Min

eral, UHP Nancy I, UMR 7555, BP 239,
54506 Vandoeuvre-l
es-Nancy Cedex, France
Received 30 July 2002; received in revised form 30 May 2003; accepted 20 July 2003
Abstract
Due to the intense development of portable electronic devices and the aim of the electric
vehicle, the preparation of batteries with higher and higher electrochemical performances is of
great interest. The best anodic material for lithium batteries should be the metal itself, but due
to the formation of lithium dendrites provoking short-circuits while the battery is cycled, one
uses graphite, since the lithium intercalation presents a high reversibility and occurs at very
low potentials versus Li /Li0 .
In order to improve the anode performance, there are two possible ways, starting from
either:
small particles of graphite obtained by grinding. In this case, the chargedischarge rate can
be improved, as well as the amount of intercalated lithium, due to the lower particles size
and to the presence of dangling carbon bonds, respectively. Unfortunately, ball-milling
leads to disordered or amorphous carbons exhibiting a high hysteresis when electrochemically cycled,
graphite intercalation compounds with a high lithium content such as LiC2 prepared at 300
C under 50 kbars. This synthesis requires a heavy apparatus and the amount of prepared
powders at once is quite small: several hundreds milligrams. Moreover, the compound is
not stable and decomposes (into a mixture of LiC6 and free lithium) as the pressure is released and the LiC2 compound is not formed back by electrochemical reaction.
Corresponding author. Tel.: +33-383-684633/912107; fax: +33-383-684634/912447.

E-mail address: daniel.guerard@lcsm.uhp-nancy.fr (D. Guerard).
0079-6425/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0079-6425(03)00050-1
R. Janot, D. Guerard / Progress in Materials Science 50 (2005) 192
By modeling and some experimental measurements, it was shown that the pressure and
temperature temporarily induced by the shocks occurring during the ball-milling can reach
values close to those used to prepare the LiC2 compound. Therefore, the grinding of graphite
lithium mixtures was studied in order to obtain superdense graphitelithium compounds
stable under ambient conditions. Due to its high ductility, lithium agglomerates readily on the
milling tools and, thus, the obtained powder, roughly LiC6 in spite of a large excess of metal
(the starting mixture is Li + 2C), is partly amorphous. This is the reason why we have added
small quantities of a liquid, inert towards lithium: the n-dodecane (C12 H26 ). The presence of
this liquid allows a good lubrication and dispersion of lithium, which does not paste on the
tools.
With appropriate milling conditions, the formation of a superdense compound with a LiC3
stoichiometry is possible. This compound is stable at room temperature under normal pressure. The electrochemical properties of the LiC3 compound were investigated as anode in
lithium-ion batteries. The primary capacity is very high (close to 1 A h/g) and the voltage
prole is low (all the lithium removal occurs below 300 mV). Unfortunately, the superdense
LiC3 compound is not formed back by electrochemical mean. The reversible capacity corresponds to the formation of the LiC6 compound and consequently is around 370 mA h/g. This
compound constitutes a good candidate as anodic material since its rst deintercalation
corresponds to a high capacity and is partly reversible with the same behavior as graphite.
In the same manner, graphite powders were milled together with dodecane. The powder
obtained after separation from the liquid (by simple evaporation) is made of well crystallized
thin particles of graphite (typically 20 nm thick, with a geometrical anisotropy of about 100).
This graphite leads to a smaller consumption of lithium (used for the so-called solid electrolyte
interface formation) than with the starting graphite powder, in spite of a much larger specic
surface area.
The previous syntheses were done with an inert liquid. In the case of graphite milled within
water in a stainless steel vial, one observes the formation of graphite particles covered by small
crystals of maghemite (c Fe2 O3 ), these last coming from the oxidation of the vial by water.
This reactive ball-milling was used in two dierent directions:
easy preparation of pure nanosized maghemite crystals. The in situ production of hydrogen
during the milling is relevant, because it favors a spinel type structure. For a milling of 48 h,
the average diameter of the particles is 15 nm. The technique is remarkable due to the narrow size distribution of the obtained particles, which is very interesting for magnetic applications,
preparation of anode materials by depositing maghemite nanograins at the surface of
graphite particles ground together with water. In this manner, the respective properties
of graphite and transition metal oxide are added: it was shown recently that such oxides
may present higher reversible capacities than graphite.
The electrochemical performances of these graphitemaghemite composites were tested. The
nanometric size of the maghemite grains, and consequently their great reactivity, allows a
partial reversibility of the reaction between iron and maghemite. The corresponding capacity
reaches 440 mA h/g and makes such composites good candidates for anodes in lithium-ion
batteries. However, the reversible capacity decreases during the electrochemical cycling due to
the coalescence of the maghemite nanoparticles.
2003 Elsevier Ltd. All rights reserved.
Contents
1.
Introduction ............................................................................................................................................... 5
1.1. The ball-milling............................................................................................................................ 5
1.1.1. Background..................................................................................................................... 5
1.1.2. The diverse milling systems...................................................................................... 6
1.1.3. Main milling parameters ........................................................................................... 9
1.1.4. Conclusion .................................................................................................................... 11
1.2. The graphite and its intercalation compounds............................................................... 11
1.2.1. The graphite ................................................................................................................. 11
1.2.2. The intercalation phenomenon ............................................................................. 13
1.2.3. The graphite intercalation compounds .............................................................. 14
1.2.4. The graphitelithium compounds ........................................................................ 15
1.3. The lithium batteries................................................................................................................ 17
1.3.1. Introduction.................................................................................................................. 17
1.3.2. Lithium batteries with a polymer electrolyte................................................... 17
1.3.3. Lithium-ion batteries: the use of insertion compounds as anodes.......... 19
1.3.4. Conclusion .................................................................................................................... 21
1.4. The maghemite (Fe2 O3 ) ....................................................................................................... 21
1.4.1. Structural aspect......................................................................................................... 21
1.4.2. Synthesis ........................................................................................................................ 22
2.
Intercalation of lithium into graphite by ball-milling...............................................................

2.1. Material used in this study....................................................................................................
2.1.1. The mill and its devices............................................................................................
2.2. Reagents.......................................................................................................................................
2.3. Synthesis conditions.................................................................................................................
2.4. Optimization of the milling conditions .............................................................................
2.4.1. Nature of lithium .......................................................................................................
2.4.2. Lithium/carbon ratio.................................................................................................
2.4.3. Charge ratio..................................................................................................................
2.4.4. Balls size.........................................................................................................................
2.4.5. Conclusion ....................................................................................................................
2.5. Ball-milling of a mixture of Li + 2C powders.................................................................
2.5.1. X-rays diraction........................................................................................................
2.5.2. TEM study....................................................................................................................
2.5.3. Density measurements..............................................................................................
2.5.4. Conclusion ....................................................................................................................
22
23
23
24
25
25
25
26
27
29
29
29
30
32
34
35
3.
Synthesis by ball-milling in a liquid medium...............................................................................

3.1. Choice of the liquid..................................................................................................................
3.2. Synthesis.......................................................................................................................................
3.3. Actual composition of the powders: chemical analyses..............................................
3.4. Characterization by X-rays diraction..............................................................................
3.5. TEM investigations ..................................................................................................................
3.5.1. Electron energy loss spectroscopy........................................................................
3.6. Density measurements by pycnometry..............................................................................
35
35
36
37
37
38
39
40
3.7.
Li NMR characterization.....................................................................................................
3.7.1. Generalities ...................................................................................................................
3.7.2. Experimental results..................................................................................................
3.7.3. Where is the doublet at 260 ppm coming from?............................................
3.7.4. Spinlattice relaxation time....................................................................................
3.7.5. Structure ........................................................................................................................
3.7.6. Comparison with the high pressure superdense phases...............................
3.7.7. Conclusion ....................................................................................................................
3.8. Characterization by electronic paramagnetic resonance.............................................
3.9. High pressure investigations .................................................................................................
3.10. Conclusion...................................................................................................................................
41
41
43
46
48
48
51
53
53
55
57
4.
Preparation of highly anisometric graphite particles................................................................

4.1. Milling within dodecane.........................................................................................................
4.2. X-rays diraction ......................................................................................................................
4.3. SEM observations.....................................................................................................................
4.4. TEM observations ....................................................................................................................
4.5. Conclusion...................................................................................................................................
57
58
59
59
61
62
5.
Synthesis of maghemite nanoparticles ...........................................................................................

5.1. Synthesis by milling within water .......................................................................................
5.2. XRD characterization .............................................................................................................
5.3. Chemical analysis......................................................................................................................
5.4. TEM observations ....................................................................................................................
5.4.1. Electron energy loss spectroscopy........................................................................
5.5. Mossbauer spectroscopy.........................................................................................................
5.6. Magnetic susceptibility measurements...............................................................................
5.7. Conclusion...................................................................................................................................
62
63
64
65
65
66
68
70
71
6.
Graphitemaghemite composites .....................................................................................................

6.1. X-rays diraction ......................................................................................................................
6.2. SEM observations.....................................................................................................................
6.3. TEM studies................................................................................................................................
71
71
72
74
7.
Electrochemical performances...........................................................................................................
7.1. Introduction................................................................................................................................
7.1.1. Carbonaceous materials...........................................................................................
7.2. Experimental...............................................................................................................................
7.3. Highly anisometric graphite..................................................................................................
7.4. LiC3 Li powder prepared by ball-milling .....................................................................
7.4.1. Comparison with LiC synthesized under high pressure..............................
7.4.2. Conclusion ....................................................................................................................
7.5. Graphitemaghemite composites.........................................................................................
7.6. Conclusion...................................................................................................................................
74
74
76
76
77
78
80
82
82
83
8.
Conclusion ............................................................................................................................................... 85
Acknowledgements ........................................................................................................................................ 86
References ......................................................................................................................................................... 87
1. Introduction
1.1. The ball-milling
The ball-milling was directly oriented to industrial applications: in 1966, Benjamin (INCO Co.) tried to improve the mechanical properties of nickel-based superalloys by high energy mechanical grinding. This technique allows to ameliorate both
the high temperature (10001300 C) properties by homogeneous dispersion of ne
oxides particles in the alloy and the medium temperature range (8001000 C) by
precipitation of an intermetallic c phase of Ni3 (Al, Ti) type. The rst publication
dedicated to this new technique appeared in 1970 and this solid-state process was
called Mechanical Alloying by Benjamin [1]. This method was then extended to
the synthesis of a large variety of materials as alloys with Cu, Al, Mg, superconductors, ceramics. . .
Several terms are used to call this technique: Mechanical Alloying when there is
a chemical reaction between dierent powders, Mechanical Grinding or Mechanical Milling when the only goal is to modify the texture and/or the structure of
a material (no chemical reaction is involved in the process). In this paper, we will use
mainly the term of Ball-Milling, which does not presuppose any kind of behavior
and which tends to be more and more used.
1.1.1. Background
The ball-milling is generally used as a mechanical co-grinding of powders, initially
dierent in nature, up to the preparation of a new powder, homogeneous in composition. The milling is done in cylindrical containers called vials and containing
balls. The nature of the milling tools can be as diverse as steel, agate, tungsten
carbide. . . The vials are generally lled under an inert atmosphere to avoid side
reactions, since the particles are fractured during the milling process and, therefore,
new highly reactive surfaces can react with the surrounding gases.
Two opposite phenomena are induced by the milling process: on one hand, the
particles split as a result of the important internal strain created by the high pressure
applied to the grains and, on the other hand, the highly divided particles tend to
agglomerate due to the high reactivity of their surfaces, in order to minimize the
surface energy [2,3]. When the initial particle size is relatively high (typically more
than 10 lm), the milling starts by a rapid splitting and, then, there is successively
splitting, crushing and coalescence of the particles (cf. Fig. 1), leading to an homogeneous powder, whose mean particle size depends on the nature of the powders
and on the milling conditions (duration, rotation rate, charge ratio: ratio between
balls and powders weights. . .).
Fig. 1. Schematic representation of the ball-milling process.
Harder and fragile the milled powder is, ner the obtained particles are [4]. This
last point is particularly important in our case since we are dealing with very ductile
materials: the alkali metals. In order to palliate this fact and to prepare ne particles,
there are two solutions. The rst one consists in the addition of a lubricant, inert
towards the material, in the milling container [5,6]. It is generally liquid but can
however act as a source of pollution. The other technique is a cryo-milling in liquid
nitrogen [7,8], the low temperature hardens the materials, which become fragile and
can be pulverized. This technique is quite dicult to handle and is rarely used.
1.1.2. The diverse milling systems
The most common mills are of planetary, vibrant, attritors, cannon-ball types.
The planetary or vibrant mills are the most used in laboratories. Their capacity is of
several grams, whereas the industry deals with attritors or cannon-ball mills, whose
capacity can be as high as several tons of powders.
1.1.2.1. The planetary mills. The vials rotate at a rotation speed x on a tray moving
in the opposite way at a speed X (cf. Fig. 2). The values for X and x are connected in
the commercial mills.Numerous authors have modelized the shocks occurring during
the milling process (both between balls and between vial wall and balls) in order to
quantify the energy transferred to the powder.
The shocks are dened by the speed and the incidence angle of the colliding
materials. The tangential shocks involve important friction phenomena, whereas
frontal shocks induce compression equivalent to a microwelding. LeBrun et al. [9]
consider three dierent milling regimes as a function of the ratio between x and X
(the rotation speeds of the vial and the tray, respectively). If this ratio is small, the
regime is qualied as chaotic: as soon as the ball strikes the wall, it is immediately
pushed back. Inversely, when the ratio is high, the ball remains on the wall and the
regime is a friction mode. In between, the motion of the ball is decomposed in two
parts: a friction followed by an impact. This model is established for one ball, neglecting the gravity forces.
1.1.2.2. The vibrant mills. Those mills are working with small vials (several tens cm3 ).
They are moved linearly by one, two or three-axial translations, whose frequency is
Fig. 2. Planetary type mill.
Fig. 3. Vibrant type mill.
several tens Hertz (cf. Fig. 3). Generally, the powder and balls occupy only 1/3 of the
volume, unless the balls speed is too low to lead to an ecient milling. This kind of
mill involves mainly frontal shocks.
Maurice and Courtney [10] have shown that, with a vibrant mill SPEX 8000, the
balls reach a speed as high as several m/s and that the shocks lead to very high instant
pressures (typically 40 kbars with stainless steel balls of 6 mm in diameter). Several
other studies to know the kinematics of the balls during the milling were done, particularly by Davis et al. [11], who recorded the balls motion in a transparent vial.
1.1.2.3. Attritors. The principle of this mill diers from the previous ones: the vial is
static and one or more stirrers are placed inside the vial and their rotation (several
hundreds rpm) mix the powders and balls together (cf. Fig. 4). The friction and shear
are then preponderant [12].
The eciency of such mills is relatively low: only a small part of the powder lies at
the place where an ecient mixing occurs: the powder tends to fall, by gravity, at the
bottom of the vial and concentrates near the vial wall, a place where the milling is
very limited. Thus, the recent models of attritors present a curved bottom in order to
favor the movement of the balls and powders towards more active parts of the vial.
1.1.2.4. Cannon-ball mills. The vial rotates horizontally around its revolution axis (cf.
Fig. 5). Part of the powder and balls is drag by the wall and falls down by gravity.
Moreover, part of the balls which arising slip down on the others. The combination
between those two movements induces shock and friction phenomena on the
Fig. 4. Attritor.
Fig. 5. Cannon-ball type mill.
powder. The relative impact of those movements depends mainly on the rotation
speed and diameter of the vial [13].
This mill is largely used in the industry, since the vial can reach several meters,
both in length and diameter, and makes possible the treatment at once of several
tons of powders. The milling duration is generally long (several hundreds hours) but,
taking into account the mass of milled powders, this system remains one of the most
interesting at the industrial scale. One should also note that some vials contain asperity, which greatly ameliorates the milling eciency.
1.1.2.5. Other milling systems.
Vibrating plateaus with a at or hemispherical bottom are also used. Due to the
vibrations, a large ball bounces on the plateau and, therefore, crushes a part of the
powder.
The use of rods instead of balls increases the shearing part of the milling [14].
1.1.3. Main milling parameters

Numerous parameters inuence the kinetics of the milling as well as the microstructure of the prepared powders. Some of those parameters depend on the type of
mill, others on the contrary can be dened whatever the mill is. Following is a nonexhaustive list of the milling parameters, classied approximately by inverse order of
importance:
milling duration,
charge ratio (ratio between balls and powders weights),
size and nature of the balls,
rotation speed (for planetary, attritor or cannon-ball types) or frequency and amplitude of the vibrations (for vibrant type),
lling rate of the vial (ratio between the balls and powder volumes and the total
volume of the vial).
1.1.3.1. Inuence of the milling duration. This parameter should generally be as low as
possible: a longer milling leads to energy consumption and increases the risk of
pollution due to the abrasion of the milling tools. The needed milling time for the
preparation of a material depends obviously on the material nature, but also on the
other milling conditions. It is generally admitted that, for a given material, longer
the milling is, smaller the particle size is. However this size tends to a limit value due
to an agglomeration process, as seen previously.
1.1.3.2. Inuence of the charge ratio. In a rst approximation, one can consider the
frequency of the shocks to be proportional to the charge ratio: as this ratio is high, as
the particles are split and more their size is decreased. The increase of the charge
ratio allows, on the other hand, to diminish the milling duration since some equivalence between those two parameters exist as shown in Fig. 6 [15].
However, in some cases, a too large intensity of the milling can involve an
amorphization of the material and one has to decrease the milling duration as it must
be done with graphite, which leads rapidly to amorphous carbons as the milling is
too violent. This particular point will be discussed later.
1.1.3.3. Inuence of the size and nature of the balls. It is obvious that, larger the balls
are, more the plastic deformations and the constraints applied to the powders are
increased. If all the other milling conditions are identical, the particles become as
small as the milling balls are larger. However, the grains size tends to a minimal
value, as calculated from the following equation (HallPetch law):
p
r r0 A= d
1
with A and r0 constants, r the limit of elasticity for the given material. As a consequence, when one wants ne particles, one has to impose large constraints.
The nature of the balls is diverse: as a function of the density, there are agate
d 2:3, alumina d 4:0, zircona d 5:7, stainless steel d 7:8 and tungsten
10
Fig. 6. Correlation between milling duration and charge ratio (after Ref. [15]).
carbide d 16:4. The most generally used balls are made of stainless steel (extra
hard, type Z200C12). One of the major problems with mechanical alloying consists
in the pollution coming from the erosion of the milling materials, which is almost
impossible to avoid. This contamination is directly connected to the hardness ratio
between balls and samples. When the millings are done with balls and vials in
tungsten carbide, there is no pollution at all [16], but the price of such milling tools is
high and, tungsten carbide being fragile, it is rarely used. Schaer and Forrester have
shown that denser the density is, more important the collision energy is [17]. It is also
interesting to note that the most energetic millings are generally done with mixtures
of balls of dierent diameters.
1.1.3.4. Inuence of the rotation speed of the vials. During the milling, the shocks
create heat due to the plastic deformation of the powder particles. That heat is
dissipated into the vial and the local temperature increases proportionally to the
collisions violence, thus, to the rotation speed. The local and instantaneous temperature increase is dicult to quantify, but Eckert et al. [18] has shown that this
local warming can reach 400 C with highly energetic millings.
This temperature increase is rapidly transmitted to the whole vial and its content.
Maurice and Courtney have shown [10] that a particle is cooled down before a new
impact, so one can consider the temperature to be homogeneous inside the vial. The
equilibrium temperature depends on the type of milling, but it can reach 100 C with
a vibrant type mill. In fact, the milling temperature is a very important parameter,
since the behavior of a powder depends strongly on the temperature. The temperature increase involves a larger ductility of the milled material, thus, a higher
diculty to decrease its particles size. Moreover, the recrystallization of an amorphous
11
phase can occurred during the milling process if the temperature increase is important [10].
1.1.4. Conclusion
The ball-milling allows the preparation of numerous and diverse powders. The
result depends on dierent choices, based on compromises, since several milling
parameters are working in opposite directions. In fact, the mechanical alloying is
generally a simple step in the elaboration of materials and, often, the resulting
powders are compacted or sintered in order to improve their mechanical properties.
One of the large interests of the ball-milling is the easiness to prepare either nanocrystalline or amorphous powders, to synthesize alloys with metals whose melting
points are very dierent, which is quite dicult by classical melting methods.
The mechanical alloying presents however several limits:
its eciency is very limited if one phase is too ductile, due to an important sticking
on the milling tools,
the pollution connected to the abrasion of the milling tools can be large and,
therefore, one has to decrease as much as possible the milling duration by optimization of the other parameters governing the synthesis (charge ratio, size and nature of the balls, rotation speed).
The choice of the mill is also drastic and depends on the powder quantity to
prepare (especially at the industrial scale). It depends also on the type of desired
shocks: vibrant type mills (SPEX) involve mainly frontal shocks, whereas the
planetary mills induce both head on and friction shocks. In the present work, we are
dealing with graphite, whose tendency to cleave is favored by friction and, thus, we
have used a planetary mill, which also helps for the intercalation of lithium.
1.2. The graphite and its intercalation compounds
1.2.1. The graphite
1.2.1.1. Structure. The lamellar structure of graphite is applied for centuries as pencil.
The graphite is a two-dimensional material and presents a large anisotropy of bonds.
The sp2 hybridization induces a covalent r type bond with three other carbon atoms
in the plane, which involves the formation of aromatic macromolecules in a hex
agonal net called graphene layer. The carboncarbon in-plane distance is 1.42 A,

shorter than that in diamond (1.54 A), an other allotropic variety of carbon characterized by a sp3 hybridization. The r bonds of graphite present, thus, a higher
electronic density, which explains their high cohesion.
The graphene layers are superimposed parallel to each other and the cohesion of
the material (between the graphene planes) is ensured by Van der Waals type bonds,
quite weak, which explains the easiness of the cleavage of graphite and the large
There are two types of
distance between successive graphene planes (3.35 A).
stacking: ABAB. . . (cf. Fig. 7), hexagonal graphite (2H) or ABCABC. . . (cf. Fig. 8),
rhombohedral graphite (3R).
12
Fig. 7. Hexagonal graphite.
Fig. 8. Rhombohedral graphite.
The hexagonal graphite, also called a graphite, is the most common form. Its
structure, rstly described by Bernal in 1924 [19], was conrmed by Mauguin in 1926
[20]. The unit cell belongs to the space group P63 /mmc with the following parame and c 2 Ic 6:70 A.

ters: a 2:46 A
13
Rhombohedral graphite, also called b graphite, is characterized by a unit cell

a 39:5 as shown by Lipson and
R 3 m with the following parameters: a 3:635 A,
Stokes in 1942 [21]. Often associated to the hexagonal form, this phase does not exist
alone. Its presence is favored by milling [22], ultrasonic treatment [23] up to 40%, but
disappears by heating above 2000 C [24] or by intercalation/deintercalation of
various species between the graphene planes.
1.2.1.2. Physical properties. Graphite is a black, soft and easy to cleave material, its
crystallographic density is 2.27, lower than that of diamond (3.54), which explains
why articial diamond can be synthesized from graphite under high pressure and
temperature [25]. The carbon atoms have four valence electrons and the sp2 hybridization deals with three electrons shared with the neighbors carbons. The fourth
electron is delocalized and this delocalization of those p electrons in the planes is
responsible of the fair electrical conductivity (rk 2 104 S/cm). In fact, the inplane conductivity of graphite occurs by holes and the number of carrier is quite
small (1018 /cm3 ): the high value of the conductivity is due to very high carrier mobility. Graphite behaves as a semi-metal in the plane with a small overlap between
conduction and valence bands. The transverse conductivity is 103 104 smaller than
that of the in-plane one: the electronic exchanges are more dicult in that direction
Like diamond, graphite presents
connected to the high interplanar distance (3.35 A).
good heat conduction, mainly due to the phonons. The weak interactions perpendicular to the planes leads to a large heat conduction anisotropy.
1.2.2. The intercalation phenomenon
Graphite reacts with a large variety of species and leads to a wide family of
graphite intercalation compounds (GICs). This phenomenon is connected to:
the lamellar structure of graphite and the weak bonding between the planes, which
favors their splitting,
the electronic structure of graphite: the planes form aromatic macromolecules,
which can accommodate electron donor as well as electron acceptor species.
By intercalation, the graphene planes remain geometrically unchanged, the intercalated species forming planar layers made, in some cases, of several planes (e.g.
with transition metal halides, there is generally three intercalated planes: halide
metalhalide). Therefore, the GIC remains with a lamellar structure.
The intercalation process results of two simultaneous reactions: oxido-reduction
and intercalation of a charged species, whose charge compensates that of the host
structure. With electron donors (typically the alkali metals), the graphite is reduced and there is intercalation of the metal cations. The electron acceptor species
are intercalated as anions into the oxidized graphite network. For the intercalation phenomenon, graphite has an amphoterous behavior. The name donor or
acceptor is also given to the GIC itself, instead of GIC with donor (or acceptor)
species.
14
1.2.3. The graphite intercalation compounds

Since 1977, International Conferences were devoted in part or totally to the GICs:
La Napoule (France) 1977 [26], Nijmegen (The Netherlands) 1977 [27], Provincetown (USA) 1980 [28], Trieste (Italy) 1981 [29], Pont-a-Mousson (France) 1983 [30],
Tsukuba (Japan) 1985 [31], Jerusalem (Israel) 1987 [32], Berlin (Germany) 1989 [33],
Orleans (France) 1991 [34], Louvain-la-Neuve (Belgium) 1993 [35], Vancouver
(Canada) 1995 [36], Arcachon (France) 1997 [37], Okazaki (Japan) 1999 [38],
Moscow (Russia) 2001 [39]. The corresponding proceedings gather a large part of the
knowledge on GICs and other intercalation compounds.
The intercalation phenomenon was rstly discovered in 1926 by Fredenhagen and
Cadenbach [40]. The intercalation compounds are now well-known, due to the development of the lithium-ion batteries based on the formation of the LiC6 compound
at the negative electrode, this last being rstly described in the sixties [41,42].
An intercalation compound is dened by several criteria:
its chemical formula, generally written as a function of one intercalated atom or
molecule (e.g. LiC6 , KC8 ),
its stage, which is the number of graphene planes lying between two successive intercalated layers. In a rst stage compound, all intervals between the graphene
layers are occupied by the intercalate,
its interplanar distance: that separating two carbon planes surrounding the intercalated layer. This distance (di ) depends on the size of the intercalated species and
(Li compounds) to 5.95
varies, for the compounds with alkali metals from 3.70 A

A (Cs compounds),
its repeat distance along the c axis Ic , which is the value directly determined by
X-ray diraction.
Those dierent values are linked by the following equation:
Ic di n 1 3:35

with Ic and di in A
The structure of the intercalation compounds is tightly connected to that of

graphite: as described just above, along the c axis, the structure corresponds to that
of graphite with some dilatation, due to the presence of the intercalated species. The
in-plane structure is also derived from that of graphite, especially in the case of the
compounds with alkali metals, where the intercalated atoms lie in epitaxy between
the center of graphite hexagons. This involves the graphite planes to be stacked in
AAA and, as a consequence, the rhombohedral phase disappears by intercalation/
deintercalation. This explains also why the formula of the intercalation compounds
is simple like KC8 or LiC6 . The structure of those compounds was qualied respectively of octal or hexal. In fact, one carbon hexagon corresponds to two
carbon atoms and a composition like LiC6 means that one site in three possible is
occupied by the lithium atoms, as it appears in Fig. 9(a). The structure of the GICs
can be also
as a superstructure of that of graphite and
p expressed
p
p the in-plane cell is
noted as ( 3 3, R30), which means that the a parameter is 3 times longer than
15
Fig. 9. In-plane structure of (a) LiC6 (rst stage) and (b) LiC18 (second stage).
that of graphite and that the graphite and compound cells are rotated by an angle of
30.
This fact involves that the graphite h k 0 reections are present in the XRD spectra
of the GICs with electron donors. In the particular case of LiC6 , an other phenomenon complicates the interpretation
p of the X-rays analysis, since the a and c
parameters are roughly in the ratio 3=2, which involves a systematic superimposition of the 0 0 l and l 0 0 reections [43].
The stacking of the intercalated layer can complicate the structure. For instance,
in LiC6 , whose composition involves the occupation of one site in three possible, all
lithium atoms are exactly superimposed. The resulting unit cell is hexagonal and
c Ic 3:70 A
[44,45]. On the
belongs to the P6/mmm space group with a 4:30 A,
contrary, in BaC6 [46] or EuC6 [47], the metal atoms occupy regularly two sites in
and
three and lead to a hexagonal unit cell, space group P63 /mmc, with a 4:30 A

c 2 Ic (respectively 10.51 and 9.75 A).
1.2.4. The graphitelithium compounds
The rst graphitelithium intercalation compounds were prepared by action of
lithium vapor on graphite. But, the lithium pressure being low (around 10 4 Torr at
400 C, the maximal temperature beyond which the formation of lithium carbide
becomes important [42]), the kinetic of the intercalation reaction is slow. Synthesis
via a solid way was then set up: lithium and graphite powders were compressed
together at a pressure of around 5 kbars [45]. The reaction is done at room temperature with a hand press placed in a glove box with a puried argon atmosphere.
The lithium intercalation occurs at room temperature and is almost complete after
one week, but a moderate heating at 200 C (under vacuum or argon atmosphere) of
the pellet allows this intercalation to be nished after 24 h.
The intercalation by compression, contrarily to the lithium vapor intercalation,
allows the synthesis of compounds with stages other than one (LiC6 ) by varying the
16
Li/C ratio. Stages 14 can be prepared by this method, which has proved a variation
of the composition for the stages higher than one: LiC12 to LiC18 for stage 2, LiC18 to
LiC30 for stage 3 for instance. All those compounds present the same interplanar
independently of the exact stoichiometry.
distance of 3.70 A,
Those experiments were re-investigated and improved under high pressure (50
kbars) and at a temperature of 300 C by a Russian team [48,49]. Their technique
leads to new phases, especially a rst stage compound called superdense phase. Its
composition is LiC2 , which corresponds to the occupation of all possible sites for
the lithium atoms (cf. Fig. 10(a)). The lithiumlithium distances are very small (2.46
compared to that of the Li2 molecule (2.67 A).
This compound, whose interA)
planar distance is the same as the classical LiC6 phase, presents, in spite of the
presence of two carbon atoms, a lithium density higher than that of metallic lithium
itself: this fact induces a negative potential versus Li0 in an electrochemical cell, as
shown by Yazami et al. [50]. The LiC2 compound is not stable and decomposes
slowly into LiC6 and free lithium as the pressure is released. Several phases can
be characterized during the decomposition process and some examples are given in
Fig. 10(b and c).
The mechanical alloying leads, as it was already seen, to local and instantaneous
conditions close to those required by the high pressure technique. This is the reason
of our investigations for the synthesis of new superdense graphitelithium phases
using this method.
The electrochemical intercalation of lithium is now daily used since the reversible
intercalation of lithium into graphite allows the energy storage: the anode of most of
the lithium-ion batteries is made of graphite. Metallic lithium should be preferred
since its capacity of 3.8 A h/g is roughly 10 times higher than that of LiC6 (372 mA h/
g). However, lithium forms dendrites during the cycling process, provoking shortcircuits between cathode and anode. The high reactivity of electrolytes towards
lithium and their possible co-intercalation with lithium into graphite was an obstacle
[51], which was overcome with the apparition of new electrolytes mainly based on
ethylene-carbonate (EC) and its derivatives [5254].
Fig. 10. (a) LiC2 compound obtained under high pressure, (b and c) phases observed during the decomposition process at ambient pressure.
17
1.3. The lithium batteries

1.3.1. Introduction
The use of lithium as negative electrode in electrochemical systems was investigated in the 1950s and a French patent on lithium batteries was rstly deposited by
Herbert and Ulam in 1957. The interests for lithium are:
its metallic character responsible of a good electronic conductivity for the electrode,
its low molecular weight (6.94 g/mol) allowing to reach an electrochemical capacity as high as 3860 mA h/g,
its very low standard potential ()3.04 V versus NHE in aqueous solutions).
This last property is at the origin of the high potential for lithium batteries and,
therefore, of their high energy densities. However, the strong reducing character of
lithium is responsible of the formation of a passivating layer on the metal surface,
due to the electrolyte decomposition. This lm was extensively studied by means of
transmission electronic microscopy [55] and impedance spectroscopy [56].
The rst primary lithium batteries, commercialized in the 1970s, were constituted
of metallic lithium and uorinated carbon (CFx ) as negative and positive electrodes,
respectively. This battery has an operating voltage close to 3 V. This system is still
commercialized today (mainly for watches), but it is often replaced by the Li/MnO2
system. When higher energy densities are required, as in military or spatial applications, SOCl2 or SO2 Cl2 are used as positive electrodes.
For secondary batteries, the use of metallic lithium as negative electrode is unfortunately not possible due to an important lack of safety. In fact, the lithium
electro-deposition is not uniformous and leads, during the electrochemical cycling, to
the formation of dendrites provoking short-circuits. To avoid this problem, two
main technologies were set up: the polymer electrolyte technology [57,58] and the
lithium-ion technology [58,59]. The rst technique consists to replace the liquid
electrolyte by a solid polymer, this last requires however a temperature above 60 C
to present a sucient ionic conductivity. The second solution is the replacement of
metallic lithium by an insertion compound, often a carbonaceous material. Both
technologies can be combined to obtain a plastic lithium-ion battery, called
PLiON [60]. The lithium-ion batteries are perfectly suitable for portable devices,
since their commercialization by Sony in 1991 [54], whereas the solid polymer batteries seem very promising as energy sources for future electric vehicles.
1.3.2. Lithium batteries with a polymer electrolyte
The rst technique allowing to avoid the formation of lithium dendrites consists
to replace the liquid electrolyte by a polymer (cf. Fig. 11). The possible application of
polymer as battery electrolytes was demonstrated by Armand et al. in the 1970s
[57,58]. These authors claimed that the crystalline complexes formed from alkali
metal salts and polyethylene oxide (PEO) were capable of demonstrating signicant
ionic conductivity. This work inspired intense research and development on the
18
Fig. 11. Schematic representation of solid polymer lithium batteries.
synthesis of new polymer electrolytes. Many works are currently aiming to nd

polymers with a high ionic conductivity (around 10 3 S cm 1 at room temperature).
To date, several types of polymer electrolytes have been developed, such as those
based on PEO, polyacrylonitrile, polymethyl metacrylate and polyvinylidene uoride. The polymers can be sort into two categories: the pure solid polymer electrolytes and the gelled polymer electrolytes.
The rst category is made of lithium salts (e.g. LiClO4 , LiBF4 , LiPF6 , LiCF3 SO3 )
dissolved in high molecular weight polyether (e.g. PEO), which act as solid solvents.
Such electrolytes commonly exhibit ionic conductivities ranging from 10 8 to 10 4
S cm 1 at temperatures above 50 C, which excludes practical applications at ambient temperature. This obstacle originates from the high degree of crystallinity,
which is not favorable for ionic conduction, and the low solubility of lithium salts.
The most striking advancement in the ionic conductivity of polymer electrolytes has
been obtained through the incorporation of substantial amounts of plasticizer and/or
solvent to the polymer matrix. This leads to the second category of polymer electrolytes: the so-called gelled polymer electrolytes [61].
The gelled polymer electrolytes are characterized by a high ambient ionic conductivity. For instance, the use of polyethylene glycol (PEG) as plasticizer within
PEO leads to a strong enhancement of conductivity. The ionic conductivity can
reach 10 3 S cm 1 at 25 C, with decreasing molecular weight of PEG and increasing
PEG content [62]. The conductivity enhancement is mainly attributed to the reduction of the crystallinity and the lowering of the glass-transition temperature of
the polymers. If the gelled polymer electrolytes have higher ambient ionic conductivities, their mechanical properties are poorer, when compared with pure solid
polymer electrolytes. In order to improve the mechanical properties, components
which can be cross-linked may be added to the gel electrolyte formulation. The
19
chemical cross-linking is a process associated with the covalent bonding of polymer

chains by means of a chemical reaction to form junction points.
1.3.3. Lithium-ion batteries: the use of insertion compounds as anodes
The second way to avoid the dendritic formation of lithium consists to replace
metallic lithium at the negative electrode by a compound able to reversibly intercalate lithium ions at low potentials [58,59]. The lithium ions are, therefore, successively intercalated/deintercalated from the negative and positive electrodes, giving
the name of rocking-chair to those batteries (cf. Fig. 12). If the lack of safety is
resolved by this technique, this system requires the association of materials with a
strong reducting character as anode and a strong oxidant character as cathode to
obtain batteries with high energy densities.
Among many materials for positive electrodes, lamellar oxides as LiCoO2 and
LiNiO2 [6365] and spinel as LiMn2 O4 [66] are very attractive. LiCoO2 is the most
widely used in commercial batteries, due to its low cost, its easy synthesis and its
good electrochemical performances. The capacity is of the order of 140 mA h/g with
an average voltage of 4 V. But, due to the high toxicity of Co, the development of
new cathodic materials is of a great interest. Polyanionic materials with the olivine
structure are very promising (e.g. LiFePO4 [67]) and represent today a good alternative to LiCoO2 .
For the anode, various materials were investigated. It appeared that carbonaceous
materials are the most relevant, since reversible lithium insertion into those materials
occurs at very low potentials. As a matter of fact, lithium is reversibly intercalated
into graphite below 0.1 V versus Li /Li and leads to the formation of the LiC6
compound, corresponding to a capacity of 372 mA h/g [52]. This process is however
Fig. 12. Schematic representation of lithium-ion batteries.
20
associated with the formation of a passivating layer at the carbon surface, due to the
decomposition of the electrolyte. Many studies were carried out in order to characterize this layer and to better understand its formation. This lm, often called
Solid electrolyte interface [68], enables the co-intercalation of solvent molecules
between the graphene sheets and, therefore, strongly limits the graphite exfoliation
during electrochemical cycling. This carbon passivation, during the rst electrochemical reduction, is responsible of a lithium loss and an irreversible capacity (cf.
Fig. 13).
Carbonaceous materials with higher capacities than graphite can be prepared:
either by a chemical mean (e.g. pyrolysis of an organic precursor [69]), either by a
physical mean (e.g. ball-milling of graphite [70]). If much more lithium can be reversibly inserted into those disorganized carbons than into graphite, leading to capacities of the order of 450500 mA h/g [71], this is unfortunately associated with a
large hysteresis of the charge/discharge process, decreasing strongly the energy
densities of the corresponding batteries. Moreover, these carbons have a large specic surface area, which is responsible of a large irreversible capacity, during the rst
electrochemical reduction, due to the formation of an important passivating layer.
An other category of anodic materials is related to the electrochemical formation
of lithium-based metallic alloys (mainly with Sn). This technique, very interesting
from the point of view of the capacity, is however not used for practical applications,
due to the important volume variation of the particles, leading to their fracture and,
nally to the loss of the electrical conductivity between the grains [72,73]. This
problem was partially resolved by the Fuji Co Ltd. [74]. Their idea was to electrochemically reduce amorphous tin oxides by lithium. This reaction leads to the formation of Sn particles dispersed in a Li2 O matrix. This matrix allows to compensate
the important volume variation, due to the formation/dissociation of the Lix Sn
alloys.
C irrev
3.0
C reversible
2.5
1st charge
1st discharge
E (V)
2.0
1.5
SEI
1.0
0.5
0.0
0
100
200
300
400
500
Capacity (mAh / g)
Fig. 13. Typical rst galvanostatic cycle of graphite as anode in Li-ion batteries.
21
1.3.4. Conclusion
Sony was the rst society, in 1991, to commercialize lithium-ion batteries using
graphite and LiCoO2 as negative and positive electrodes, respectively. These batteries are assembled at the discharged state (lithium-free graphite). The rst charge is
a very important step, since it corresponds to the formation of the passivating layer
onto the carbon surface and, therefore, it is responsible of the electrochemical performances during the following cycles. At the present, graphite (either natural, either
synthetic) is still the best anodic material for lithium-ion batteries, since lithium
intercalation/deintercalation processes occur below 0.1 V. Moreover, the cyclability
and durability of graphite are excellent when appropriates electrolytes are used.
1.4. The maghemite (c Fe2 O3 )
The maghemite is an iron III oxide (c Fe2 O3 ) largely used as material for magnetic
storage. Its structure is of spinel type slightly derived from that of magnetite (Fe3 O4 )
and this oxide presents a ferromagnetic behavior.
The purpose for the preparation of maghemite nanoparticles is mainly due to
their potential applications: magnetism, catalysis, electrochemistry. . . This last point
is developed in this paper because transition metals oxides (especially with Fe, Co,
Ni), with a nanometric particles size, are good candidates to replace graphite as
anodes for lithium-ion batteries [75]. For instance, CoO particles with a diameter in
the 1020 nm range present a reversible capacity around 700 mA h/g and an excellent
cyclability. This is due to the reversibility of the following reaction:
CoO 2Li () Li2 O Co
From the thermodynamic point of view, the reaction is displaced deeply to the
right. During the rst charge, the CoO reduction (at 0.8 V versus Li /Li) leads to the
formation of cobalt nanoparticles (2 nm in diameter), whose high reactivity allows
the oxidation and, thus, ensures the reversibility of reaction (3). It was interesting to
investigate such kind of behavior on the maghemite nanoparticles.
1.4.1. Structural aspect
The basic structural unit for all Fe oxides is an octahedron, in which each Fe atom
is surrounded by six O ions. The O ions form layers which are approximately hexagonally close-packed (hcp), as in hematite, or cubic close-packed (ccp), as in maghemite. In both hcp and ccp structures, tetrahedral interstices also exist between
three O in one plane and an other O atom in the plane above. The hcp form is termed
a phase, whereas the corresponding ccp form is termed c phase. The a phase is more
stable than the c phase.
Hematite (a Fe2 O3 ) consists of layers of FeO6 octahedra, which are connected by
edge and face sharing (as in corundum a Al2 O3 ) and stacked perpendicular to the c
direction. Two-thirds of the octahedral interstices are lled with Fe3 . The face
sharing is accomplished by a slight distortion of the octahedral which causes a
regular displacement of the Fe ions.
22
Maghemite (c Fe2 O3 ) has the composition of hematite, but the structure of

magnetite. It can be considered as a fully oxidized magnetite. In the cubic structure
of both magnetite and maghemite, 1/3 of the interstices are tetrahedrally coordinated
with oxygen and 2/3 are octahedrally coordinated. In magnetite, all these positions
are lled with Fe. Magnetite is an inverse spinel: the tetrahedral positions are
completely occupied by Fe3 , the octahedral ones by equal amounts of Fe3 and
Fe2 . In maghemite, only 5/6 of the total available positions are lled and only by
Fe3 , the rest are vacant (h): Fe2:67 h0:33 O4 . Maghemite can have dierent symmetries depending on the degree of ordering of the vacancies. Completely ordered
maghemite has a tetragonal symmetry, otherwise it is cubic.
1.4.2. Synthesis
In fact, the stabilization of c Fe2 O3 is favored by a small particles size: above 50
nm, the stable form of iron III oxide is a Fe2 O3 , whereas the c form is stabilized
below 10 nm. This phenomenon is considered as a phase transition assisted by the
particles size. The development of new synthesis methods for maghemite nanoparticles is currently very active. The most used method was set up by Massart [76] and
consists in two steps: rstly, a co-precipitation of ferrous and ferric cations in alkaline solutions leading to magnetite (Fe3 O4 ) nanoparticles, which are then oxidized
in air at 200250 C. With appropriate conditions, mainly the choice of the pH, one
obtains 10 nm maghemite particles. More recently, other techniques, which are quite
complicated and/or require expansive apparatus, were discovered. For instance, very
nely divided and monodisperse maghemite is prepared by microwave plasma from
FeCl3 or Fe3 (CO)12 [77] or by electrochemical techniques allowing the formation of
iron clusters, which are then softly oxidized [78].
The ball-milling constitutes a process, leading easily to nanosized particles [79].
Phase transitions are also induced by mechanical alloying e.g. with transition metal
oxides like TiO2 , Y2 O3 , WO3 . . . [80,81]. In the same manner, hematite (a Fe2 O3 ) can
lead to maghemite (c Fe2 O3 ) using special milling techniques. For instance, when a
dispersion of hematite in methanol is placed between two discs rotating alternatively
in opposite directions, maghemite is obtained. The important shearing eect created
by such device provokes a sliding of the oxygen planes followed by a cationic reorganization. However the transformation is not fully achieved, even after 55 days:
only 57% of hematite are transformed into maghemite and the particles size is larger
than 50 nm [82]. More recently, a similar reaction was described using a planetary
type mill. The results are relevant (particles size between 4 and 20 nm after 48 h), but
the reaction remains incomplete even for long milling durations [83].
2. Intercalation of lithium into graphite by ball-milling

The pressure and temperature induced to the particles by the shocks occurring
during the milling are of a great importance to understand the mechanism for
the ball-milling synthesis. Unfortunately, those values are dicult to determine since
23
the phenomena are short and very localized. They can be nevertheless estimated
indirectly: for instance, in the case of amorphous alloys, it is possible to know if the
recrystallization temperature was reached or not, as it can be proved by microstructural investigations or enthalpy measurements [18].
Several authors [10,11] have shown that the highly energetic milling leads to instantaneous and local temperature and pressure (40 kbars, 300 C). Those values are
close to that used for the high pressure technique (50 kbars, 300 C). The intercalation of lithium into graphite under high pressure leads to superdense phases, but
requires a special and complex material for a low rate of several hundreds milligrams at once. It is therefore interesting to develop the intercalation of lithium by
ball-milling, since this technique is easier to handle and the quantity of prepared
powders can be much higher: several grams instead of several hundreds of milligrams.
2.1. Material used in this study

2.1.1. The mill and its devices
The planetary type mill, model Retsch PM400, and the vial are represented in Fig.
14.
The maximal rotation speed is 400 rpm and the vial rotates at the same speed as
the tray, but in the opposite direction. The vials are made of special hard steel
(Z200C12, 12% of chromium, 2% of carbon in weight). The volume of 270 cm3 allows the synthesis of 5 g of powders at once. A rubber ring placed on the cover
ensures the tightness of the vial, which is lled under the inert atmosphere of a glove
box with puried argon circulation. Three dierent sizes of balls are used as it appears in Table 1.
It seems important to examine the abrasion of the milling tools. For instance,
when 5 g of graphite powder are milled with 200 g of balls at a rotation speed of 200
rpm, the contamination, as measured by microprobe, is as follows:
Fig. 14. Planetary mill (left) and 270 cm3 stainless steel vial (right).
24
Table 1
Characteristics of the stainless steel balls used in this work
Diameter (mm)
Mass (g)
Steel
5
10
20
0.6
4
32
11C6
100C6
Z200C12
when stainless steel balls (softer than the vial material) with 5 or 10 mm diameter
are used, the pollution remains low: the iron content in the graphite powder is below 0.1% after 24 h and 1% after 96 h,
with balls of 20 mm, made of the same steel as the vial, the iron contents are respectively 1% and 3% in the same conditions. Therefore, the use of such 20 mm
balls should be avoided for long millings.
2.2. Reagents
Ceylon type graphite, commercialized by Alfa, was generally used. Its purity is
99.5% in carbon. The spheroid particles present a mean size below 40 lm. Before its
introduction in the glove box, the graphite is outgassed under vacuum at 800 C for

12 h. The XRD transmission pattern is given in Fig. 15 (kMo 0:70926 A).
The graphite is well organized as pointed out by the narrowness of the reections,
which proves the good stacking of the graphene planes along the c axis, since the
An enlargement of the 1822 (in 2h) domain shows
interplanar distance is 3.35 A.
up the presence of rhombohedral phase, coming probably from the grinding done by
the manufacturer: the milling increases the amount of the rhombohedral phase. This
rhombohedral phase is revealed by the reections (1 0 1) and (1 0 2) at respectively

Fig. 15. XRD pattern of initial Alfa graphite (k 0:70926 A).
25
19.6 and 20.8. The rhombohedral phase content can be estimated around 78%. In
fact, pure hexagonal graphite is quite rare and one has to heat natural graphite at
2000 C to entirely remove the rhombohedral phase [84].
The lithium is either in granules (16 mm, Alfa, purity 99.4%), or in powder
(mean size 170 lm). This last was prepared by the CEA (Commissariat a energie
atomique, France) using a method derived from that set up by Hansley [85]: its
oxygen and nitrogen content is lower than 0.1% in weight.
2.3. Synthesis conditions
The vial with the balls is introduced in the glove box. The argon purication is
obtained by passing the gas through molecular sieves for the water retention and
titaniumzirconium chips whose heating at 800 C allows eliminating both oxygen
and nitrogen.
The reactants are weighted in the glove box within an accuracy of 0.1 mg and
placed in the vial, which is tightly closed by screwing the cover on the vial body. The
vial is then removed from the glove box and placed on the tray of the mill. After
milling, the vial is opened in the glove box and the separation between the powder
and the balls is simply done with a sieve.
2.4. Optimization of the milling conditions
As it was previously seen, there are numerous parameters in the ball-milling. The
goal was to obtain a homogeneous powder and to avoid the agglomeration on the
balls, which makes dicult the separation of the reaction products. The optimization
was done mainly on the following parameters:
size of the lithium (granules or powder),

lithium/carbon ratio (from Li + 2C to Li + 6C),
charge ratio (from 20 to 80),
balls diameter (5, 10 or 20 mm),
milling duration (from 12 to 24 h).
In this manner, we have chosen the best conditions for the preparation of the
rst stage graphitelithium compounds and, then, the synthesis for the superdense
phases.
2.4.1. Nature of lithium
The use of lithium granules was rapidly shown as inadequate: Fig. 16 represents
the XRD patterns of the resulting products of a mixture with a C/Li ratio of 2
prepared from lithium granules and powders respectively. All other conditions are
the same for the synthesis:
5 g of reactants (graphite: 3.87 g, lithium: 1.13 g),
200 g of balls (diameter 5 mm),
26
Fig. 16. XRD of a Li + 2C mixture: with lithium powder (top), with lithium granules (bottom).
charge ratio: 40,

rotation of 200 rpm.
With granules of lithium, there is no real intercalation of lithium and the size of
the granules is almost unchanged, which involves some amorphization of the
graphite matrix: the 1 0 0 and 1 0 1 reections of graphite are weakened. The graphite
showing up some organization of the graphite,
0 0 2 distance is still close to 3.35 A,
but the presence of a shoulder at lower angles proves either the apparition of turbostratic carbon or that of some high stage graphitelithium compounds.
With lithium powder (mean size of 170 lm), the intercalation occurs after 12 h of
milling as it appears on the XRD diagram shown in Fig. 16, where the reections of
the normal rst stage compound appear clearly. The excess of metallic lithium,
visible at 2h 16:4 (1 1 0 reection) is in good agreement with the relative intensities
of the classical graphitelithium rst stage compound: no formation of a superdense
phase can be detected at this point. When the milling duration is increased up to 24
h, there is no real change, which means that the lithium excess acts as a lubricant.
From those experiments, it appears clearly that the granules have to be avoided for
the ball-milling synthesis.
2.4.2. Lithium/carbon ratio
Due to its high ductility, lithium tends to agglomerate on the balls during the
milling process. This agglomeration inuences largely the shocks eciency, the
27
constraints applied to the powders, and, thus the microstructure of the obtained
phases. The C/Li ratio is, then, a very important parameter. The milling conditions
are similar to those previously announced and lithium powder is preferred to
granules. The following XRD patterns are relative to milling duration of 24 h.
Li + 6C: The synthesized powder is made of a mixture of rst and second stage
in the apcompounds, whose main reections are respectively 3.70 and 3.52 A,
proximate ratio 2/1. Lithium excess seems necessary to reach a pure rst stage
compound, which compensates the loss of metal by agglomeration on the milling
tools.
Li + 4C: When the amount of lithium is higher (Li + 4C), the XRD diagram
corresponds to a pure LiC6 compound. All reections can be indexed in the hex and c 3:70
agonal P6/mmm unit cell of the rst stage compound (with a 4:30 A

A). However, one should note that the compound is not well crystallized: the
background is quite high and the width at half height of the reections is relatively
large, especially for the 0 0 l reections. This points out the presence of stacking
faults due to the violence of the shocks. No excess of lithium can be detected, which
can easily be explained by the low electron number for lithium atom. Moreover, the
lithium forms probably very small particles unable to diract the X-rays.
Li + 2C: When the ratio reaches Li + 2C, the powder is yellow, typically the color
of LiC6 . This initial composition allows to obtain the pure rst stage after 12 h of
milling, instead of 24 h for a C/Li ratio of 4. The relative intensities of the observed
reections correspond to that calculated for LiC6 . One should note that this compound is better crystallized than when the starting composition is Li + 4C. This
dierence results of the role of lubricant plaid by the excess of lithium, which
weakens the violence of the shocks. Thus, the carbon matrix is less disorganized.
As a result of these previous experiments, an initial Li + 2C composition seems to
be the best compromise for the ball-milling synthesis: the resulting phase is LiC6 and
the excess of lithium acts as a lubricant, which avoids a too large degradation of the
graphite network.
2.4.3. Charge ratio
Normally, the intensity of the shocks is directly proportional to the charge ratio:
higher is this ratio, higher is the frequency of the shocks and, thus, the milling is
more energetic. In our case, we have determined the inuence of the charge ratio on
the microstructure of the compounds starting from 5 g of a graphite + Li mixture.
We have varied the mass of the balls for a charge ratio between 20 and 80. One has to
note here that this charge ratio is connected with the lling rate of the vial, which
value ranges from 5% to 20%. One can admit that this variation does not inuence
drastically the reaction since the free volume in the vial remains quite high even with
a charge ratio of 80 and one can consider that the speed of the balls is sucient to
achieve an ecient milling.
The XRD data shown in Fig. 17 correspond to the following conditions:
mixture composition Li + 2C,
5 mm balls,
28
Fig. 17. XRD of a Li + 2C mixture: with a charge ratio of 20 (top) with a charge ratio of 80 (bottom).
rotation speed: 200 rpm,

24 h of milling.
With a charge ratio of 20 (100 g of balls), the powder is a mixture of rst and
second stage compounds, in good agreement with the brown color of the powder. A
shoulder appears on the right (short distances) of the main peak. One can estimate
the content of this mixture: 70% of LiC6 , 30% of LiC12 . A longer milling is necessary
to obtain a pure rst stage, but pollution by metals (in particular iron) due to the
abrasion of the milling tools appears. This result agrees well with some equivalence
between the milling duration and the charge ratio [15]. When the charge ratio is 40,
the XRD diagram of a pure and well crystallized rst stage compound is observed.
With higher charge ratios (60 or 80), the rst stage compound is less and less crystallized as the charge ratio is increased, in particular, the relative intensity of the 1 1 0
reection versus 0 0 1 indicates that the graphite planes are more fractured than in
the presence of a smaller charge ratio.
29
Therefore, the choice for the most appropriated charge ratio results of a compromise between a long milling duration (which leads to a contamination by the
milling tools) connected to a low ratio and the risk of an important amorphization
when large charge ratios are used. The value taken for the synthesis of rst stage
graphitelithium compounds is 40 in the following.
2.4.4. Balls size
Three dierent ball sizes are available: 5, 10 and 20 mm in diameter. All the other
milling conditions are similar and correspond to that previously used with a charge
ratio of 40 (200 g of balls), 200 rpm and 24 h of milling for 5 g of a Li + 2C powders.
With 5 mm balls, we have seen previously that the powder is a pure and well crystallized rst stage compound (cf. Fig. 16). With a ball size of 10 mm, the compound
is also a pure rst stage, but contains obviously more defects. The milling done with
balls of 20 mm is totally inecient: one obtains mainly graphite. This ineciency can
be related to the low balls number: 6 and their tendency to remain on the vial wall
under the eect of the centrifuge forces and do not participate properly to the
milling. Moreover, due to the large size of the balls, there are large dead zones
(especially between the vial and its cover) in which the powders are not crushed. On
the other hand, those balls are made of the same hard steel as the milling container,
which involves a large abrasion and, therefore, the contamination by iron reaches
around 0.5 at.%.
2.4.5. Conclusion
The study of the relative inuence of the dierent parameters leads to the following optimized conditions for the ball-milling synthesis of rst stage graphite
lithium compounds:
5 g of a mixture of graphite (mean size: 40 lm) and lithium (170 lm) powders,
lithium/carbon ratio: 1/2,
charge ratio: 40 (200 g of balls),
ball size: 5 mm in diameter,
rotation speed: 200 rpm,
milling duration: 12 h.
2.5. Ball-milling of a mixture of Li + 2C powders

The milling conditions are those determined just above and the following investigations are done on the resulting powder:
X-rays diraction, in order to determine the optimal rotation duration leading to
a well crystallized rst stage graphitelithium compound,
density measurements, which allow to calculate easily the amount of non-intercalated lithium and, consequently, the real stoichiometry of the intercalation compound,
30
electronic microscopy (both SEM and TEM), for the determination of the size
and texture of the crystallites.
2.5.1. X-rays diraction
Numerous studies of the eect of ball-milling on graphite (without the presence of
lithium) point out the tendency of graphite to be rapidly disorganized and to lead to
amorphous carbons [8693]. Later in this paper, as introduction to the preparation
of highly anisometric graphite (HAG), it will be presented, in particular from the
work done by Salver-Disma [94,95], that the structure and microtexture of ballmilled graphites depend strongly of the mill type. It appears that the planetary type
mill is adequate for this work since it favors the friction and, as a result, the cleavage
of graphite. Moreover, in the case of co-milling of graphite and lithium powders, the
presence of the later in large quantity (its initial volume represents 55% of the total
volume for a Li + 2C composition) decreases the violence of the shocks and, thus, the
graphite amorphization.
The product of the milling of a Li + 2C mixture is not really a ne powder, it looks
more like chips: as already explained, the ball-milling consists in both breaking and
agglomeration of particles. Due to the large lithium excess (42% in volume if one
considers the graphite intercalation compound to be LiC6 ), the milling leads to an
important agglomeration and results in a large distribution of the particles size. This
agglomeration problem is quite drastic and it is very dicult to get back the whole
amount of powders due to the tendency of the particles to paste on the milling tools.
This is the reason why we have set up a new synthesis method by addition of a liquid
in the milling container (acting as a lubricant), as it will be developed in Part 3.
XRD characterization is performed by introducing the powders prepared by ballmilling in a tube made of Lindemann glass (inside diameter 1 mm, wall thickness
0.01 mm). The tube is then placed on an INEL diractometer equipped with a quartz
monochromator and a scintillation detector. The wavelength is that of molybdenum:
and the data are analyzed with the Dirac-AT software. Fig. 18
kKa 0:70926 A
shows the XRD diagrams of powders prepared with a Li + 2C initial composition
and milling duration of 6, 12, 24, 48 and 96 h.
First of all, the maximal intensities are decreasing as the milling time is increased:
its value of 550 counts per minute (for a milling of 6 h) becomes less than 100 cpm
(for 96 h). This is the consequence of the amorphization of the carbon matrix. After
a milling for 6 h, the powder consists in a mixture of 1st and 2nd stage compounds,
the reections are quite sharp and the miller indices, indicated in Fig. 18, are based
and, respectively,
on the hexagonal lattices whose parameters are: a 4:30 A

c 3:70 (for LiC6 ) and c 7:05 A for LiC12 . A pure and well-crystallized rst stage
compound is obtained after a milling of 12 h. The free lithium excess is visible at

2h 16:4 (2.49 A).
For longer milling duration, the reections remain sharp and they are not widen
by a large decrease of the particles size. However, the background is increased, sign
of the appearance of some disorder. Even after 96 h of milling, the reections present
relative intensities compatible with a pure LiC6 rst stage compound. Traces of
Li2 C2 lithium carbide are still not visible, in spite of a long and energetic milling. On
31
Fig. 18. XRD of Li + 2C powders after various milling durations.
the same manner, there are no traces of lithium nitride or oxide, which proves the
excellent tightness of the vials. The 96 h ball-milled powder is made of large and very
anisotropic particles, susceptible to be slightly out of the rotation center of the
goniometer and, therefore, the diraction can be given by two parallel particles,
responsible for a twinning of the reections.
The XRD pattern of the powder obtained after a milling for 12 h is typical of that
given by a pure rst stage LiC6 . However, the dierences between the XRD diagrams
of LiC6 and of superdense phases obtained under high pressure (50 kbars, 300 C), as
32
Fig. 19. Two-dimensional structures of LiC6 (a) and compounds coming from the decomposition of LiC2
(b).
well as their derivatives formed by decomposition of LiC2 (Li9 C24 or Li7 C24 ), are
quite small [96]. Moreover, the powdered state of the ball-milled compounds does
not allow a separate study of the dierent reections families (0 0 l, h k 0 or h k l)
[97,98] and, thus, it is dicult to determine easily the two-dimensional structure of
the intercalated layer by XRD.
2.5.1.1. Some crystallographic particularities of the graphitelithium compounds. The
structural study of the LiC6 compound is made dicult for the following reason:
the
and c 3:70 A
(Fig. 19(a)) and a=c p 3=2
hexagonal structure with a 4:30 A
[43] involves an identical norm for the reciprocal vectors a , b and c and, thus, a
systematic superimposition of the h 0 0 and 0 0 h reections. With a powder, those
reections cannot be distinguished by XRD. Moreover, the reticular distance of 1.85
gathers nothing less than three reections with the following Miller indices: 2 0 0,
A
0 0 2 and 1 1 1, the last one being the most intense.
The lithium density in the intercalated layers can be deduced from the comparison

of the relative intensity for the reections observed at respectively 3.70 and 1.85 A.
This ratio increases as the lithium content is increased, as shown in Fig. 20: from 33%
in LiC6 x 1 to 75% in LiC2 x 3. The experimental ratio for powders prepared
by mechanical alloying (Fig. 18) is around 30%, in good agreement with the formation of LiC6 . The synthesis of superdense phases by ball-milling seems excluded.
One can conclude of this study that the ball-milling of Li + 2C powders mixture
leads, after 12 h, to a rst stage LiC6 compound, but the presence of large quantities
of free lithium induces an important agglomeration on the balls. It results that the
product presents a large distribution of particles size. The XRD diagrams exhibits
well crystallized compounds, even after a milling duration of 96 h. No trace of
lithium carbide, nitride or oxide appears and the formation of superdense phases
seems to be excluded.
2.5.2. TEM study
Under the inert atmosphere of the glove box, the synthesized powder is placed on
amorphous carbon lm. The grid is then put
a copper grid covered by a thin (100 A)
on a tight sample holder before its introduction into the microscope column (Philips
33
100
90
I1,85 A / I 3,70 A ( %)
80
70
60
50
40
30
20
0
0.5
1.5
2.5
3.5
x in LixC6
versus that at 3.70 A,

as a function of the lithium
Fig. 20. Relative intensity of the reections at 1.85 A
content.
CM20, 200 kV). In spite of the tightness of the sample holder, there appears some
oxidation, as it will be seen later on. This is due to the high reactivity of lithium and
to the small size of the particles. This problem does not inuence the results concerning the particles size and their shape since the oxidation does not involve any
exfoliation of the carbon matrix.
The larger particles (several lm in diameter) are highly anisometric since their
thickness does not exceed 100 nm. The electronic diraction pattern shown in Fig.
21(a) exhibits the six equivalent 1 0 0 reection of graphite. At this stage, it cannot be
concluded that those spots correspond or not to the 1 1 0 reection of LiC6 : it should
be associated with an other set of six spots (1 0 0 reection of the LiC6 hexagonal unit
cell) closer to the direct beam. The absence of the 1 0 0 reection can be explained by
Fig. 21. Electronic diraction on graphitelithium particles: (a) 5 lm, (b) 200 nm.
34
Table 2
Reections observed by electron diraction on small particles (cf. Fig. 21(b))

d (A)
3.33
2.66
2.07
1.64
1.39
hkl
G 0 0 2 (2 spots)
Li2 O 1 1 1
G 100
Li2 O 2 2 0
Li2 O 3 1 1
1.24
1.16
G 110
G 112
its low intensity (20% of the 1 1 0 reection). One has also to note the absence of
lithium oxide, which appears clearly in the diraction pattern of a smaller particle
(cf. Fig. 21(b)). In the small particles, there is a visible oxidation of the LiC6 compound, revealed by the presence of Li2 O reections (cf. Table 2).
2.5.3. Density measurements
The lithium density is much smaller (0.53) than that of graphite (2.27) or
graphitelithium intercalation compounds (cf. Fig. 22), thus, the determination of
the powder density should allow the estimation of the composition of the intercalated phase. The densities are calculated on the basis of an interplanar distance of
which corresponds to that of the normal LiC6 compound [44] as well as of
3.70 A,
the superdense phases [96].
The experimental densities were rstly determined by uniaxial compression realized with a small hand press in the glove box. However, this technique appears inadequate since the pellets are fragile, due to the partial amorphization of graphite,
especially when the milling time is long. Moreover, the applied pressure remains
quite low (5 kbars) and the compactness is not sucient. For instance, with graphite
whose theoretical density is 2.27, the experimental value is only 2.10. This is the
reason why we managed further density measurements by liquid pycnometry within
n-dodecane (C12 H26 , Acros Organics, 99%).
3
Density
2.5
1.5
Calculated density of the compounds
1
density of mixture whose global composition is LiC2
0.5
0
0.5
1.5
2.5
x in LixC6
Fig. 22. Calculated densities of several graphitelithium intercalation compounds and of a powder with a
Li + 2C initial composition as a function of the amount of intercalated lithium.
35
With a powder whose initial composition is Li + 2C, the experimental density is

1.50, which corresponds to x 1 (cf. Fig. 22) in the following equation:
3LiC2 ! Lix C6 3 xLi
It seems that the intercalated phase is the classical LiC6 compound, in good
agreement with the above results: the superdense phases are not prepared by ballmilling.
2.5.4. Conclusion
The ball-milling constitutes a new technique for the intercalation of lithium into
graphite powders. The parameters for this synthesis are optimized and one obtains a
powder of rst stage LiC6 after 12 h of milling. With longer millings (up to 96 h),
there is no real degradation of the carbon matrix. The X-rays reections remain
sharp and can be indexed in the hexagonal P6/mmm unit cell whose parameters are
and c 3:70 A.
The observed intensities agree well with a pure LiC6
a 4:30 A
compound. The experimental density (measured by pycnometry) of the powders t
well with a mixture of LiC6 and excess of free metal when the initial composition is
Li + 2C. It remains however some problems for the practical use of ball-milling: a
large part of lithium agglomerates on the milling tools and therefore, the yield of the
preparation is only 1020%. Starting from the observation that the presence of a
large lithium excess (which acts as a lubricant) avoids an important amorphization of
graphite, the milling conditions were modied by adding a liquid to the graphite
lithium mixtures.
3. Synthesis by ball-milling in a liquid medium

3.1. Choice of the liquid
The ball-milling in liquid media are realized for a long time, but remain quite rare
[4,5,99]. One can classify those syntheses in two categories, according to the liquid
role:
lubricant and/or dispersal medium. It allows avoiding the agglomeration on the
milling tools and the formation of aggregates. Therefore, the preparation of nely
divided powders is possible using this technique. This is what we are looking for in
the case of the ball-milling of graphitelithium mixtures,
reactant with the other present species: for instance, the synthesis of maghemite (c
Fe2 O3 ) by ball-milling of iron within water, as it will be developed later in this
paper (cf. Part 5).
The choice of the liquid is of a major interest, especially for the synthesis of
graphitelithium compounds, due to the high reactivity of lithium powder. Among
the alkanes, which are known to be inert towards the alkali metals, the C8 to C15
series presents a liquid domain at room temperature (cf. Fig. 23), but the choice
36
Temperature (C)
400
350
Melting point
300
Boiling point
250
200
150
100
50
0
-50
-100
5
11
13
15
17
19
number of carbon atoms
Fig. 23. Melting and boiling points of some linear alkanes.
remains limited since the solvent should have a low viscosity and a low vapor
pressure at room temperature.
Dodecane (C12 H26 ) was chosen. Its main properties are:
melting point: )9.6 C,
boiling point: 216.3 C,
vapor pressure at 25 C:16 Pa,
viscosity: 1.383 mPa at 25 C, to be compared with that of water (0.890) or ethanol (1.074),
density: 0.740.75,
insoluble in water, soluble in acetone.
3.2. Synthesis
The synthesis is done with a Li + 2C mixture since, this composition corresponds
to that of the phase with the most dense single intercalated layer, where all possible
sites in epitaxy on the graphene sheets are occupied by lithium atoms [49]. The
synthesis conditions [100,101] are as follows:
5 g of powders (3.7 g of graphite, 1.13 g of lithium),

200 g of 5 mm balls,
charge ratio of 40,
12 h of milling at 200 rpm.
The volume of dodecane is in the 0.550 cm3 range. In all cases, the nal compound is a yellow shiny powder mixed together with dodecane. No agglomeration of
the powders occurs and the dodecane is simply removed by pumping under vacuum
at room temperature. This procedure has to be improved since there appears a thin
37
layer of dodecane on the powder surface. Moreover, this operation requires quite a
long time.
3.3. Actual composition of the powders: chemical analyses
In order to evaluate the lithium loss due to sticking on the milling tools, the
powders are analyzed by reaction with water, according to
Li H2 O ! LiOH 1=2 H2
The solid part (which contains the graphite and a part of LiOH) is ltered and
heated in the air at 450 C. As a result, graphite burns and LiOH is transformed into
Li2 CO3 . Since the lithium carbonate in water insoluble, one should rst add an
excess of hydrochloric acid and back neutralize the solution. Those analyses show up
the lithium loss to be less than 2% when the milling is done in the presence of 1 cm3
of dodecane and less when the amount of dodecane is larger. One can, then, consider
that the lithium loss is negligible and the nal composition of the powder is really
LiC2 .
3.4. Characterization by X-rays diraction
Fig. 24 presents the XRD diagrams of the Li + 2C powders obtained with 1, 5 and
10 cm3 of dodecane, respectively. In all cases, the main reection at a reticular
Fig. 24. XRD diagram of a Li + 2C powder milled with various volumes of dodecane: (a) 1 cm3 of
dodecane, (b) 5 cm3 of dodecane and 10 cm3 of dodecane.
38
is a sign of the synthesis of a rst stage graphitelithium comdistance of 3.70 A,

pound. All reections can be indexed in the unit cell of LiC6 and the relative intensity
(0 0 2, 2 0 0 and 1 1 1) is in the 3040% range, in good
of the reections at 1.85 A
agreement with that calculated for LiC6 . Thus, by XRD, there is no evidence for the
formation of a superdense compound.
The powders are well crystallized: the reections are sharp and the background
very low. The crystalline state increases with the increase of the dodecane volume,
but with 5 and 10 cm3 of dodecane, one observes the presence of free lithium and of a
which may correspond to the diraction of dodebump around 9 in 2h (4.50 A),
cane: since the removing of dodecane is quite dicult and requires a long pumping
value
procedure, it is possible that dodecane traces remain in the powder. The 4.50 A
corresponds roughly to the separation between two linear chains of the alkanes
[102,103].
The addition of dodecane is, therefore, relevant: it avoids the lithium sticking on
the milling tools. This is true even with quantities as small as 1 cm3 for 5 g of
powders. A larger quantity leads to a better crystallized powder, but XRD patterns
indicate that a large part of lithium remains not intercalated. The best compromise
for the synthesis is 1 cm3 of dodecane, quantity that is also much easier to remove
than larger amounts. It will be seen later that the ball-milling of a Li + 2C mixture
with 1 cm3 of dodecane leads to a superdense phase.
3.5. TEM investigations
The diameter of the particles is in the 100 nm3 lm range, the smaller ones are
gathered as aggregates whereas the larger remain mainly isolated. Fig. 25 shows one
of those large particles deposited on the grid perpendicularly to the electron beam.
Its thickness is around 150 nm and does not present any signicant deformation. The
Fig. 25. TEM micrograph (a) and corresponding electronic diraction pattern (b) of the powder obtained
by ball-milling with 1 cm3 of dodecane.
39
electronic diraction pattern of this particle exhibits the reections of graphite. Once
more, as it was seen previously, one cannot see any superstructure reection corresponding to LiC6 (too weak intensity or oxidation?). Lithium oxide reections are
also absent, and there is no proof either for the oxidation of the intercalation
compound.
3.5.1. Electron energy loss spectroscopy
This technique allows the characterization of light elements like lithium. The
energy loss peaks are connected to the electronic transitions and lead to the
knowledge of the bonding status of a given atom to its neighbors. The spectrometer
connected to the TEM is Gatan 666 and the spectra shown in Figs. 26 and 27 are
taken from the particle represented on Fig. 25. The high energy loss region (250450
1s- *
293 eV
Intensity
C-K
1s- *
285 eV
200
250
300
350
400
450
500
Energy loss (eV)

Fig. 26. EELS spectrum of a Li + 2C particle (high energy region).
6.E+04
Plasmons
Intensity
5.E+04
4.E+04
3.E+04
61 eV
2.E+04
66 eV
1.E+04
0.E+00
20
40
60
80
100
120
140
Energy loss (eV)
Fig. 27. EELS spectrum of a Li + 2C particle (low energy region).
40
eV) is represented in Fig. 26. The spectrum is typical of well crystallized graphite and
two transitions corresponding to the K level of carbon atom are visible:
transition 1s ! p whose edge is 285 eV,
transition 1s ! r (293 eV).
Electron energy loss spectroscopy (EELS) also prove the single crystal character
of the particle, as seen by electronic diraction, since the peak at 285 eV (1s ! p )
varies as the orientation of the crystal with respect to the electron beam is changed.
The low energy loss region (0150 eV) is represented in Fig. 27. The peak corresponding to the plasmon (excitation of the conduction band electrons) is centered
at 19 eV, value particularly low since, a LiC6 compound (synthesized by a classical
method) examined under the same conditions leads to a plasmon peak at more than
25 eV. This fact indicates that the conduction band of the ball-milled sample could
contain more electrons than LiC6 and, consequently, that the compound prepared by
ball-milling has a higher intercalated lithium content.
The ionization K level of lithium is normally visible around 6065 eV. One observes, in the present case, two peaks whose signication is still not clear. The rst
one, at 61 eV, can be correlated with the ionization of metallic lithium, which
could correspond to lithium clusters lying between the GIC particles. The value for
the second peak, 66 eV, is very close to the lithium edge in an ionic compound like
LiCl, used as a reference (65 eV). Part of lithium appears more ionic in the ballmilled compound than in LiCl, which looks very surprising, especially if one considers this compound as superdense with very short LiLi distances involving a
partial covalent character to the bonds [96].
It is generally admitted that the edge of intercalated lithium is close to that of the
metallic clusters: 61 eV. What could be the origin of the edge at 66 eV? The presence
of strongly ionic bonds between lithium and carbon (consecutive either of the lithium
carbide formation or reaction of Li with pending bonds of carbon) seems to be
excluded since no Li2 C2 appears (by XRD or by chemical analysis since no formation of acetylene is noticed by reaction of the compound with water). It could be due
to the oxidation of the sample during the transfer from the glove box to the electronic microscope, but no trace of oxygen or nitrogen is present in the EELS or
EDXS spectra. The question remains open.
EELS is a powerful mean for the determination of the oxidation state of the
atoms and their neighboring. However, for the particular case of lithium, it has to be
improved from the experimental point of view (problems of possible oxidation or
degradation of the powder under the electron beam) as well as from the spectra
interpretation (especially peaks deconvolution).
3.6. Density measurements by pycnometry
For Li + 2C mixtures milled for 12 h at 200 rpm in the presence of 1 cm3 of
dodecane, the experimental density is 1.85, which corresponds to a value of x 2
(LiC3 ) in the Fig. 22. The reaction can be written:
3Li 2C ! 2LiC3 Li
41
The actual value corresponding to the left part of the preceding equation is 1.93.
Therefore, the synthesis seems to lead to a superdense compound. This composition is
intermediate between that of the Li9 C24 and Li7 C24 phases, which appear during the
decomposition process of LiC2 compound synthesized under high pressure (50 kbars).
The liquid pycnometry is thus an ecient mean for showing up the formation of
superdense phases. However, there are two possible errors using this method:
a bad wetting of the powder by dodecane, which involves an overestimation of the
volume. For instance, the density of graphite, measured by this technique is
around 2.102.15 instead of the 2.27 theoretical value. The underestimation for
the density is, thus, of the order of 7%.
the presence of dodecane traces remaining from the synthesis and leading to a
density underestimation, since the density of dodecane (0.75) is largely smaller
those that of the GICs (cf. Fig. 22).
Those two errors are going in the same direction: an underestimation of the
density and, therefore, the formation of a graphitelithium superdense compound is
not contradicted.
3.7. 7 Li NMR characterization
According to the density measurements the intercalated phase is LiC3 and the Xrays diraction pattern give an interplanar distance similar to that of the classical
LiC6 compound. Let us characterize the in-plane structure of the lithium sheets.
Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool since this
technique gives precise informations on the neighborhood of the lithium atoms.
3.7.1. Generalities
The magnetism of the charge carriers in a conductor has two origins:
the spin magnetism, which is proportional to the density of states on the lithium
orbitals at the Fermi level. It depends on the free carriers number and on the
shape of the conduction band,
the orbital magnetism, created by the motion of the carriers in a magnetic eld
and including the whole of the conduction band as well as a specic participation
of the states close to the Fermi level.
The study of the charge carriers magnetism enables the understanding of the
electronic properties of the intercalation compounds, particularly concerning the
localization of the charge given by the intercalated species. Three main techniques are
used for the study of the carriers magnetism: the electronic paramagnetic resonance
(EPR), the NMR and the magnetic susceptibility measurements. NMR is the technique giving the maximum of local informations since, the resonance phenomenon
42
depends directly of the local eld induced by the electronic environment. Moreover,
the study of quadrupolar nuclei (7 Li with a spin of 3/2 is one of them) informs on the
local symmetry of the site.
In the conductors, the resonance shift is the representation of the electronic elds
at the nucleus position. There are two categories of elds:
the local eld, called hyperne, itself made of two terms: the contact term resulting from the Fermi interaction and the dipolar term due to dipolar interaction at
long distance. Both are proportional to the Pauli susceptibility and, consequently,
to the density of states at the Fermi level, seen by the wave function of lithium.
The contact term (Knight) is also proportional to the electronic spin density produced on the nucleus by the s function of lithium.
the orbital eld resulting of the interaction between the nucleus moment and the
currents created by the electrons motion. This eld is not proportional to the
Fermi level, it is the sum of local contributions implying the whole of the conduction band and a specic contribution of the states close to the Fermi level. This
specic contribution is not negligible in the case of 7 Li and can be, in a rst approximation, taken into account as a mean macroscopic internal eld.
The shifts of the resonance lines are not referred to the applied eld, or to the
theoretical frequency corresponding to that of an isolated nucleus placed in that eld
since, neither the eld value, nor the gyromagnetic ratios of the nuclei, are known
with enough accuracy. This is why the shifts are measured by comparison with a
chemical specy used as reference. For the alkali metals, this reference consists in an
aqueous solution containing the alkali cation.
The 7 Li NMR allows obtaining the following informations:
the Knight shift, which corresponds in fact to the measure of the density of states
at the Fermi level on the wave function of the studied nucleus and, consequently,
to the oxidation state of the atom,
the spinlattice relaxation time allowing to corroborate the informations coming
from the Knight shift with the Korringa relation:
T 1 T K 2 S0
with T1 spinlattice relaxation time (in s), T temperature (in K), K Knight shift (in
106 ppm) and S0 the Korringa constant (1.742 10 6 for 7 Li),
the quadrupolar splitting, which gives informations on the local electric eld gradient and on the site symmetry,
the line width evolution as a function of the temperature related to the nuclei mobility.
From those results, one can deduce structural informations on the intercalated
layer [104].
43
3.7.2. Experimental results

A Br
uker spectrometer coupled with a superconducting coil giving a 8.45 T eld is
used. The frequency resonance of lithium in this eld is 139.96 MHz. The external
reference is a LiCl solution. The study is focused, in this paper, on the compounds
with an initial Li + 2C composition and prepared by 12 h of milling with 1 cm3 of
dodecane.
Two resonance lines are clearly visible in Fig. 28, which presents the spectrum at
room temperature of the ball-milled Li + 2C composition. The rst one, at 41 ppm, is
surrounded by two satellites at 136 and )54 ppm, sign of a quadrupolar coupling,
and is characteristic of the hexal structure of LiC6 . The measured electric eld
gradient (26 kHz) conrms the values given in the literature [104107]. The shift of
41 ppm points out the partial metallic character of the intercalated lithium in spite of
in LiC6 . This metallic character is explained
a large LiLi in-plane distance (4.30 A)
by the overlap between the p orbital of graphite and the s and p orbitals of lithium.
The overlap is responsible of the good in-plane and perpendicular electrical conductivity of LiC6 , which presents a low anisotropy (10 instead of 103 104 for the
pristine graphite).
The second intense resonance peak at 260 ppm is very close to that of metallic
lithium (262 ppm). It does not present any quadrupolar eect. This peak is also
observed on phases coming from the decomposition of the LiC2 compound
synthesized under high pressure. At low temperature, this last becomes a doublet
Fig. 28. 7 Li NMR spectrum at 293 K of a powder whose initial composition is Li + 2C.
44
attributed to the resonance of at Li7 clusters [108,109]. The NMR investigations of

the ball-milled compounds at low temperature seem then very attractive.
Spectra are performed every 10 K in the 293153 K range. Fig. 29 gathers the
most representative of them. Concerning the peak at 41 ppm, which corresponds to
LiC6 , one can note the following informations:
the shift is weakly sensitive to the temperature, underlining a high Fermi temperature and a negligible diamagnetic contribution, that is to say a clear metallic
character,
the quadrupolar eect increases with the temperature decrease: the electric eld
varies from 26 kHz at room temperature to 33 kHz at 153 K. This increase is generally attributed to the lattice contraction,
the line presents a widening during the cooling: the width at half maximum goes
from 1.5 G at room temperature to 2.5 G at 153 K. This phenomenon is due to the
Fig. 29. Variation versus temperature of the 7 Li NMR spectrum of a powder whose initial composition is
Li + 2C.
45
lowering of the lithium diusion coecient: at room temperature, the lithium atoms keep on their site for a very short time, they hop easily from one site to the
other of the hexal structure and their kinetic energy is large enough to jump over
the energy threshold between the centers of carbon hexagons. As a result, the resonance peak is narrow and has a lorentzian shape. While the sample is cooled
down, the atoms motion is slowed down, which involves the peak widening. Its
shape becomes gaussian. In fact, at low temperature, the width is directly proportional to the local eld induced by the neighbors as it will be seen later in more
details for the study of the 260 ppm peak.
The 260 ppm line, sharp at room temperature, presents an important widening by
cooling. Its width at half maximum reaches 8.7 G at 233 K, whereas the value for
metallic lithium is only 6 G at the same temperature. The line cannot, then, be attributed to metallic lithium resonance. The linewidth is roughly the same as that
observed on the transitory phases obtained by decomposition of the superdense LiC2
compound [108] (cf. Fig. 30), which conrms the superdense character of the compounds prepared by ball-milling.
The shape evolution of the 260 ppm resonance peak is of a great interest in order
to characterize the two-dimensional structure of the intercalated layer. Between 293
and 243 K, a simple widening occurs. The formation of a doublet is observed from
233 K. This one becomes perfectly dened at 153 K, as shown in Fig. 31. It is still
centered at 260 ppm, like for lithium, but cannot be attributed to this last since its
shape remains independent of the acquisition delay. Moreover, a nely divided
powder should lead to a wide gaussian peak, not to a doublet. In fact, the particles
obtained by ball-milling present a high anisotropy and tend to be oriented perpendicularly to the applied eld, due to their paramagnetism. The c axis of the particles
10
LiC6
metallic lithium
Li7C24
our compound
Line width (G)
8
7
6
5
4
3
2
1
0
150
170
190
210
230
250
270
290
310
330
350
T (K)
Fig. 30. Full width at half maximum as a function of the temperature of several graphitelithium compounds compared to metallic lithium.
46
Fig. 31. 7 Li NMR spectrum at 153 K of a powder with an initial Li + 2C composition.
becomes mainly parallel to the eld and therefore, the study becomes close to that of
pyrolytic graphite, the starting material used for the NMR studies on the compounds
prepared at high pressure [108,109].
3.7.3. Where is the doublet at 260 ppm coming from?
A similar doublet is actually observed in the case of the superdense phases obtained under high pressure, but it is then surrounded by two satellites around 200
and 320 ppm (as it is shown in Fig. 37). It is attributed to the resonance of at Li7
clusters. The lack of those satellites in the case of the ball-milled compounds seems to
exclude the formation of such clusters and suggests the lithium to be surrounded by
an odd number of neighbors.
The doublet width is a function of the local eld and depends directly on the LiLi
distances. The local eld produced by each neighbor is generally described by the
equation:
H l3 cos2 h 1=R3
with l the magnetic moment of the 7 Li nucleus, h the angle between the applied eld
and the vector connecting two lithium neighbors and R the distance between two rst
neighbor atoms.
From this relation, it is possible to calculate the theoretical width as a function of
the LiLi distance. The results are shown in Fig. 33. Two cases can be considered:
47
the lithium atoms form a at sheet in the medium plane between the graphene layers, the atoms being not necessarily in epitaxy on the graphite network. The h angle equals p/2 and the width varies only as a function of 1=R3 . One should note
distance (identical to that encountered in metallic lithium) leads
that a 3.05 A
to a peakpeak distance of 3.4 G, value lower than that measured for the compounds prepared by ball-milling (4.2 G). This points out the high density of the
lithium layer,
the intercalated atoms are exactly above the centers of the carbon hexagons, but
shifted up or down from the medium plane, increasing the LiLi distances. The h
angle becomes, then, dierent of p/2. Fig. 32 represents schematically this correlation. One can deduce the following relation:

cos h cosp=2 a sin a sinarc cos2:46=R with R in A
It is then possible to express H as a function of R:

H l3 sinarc cos2:46=R2 1=R3
10
H0
Lithium atom
Graphene plane
2.46
Graphene plane
Distance between the components

of the doublet (G)
Fig. 32. Schematic representation of the h angle as a function of the LiLi distance.
Atoms in registry
Flat lithium sheet

5
4
3
2
1
0
2.4
2.9
3.4
3.9
4.4
Distance between the lithium atoms (Angstrm)
Fig. 33. Distance between the two components of the doublet versus the distance between the lithium
atoms.
48
The experimental distance between the two components of the doublet is 4.2 G,
(at sheet of lithium in the
which corresponds to LiLi distances either 2.85 A

medium plane) or 2.58 A (lithium atoms in registry with respect to the graphite
and can be
network). Both distances are shorter to that in metallic lithium (3.05 A)
explained by a participation of the 2p states of lithium in the chemical bond
[108,109].
3.7.4. Spinlattice relaxation time
From the Korringas law, the measurement of the spinlattice relaxation time
allows to correlate the informations given by the Knight shift. At room temperature,
the relaxation time measured on the ball-milled compound is only 50 ms, whereas it
is around 2 s for LiC6 [110]. This value seems nevertheless coherent since the product
T1 K 2 presents the same value in both cases (if one takes K 260 and 41 ppm for
ball-milled compound and LiC6 , respectively). It should be noted that the relaxation
time for metallic lithium is around 150 ms at room temperature. Therefore, for the
same Knight shift, the ball-milled LiC3 compound and metallic lithium present a
dierent relaxation time.
One important feature is the discrepancy towards the Korringas law for the ballmilled compound as well as for LiC6 since the value of T1 T K 2 is close to 10 6 ,
whereas the theoretical value is 1.74 10 6 . Lauginie [104] examines the whole
phenomena responsible of the discrepancies to Korringas law. The main one is the
quadrupolar interaction between nucleus and conduction electrons: this contribution
tends to decrease signicantly the relaxation time. It should be interesting to measure
the relaxation time at various temperatures in order to determine if it is actually a
linear dependence versus temperature.
3.7.5. Structure
From the previous results showing that the stoichiometry is close to LiC3 , the Li
and the unit cell similar to that of LiC6 , one can
Li distances either 2.58 or 2.85 A
now determine precisely the in-plane structure of the intercalated layer and the actual unit cell of the compound synthesized by ball-milling. The hypothesis con distance is
cerning a at lithium layer is not valid since, the corresponding 2.85 A
incommensurate with the graphite network. This leads to a localization of part of the
lithium atoms directly on top of carbon atoms, which is incompatible with the
compound stability or with the interplanar distance equal to that of LiC6 . Moreover,
that distance (15% larger than that between two atoms intercalated in registry with
the graphite network) does not account for a LiC3 stoichiometry. Indeed, if one
considers the fact that three neighbors at 120 should surround each lithium atom,
the stoichiometry is LiC4 and one should consider the powder to be a mixture of
LiC4 and free lithium, according to
2Li 2C ! LiC4 Li
11
The resulting powder should present a density of 1.70 instead of the measured one:
1.85. As a result of this hypothesis of one at lithium intercalated layer, it appears
clearly an incompatibility between density measurements and NMR spectroscopy.
49
Thus, one should consider the position of the lithium atoms to be in epitaxy on the
graphene sheets, favoring the stability since the lithium atoms are then placed in the
potential wells between the centers of the carbon hexagons. Moreover, the atoms can
be slightly shifted up or down from the medium plane between the carbon layers,
value. Due to the neighboring
which leads to a LiLi distance larger than the 2.46 A
of the lithium atoms (three neighbors at 120), their up and down positions can be
drawn without any frustration. Fig. 34 shows the intercalated layer of the compound
synthesized by ball-milling as it can be established from the whole of the dierent
studies. In registry with respect to the graphite network, three neighbors at 120
surround each lithium atom. This structure corresponds to the same in-plane cell than
but contains two lithium atoms. For comparison, the cell
that of LiC6 (a 4:30 A),

(with a 8:63 A) corresponding to the Lix C24 phases coming from the decomposition
of the superdense LiC2 compound is also represented in this gure. It is four times
larger and contains at Li7 clusters for x 7 or 9.
It was shown previously that the reections on the XRD diagram of the ballmilled compound exhibit intensities close to that of LiC6 , in particular for the in versus that at 3.70 A:
around 38%. For a
tensity ratio of the reections at 1.85 A
LiC3 composition, as suggested by the density measurements (cf. Eq. (4)) and by
should be around 50% (cf.
NMR investigations, the whole of the reections at 1.85 A
Fig. 20) for at lithium intercalated layers. This discrepancy is explained by the
registry of the lithium atoms with respect to the graphite network and by the splitting
from the medium plane, as
of the intercalated lithium layer in two planes at 0.44 A
is calculated as a
shown in Fig. 35. The relative intensity of the reection at 1.85 A
function of the lithium layer splitting. Its value decreases rapidly when the lithium
the calatoms separate from the medium plane. For a splitting of around 0.44 A,
culated value for I1:85 =I3:70 becomes 35%, close to the observed one: 38%.
Taking into account all the previous observations, one can draw the unit cell of
LiC3 , represented in Fig. 36. It belongs to the space group P63 /mmc with the
and c 2 Ic 7:40 A.
The lithium atoms are in
following parameters: a 4:30 A
Fig. 34. Bidimensional structure of the intercalated lithium layer (the large cell corresponds to that observed for the phases resulting of the LiC2 decomposition).
50

55
50
I1.85 A / I 3.70 A (%)
45
40
35
30
25
20
15
10
0
0.2
0.4
0.6
0.8
Splitting of the lithium layer from the medium plane (Angstrm)
(versus that at 3.70 A)

as a function of the
Fig. 35. Relative intensity of the whole of reections at 1.85 A
lithium layer splitting.
b
c
PowderCell 2.0
PowderCell 2.0
Fig. 36. Structure of the ball-milled LiC3 compound with Li atoms shifted from the medium plane by 0.5
This shift leads to LiLi distance of around 2.70 A
both in the lithium layer and perpendicular to the
A.
graphene sheets.
with respect to
position 4f with z 0:059 (corresponding to a distance of 0.44 A
the medium plane) and the carbon atoms are in position 12j with x 1=3, y 0.
51
3.7.6. Comparison with the high pressure superdense phases

At 300 C under 50 kbars, a LiC2 compound is obtained in 24 h, this composition
being deduced from the volume variation due to the lithium intercalation [48,49].
This superdense LiC2 phase is metastable under ambient pressure and cannot be
easily analyzed. The decomposition leads to intermediate compounds whose stoichiometry are close to LiC3 . 7 Li NMR spectra of those intermediate phases are
represented in Fig. 37 [109].
The spectrum is quite close to that of the ball-milled compound (cf. Fig. 31): one
observes particularly a peak at 40 ppm, characteristic of LiC6 . A wide peak (9 G at
half maximum), centered at 259 ppm, cannot be attributed to metallic lithium since it
is too wide and forms at low temperature a doublet with shoulders at both sides. This
doublet and its shoulders are due to the presence of Li7 clusters, as shown in Fig.
36(a) (experiment) and (b) (simulation). When the atoms are enough distant, the
spectrum is made of a well-dened doublet accompanied by two satellites. If the
atoms are closer, the local elds due to the second neighbors increase and, consequently, the lines are widened. This involves a progressive disappearance of the
doublet and the satellites become only shoulders of the main line. A LiLi distance
(slightly less than the distance between the centers of carbon hexaaround 2.42 A

gons: 2.46 A) leads to the best t of the experimental spectrum.
Among the lithium clusters studied by dierent experimental and theoretical
techniques, Li7 is considered as quite stable [111,112]. Classically, it is a pentagonal
based bipyramid, but the other forms present a similar stability. The at Li7 clusters
distance
are stabilized by the constraints imposed by the graphene sheets. The 2.42 A
between two adjacent lithium atoms is much smaller than the distance in the Li2
Fig. 37. 7 Li NMR spectra of superdense Lix C24 phases produced by LiC2 decomposition: (a) experimental, (b) simulation as a function of the LiLi distance (see text).
52
An explanation could be related with a partial occupation of the

molecule (2.67 A).
2p orbitals of lithium, which implies a large covalent character to the LiLi bonds.
Although their NMR spectra are quite similar, in a rst approach, to those of the
ball-milled compounds, their bidimensional structures dier, as it appears in Fig. 38.
The structural dierence can be explained by the synthesis conditions themselves:
under isostatic compression (50 kbars, 300 C), the nal compound is LiC2 as calculated from the volume decrease produced by the lithium intercalation. Due to
its metastability, this compound is decomposed progressively as the pressure is released and all compositions between LiC2 and LiC6 (the normal 1st stage compound) can be formed. The high stability of the Li7 clusters leads to the
formation of Li9 C24 and Li7 C24 phases. The Li8 C24 (LiC3 ) compound seems to
be not formed since, there is no evidence at all of its formation during the LiC2
decomposition, this last being quite low: over 12 months between LiC2 and LiC6 .
The reason why Li8 C24 is not produced is probably due to the absence of Li7 clusters in its structure. This involves that the transformation of Li9 C24 goes directly
to Li7 C24 (by removing of the square atoms of Fig. 38) without any formation of
Li8 C24 (LiC3 ), which would imply the destruction of the highly stable Li7 clusters.
by ball-milling, the synthesis conditions are less drastic and form LiC3 . In this
compound, the lithium atoms, shifted upwards or downwards with respect to
Fig. 38. 2D structures of the superdense phases. Top: phases produced by decomposition of LiC2 prepared at high pressure, with Li7 clusters, bottom: LiC3 prepared by ball-milling.
53
the medium plane, can be more distant, in fact, at a distance close to that present
if the shift value is 0.5 A.

in the Li2 molecule (2.67 A)
The stability of the compound LiC3 is particularly high since, after 2 years, there
appears neither any evolution of the NMR spectra nor density variation. This
structure seems to be the most representative of superdense phases. A band structure
calculation similar to that made by Rabii on LiC2 [113] is in progress and could
answer the question of stability.
3.7.7. Conclusion
The NMR study has pointed out the presence of lithium atoms in registry with
respect to the graphite network. The lithium atoms are surrounded by three neighbors, leading to a triangular lithium lattice, where the atoms can be shifted upwards
or downwards from the medium plane without any frustration. The exact splitting
value should be more precisely determined if a detailed structural study would be
possible by XRD (especially by a separated study of 0 0 l and h k 0 reections). Such
a determination is possible only with single crystals, which are obviously impossible
to obtain by ball-milling.
7
Li NMR has shown that the powder is a mixture of LiC3 , LiC6 (in the molar
ratio 8/1, according to the relative intensities of their resonance lines) and free
lithium. Eq. (5) can now be written as follows:
15Li 2C ! 8LiC3 LiC6 6Li
12
This reaction is not incompatible with Eq. (6) and the calculated density for the
nal powder (1.83) is close to the experimental one (1.85). The lithium excess is not
seen by NMR, which seems very surprising. The explanation is as follows: the free
metal is made of nanometric particles (which explains also why it is not seen by
XRD). Those particles are anisotropic and included between the intercalation
compound crystallites. Their size is less than 105 atoms (25 nm in diameter for 5 nm
in thickness) and therefore, the particles present a Curie paramagnetism responsible
of a large widening of the NMR resonance peaks (typically several thousands of
ppm) making them dicult to be detected. Additional EPR measurements at various
temperatures should be done in order to prove the presence of a Curie paramagnetism and the existence of such lithium nanoparticles.
3.8. Characterization by electronic paramagnetic resonance
EPR is a technique devoted to the study of the magnetism of single electrons and
is, thus, used here to point out the Curie paramagnetism resulting from the lithium
nanoparticles. A linear variation of the magnetism versus temperature would show
the existence of such paramagnetism and one could conclude on the presence of such
nanoparticles. This study, performed with a Br
uker spectrometer using X band (9.77
GHz) and a power of 2 mW, is currently in progress and one can only present in this
paper the results obtained at room temperature.
54
The presence of ferromagnetic particles causes obviously many problems for EPR
study. It was shown previously that the ball-milling leads to a low contamination
(0.02 at.% of iron after 12 h of milling) due to the abrasion of the milling tools. This
pollution has to be taken into account since it is impossible to avoid it and to remove
the metal in the prepared powders (with hydrochloric acid for instance) due to the
high lithium reactivity.
Fig. 39 presents the derivative spectrum, obtained at room temperature, of the
ball-milled Li + 2C composition. There are two signals, one being sharp and symmetrical at 3481 G and the other larger and asymmetrical at 3489 G. The rst one
corresponds to the chloranyl radical used as a reference, its Lande factor is
g 2:0058. The other signal, corresponding to the ball-milled compound, is large
and its dysonian shape is characteristic of conductors. The corresponding g factor,
around 2.0035, is close to that of free electron, slightly higher than that measured on
LiC6 g 2:0022 [106,114,115], but much smaller than that of graphite
g 2:0458. The low g value for the graphitelithium intercalation compounds is
explained by a large displacement of the Fermi level, consequence of the charge
transfer from the metal to the conduction band, which shifts the Fermi level outside
of the degenerescence region of the graphite bands.
The half width of the LiC2 signal is around 4 G. The width is an inverse function
of the transverse relaxation time of the spin polarization. This value of 4 G corresponds to a relaxation time of 1.5 10 8 s, slightly smaller than that for LiC6
(2.5 10 8 s). This dierence can probably be interpreted in terms of lithium atomic
orbitals occupation. Indeed, several authors explain in this manner the reason of a
rapid relaxation time decrease (thus the line widening) when the atomic number of
the intercalated atom is increased [104]. The s orbital is partially occupied at the
Fig. 39. EPR spectrum at 293 K of ball-milled Li + 2C composition (the sharp signal corresponds to a
chloranyl radical used as reference).
55
Fermi level and, thus, the conduction electron comes under a relaxation due to the
spinorbital modulation by the phonons. The intensity of that interaction increases
with the atomic number of the considered atom. Concerning the compound prepared
by ball-milling, it was shown by 7 Li NMR that the lithium intercalated layer is superdense since the stoichiometry is LiC3 and the LiLi distance particularly short
The chemical bond presents a high covalent character, made
(around 2.70 A).
possible by the partial occupation of the 2p orbitals of lithium, which increases the
spinorbital interaction and leads to a shorter relaxation time for the conduction
electron.
The EPR signal is asymmetrical and the A=B ratio is close to 4.5, whereas it is 15
and 8 for LiC6 and LiC12 , respectively [115]. The superdense compound prepared by
ball-milling seems then to be less conductor than LiC6 . Conductivity measurements,
unfortunately dicult to handle with highly reactive powders, should be interesting
in order to conrm those observations. One should however note that the ball-milled
compound is made of small (mean size less than 3 lm) and quite anisotropic particles
(geometrical factor around 50): the skin depth d could be larger than the particles
thickness aecting the A=B ratio, which is connected to the diusion time through the
skin depth. For instance, with LiC6 , the values of d are 3 and 1 lm (in the a and c
direction, respectively), probably higher than the particle thickness. The electron can
be reected on the particle wall before its spin op. This phenomenon can strongly
aect the experimental A=B ratio [116,117].
3.9. High pressure investigations
Several comparisons were already made between the compounds prepared by
ball-milling and those synthesized under high pressure (50 kbars, 300 C) [49]. A
study under pressure of the ball-milled compounds was then interesting to perform.
Fig. 40 shows that the density of the ball-milled Li + 2C composition is equal to 1.91
2.10
2.08
2.06
Density
2.04
2.02
2.00
1.98
1.96
1.94
1.92
1.90
10
15
20
25
30
P (kbars)
Fig. 40. Compression of a Li + 2C powder prepared by ball-milling.
56
at low pressure, a value close to the experimental value obtained by liquid pycnometry (1.85) and in good agreement with Eq. (5) (calculated density 1.93). This
conrms that the intercalated phase is really LiC3 .
The intercalation of the metallic lithium excess to form the LiC2 superdense
compound does not occur since the pressure (and temperature) is too low for that
synthesis. If one considers the lithium quantity as an invariant, one can calculate the
volume (and density) variation for the intercalated compound since the lithium
compressibility is well known. The variation of the density of the intercalation
compound is represented in Fig. 41.
The compressibility is dened by the Bridgman equation:
V =V0 1 a P
13
with V0 the volume at ambient pressure and a the compressibility.

The compressibility for LiC3 is 1.4 10 11 Pa 1 between 0 and 25 kbars. In fact, the
compressibility is decreasing when the pressure increases, the density varying logarithmically. In Table 3, the compressibility in various pressure ranges are compared
to those determined by Avdeev et al. on several graphitelithium intercalation
compounds [49]. Normally, denser is the intercalated layer and lower is the compressibility. This is also the case with the ball-milled LiC3 compound, since its
compressibility is intermediate between LiC6 (2.3 10 11 Pa 1 ) and LiC2 (0.9 10 11
Density of the compound LiC3
2.56
2.54
2.52
2.5
2.48
2.46
2.44
2.42
0
10
15
20
25
30
P (kbars)
Fig. 41. Density versus pressure of the LiC3 compound prepared by ball-milling.
Table 3
Mean compressibility for various graphitelithium compounds
a 10 11 Pa 1
Graphite
Lithium
LiC6
Li7 9 C24
LiC2
LiC3 (ball-milled)
0 < P < 25 kbars

0 < P < 10 kbars
10 < P < 25 kbars
1.6
2.4
1.1
6.1
7.2
5.4
2.3
3.5
1.5
1.4
2.1
1.0
0.9
1.4
0.6
1.4
2.5
0.6
57
Pa 1 ). It is very close to those of the phases produced by LiC2 decomposition, which

contain Li7 clusters and whose stoichiometry are similar.
There is nevertheless a slight dierence between the compressibility variation for
LiC3 and the Li9-7 C24 phases: the former is more compressible under moderate
pressures, in the 010 kbars range (2.5 instead of 2.1 10 11 Pa 1 ). This accounts for
the proposed structure in which the lithium layer is split. The rst eect of the
pressure is to gather the two lithium layers whereas, in the Li9-7 C24 phases, the intercalated layer made of Li7 clusters is less deformed. In the 1025 kbars range, the
situation is the converse: the compressibility of the Li9-7 C24 compounds is higher.
This could be due to the vacant sites between the Li7 at clusters where the graphene
planes can be deformed. This deformation is probably responsible of the higher
compressibility above 10 kbars. This does not appear in the ball-milled LiC3 compound, in which the lithium atoms are regularly placed on the graphite network.
3.10. Conclusion
The ball-milling in the presence of an inert liquid is particularly relevant for the
synthesis of graphitelithium intercalation compounds:
the intercalation occurs at room temperature and does not need heavy apparatus
(as for the synthesis under high pressure),
it leads to superdense compounds (LiC3 stoichiometry) when small quantities of
liquid are added to the reactional mixture,
the presence of dodecane on the particles surface protect them from oxidation,
the superdense compounds are stable under ambient pressure,
the quantities of prepared powders are large: 510 g at once at the laboratory
scale,
the synthesis is rapid (12 h) and the technique is easy to transfer at an industrial
scale.
4. Preparation of highly anisometric graphite particles

Highly divided graphite presents a great interest in electrochemistry since the
route for the intercalated species is reduced, as the particle size is shorter. This is
particularly true for the diameter, but the thickness plays also an important role on
the intercalation/deintercalation kinetics, due to the pressure applied by the graphitic
matrix on the intercalate [118].
The ground graphite present dierent properties, according to the milling technique. Salver-Disma has compared the texture of graphite milled with vibrant and
planetary type mills [119]. A planetary mill involves mainly friction and maintains
the three-dimensional order of graphite since the interplanar distance is slightly in after 100 h of milling). The coherent domains are quite
creased (from 3.35 to 3.38 A
small and present a low anisotropy, the values for Lc (coherence length along the c
respectively. A
axis) and La (in-plane coherent length) are around 100 and 300 A,
58
vibrant mill (SPEX type) implies much violent shocks and the 3D graphite organization is destroyed: even after short milling times, the graphite is almost amorphous
Those materials can be
and the interplanar distance becomes as large as 3.60 A.
compared with the hard or not graphitable carbons and their low coherence
after a milling for 20 h) are accompanied by defects and dislengths (around 30 A
locations inside the crystallites. The individual particles are particularly small but
form agglomerates, which decrease the surface energy.
The classical milling techniques lead to ne graphite powders whose diameter and
thickness are of the same order and the amorphization is such that the irreversible
capacity, due to the passivating layer formation, is particularly important. On the
other hand, the deintercalation potential is quite high versus metallic lithium [120],
which leads to a decrease of the battery power using such carbon as anodic material.
A preparation method for very anisotropic graphite was set up in 1990 [121] and
leads to the so-called GMP (in french: graphite micronique plat). This complex
technique involves several steps:
intercalation into graphite of an electron acceptor species (typically HClO4 or
HNO3 . . .),
exfoliation by abrupt heating, which provokes a rapid evaporation of the intercalate and the exfoliation of the graphitic matrix [122],
dispersion of the expanded graphite in a wetting liquid (e.g. benzene, cyclohexane,
toluene),
milling by alternate use of ultrasounds and a rotating mill with shearing eect.
Those particles present a diameter of several lm and a thickness around 100 nm
and can be used for many applications, for instance, as lubricant.
In order to avoid this long procedure, we have taken the chance to combine the
use of a planetary mill (which induces mainly frictions and therefore favors the
graphite particles cleavage) and that of a liquid introduced in the milling container
and acting as lubricant and dispersal medium. In a rst experiment, water was used
as liquid medium and, although the results concerning the shape and size of the
particles (a diameter around 1 lm for a thickness of 20 nm) were relevant, an important pollution was observed, due to the reaction of water with the milling tools.
This point will be discussed later in this paper about the preparation of maghemite (c
Fe2 O3 ). When an inert solvent as dodecane is used instead of water, the particles
consist in pure graphite and the size and shape of the particles are similar [123].
4.1. Milling within dodecane
The experiments are done with natural, Ceylon type graphite. The initial particles
size is less than 40 lm and the shape is quite isotropic with a form factor close to 5 as
seen by SEM. The corresponding XRD diagram is shown in Fig. 15, it is typical of
well-organized graphite with around 78% of the rhombohedral phase. This graphite
is milled within dodecane using a planetary type mill since it is known to involve
mainly frictions leading to a thinning of the graphite particles. After the milling, the
59
vial content is a black paste and the dodecane is easily removed by heating in a
drying oven at 100 C.
4.2. X-rays diraction
The powders are analyzed by XRD using Mo, Ka1 radiation. The results are shown
in Fig. 42 and correspond to powders ball-milled for 12 and 48 h with 5 mm diameter
balls (a and b, respectively) or 10 mm diameter balls (c and d, respectively). In the four
cases, the main reections of graphite are sharp, which evidences the crystallites size
to be not drastically reduced upon milling. The backgrounds remain small, even with
the 10 mm balls and a 48 h milling time, showing a limited graphite amorphization.
This emphasizes the dodecane eciency about its lubricant and dispersal role.
Depending on the balls size, the (1 0 l) peak (between 18 and 22 on the XRD
diagrams) appears quite dierent: with 5 mm balls, the whole of the peaks remains
well modulated, even after 48 h of milling (cf. Fig. 42(b)). The relative intensity of the
reections points out a slight enrichment in the rhombohedral phase, up to 20% after
48 h. With 10 mm balls, the rhombohedral graphite content increases faster since,
after 12 h, the pattern is very close to that obtained with small balls after 48 h. From
this point of view, some equivalency appears between milling duration and balls size.
A grinding for 48 h (with the 10 mm balls) leads to a less dened (1 0 l) peak and it is
quite dicult to distinguish hexagonal and rhombohedral phases. This is the sign of
some disorders, although the compound remains quite well crystallized as shown by
a low background, the sharpness of the reections and the interplanar distance (3.35
The inuence of the balls diameter follows then a classical evolution: bigger are
A).
the balls and more disorganized is the graphite.
From those experiments, the conditions chosen for the preparation of HAG are as
follows:
5 g of graphite,
50 cm3 of dodecane,
200 g of balls (5 mm of diameter), charge ratio: 40,
200 rpm for 12 h.
4.3. SEM observations

Fig. 43 represents graphite particles prepared by the previously described milling
conditions (a) and, for comparison, the same graphite milled without dodecane (b). The
textural dierence is obvious: a dry milling leads to an important fracture of the particles
and the diameter is much smaller than that obtained by ball-milling within dodecane. The
particles stack on top of each other and the apparent thickness is larger than the initial
one. With dodecane, the particles are in the 110 lm range and are particularly planar.
They lie on the grid, which is useful for the thickness determination: by varying the acceleration voltage of the electronic beam, the particles become transparent to the electrons
and the copper of the sample holder can be seen through the particle. The corresponding
voltage E (in kV) and the thickness particle e (in lm) are connected by the relation:
60
Fig. 42. XRD diagrams of graphite ball-milled within dodecane: (a) and (b) with balls of 5 mm in diameter during 12 and 48 h, (c) and (d) balls of 10 mm in diameter during 12 and 48 h.
e 0:007556 E1:67 =Z 0:89 q

with Z 6 (carbon), q 2:27 (graphite density).
14
61
Fig. 42 (continued)
Fig. 43. SEM micrographs of ball-milled graphite: (a) with and (b) without dodecane.
In the case of the large particle shown in Fig. 43(a), the acceleration voltage corresponding to the transparency eect appearance is 6 kV and the corresponding
thickness 15 nm. The form factor of this particle is, therefore, higher than 100 and
makes of it a HAG. The grinding of graphite in the dodecane presence leads to
particles whose geometrical anisotropy is around 100, at least one order of magnitude
higher than that of classical graphite powders obtained by dry milling (Fig. 43(b)).
4.4. TEM observations
The large size distribution (mean diameter between 1 and 10 lm) is conrmed by
TEM. The crystallites edges, seen when a particle lies parallel to the electron beam,
62
Fig. 44. Electronic diraction patterns of HAG: (a) h k 0, (b) 0 0 l reections.
exhibit a maximal value of thickness of 50 nm. The electronic diraction shows that
most of the particles are single crystals. The reections are characteristic of welldened graphite: Fig. 44(a) displays the hexagonal symmetry of graphite. The 0 0 l
and some 1 0 l reections appear in Fig. 44(b), which corresponds to the diraction
pattern performed at the particle edges. For the 1 0 l reections, the l indices of the
more intense are odd as it is in the hexagonal graphite. Between those reections, one
can observe small spots, but it remains dicult to conclude on the presence (or
absence) of the rhombohedral phase.
4.5. Conclusion
The presence of a liquid, together with graphite, decreases the violence of the
shocks in the milling container and allows the preparation of HAG. This graphite,
whose properties are close to those of the exfoliated graphite, can probably be used
as precursor in the manufacturing of graphite cardboards (Papyex or Grafoil ). It
presents a large advantage towards exfoliated graphite, since this last is prepared
from graphite intercalated with sulfuric acid, which involves the presence of impurities in the material. Moreover, the exfoliation is possible only when the starting
graphite is made of large crystals, namely Madagascar graphite.
5. Synthesis of maghemite nanoparticles

The maghemite is an iron III oxide (c Fe2 O3 ) largely used as material for the
magnetic storage. Its structure is of spinel type slightly derived from that of magnetite (Fe3 O4 ) and this oxide presents a ferromagnetic behavior. On the other hand,
its nanosized particles (typically below 15 nm) are known to be superparamagnetic. Its paramagnetism is due to the thermal agitation, large enough to lead to a
63
uctuation of the magnetic moments (Neel rotation) and, consequently, a loss of the
magnetism.
5.1. Synthesis by milling within water
It was seen previously that the milling of graphite in the presence of water leads to
thin at graphite particles with a diameter of 110 lm and a thickness of 20 nm. This
powder presents a magnetic behavior incompatible with a simple pollution due to the
milling tools abrasion, since the impurities content is of several wt.%. This important
contamination comes from the water reduction by the iron of the milling tools,
according to the equation:
2Fe 3H2 O ! c Fe2 O3 3H2
15
The corresponding X-rays diraction pattern is shown in Fig. 45. The graphite
reections, indicated in italic bold characters, are accompanied by that of a cubic cell
whereas a 8:39 A
for
whose parameters are close to that of magnetite (a 8:35 A,
magnetite). The amount of this phase was too low to determine its real composition.
The answer to this question was obtained by mixing together graphite and iron
powders in the presence of water: the amount of the cubic phase is increased as more
iron powder is added to the mixture and a chemical analysis proved that the iron
oxidation state is +3.
From the previous results, we decided to set up a new technique allowing the
synthesis of well monodispersed nanoparticles of maghemite. The preparation is
done using the following conditions:
5 g of iron powder (Koch-Light Laboratories, 50 lm),
200 g of balls with 5 and 10 mm diameters, in the ratio 1/1 in weight,
Fig. 45. X-rays pattern of the powder prepared by ball-milling of graphite in the presence of water
All the reections, except that in italic bold characters (graphite), are indexed with a cubic
(k 0:70926 A).

unit cell with a 8:39 A.
64
charge ratio 40,

50 cm3 of water,
200 rpm.
The milling duration is in the 672 h range and the mixture of balls with two
dierent diameters allows to increase the violence of the shocks and to limit the
inactive regions of the milling container (where the powder cannot be crushed by any
ball).
According to Eq. (12) and a starting weight of iron equal to 5 g, the volume of
hydrogen produced by the water reduction is around 3 l (NTP), which means a 20
bars pressure in the vial (inside volume: 250 cm3 ). A valve placed on the cover allows
decreasing the pressure before opening. The role plaid by the in situ formed hydrogen is important since it favors the formation of a spinel structure [124]. In fact, it
seems that a high hydrogen pressure is not required: the reaction occurs without any
gasket on the milling container. The presence of oxygen gas, is also not necessary:
when starting with boiled water and working under an argon atmosphere, one obtains the same reaction. After milling, the product consists in a black paste, easy to
dry at 80 C.
5.2. XRD characterization
of Fig. 46 correspond to powders obThe diractograms (kMo;Ka 0:70926 A)
tained after 12 and 48 h of milling. The presence of non-reacted iron or hematite is
not detected, even for a short milling time. All reections can be indexed with a cubic
unit cell, but it is dicult to distinguish magnetite and maghemite, whose a
for Fe3 O4 , 8.35 A
for c Fe2 O3 . Moreover, the
parameters are very close: 8.39 A
relative intensity of the dierent reections is quite similar in both cases. Never-
Fig. 46. XRD for maghemite prepared by ball-milling: bottom 12 h, top 48 h.
65
theless, one slight dierence has to be noted between the two XRD diagrams: the 12
h ball-milled powder presents several large reections, which could be the sign of a
convolution of the magnetite and maghemite reections. This is especially remarkable for the (4 2 2), (5 1 1) and (4 4 0) reections. When the milling duration is higher
than 48 h, the XRD diagrams do not present signicant evolution.
5.3. Chemical analysis
In order to dierentiate maghemite and magnetite, the Fe2 content is measured
according to the following procedure: the powders are dissolved by hydrochloric
acid at room temperature and Fe2 ions are titrated by potassium dichromate in
phosphosulpuric acid in the presence of diphenylamine sulfonate [125]. The whole
iron content is measured after reduction of the Fe3 ions by stannous chloride,
whose excess is eliminated by mercuric chloride. For the 12 h ball-milled powder, the
Fe2 concentration is around 12% in weight, which means an equimolar maghemite
magnetite composition, since pure Fe3 O4 corresponds to 24% of Fe2 . A milling of
48 h leads to less than 1% of Fe2 . By addition of the XRD, which shows that the
compound has a spinel structure, and the chemical analysis proving the Fe2 absence, one can now assert that the powder obtained after 48 h of grinding is actually
a pure maghemite.
Other attempts for the maghemite synthesis were made in order to decrease the
milling duration, in particular by using a solution with 30% in volume of hydrogen
peroxide. Unfortunately, the results are similar to those obtained with pure water.
The optimal milling duration for the preparation of pure maghemite is, therefore, 48
h. There is no real change (Fe2 content or particles size) when the grinding is
longer.
5.4. TEM observations
The black paste resulting of the milling is diluted into water and one drop of this
suspension is put on a carbon-coated copper grid and then introduced in the TEM
chamber. Fig. 47(a) and (c) represent the micrographs of the compounds obtained
after 12 and 48 h of milling, respectively. A milling for 12 h leads to a large range for
the particles size: between 10 and 100 nm. The larger present a hexagonal shape
indicating a good crystallinity, as shown by the electronic diraction pattern (cf. Fig.
47(b)). The reections are well dened and one observes the reections of the same
parity, corresponding to a spinel structure. It is interesting to note that the spots are
not perfectly punctuated, but are rather crosses, which could be the signature of the
coexistence of maghemite and magnetite. After a milling of 48 h, the size of the
particles becomes homogeneous with a mean size of 15 nm, which is interesting since
the magnetic properties of maghemite depend strongly of the particles size. The
electronic diraction reveals a pattern typical of a nanocrystallized powder (cf. Fig.
47(d)): the rings correspond to a spinel structure, but it remains impossible to distinguish maghemite and magnetite.
66
Fig. 47. TEM micrographs and corresponding electronic diraction patterns of 12 h (a and b) and 48 h (c
and d) ball-milled maghemite powders.
5.4.1. Electron energy loss spectroscopy

EELS is used to determine the iron/oxygen ratio and the oxidation state of iron.
The O/Fe atomic ratio is determined by the relative intensity of the Ka lines. After a
12 h milling, the ratio is around 1.5 in good agreement with the Fe2 O3 stoichiometry,
but one should remember that the accuracy of those measurements is not sucient to
denitively conclude on the absence of magnetite. After 48 h, the ratio reaches 1.77, a
value higher than that for maghemite, which is quite surprising. The explanation
could be related to the presence of water molecules adsorbed at the surface of the
nanoparticles and whose bonding is high enough to prevent desorption under the
electron beam.
During the milling, water is reduced by iron, which involves the hydrogen formation and an alkaline pH, according to
H2 O e ! 1=2 H2 OH
67
16
This pH increase, combined with the nanosize of the particles (and therefore, the
presence of an important part of iron atoms at the particles edges), favors probably
the formation of hydroxyl groups at the surface and, thus, increases the oxygen
content. Such hydroxyl groups make possible the formation of ferrouids, these last
being named ionic since the particles aggregation does not occur, due to the ionic
repulsion between the charges carried by the particles [126]. Many researches aim to
connect dierent ligands on those surface groups in order to prepare ferrouids
stable in a large pH range [127].
EELS is a technique very sensitive to the ion environment, since it is based on the
interactions between the incident electron and the electronic shell of the considered
atom. In the case of iron, the 2p1=2 and 2p3=2 transitions towards the unoccupied 3d
states are responsible of the L2 and L3 lines, respectively. The L3 =L2 intensity ratio is
connected to the occupation of the 3d orbitals of the metallic cations and thus, gives
some information on the oxidation state. This ratio is maximal for a d5 electronic
conguration and decreases from d5 to d0 and from d5 to d10 [128,129].
Several iron oxides were studied as standards and their spectra are presented in
Fig. 48. The background is subtracted, the peaks are tted as gaussians and the L3 =L2
values determined from the deconvoluted peaks. The characteristic L3 edge increases
with the oxidation state: from 708 eV for Fe0 to 711 eV for Fe3 , this shift being
noticeable since the spectrometer resolution is around 0.4 eV. Table 4 gathers the
dierent L3 =L2 ratio values. The maximum value is obtained for Fe2 O3 , in good
agreement with the above mentioned results.
4
3.5
Fe2O3
Intensity
3
Fe3O4
2.5
2
1.5
FeO
1
Fe metal
0.5
0
700
710
720
730
740
E (eV)
Fig. 48. EELS spectra of metallic iron and several iron oxides used as standards.
68
Table 4
L3 /L2 ratio for iron and diverse iron oxides
L3 =L2
Fe
FeO
Fe3 O4
Fe2 O3
3.71
5.06
6.40
6.65
Ball-milling
12 h
48 h
6.50
6.94
Fig. 49. EELS spectra of maghemite prepared by ball-milling.
Fig. 49 represents the EELS spectra of 12 and 48 h ball-milled maghemite samples. The L3 and L2 edges are measured at 711 and 724 eV, respectively. The L3 =L2
ratio increases with milling time. After 12 h of milling, the ratio is 6.5, a value between those of maghemite and magnetite (in good agreement with the results obtained by chemical analysis). A grinding of 48 h leads to a L3 =L2 ratio of 6.94,
indicating a higher oxidation state for iron.
From those experiments, one can conclude that the maghemite synthesis is
achieved after a 48 h ball-milling and leads to a particularly monodisperse sample
(mean diameter around 15 nm). Hydroxyl groups, due to the basic pH of the reactional mixture, seem to be present at the nanoparticles surface.
5.5. M
ossbauer spectroscopy
The M
ossbauer eect is based on the absorption of c photons by a nucleus, with
neither energy loss due to the nucleus backward movement, nor resolution loss by
thermal agitation. Sensitive to the immediate environment of the chosen isotope, the
M
ossbauer spectroscopy is an investigation mean both selective and local. The absorption of a c photon induces nuclear transitions between the fundamental state
69
I 1=2 and the excited state I 3=2. It concerns a specic energy: 14.4 keV for
57
Fe, whose abundance is around 2.5% in natural iron.
The electrostatic interaction between the nucleus and the electric eld displayed
by its neighboring modies its nuclear energy levels. Moreover, in a magnetically
organized material, a magnetic inuence superimposes on this electrostatic interaction. The degeneracy aects both the fundamental and excited states. In the presence
of a hyperne magnetic eld, the M
ossbauer spectrum consists in a sextuplet corresponding to the six possible transitions. Such sextuplet can be observed only when
the electrostatic interaction is weak compared to the magnetic interaction.
M
ossbauer eect leads to the knowledge of the isomeric displacement d, the quadrupolar displacement e and the internal magnetic eld H.
This experimental technique requires:
a source in which the ssion of a radioactive isotope ejects c photons. In the present case, it is a 25 mCi 57 Co source, 57 Co being the radioactive parent of 57 Fe,
a device allowing the motion of the source in front of the sample with a constant
acceleration, which modies, by Doppler eect, the c photons energy on both
sides of the nuclear transition edge.
The absorption spectrum is obtained by measuring the photon ow transmitted
by the sample as a function of the source speed. The adjustment between the calculated and experimental spectra is done by least square tting. The eld intensity (in
kG) is calculated by multiplying the inter-peak distance (in mm/s) by 31.12 in the
present case. Fig. 50 represents the spectra of 48 h ball-milled maghemite and
magnetite used as reference. Magnetite is an inverse spinel: the tetrahedral sites are
occupied by Fe3 ions, whereas the octahedral sites contain both Fe2 and Fe3 ions.
It can be written:
Fig. 50. M
ossbauer spectra of magnetite (top) and 48 h ball-milled maghemite (bottom).
70
Fe3 T Fe3 Fe2 O O4

The M
ossbauer spectrum of magnetite presents two hyperne elds at 491 and
456 kG corresponding respectively to the tetrahedral and octahedral sites. At room
temperature, there is an electronic exchange between the Fe3 and Fe2 ions located
in the octahedral sites [130], which involves a mean spectrum of those two contributions without any quadrupolar eect.
The maghemite (c Fe2 O3 ) presents the same spinel structure as magnetite, but the
Fe2 cations are replaced by Fe3 and vacancies, all vacancies are located in the
octahedral sites. The anti-parallel alignment involves the ferrimagnetic behavior of
maghemite. The observed M
ossbauer spectrum is resolved by a sextuplet whose
hyperne eld is 496 kG, attributed to the Fe3 ions both in tetrahedral and octahedral sites: Fe3 possesses a 3d5 electronic conguration, thus, it is not sensitive to
the crystallographic environment. It is possible to separate the contributions, due to
the two sublattices, by applying an external magnetic eld. The octahedral and
tetrahedral sites align respectively parallel and anti-parallel with respect to the applied eld and the two resulting elds are dierent [131]. This M
ossbauer study
points out the absence of magnetite in the 48 h ball-milled sample, since the characteristic shift of the Fe3 ions located in the octahedral sites is absent. This conrms
that the milling leads to pure maghemite after 48 h.
5.6. Magnetic susceptibility measurements
Fig. 51 shows the magnetic susceptibility dependence versus temperature: a ferromagnetic to paramagnetic transition is clearly observed at 480 C. This transition
is due to the structural transformation between c (maghemite) and a Fe2 O3 (hematite). This irreversible transition (the powder remains paramagnetic after cooling)
was also checked by XRD. The temperature of 480 C for the transition is in accordance with the literature.
45
40
x (uem / mol)
35
30
25
20
15
10
5
0
0
100
200
300
400
500
600
700
T (C)
Fig. 51. Magnetic susceptibility of ball-milled maghemite as a function of the temperature.
71
5.7. Conclusion
A new method for the synthesis of maghemite (c Fe2 O3 ) has been set up. Based on
the milling of iron powder in the presence of water, it leads to the preparation of well
crystallized nanoparticles (mean diameter 15 nm) after 48 h of milling. The powders
are characterized by several techniques, which reveal the quasi-absence of Fe2 ions
(less than 1 wt.% as proved by chemical analysis). Further developments of the ballmilling conditions are in progress, in order to synthesize very ne particles for
preparing ionics ferrouids.
6. Graphitemaghemite composites
The purpose for the preparation of graphitemaghemite composites is mainly due
to their potential applications as anodes in lithium-ion batteries. It is now well established that some transition metal oxides (as CoO) can reversibly react with lithium if their particles size is suciently small [75]. It was interesting to investigate
such kind of behavior for the maghemite nanoparticles. Those particles are deposited
on HAG, whose role is double: avoid a fast aggregation of the maghemite nanocrystals and ensure the electrical conductivity between the grains, as it is demonstrated in the case of graphiteSnO composites [132]. According to the starting
materials (iron or maghemite, natural graphite or HAG), there are four dierent
manners to prepare graphitemaghemite composites.
6.1. X-rays diraction
All the composites presented in Fig. 52 correspond to a maghemite content of 22
wt.%. It appears clearly that starting from iron leads to disorganized graphite,
particularly with HAG whose thin crystals are particularly fragile (cf. Fig. 52(a)).
Natural graphite (Alfa) mixed together with iron (cf. Fig. 52(b)) presents a 0 0 2
reection enlarged towards the small angles, indicating a slightly higher value of
d 0 0 2 , sign of a partial turbostratic stacking of the graphene planes.
Starting from already synthesized maghemite leads to better organized composites. There is however a noticeable dierence between the XRD diagrams of Fig.
52(c) and (d), concerning the relative intensity of maghemite and graphite reections
(3 1 1 and 0 0 2 reections, respectively). The maghemite peak seems much intense
when starting from HAG, instead of natural graphite, in spite of a maghemite/
graphite ratio identical in both cases. The explanation could be the following: the
graphite particles cleavage is probably less ecient within water, maybe related with
a lower viscosity of water compared to dodecane and, thus, the graphite particles
tend to stack around maghemite aggregates. Moreover, in the case of composites
prepared with HAG, this last can be covered by a thin dodecane layer (not removed
by heating), which could prevent the graphite particles to agglomerate in water. This
results in a simple dispersion of the maghemite nanocrystallites on the surface of at
and isolated graphite particles.
72
Fig. 52. XRD diagrams of four dierent graphitemaghemite composites (according to the starting materials, indicated on the gures), 22 wt.% of Fe2 O3 .
6.2. SEM observations

Fig. 53 represents the micrographs of two composites prepared by the following
methods:
73
Fig. 52 (continued)
Fig. 53. SEM micrographs of graphitemaghemite composites, 22 wt.% of c Fe2 O3 (a) simple mixture of
HAG and maghemite, (b) direct synthesis starting from graphite and iron powders.
(a) by separate preparations of maghemite and HAG and, then, addition of this
HAG (after drying) to the maghemite mixed within water. The nal milling is
done with a lower rotation speed (150 rpm instead of 200) for a short time (2
h) to prevent a too large degradation of the HAG,
(b) by direct synthesis from Alfa graphite and iron powder in water.
The preparation method inuences greatly the particles shape: when starting with
HAG and maghemite, the agglomeration is limited (a), whereas the direct synthesis
from graphite and iron powders leads to large aggregates (b), the graphite particles
surrounding maghemite clusters. For the following studies, especially those concerning the electrochemical applications, the best synthesis method consists in the
separate preparation of:
74
Fig. 54. TEM micrograph and electronic diraction pattern of a graphitemaghemite composite (22 wt.%
of c Fe2 O3 ).
Table 5
Reections visible in Fig. 54(b)
4.79
dh k l (A)
3.33
hkl
c Fe2 O3
111
Graphite
002
2.92
2.55
2.10
1.71
1.62
1.48
c Fe2 O3
220
c Fe2 O3
311
c Fe2 O3
400
c Fe2 O3
422
c Fe2 O3
511
c Fe2 O3
440
HAG by ball-milling of natural graphite within dodecane, according to the conditions described in Part 4.1,
maghemite nanoparticles by grinding of iron powder within water (cf. Part 5.1),
composites by a moderate milling (150 rpm for 2 h) of a mixture of previously synthesized HAG and maghemite.
6.3. TEM studies
Fig. 54 represents a TEM micrograph of the graphitemaghemite composite
prepared in three steps and the corresponding electronic diraction pattern. Maghemite nanoparticles are deposited on the surface of the at graphite particles. The
size of maghemite is still 15 nm, but there is some tendency for the particles agglomeration, since the nanoparticles do not form a regular lm. However, the particles aggregates remain quite small (less than 100 nm in diameter). The electron
diraction indicates punctuated rings and the particles are mostly as single crystals.
The observed reections are gathered in Table 5.
7. Electrochemical performances
7.1. Introduction
Graphite is currently the best anodic material for lithium-ion batteries, since the
formation of LiC6 leads to a reversible capacity of 372 mA h/g associated with a
75
potential below 0.3 V versus metallic lithium. In order to increase the lithium intercalated content, it was shown previously that the ball-milling constitutes a good
tool since graphitelithium superdense phase, whose stoichiometry is LiC3 , can be
synthesized. The electrochemical performances of this new compound are compared
to those exhibited by the LiC2 compound obtained under high pressure [133].
Since 10 years, the need for secondary batteries with high energy density is increasing (cellular phones, portable devices, electric vehicles). Metallic lithium, whose
specic capacity is 3.8 A h/g, cannot be used as anode due to the dendrites formation,
during the charge process, which provokes short-circuits. Thus, the carbon materials
became the best anodic materials and a battery using C and LiCoO2 as anode and
cathode, respectively, was rstly commercialized by Sony in 1990 [54]. The chargedischarge process is ensured by the back and forth movement of the lithium ions
between the two electrodes and such systems are called rocking-chair or, more
commonly, lithium-ion batteries.
The reaction can be written:
at the anode :
at the cathode :
xLi xe 6C () Lix C6
LiMO2 () Li1 x MO2 xLi xe
17
18
During the charge, both equations are moved to the right, and the reverse at the
discharge. The battery is generally assembled at the discharge state, the cathode
playing the role of lithium reservoir. The rst charge is accompanied by irreversible
phenomena connected to the electrolyte reduction, which precipitates a passivation
lm at the carbon surface: the solid electrolyte interphase (SEI). With the most
commonly used solvents (based on carbonates), the lm is mainly made of lithium
carbonate Li2 CO3 and alkyl carbonates ROCO2 Li [134136]. This SEI plays a major
role during the charge process since it prevents the solvent co-intercalation and
presents a good ionic conductivity, allowing lithium to pass through it easily.
However, the co-intercalation of solvents such as propylene carbonate (PC),
tetrahydrofurane or dimethylsulfoxide is reported. In the case of PC, the solvent
decomposition between the graphene planes involves a large degradation of the
electrode due to the graphite exfoliation [136]. In fact, in spite of a large variety of
organic solvents inert towards lithium, the choice for a good electrolyte remains
dicult due to the required following properties:
a high stability on oxidation, due to the use of high potential cathodes: more than
4 V with the current oxides (LiMn2 O4 , LiCoO2 , LiNiO2 . . .) [6466] and almost 5
V with the future materials like phosphates or vanadates (4.8 V with LiCoPO4
[137]),
a high dielectric constant for the dissociation of the lithium salts,
a low viscosity to favor the ions migration.
At the present time, the best solvents remain the carbonates, either cyclic (EC. . .)
or linear (dimethyl carbonate DMC, diethyl carbonate). The lithium salts are essentially LiClO4 , LiPF6 , LiBF4 , LiAsF6 . . .
76
7.1.1. Carbonaceous materials

The lithium intercalation is possible into graphite, but also into other carbon
materials, more or less organized. Among the graphitable carbons, petroleum coke
was particularly studied and it was demonstrated that the lithium intercalated
content depends directly of the heat treatment [138]. The non-graphitable carbons
present a capacity twice that of graphite, but the charge-discharge cycle exhibits a
large hysteresis [139,140]. The extra intercalation of lithium is generally connected to
the presence of hydrogen. For instance, the carbonization at low temperature (700
C) of epoxy resins allows the preparation of interesting carbonaceous materials: the
capacity is directly proportional to the hydrogen content [141].
The ball-milling of graphite leads also to carbons with promising electrochemical
properties [142]: after a milling of 80 h with a vibrant type-mill, graphite presents a
capacity around 650 mA h/g. Unfortunately, the intercalation of lithium occurs in a
large potential range and the charge-discharge curves present a high polarization
[141,142]. The electrochemical intercalation of lithium into carbon bers leads to
high reversibility and current densities [143145]. In fact, all carbon materials
present a faradic loss during the rst charge due to the SEI formation at the
electrode surface and, in a rst approximation, one should admit that this loss is
proportional to the specic surface area of the material. That is the reason why
fullerenes and nanotubes exhibit an important irreversibility when used as anodes
[146].
The challenge for preparing a better material than graphite is still up to date since
a larger reversible capacity occurs generally at the expanse of a low intercalation
potential and a good cyclability. A recent review paper gathers the electrochemical
performances encountered with most of the carbon materials [147].
7.2. Experimental
The electrochemical performances are tested in a three electrodes Teon cell. The
reference and counter electrodes are made of lithium ribbons, whereas the working
electrode consists in a pellet made with the investigated material. The powder is
simply pressed on a copper grid in order to form a thin layer. The sample mass is
typically around 5 mg. The electrolyte is a 1 M LiClO4 solution in a mixture 1/1 (in
weight) of EC and DMC (Table 6). The use of such EC/DMC mixture allows the
addition of the low viscosity of DMC and the high dielectric constant of EC. Table 4
gathers the main properties of those solvents.
Table 6
Properties of EC and DMC
EC
DMC
Melting
point (C)
Boiling point
(C)
Viscosity
(cP)
Dielectric
constant
Density
Molecular
weight
36.3
4.9
248
91
1.93
0.59
89.8
3.1
1.32
1.07
88
90
77
0.05
1st cycle
2nd cycle
0.00
-0.05
0.00
I / mA
-0.01
-0.10
-0.02
1st
2nd
I / mA
-0.03
-0.15
-0.04
S.E.I.
-0.05
-0.20
-0.5
0.50
0.75
1.00
1.25
1.50
E/V
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
E/V
Fig. 55. Voltammogram of pristine Alfa graphite.
7.3. Highly anisometric graphite

Before the study of the ball-milled compounds, the electrochemical behavior of
the starting graphite was investigated. Fig. 55 represents the voltammogram obtained with a scanning rate of 1 mV/s. The curve shows clearly the SEI formation,
which occurs in two steps on reduction (peaks at 1.3 and 0.7 V). The SEI formation
is not completed at the rst cycle since the peaks are still visible during the second
cycle. The curve is typical of a well crystallized graphite: the lithium intercalation
occurs by successive stages as shown by the shoulder at 0.2 V on reduction and the
lithium deintercalation is complete at 0.3 V.
Fig. 56(a) shows the rst galvanostatic cycle for pristine Alfa graphite obtained
under a 100 lA current, corresponding to a C/10 charge rate (e.g. LiC6 formed in 10
Fig. 56. First cycle of pristine Alfa graphite (a) and HAG prepared by ball-milling (b).
78
h). The rst charge presents a capacity around 500 mA h/g, including 150 mA h/g due
to the SEI formation. The reversible capacity is, thus, 350 mA h/g, 94% of the theoretical one for the LiC6 formation and remains 300 mA h/g after 30 cycles.
The irreversible capacity of the ball-milled graphite is much smaller than that of
the starting material: around 80 instead of 150 mA h/g (cf. Fig. 56(b)). This behavior
is opposite to the general idea according an irreversible capacity proportional to the
specic surface area of graphite [138]. In fact, the ball-milled graphite presents a large
surface, roughly 100 times higher than that of the initial graphite, but the grinding
provokes a cleavage of the particles (and not a breaking). This cleavage occurs
probably at the most fragile parts of the graphite grains (e.g. at the defects between
graphene sheets) and involves a recovery of those defects, in which the SEI formation is important. The defects increase the active surface (presence of dangling
bonds) and, therefore, their elimination decrease strongly the SEI formation. This
explains why the irreversible capacity can be lowered by ball-milling in dodecane and
proves that the milling conditions are very mild.
The cycling of a battery based on HAG (cf. Fig. 57) is quite comparable to that
with Alfa graphite and the capacity is around 80% of the theoretical one after 30
cycles. The advantage is a less consumption of lithium to form the SEI layer during
the rst intercalation. Cycling under higher charge rates are in progress in order to
show that the low thickness of the particles allows a high lithium intercalation/
deintercalation kinetic.
7.4. LiC3 + Li powder prepared by ball-milling
Just after the preparation of the electrochemical cell, the open circuit voltage
(OCV) is particularly low: around 20 mV versus lithium (cf. Fig. 58). It decreases
120
Capacity (%)
100
80
60
deintercalation
intercalation
40
20
0
0
10
15
20
25
30
35
Number of cycles
Fig. 57. Cycling of a battery based on HAG.
79
20
18
16
OCV (mV)
14
12
10
8
6
4
2
0
0
10
15
20
25
30
Time (mn)
Fig. 58. Evolution of the OCV for a Li + 2C powder prepared by ball-milling.
rapidly and reaches a stable value close to 0 mV, which is quite dicult to explain
since the SEI formation occurs as soon as the electrode is dipped in the electrolyte.
This is probably due to the presence of free lithium in the powder: initially, the
potential is governed by the intercalation phase and decreases as the free lithium
migrates through the intercalated particles. Anyway, the OCV value is much lower
than that of LiC6 (around 90 mV), in good agreement with the high lithium content
of the intercalation compound in which, the lithium concentration is close to that of
metallic lithium: the volume containing one mole of lithium atom is 17.5 cm3 (in spite
of the presence of the carbon matrix), instead of 13.1 cm3 for metallic Li or 11.7 cm3
for superdense LiC2 prepared under high pressure, this last leading to a negative
potential versus Li0 [50].
Fig. 59 represents the rst galvanostatic cycle of the Li + 2C ball-milled powder.
The rst deintercalation capacity is around 1 A h/g, value close to that of the theoretical one corresponding to a LiC2 stoichiometry. The derivative of the curve is
shown in insert and allows a better determination of the potentials of the successive
electrochemical processes [148]. The respective capacities corresponding to the different plateaus (revealed in the Fig. 59 by the peaks of the derivative curve shown in
the insert) are in good agreement with the following reactions:
at 34 mV 3LiC2 ! LiC6 2Li
19
at 102 mV LiC6 ! 0:5LiC12 0:5Li
20
at 139 mV 0:5LiC12 ! 0:33LiC18 0:17Li
21
at 226 mV 0:33LiC18 ! 6C 0:33Li
22
Four peaks are observed during deintercalation at 34, 102, 139 and 226 mV, respectively. The rst one corresponds both to the desorption of the lithium nanoparticles and to the transformation of LiC3 into LiC6 , but it seems impossible to
dissociate the two phenomena. The other peaks are those, which appear for a
80
intercalation
deintercalation
3.0
16000
34
12000
2.5
102
2.0
139
4000
dQ /
Potential (V)
8000
226
200
1.5
-4000
107
-8000
1.0
-12000
71
-16000
0.5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Potential
0.0
0
100
200
300
400
500
600
700
800
900 1000
Capacity (mAh/g)
Fig. 59. First galvanostatic cycle for a Li + 2C powder prepared by ball-milling, inset: the derivative of the
curve, which points out the potentials.
classical deintercalation from LiC6 to graphite through successive stages. The reversible process (LiC6 formation) is observed during intercalation (peaks at 71, 107
and 200 mV). The rst intercalation leads to a capacity of 320 mA h/g, value close to
the classical intercalation into graphite leading to LiC6 . Thus, the superdense phase
is not formed by electrochemistry, as well as it appears for the other superdense
phases synthesized under high pressure.
The cycling of the corresponding battery is represented in Fig. 60. After 30 cycles,
the capacity is around 280 mA h/g (75% of the theoretical value based on the LiC6
formation).
7.4.1. Comparison with LiC2 synthesized under high pressure
The rst galvanostatic cycle of the high pressure LiC2 compound is shown in Fig.
61. The experimental conditions are the same as for the ball-milled phase and the
electrochemical behavior looks very similar with roughly the same potential values,
both in intercalation and deintercalation. Nevertheless, the plateaus seem less dened for the high pressure phase.
Their relative lengths are not compatible with the transitions corresponding to the
Eqs. (19)(22), as pointed out by Bindra et al. [133]. These authors explain the
dierent plateaus as follows:
at 27 mV 3LiC2 ! 0:25Li9 C24 0:75Li
23
at 102 mV 0:25Li9 C24 ! 0:25Li7 C24 0:5Li
24
81
350
300
deintercalation
Capacity (%)
250
intercalation
200
150
100
50
0
0
10
15
20
25
30
Number of cycles
Fig. 60. Capacity of a Li + 2C powder prepared by ball-milling.
Fig. 61. First galvanostatic cycle for a LiC2 compound synthesized under high pressure, inset: the derivative of the curve, which points out the potentials.
at 142 mV 0:25Li7 C24 ! LiC6 0:75Li
25
at 227 mV LiC6 ! 6C Li
26
The relative capacities are in good agreement with the lengths of the plateaus, but
the potentials are unrealistic: the rst stage Li7 C24 phase cannot exist at a potential as
high as 142 mV, whereas LiC6 (with a lithium content two times lower) is not stable
82
above 90 mV [149]. In fact, the explanation could be related to a kinetic eect, since
the particles size of the high pressure compound is much larger (100 lm) than that of
the ball-milled one (15 lm).
7.4.2. Conclusion
The compounds prepared by ball-milling present an electrochemical behavior
very similar to that of the high pressure phases: they can both be considered as
primary batteries with a fairly high capacity (close to 1 A h/g) and with the possibility to be partially recharged with a reversible capacity corresponding to the LiC6
formation.
7.5. Graphitemaghemite composites
The working electrode consists in a mixture of c Fe2 O3 (22 wt.%) and graphite,
the reference and counter electrodes are made of a ribbon of metallic lithium. The
electrolyte is a 1 M solution of LiClO4 in a 1/1 in weight mixture of EC and DMC.
The voltammogram of the rst cycle (scan rate 1mV/s) is shown in Fig. 62. The initial
potential is higher than that of pure graphite: around 3.5 V instead of 2.8 V.
During the rst reduction, besides the classical lithium intercalation into graphite
via dierent stages observed at low potential (below 0.3 V), one can observe three
peaks at 1.6, 1.0 and 0.7 V. Those peaks cannot be only attributed to the formation
of the SEI, which occurs normally at 0.70.8 V. In fact, these potentials are similar to
those observed by Pernet et al. [150]: the small peaks (1.6 and 1.0 V) correspond to
the lithium insertion in the dierent vacant octahedral sites of the spinel structure
0.2
intensity (mA)
0.1
0.0
-0.1
-0.2
-0.3
0
Potential (V)
Fig. 62. First voltammogram of a graphitemaghemite composite. The arrow indicates the way, starting
from an initial potential of 3.5 V. The points 1, 2 and 3 correspond to the XRD shown in Figs. 6365.
83
(0.25 Li per c Fe2 O3 ). The 0.7 V peak is the sign of the oxide reduction, which involves a structural reorganization of the material, and, thus, an important energy
consumption.
On oxidation, one observes rstly the deintercalation of lithium from the graphite
matrix at potentials below 0.3 V. An other peak, whose meaning is still not clear,
appears at 0.5 V. It cannot be related to a reduction one, which should occur at a
lower potential, taking into account a kinetic eect and does not appear during the
reduction process. It could be attributed to the desorption of lithium weakly bonded
to oxygen atoms present at the surface of the maghemite nanoparticles. A large peak
between 1.0 and 2.5 V reveals the iron oxidation.
The structural evolution of maghemite was checked at three dierent steps of the
voltammogram (points 1, 2 and 3) by XRD (cf. Fig. 62). As it will be seen later, the
maghemite reduction leads to the formation of amorphous species and, therefore,
diraction on pure maghemite was necessary to observe signicant evolution on the
XRD diagrams.
After the reduction down to 1.2 V (cf. point 1 in Fig. 62), there is still a wellcrystallized spinel, in good agreement with the intercalation of lithium into the
lacunar octahedral sites (cf. Fig. 63(a)). At 0.4 V, the structural transformation of the
maghemite has been achieved and the resulting material becomes amorphous, except
metallic iron, which appears by sharp reections (cf. Fig. 63(b)). During the oxidation process, the iron is partially oxidized into wustite FeO, as shown in Fig. 63(c).
No formation of maghemite is detected suggesting an important irreversible capacity
at the rst cycle.
The galvanostatic cycling of a graphitemaghemite composite (22 wt.% of maghemite) is shown in Fig. 64. The rst lithium intercalation corresponds to a capacity
around 760 mA h/g. It includes a large irreversible part associated to the formation
of a passivating layer and to the irreversible reduction of maghemite, since the
metallic iron is only oxidized into wustite by electrochemical way.
During the following cycles, the reversible capacity decreases slightly and becomes
close to that of pure graphite. The decrease of the capacity is connected to the coalescence of the iron particles while the cell is cycled: the reversible oxidation of iron
into wustite, made possible by the high reactivity of the nanometric crystals, becomes
limited as that size is increased. However, the capacity remains quite large after 12
cycles: more than 300 mA h/g (cf. Fig. 65).
7.6. Conclusion
The compounds prepared by ball-milling present interesting electrochemical
properties, particularly a low irreversible capacity and a low potential of lithium
intercalation/deintercalation (both for graphitelithium phases and HAG particles),
a partial reversibility with graphitelithium superdense compounds (the primary
capacity of 1 A h/g is not recovered at the second cycle, but reaches the classical
values relative to the LiC6 formation).
Those investigations are still in progress in order to improve the charge rate with
HAG, the reversibility in the case of graphitelithium phases (reformation of the
84
Fig. 63. XRD diagrams of maghemite reduced at 1.2 V (a), reduced at 0.4 V (b) and re-oxidized at 2.8 V
(c).
85
1st cycle
3.0
2nd cycle
Potential (V)
2.5
2.0
1.5
1.0
0.5
0.0
0
200
400
600
800
Capacity (mAh/g)
Fig. 64. 1st and 2nd galvanostatic cycles of a graphitemaghemite composite (22% of c Fe2 O3 in weight).
450
discharge
charge
Capacity (mAh/g)
400
350
300
0
10
12
Cycle number
Fig. 65. Cycling of a battery based on graphite/c Fe2 O3 (22 wt.%) prepared by mechanical alloying.
superdense compound by electrochemical way) and to limit the maghemite nanoparticles coalescence during the electrochemical cycling for the graphitemaghemite
composites.
8. Conclusion
Although the ball-milling is now a well-known technique, the reactive milling is
still quite rare. The role of a liquid is often limited to the moderation of the shocks
violence and, therefore, to avoid a strong amorphization of the material. We have
86
investigated this way by using an inert liquid: the dodecane, which leads either to
superdense graphitelithium compounds or to HAG particles.
The addition of water together with graphite in a milling container leads, surprisingly, to graphitemaghemite composites: the metal of the vials has been oxidized
by water to form c Fe2 O3 . Taking this reaction into account, we have set up the
synthesis of maghemite particles, whose nanosize can be interesting for applications
in electrochemistry or magnetism. Other transition metal oxides can be synthesized
by ball-milling within water.
The compounds were studied as anodic materials for lithium-ion batteries and the
preliminary results are promising: the potentials versus metallic lithium are very low
as well as the irreversible capacity, the primary capacity being up to 1 A h/g in the
case of superdense graphitelithium compounds.
Finally, the ball-milling constitutes a simple mean for preparing quite competitive
materials:
superdense stable intercalation compounds of lithium into graphite,
HAG with a typical thickness of 20 nm,
nanoparticles of maghemite, which can be deposited on HAG to form composites
with good electrochemical properties.
Since the ball-milling synthesis does not require any special care or apparatus, it
should be easy to develop it at an industrial scale.
Acknowledgements
This paper is based on the research performed during the thesis defended by
Raphael Janot at Universite Henri Poincare Nancy I in October 2001. Laurence
Antoine was a very ecient and friendly initiator at the beginning of the thesis.
We would like to thank the persons who have contributed to this research: Jaafar
Ghanbaja, whose help was particularly precious on the interpretation of the TEM
and EELS results, Bernard Malaman and Richard Welter for the magnetism measurements on maghemite. Bruneau Wyncke, Alain Kohler and Jean-Claude Gachon
at UHP Nancy I have also participated to interesting experiments and useful discussions.
Jacques Conard and Pierre Lauginie (CRMD Orleans) were key persons for the
interpretation of the NMR and EPR experiments obtained with the participation of
Marie-Pierre Faugeres.
The electrochemical investigation was performed at the Department of Chemistry,
in the Laboratory of Electrochemistry, University of Camerino, Italy. Professor
Roberto Marassi and his group (Roberto Tossici, Francesco Nobili) are thanked, not
only for their help in this project, but also for their hospitality during our dierent
stays in the laboratory. Those thanks are also due to Dmitry Sklovsky and Alexei
Filatov, University of Moscow, where the high pressure experiments were done.
87
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Ball-Milling in Liquid Media - Applications To The Preparation of Anodic Materials For Lithium-Ion Batteries

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Progress in Materials Science 50 (2005) 192

Laboratoire de Chimie du Solide Min

Corresponding author. Tel.: +33-383-684633/912107; fax: +33-383-684634/912447.

R. Janot, D. Guerard / Progress in Materials Science 50 (2005) 192

R. Janot, D. Guerard / Progress in Materials Science 50 (2005) 192

Intercalation of lithium into graphite by ball-milling...............................................................

Synthesis by ball-milling in a liquid medium...............................................................................

R. Janot, D. Guerard / Progress in Materials Science 50 (2005) 192

Preparation of highly anisometric graphite particles................................................................

Synthesis of maghemite nanoparticles ...........................................................................................

Graphitemaghemite composites .....................................................................................................

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R. Janot, D. Guerard / Progress in Materials Science 50 (2005) 192

Fig. 1. Schematic representation of the ball-milling process.

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Fig. 2. Planetary type mill.

Fig. 3. Vibrant type mill.

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Fig. 5. Cannon-ball type mill.

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1.1.3. Main milling parameters

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Fig. 7. Hexagonal graphite.

Fig. 8. Rhombohedral graphite.

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Rhombohedral graphite, also called b graphite, is characterized by a unit cell

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1.2.3. The graphite intercalation compounds

The structure of the intercalation compounds is tightly connected to that of

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1.3. The lithium batteries

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Fig. 11. Schematic representation of solid polymer lithium batteries.

synthesis of new polymer electrolytes. Many works are currently aiming to nd

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chemical cross-linking is a process associated with the covalent bonding of polymer

Fig. 12. Schematic representation of lithium-ion batteries.

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Maghemite (c Fe2 O3 ) has the composition of hematite, but the structure of

2. Intercalation of lithium into graphite by ball-milling

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2.1. Material used in this study

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R. Janot, D. Guerard / Progress in Materials Science 50 (2005) 192

size of the lithium (granules or powder),

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charge ratio: 40,

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rotation speed: 200 rpm,

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2.5. Ball-milling of a mixture of Li + 2C powders

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Fig. 18. XRD of Li + 2C powders after various milling durations.

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versus that at 3.70 A,

is a sign of the synthesis of a rst stage graphitelithium comdistance of 3.70 A,

(versus that at 3.70 A)

An explanation could be related with a partial occupation of the

e 0:007556 E1:67 =Z 0:89 q