SOLID

STATE
ELSEYIER Solid State Ionics 86-88 (1996) 891-896
IONICS

Intercalation materials for lithium rechargeable batteries

D. Rahner”, S. Machill, H. Schlijrb, K. Sky, M. Klo13, W. Plieth

Dresden University of Technology, Institute of Physical Chemistry and Electrochemistry, D-01062 Dresden, Gemany

Abstract

In this contribution an overview will be given about the intercalation materials both for the negative and positive electrode
of lithium batteries in comparison with results of our own research. Besides lithium metal as a negative electrode, interest is
focused on insertion materials based on aluminium alloys. In the case of the positive electrode metal-oxides, those based on
manganese, nickel and cobalt are discussed.

Keywords: Intercalation materials; Lithium battery; Electrode

1. Introduction oxides, lithium spinels in particular have been rec-

ommended.
The realization of rechargeable lithium batteries
with sufficient capacity requires an improvement in
the cycleability of the negative and the positive 2. Anode materials
electrode. However, using lithium in secondary
batteries is not without problems. High energy The cycleability of the lithium electrode can be
densities could only be observed in secondary bat- improved by the use of lithium-inserting substrates.
teries with pure lithium as the anode material. The most common materials are lithium-carbon and
During charging, lithium is often deposited in a lithium-aluminium. Other suitable alloying sub-
dendritic form. A possibility for improving the strates are Sn, Pb, Bi, Sb, As and others.
cycleability of lithium batteries is the “swing” The anodes based on LiAl alloys can be cycled up
concept or the “lithium ion battery” concept, which to 1000 times, depending on the cycling conditions.
accords with the following reaction scheme One should emphasize that the depth of discharge
(DOD) reaches only 1 to 10% of the value of the
Li(Me,C)tiLi’(oxide) + e-
comparable primary lithium batteries.
This type of intercalation battery demands excellent Using substrate forming alloys or intercalation
host materials concerning the insertion/reinsertion of compounds with lithium, the reactivity against the
lithium and lithium ions. For the negative electrode, electrolyte or the solvent can be decreased. There-
intercalation materials based on carbon or lithium fore, the lithium in the host material will be
alloys are used and for the positive electrode metal “shielded” and the formation of dendrites will be
reduced or avoided if the diffusion velocity inside
*Corresponding author. the host material is high enough. However, a po-

0167-2738/96/$15.00 Copyright 01996 Elsevier Science B.V. All rights reserved

PII SO167-2738(96)00202-O
892 D. Ruhner et al. / Solid Stute Ionics 86-88 (1996) 891-896

tential shift occurs and leads to a decrease in the
energy and power density. For some purposes, the
increase in cycleability compensates for these dis-
advantages.
The diffusion of lithium in the alloy matrix
determines the charge/discharge rate of the battery
and limits its use as a low or high rate cell. The
diffusion process itself is determined by the nature of
the host material and its morphology.
The main problems of lithium alloy electrodes are
connected with the significant differences in volume
between the pure basic material and the formed
lithium alloy. Therefore, during cycling, mechanical
stress and cracks are induced by these volume
differences (LiAl 96.8% [l] in relation to the host
lattice). In the case of carbon, the volume difference
during the formation of LiC, is only 9.4% [2].
Carbon has therefore been the most favoured host
material in recent years.
2.1. Insertion into carbon
Carbon is a low cost material for the battery
industry. Many different kinds of carbonaceous
materials have been developed, such as graphite,
coke or carbon fibre materials [3]. Due to its layered
structure, it can insert lithium according to the
following scheme:
xLi + 6CeLi,C,
with O<x~l [4].
The higher the lithium content the lower is the
potential of the carbon electrode. With increasing X,
the potential approaches the value of metallic
lithium. This is the next reason for choosing carbon
as the favoured host material.
During the first lithium uptake, an irreversible loss
of capacity occurs. It forms a surface layer which is
similar to the layer formed on lithium [5]. After
some cycles, a reversible response of the Li,C,
electrode is observed.
Nevertheless, the disadvantages of metallic lithium
during cycling can be avoided. However, it should be
mentioned that all alloying materials (carbon, metals)
have not as yet shown the high-energy-density
properties that have been displayed by batteries
based on lithium metal.
2.2. Insertion into aluminium alloys
Alloys have been under investigation since Dey in
1971 [6] demonstrated the possibility of electro-
chemical alloying with lithium in organic elec-
trolytes. The use of alloys as the negative electrode
is based on the reversible insertion of lithium into the
host material in accordance with the reaction
xLi+ + Al + xe-ttLi,Al.
Anodes of this alloy can be cycled many times,
without side reactions such as the rapid decomposi-
tion of the organic electrolyte or dendrite formation.
However, the anode is covered by a fairly stable,
thin, passivating layer [7].
As in the case of lithium, the structure of the thin
passivating surface layer is also strongly influenced
by the composition of the electrolyte solution. Many
researchers described the positive effect obtained by
adding small amounts of organic or inorganic com-
pounds.
Recently, we studied the effect of dilithium-
phthalocyanine on cycling efficiency, cycle life and
corrosion behaviour of different anodes in 1 M
LiClO,-propylene carbonate solution [8]. It was
shown by electrochemical impedance spectroscopy
and current-potential measurements that the addition
of dilithium-phthalocyanine reduces the thickness of
the surface layer. Probably, the freshly deposited
lithium is either not as reactive or a modified film
with enhanced migration properties for lithium ions
is growing. In the case of lithium-aluminium alloy
anodes, the addition of dilithium-phthalocyanine has
a positive influence on long term cycling (Fig. lb).
In the electrolyte without additive, “normal” be-
haviour of the aluminium electrode is observed (Fig.
la).
In the absence of an additive, the overvoltage
increases during cycling due to a hindered lithium
transport through the formed surface film. After
about 80 cycles the lithium transfer is blocked and
the aluminium electrode stops working as an inser-
tion material. In the electrolyte with an additive, a
 D. Rahner et al. I Solid State Ionics 86-88 (1996) 891-896 893

metal) is the central problem in the development of

rechargeable negative electrodes for lithium cycling.
Attempts have been made to avoid this problem by
creating “dimension-stable” alloying electrodes in
such a way that (i) small particles of the active phase
of LilMe are embedded in a stabilizing matrix [9,10]
or (ii) the aluminium host previously formed an
alloy with other metals that are soluble in aluminium
or form intermetallic compounds with it, but do not
form alloys with lithium, e.g., nickel. In this way one
creates an alloy matrix of modified grain size with
stabilizing properties towards “mechanical stress-
ing” during charge/discharge processes of lithium
[11,12].
Therefore, the suitability of different binary Al-
Ni, Al-Mn and Al-Be alloys as anode substrates in
rechargeable lithium batteries have been tested,
compared with pure aluminium.
The changed composition by alloying of alumin-
ium with a second metal does dramatically influence
the mechanical properties and the electrochemical
behaviour. On the other hand, the electrochemical
properties of these substrates are also determined by
the macro- and microstructure. In particular, the
eutectic mixture of Al-N1 (Al/Al,Ni) seems to be an
interesting substrate material in rechargeable lithium
batteries. The Al,Ni phase does not form an alloy
0 5M Iwo 1500 2m 25w with lithium and acts only in the improvement of the
Time [sl
mechanical stability. The second phase of pure
Fig. 1. (a) Galvanostatic cycling behaviour of an aluminium aluminium can receive the incorporated lithium.
substrate in proplylene carbonate-l M LiClO, solution without We investigated some different qualities of this
additive. (b) Galvanostatic cycling behaviour of an aluminium
eutectic mixture. By fast quenching one gets very
substrate in propylene carbonate-l M LiC10,-10-2 M dilithium-
phthalocyanine solution.
finely spread segregations of the Al,Ni phase. A
direct heat flow (vertical Bridgeman method) leads to
a directionally solidified rodlike Al-Al,Ni eutectic.
This directionally solidified eutectic consists of an Al
modified surface film is obviously growing on top of matrix of faceted Al,Ni rods grown into it nearly
the aluminium surface. This film shows no changes parallel to each other and in the direction of heat
in its properties, however, a small overvoltage is flow.
observed during subsequent cycling. The layer is not The usefulness of a new anode material can be
a hindrance for the transfer of lithium in the alu- examined only under real conditions. The consumer
minium host material. is interested in a maximum number of charge/dis-
It seems that the combination of lithium alloys and charge cycles with highest power density, if possible.
dilithium-phthalocyanine gives a synergetic improve- Fig. 2 presents a set of typical cycling curves of
ment in the lithium cycleability. an aluminium substrate. The cycling efficiency was
The change in volume due to changes in the estimated to be 88% under the conditions used
morphology of LiAl and other Li,Me alloys (Me= (DOD: 10%). The reversible behaviour is lost for
894 D. Raker et d. / Solid State Innics 86-X8 (1996) 891-896

formed by an alternating arrangement of two double

chains and one single chain of MnO, octahedrons.
The reversibility of the lithium intercalation into
MnO, depends on the degree of discharge.

xLi+ + MnO, + xe-wLi,MnO, (0 <x 4 0.2)

In y-MnO,/Li cells the lithium insertion during

discharge occurs mainly into the (2 X 1) tunnels. The
-I
intercalation of Li + into the (1 X 1) tunnels leads
5co Km 1500 2crQ 25RJ 3001, 3m 4m 4500 mx
0
only to a ratio of 0.2 Li’/Mn in these domains. A
Time [s]
higher lithium intercalation causes a change of the
Fig. 2. Galvanostatic cylcling of an aluminium substrate. (1 X 1) domains into a [Mn,]O,-spinel-type lattice
[13]. The original lattice is destroyed and cannot be
renewed during recharge. However, the spinel-type
lattice shows a more or less reversible Li + intercala-
tion. For practical purposes this is insufficient,
however, the properties of manganese dioxide de-
scribed above have lead to concerted efforts to
synthezise MnO,-forms that could be suitable in
secondary lithium batteries. That the spine1 form is a
lithium insertion compound was lirst shown by
Hunter [14], who has reported the extraction of
lithium from LiMn,O, by acid treatment. The re-
sulting material was identified as A-MnO,, where the
[Mn,O,] framework remains as a spine1 structure
Fig. 3. Average cycling efficiency of various substrates. and allows the intercalation and deintercalation of
Li+ ions.
Therefore, the lithium spine1 Li[Mn,O,] is of
cycle numbers much larger than 100. Comparable great interest in the system Li-0-Mn. The transport
curves were obtained with the other substrates. With
of Li+ is achieved at interstitial places in the
an increasing content of manganese or nickel, the [Mn,]O, sublattice. The spine1 itself is stable over a
cycling efficiency decreases dramatically (Fig. 3). wide range of stoichiometry Li,TIMn,O,] (0~x12).
Starting from the LiMn,O, phase, one has two
possibilities:
3. Cathode materials

3. I. Lithium-manganese oxides (i) intercalation of a second Li+ gives the com-

position 1 <x52 which can be cycled in the po-
Manganese dioxide is an interesting material for tential range of about 2.5-3.5 V
battery applications. In principle it is suitable for the (ii) cycling of only one Li.+ in the composition
intercalation of small ions (H+, Li+) and it is also range O<x< 1 occurs in the potential range of about
inexpensive, non-polluting and readily available. It 3.5-4.5 v.
occurs in various modifications, among them the
most used for industrial purposes is y-MnO,, which In the first case, (1 <x52) a Jahn-Teller distortion
can be synthezised either chemically (CMD-MnO,) can be induced with increasing lithium content in
or electrochemically (EMD-MnO,). accordance with an average manganese ion valency
This oxide is characterised by a tunnel-structure of below 3.5. The result is a transformation of the
 D. Rahner et al. I Solid State Ionics 86-88 (1996) 891-896 895

crystal symmetry from cubic to tetragonal. The width I

08
of this two-phase domain (characterized by a flat
0.6 t
discharge curve) allows cycling in the composition
range 1.1 <x5 1.8 [15]. In the second case, (O<XS 1)
the system is stable. The cubic structure remains and
allows the insertion and reinsertion of Li+. The
insertion and reinsertion process occurs in two steps
[ 161. In the first step lithium is approximately cycled
between l>x>OS and in the second step between
os>x>o.
Fig. 4 shows the cycling behaviour of Li,Mn,O,. 34 3.6 3.8 4.0 42 44 46 48

The two intercalation processes of lithium are clearly Potential vs. Li IV]

visible. Investigations in the area of 3.5-4.5 V show

Fig. 5. Cycling behaviour of the Li-Mn spine1 described in Fig. 4
the good reversibility of the spine1 in this potential in the high voltage area, sweep rate 10 pV/s.
region and the electrolyte stability up to 4.5 V (Fig.
5).
Although the spinel-type manganese oxide is very alternating layers of octahedral sites in a cubic,
promising, there are a lot of investigations being close-packed, lattice of oxygen ions.
undertaken in order to improve the stability of the The compounds Li,_,NiO, (0~~50.5) and
structure by doping with metal-ions like Ni, Co, Fe, Li, _CoO, (0~~~0.5) are suitable cathode materi-
Mg or Zn [ 171. The complete exchange of man- als for 4 V rechargeable lithium cells using a carbon
ganese by nickel or cobalt leads to a layered anode (“lithium ion” battery). The cell reaction in
structure of the Li-metal oxides. the C/LiMeO, systems can be summarized by the
following electrochemical process:
3.2. Layered lithium-metal oxides
LiMeO, + 6CwLi, _.MeO, + Li,C, .

Lithiated nickel and cobalt oxides of the general Broussely et al. [ 181 investigated the mechanism of
formula LiMeO, (where Me=Ni, Co or Ni/Co) are Li insertion/reinsertion by cyclic voltammetry. This
insertion compounds for high-voltage lithium bat- mechanism is quite different for nickel and for cobalt
teries. These materials possess a layer structure oxide. The first charge and discharge curve of a
where lithium and the transition metal ions fill LiNiO, cathode is totally different from subsequent
cycles. The Li from LiNiO, cannot be fully inserted
during the subsequent reduction step due to a
structural transformation to Li,_.NiO,. After a few
cycles, the reversible reaction (shown in Fig. 6) can
be described as follows:

Li,,,SNiO,t+Li oXsNiO, + O.SLi+ + 0.5e

The practical specific capacity of Li-Ni oxides is

about 125-150 mAh/g [l&19].
Contrary to these observations, in the case of
LiCoO,, the lithium after the first charging process is
-2.0’
completely inserted during the following discharge
1.5 2.0 2.5 30 3.5 4.0 45 50
process [18].
U vs. Li [VI
The overall reaction of the LiCoO, charge/dis-
Fig. 4. Cyclic voltammogram of Li,Mn,O, (low temperature charge is
synthesis) in propylene carbonate-l M LiClO,, sweep rate 50
PVIS. LiCoO,&i, ,CoO, + 0.5Li+ + 0.5e-
896 D. Rahner et al. I Solid State lonics 86-88 (1996) 891-896

2.0 1 1
den, for the preparation of the directionally solidified
-6th cycle rodlike Al-Al,Ni eutectic mixtures.
-----7thcycle
..... 8thcycle
1.0 t

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Acknowledgments
Financial support from the “Deutsche Forschungs-
gemeinschaft” and the “Bundesministerium fur Bil-
dung und Forschung” is gratefully acknowledged.
The authors would like to thank Dr. W. Loser,
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