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Efficient Aluminum Chloride−Natural Graphite Battery

Kostiantyn V. Kravchyk,†,‡,§ Shutao Wang,†,‡,§ Laura Piveteau,†,‡ and Maksym V. Kovalenko*,†,‡
†
Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1,
CH-8093 Zürich, Switzerland
‡
Laboratory for Thin Films and Photovoltaics, Empa-Swiss Federal Laboratories for Materials Science and Technology,
Ü berlandstrasse 129, CH-8600 Dübendorf, Switzerland
*
S Supporting Information

ABSTRACT: The quest for low-cost and large-scale stationary

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storage of electricity has led to a surge of reports on novel

batteries comprising exclusively highly abundant chemical
elements. Aluminum-based systems, inter alia, are appealing
because of the safety and affordability of aluminum anodes. In
Downloaded via 83.47.141.56 on June 24, 2018 at 10:40:43 (UTC).

this work, we examined the recently proposed aluminum−ionic

liquid−graphite architecture. Using 27Al nuclear magnetic
resonance, we confirmed that AlCl4− acts as an intercalating
species. Although previous studies have focused on graphitic
cathodes, we analyzed the practicality of achievable energy
densities and found that the AlCl3-based ionic liquid is a capacity-limiting anode material. By focusing on both the graphitic
cathode and the AlCl3-based anode, we improved the overall energy density. First, high cathodic capacities of ≤150 mAh g−1 and
energy efficiencies of 90% at high electrode loadings of at least 10 mg cm−2 were obtained with natural, highly crystalline graphite
flakes, which were subjected to minimal mechanical processing. Second, the AlCl3 content in the ionic liquid was increased to its
maximal value, which essentially doubled the energy density of the battery, resulting in a cell-level energy density of ≤62 Wh
kg−1. The resulting batteries were also characterized by high power densities of at least 489 W kg−1.

■ INTRODUCTION
Secondary (i.e., rechargeable) batteries are deeply integrated
into every aspect of human life, including portable devices
(smartphones, tablets, and laptops) and transportation
(electrical cars, buses, bikes, etc.). Additionally, batteries are
increasingly seen as global players in the efficient management
of electricity from sustainable and renewable sources as well as
for the stabilization and decentralization of the electrical grid.
The simplest management concept is a household utility-level
system combining a stationary battery with solar or wind
electricity.1−3 Even for medium-level storage, the kilowatt-hour
cost per charging cycle, in addition to the gravimetric and
volumetric energy densities, becomes a major consideration for
the commercial success of stationary storage systems.4,5 The
volumetric energy densities are the highest for Li-ion batteries.
However, for eventual deployment on the terawatt-hour scale,
which is the scale of current worldwide hydroelectric storage,
low manufacturing costs and high natural abundances of all the
chemical elements constituting the battery become critical
factors.
With these goals in mind, battery technologies based on
highly abundant metals, such as Na,6−10 Mg,11−14 and Al,15−30
as charge carriers and/or electrodes have become a major
research focus. In particular, batteries that employ metallic Al as
an anode can harness numerous advantages, such as its high
natural abundance, high charge-storage capacity, and
safety.31−34 In addition, Al can be reversibly deposited and
stripped in chloroaluminate ionic liquids with a high
Coulombic efficiency of >99.5%, without formation of
dendrites.35−38 Batteries employing chloroaluminate ionic
liquids have received a great deal of attention since a
publication by the group of Dai in 2015,15 wherein a metallic
Al anode, two synthetic forms of graphite as cathodes (CVD-
grown graphitic foam and pyrolytic graphite), and an
AlCl3:EMIMCl (1-ethyl-3-methylimidazolium chloride) ionic
liquid were combined into a battery, which is schematically
depicted in Figure 1a. This battery design assumes that the
intercalating species are AlCl4− ions, as described in early
electrochemistry reports from the late 1970s.16,39,40 This
assumption is in agreement with our 27Al nuclear magnetic
resonance (NMR) spectroscopy results presented below. The
graphitic cathodes in ref 15 delivered cathodic capacities of 67
mAh g−1 at an average discharge voltage of 2.0 V. The authors
of ref 15 initially stated that natural forms of graphite exhibited
performances much poorer than those of both tested synthetic
graphitic forms. The high porosity of the synthetic graphite was
considered an important factor for the fast and highly reversible
intercalation of AlCl4− ions. Subsequent studies by the same
group and by others further increased the capacities and power
densities using porous synthetic graphitic materials, such as
graphitic foams41 and graphene nanoribbons (record-high
capacity values of 148 mAh g−1).42 However, the use of costly
Received: March 14, 2017
Revised: May 1, 2017
Published: May 1, 2017

© 2017 American Chemical Society 4484 DOI: 10.1021/acs.chemmater.7b01060

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Chemistry of Materials
Figure 1. Aluminum chloride−graphite battery. (a) Schematics of the charging process. (b) Comparison of the calculated (curves) and experimental
(data points) cell-level energy densities. The curves are computed from eq I, which describes the dependency of the energy density vs Cc at various
values of r assuming an average discharge voltage of 2 V. The experimental data points represent this work or estimates from reported voltages and
Cc.15,42−45 (c) Graphite ore. (d) Large natural graphite flakes produced commercially from graphite ore.
CVD processes could pose an unsurmountable obstacle for the
further practical use of such batteries, fully neutralizing the cost
benefits associated with the simplicity of the battery and the
abundance of the constituent elements. In parallel, similar
charge-storage capacities were obtained from electrodes made
of carbon paper,25,27,43 which presumably was produced from
natural graphite,27 and from a few-layer graphene aerogel.44
The latter was also derived from natural graphite through its
oxidation into graphite oxide followed by reduction.
Encouraged by both the initial report and some of these
recent publications, herein, we sought to thoroughly test the
most basic and inexpensive form of natural graphite, graphite
flakes, as the cathode material in such Al batteries. We found
that natural graphite flakes, with minimal processing by
sonication, delivered a charge-storage capacity of 148 mAh
g−1, at an average voltage of 2 V. We observed that open
graphite edges and flaky morphology with preserved pristine
crystalline structures (low density of crystalline defects) were
crucial for achieving such high charge-storage capacity. Notably,
Dai et al. also reported on natural graphite flakes as cathodes
during the preparation of this work, using a somewhat different
electrode formulation and achieving a high charge-storage
capacity of 110 mAh g−1 at a current density of 99 mA g−1.45
We also present direct spectroscopic evidence of the
intercalation of AlCl4− using solution- and solid-state 27Al
NMR spectroscopy. Furthermore, we analyze and discuss the
challenges related to the eventual practical use of this battery
technology. Moreover, we emphasize that an Al chloride−
graphite battery is not a rocking-chair battery, contrary to Li-
ion batteries, and should not be called an “Al-ion battery”
because the species that intercalate and/or deintercalate into
the graphitic cathode (AlCl4−) are different from those involved
in the simultaneous anodic process (i.e., exclusive deposition
and stripping of Al atoms and/or ions from the Al foil). This is
not only a matter of correct definitions. A portion of AlCl3 acts
as an anode material during the charging process, whereby it is
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reduced to Al atoms for electrodeposition and simultaneously
generates AlCl4− for intercalation. Therefore, severe require-
ments are posed on the amount of used ionic liquid, as the
ionic liquid, in fact, acts as a capacity-limiting liquid anode and
not just as an electrolyte. Thus, we tested AlCl3-rich
formulations of this battery up to the highest achievable
AlCl3:EMIMCl ratio of 2 and thereby improved the cell-level
energy density to 62 Wh kg−1. We discuss the reasons why a
further substantial increase in energy density is likely
impossible. However, we highlight the high energy efficiencies
(≤91%) and excellent power densities of the Al chloride−
graphite batteries with values of at least 489 W kg−1 at high
areal loadings of graphite (≥10 mg cm−2).
■ RESULTS AND DISCUSSION
Operation Mechanism and Energy Density of the Al
Chloride−Natural Graphite Flake Battery. Contrary to a
Li-ion battery utilizing graphite as an anode, an Al chloride
battery exploits the reversible oxidation of the graphite
network, i.e., its cathodic functionality. The non-rocking-chair,
i.e., mixed-ion, operation of the battery is clearly seen from
Figure 1a. The following half-reactions take place upon
charging:
on anode: 4Al 2Cl 7− + 3e− ↔ 7AlCl4 − + Al (I)
on cathode: xC + AlCl4 − ↔ Cx (AlCl4 −) + e− (II)
There is no unidirectional flow of Al ions or any other Al
species from one electrode to the other. For this reason, it is
misleading to call this battery an “Al-ion battery”, although this
term has become commonplace since the publication by Dai et
al.15 The actual operation mechanism is, however, fundamen-
tally different from that of metal-ion batteries: Al species are
depleted from the liquid phase during the charge process
(Figure 1a). AlCl3:EMIMCl (i.e., EMIM+ + AlCl4−), a mixture
of two solids that become a liquid at room temperature (an
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Figure 2. Electrochemical characterization of the pristine flakes (black) and processed smaller flakes (blue) compared to potato-shaped particles
produced commercially (red) and in house (light green). (a) Representative SEM images of the pristine graphite flakes and of two products of their
mechanical processing by sonication (smaller flakes) and by knife-milling (partially spheroidized, i.e., potato-shaped). (b and d) Galvanostatic charge
and discharge voltage curves and (c and e) cycle stability measurements for the pristine, processed smaller flakes and both potato-shaped specimens
with respect to Li+- or AlCl4−-ion storage. The same color in the legend represents the same material throughout all plots. Electrochemical
measurements in Li-ion half-cells [with 1 M LPF6 in ethylene carbonate/dimethyl carbonate (1:1 vol %) as an electrolyte and metallic lithium as a
counter electrode] and in AlCl3−graphite batteries (r = 1.3). Panel c also plots the Coulombic efficiency, whereas panel e presents the energy
efficiency. Typical Coulombic efficiencies of the AlCl3−graphite batteries are presented in Figure S3.

ionic liquid) due to the acid−base reaction forming AlCl4−, is battery an Al chloride−graphite battery, highlighting the fact
not only an electrolyte but also a source of electroactive species. that AlCl3 can be viewed as an actual anode material dissolved
AlCl3 is added in excess to allow Al2Cl7− ions to form. The in a stoichiometric mixture of AlCl3 and EMIMCl. Therefore,
electrodeposition of Al ions from chloride-based ionic liquids anodic reaction I can be reduced to
has been thoroughly studied in the past, leading to the 3 − 3 1
consensus that Al2Cl7− ions allow the electroplating of AlCl3 + e ↔ AlCl4 − + Al
4 4 4 (III)
Al.35,36,46−53 Al does not deposit from neutral or basic melts
(excess of EMIMCl). Clearly, the amount of Al2Cl7− ions, and The quantity of the neutral AlCl3:EMIMCl melt is linked to
hence the whole mass of the liquid phase, must match the the excessive AlCl3 via r. Considering the whole mass of the
capacity of the graphitic cathode. For each electrodeposited Al liquid anode, the theoretical charge-storage capacity of this
atom, three AlCl4− anions simultaneously intercalate into battery on a cell level can be determined starting from the
graphite. The charging process ends when there are only AlCl4− standard relationship Ctotal = (CACC)/(CA + CC),55,56 wherein
ions left, i.e., the neutral melt forms (AlCl3:EMIMCl = 1), or the weights of both the cathode and liquid anolyte are factored
when the maximal capacity of the graphitic cathode is reached. in
The highest molar ratio (r) of AlCl3 to EMIMCl that still forms Fx(r − 1)CC
a usable ionic liquid is ∼2:1; above this ratio, AlCl3 no longer C total =
Fx(r − 1) + CC(rMAlCl3 + MEMIMCl)
dissolves in the solution. The operation of such a battery is not
uniquely limited to EMIM-based formulations: AlCl3−urea28,54 20.1(r − 1)CC × 103
or fully inorganic NaAlCl4 melts27 have been recently presented =
20.1(r − 1) × 103 + CC(rMAlCl3 + MEMIMCl)
as cost-efficient alternatives. We also note that starting with an
Al anode is not a necessity. Any current collector supporting (1)
−1
the initial electroplating of Al or coated with a minimally thin where F = 26.8 × 10 mAh mol (Faraday constant), x = 3/4
3

Al film as a seed layer is sufficient. Therefore, we call this (number of electrons used to reduce 1 mol of the anodic
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material, i.e., AlCl3), r is the AlCl3:EMIMCl molar ratio, CC and
CA are the specific capacities of the cathode and anode,
respectively, in milliampere-hours per gram, MAlCl3 is the molar
mass of AlCl3 in grams per mole, and MEMIMCl is the molar
mass of EMIMCl or of any other Cl− source (i.e., HCl in the
simplest case) in grams per mole. Ctotal is an upper bound for a
capacity, as in the commercial battery it is further reduced by
25−50% because of the weight of current collectors, separators,
and packaging (determined by the battery design).
Using eq I, we analyzed the effects of increasing r and CC on
the overall energy density of this battery (E = CtotalV). In Figure
1b, we assume an average voltage of the battery to be constant
at 2 V for all theoretical curves. This value of the average
discharge voltage is the highest value we obtained exper-
imentally at r = 1.3. At r > 1.3, the measured average voltage
dropped progressively by up to 0.2 V [from ∼2 to ∼1.8 V
(Figure S1)]. The primary conclusion is that parameter r is the
most useful variable, in addition to the cathodic capacity of
graphite, for improving the energy density of the battery
because of the capacity-limiting effect of the ionic liquid. This
capacity-limiting effect can be illustrated by calculating the
theoretical CA, considering the whole mass (volume) of the
ionic liquid as a liquid anode (i.e., as an anolyte). The resulting
values are 48 mAh g−1 (63 Ah L−1) and 19 mAh g−1 (24 Ah
L−1) for r values of 2 and 1.3, respectively. Hence, to achieve an
optimal energy density, the highest capacity of the cathode
(CC) must be harnessed and a concomitant increase in r must
also be included. As a reference point, we analyzed all available
literature on AlCl3−graphite batteries and identified the highest
experimental energy density of ∼45 Wh kg−1 for an
AlCl3:EMIMCl anolyte at r = 1.8, a graphitic capacity of 57
mAh g−1 (obtained at r = 1.8), and a corresponding discharge
voltage of 1.88 V (see the Supporting Information of ref 15).
All other reported data in the literature were obtained at r = 1.3.
At this lower value of r, the energy density does not exceed 30
Wh kg−1 for experimental graphitic capacities of 70−110 mAh
g−1. An increase in r leads to a concomitant substantial decrease
in CC and the average discharge voltage, as also mentioned in
ref 15, and is also apparent from our measurements (Figure
S1). As detailed below, we have experimentally examined this
trade-off for natural graphite flakes, leading to the highest-
reported energy density of 62 Wh kg−1 (91 Wh L−1) calculated
from a capacity of 124 mAh g−1 (273 Ah L−1) at r = 2 and an
averaged discharge voltage of 1.77 V (Figure S1). For
comparison, the highest graphitic capacity of ∼150 mAh g−1
(330 Ah L−1) was obtained at r = 1.3; nevertheless, this
corresponds to a much lower energy density of 33 Wh kg−1 (45
Wh L−1).
With the most inexpensive form of graphite (natural flakes)
as a cathode and all other components being composed of
highly abundant elements (Al, Cl, C, N, and H), the AlCl3−
graphite battery might become a viable technology for large-
scale stationary storage purposes. In this domain, this battery
may find use as a nontoxic alternative to the primary battery
technologies of similar energy densities: lead−acid (30−50 Wh
kg−1; 50−80 Wh L−1) and vanadium redox-flow batteries
(VRB; 10−30 Wh kg−1; 50−80 Wh L−1).4 AlCl3−graphite
batteries exhibit high energy efficiencies (∼90%), which are,
again, on par with those of lead−acid batteries (90%) and VRB
(85%) or even Li-ion batteries (90−95%).
Testing Natural Graphite Flakes as Inexpensive
Cathodes. To comply with stringent cost requirements, we
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have focused exclusively on natural graphite flakes and the use
of minimal processing or the simplest processing of these flakes
by mechanical means. We started with large commercial natural
graphite flakes (pristine; 0.2−1 mm in lateral size), which were
commercially produced from graphite ore by mechanical means
(crushing, wet milling, and floatation). The production is often
combined with acidic chemical treatment for additional
purification. In addition to using these pristine flakes as
received, we also fragmented them into smaller particles,
resulting in either a retained flat morphology with unfolded
edges [processing by sonication; ∼40 μm in lateral size (Figure
2a, left)] or an imparted partial spheroidization [∼50 μm;
processed by knife-milling (Figure 2a, right)]. The particle
shape after spheroidization resembled the “potato” graphite
particles commonly used in Li-ion batteries.
A custom-made cell design with Swagelok fittings was
employed for the electrochemical tests (Figure S2). The cell
consisted of aluminum (anodic side) and tungsten or glassy
carbon (cathode side) current collectors combined inside a
fully plastic housing. The cathodes consisted of pure graphite
(10 mg cm−2), without the use of any binder or conductive
additives, to ensure that the measured electrochemical
characteristics could be fully attributed to graphite itself. The
electrodes were moderately pressed against each other with a
glass-fiber separator between them. No preferential orientation
of the graphite flakes with respect to the current collectors was
observed by optical microscopy.
All graphite electrodes were tested not only as cathodes in
the AlCl3−graphite cells but also in standard Li-ion cells. All
such comparative tests were conducted at moderate current
densities of 100 mA g−1. Our findings are indeed orthogonal
between the experiments of Li-ion storage (Figure 2b,c) and
intercalation of AlCl4− ions (Figure 2d,e; all Al cells tested at r
= 1.3). In particular, the Li-ion tests readily confirm that the
commercial potato-shaped particles and our spheroidized
particles (also termed potato-shaped in Figure 2) deliver
capacities of at least 360 mAh g−1, near the theoretical charge-
storage capacity (372 mAh g−1). The 2−3-fold poorer Li-ion
storage in the flaky graphite particles is in good agreement with
results of numerous kinetic studies of the effects of their
orientation and microstructure,57−61 which have all highlighted
the accessibility of the edges and particle sizes as key factors for
Li-ion storage. In this context, a recent study by Billaud et al.62
showed that dense vertical staking of graphite flakes
perpendicular to the current collectors allowed for fast
intercalation into laterally large flakes. In the absence of such
favorable orientations, the potato-shaped particles remain an
optimal morphology for industrial applications. However, a
strikingly different scenario is found for the insertion of AlCl4−
ions. With large pristine flakes, a high capacity of 95 mAh g−1
(Figure 2d,e) and a high energy efficiency [90% (Figure 2e)] at
an average discharge voltage of ∼2 V were observed. A further
capacity increase to 132 mAh g−1 was obtained with smaller
flakes, retaining the superb flatness of the voltage profiles. On
the other hand, commercial and in-house potato-shaped
graphite particles exhibited lower capacities for AlCl4− ions,
which is in striking contrast to the results for Li-ion storage.
Importantly, while the graphite anodes are prone to irreversible
capacity loss, as seen from the reduced Coulombic efficiencies
of 70−80% (Figure 2d) in the initial cycles as a result of the
formation of a solid−electrolyte interface (SEI), the operation
of AlCl3−graphite batteries proceeds from the beginning with
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higher Coulombic efficiencies of >92% (Figure S3), suggesting
SEI-free operation.
CCCV Charging Protocol for Combining High Capaci-
ties and High Power Densities. Having established that the
mechanically processed graphite flakes offer higher charge-
storage capacities, we examined this form of graphite in greater
detail (Figure 3). First, we found that the CCCV (constant
Figure 3. Electrochemical performance of the processed graphite
flakes in the AlCl3−graphite battery (r = 1.3). (a and b) Galvanostatic
charge−discharge voltage curves and cycling performance measured
using CC and CCCV protocols. (c) Rate capability measurements
obtained with two protocols: standard (same current densities for
charge and discharge during the cycle) and CCCV (50 mAh g−1
CCCV charge and different discharge currents).
current−constant voltage) charging protocol, which involves
constant charging up to 1.9 V followed by one or more
constant voltage steps (in the range of 1.9−2.1 V; terminated at
a current drop of 90%), boosts the subsequent discharge
capacity to 150 mAh g−1. It should be noted that constant
voltage steps at higher voltages (>2.1 V) were detrimental
because of side reactions that reduced the Coulombic
efficiency. Constant voltage steps at lower voltages (<1.9 V)
were of limited effect. Additionally, the rate capability
measurements were performed using conventional constant
current (CC) and CCCV protocols (50 mAh g−1 CCCV
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charge, followed by various discharge rates). As seen in the
standard CC measurements (Figure 3c; same rates for charge
and discharge), higher discharge capacities were obtained at
charging/discharging current densities of ≤200 mA g−1, which
decreased at higher rates. A slower CCCV (50 mAh g−1 for a
CC step) protocol indicates the unique rate capability of these
batteries: the same high discharge capacities were obtained up
to the highest tested discharge rates of 2.5 A g−1, i.e., 3.6 min
for the complete discharge. The corresponding power density
was as high as 489 W kg−1, which compares favorably with
those of the other stationary battery technologies such as lead
acid (75−300 W kg−1)4 and VRB (60−100 W L−1).63
We then examined the effect of the AlCl3 molar fraction by
adjusting parameter r in the range of 1.1−2.0 (highest possible)
while applying the CCCV charging protocol. A clear trend was
observed in which a higher r resulted in a greater loss of voltage
(by ≤0.2 V). Also, the graphitic capacities dropped from ∼150
mAh g−1 (r = 1.3) to ∼124 mAh g−1 (r = 2). These losses are
lower than the theoretically expected energy densities (stars as
data points in Figure 1b). Despite these effects, the highest
energy density of 62 Wh kg−1 was obtained at r = 2,
highlighting the importance of the concerted focus on both the
cathode and the anode.
Benefits of the Flaky Morphology for Achieving
Higher Capacities from Natural Graphite. Powder X-ray
diffraction (XRD) patterns of the charged graphite flakes [a
capacity of ≤132 mAh g−1 (Figure 4a)] indicate that the (002)
graphite peak fully vanishes, and the appearance of three
additional peaks indicates that the intercalation of the ions
occurs in an alternating manner. Such a “staging” intercalation
mechanism is known for various intercalation compounds with
graphite (see the illustration of stages 0−6 in Figure S4).64,65 A
lower stage number indicates a higher intercalant concen-
tration. Recent theoretical calculations24 have shown that
intercalation of AlCl4− into graphite can be observed by the
formation of stages 4, 3, and 2. Simulated XRD peak positions
qualitatively fit the experimental pattern, suggesting a mixed
stage 3−4 intercalation (Figure 4a). The insertion of ions leads
to the expansion of the graphite volume. Larger AlCl4− anions
(295 pm) lead to a drastic expansion by up to 80%, as seen
from recent experimental and theoretical works,24,42,45,54,66−68
which is in sharp contrast to the minor (∼10%) effect from
smaller Li+ ions (90 pm).69 This may explain the highly
beneficial role of the flake morphology: large volumetric
changes are easily accommodated by the homogeneous increase
in thickness. On the other hand, folding, bending, or other
geometric constrains present in other shapes, such as in potato-
shaped graphite, might hamper the high loading of intercalating
anions.
It is natural to expect that variations in the synthesis/
processing conditions not only modify the overall shape of the
graphite particles but also introduce various degrees of
structural disorder into the idealized lattice of crystalline
graphite, which might also contribute to the electrochemical
performance. For example, powder XRD patterns of pristine,
flake, and spherical graphite particles revealed an increase in the
interplanar graphene−graphene distance from 3.354 to 3.369 Å
(see Table S1), as can be clearly observed from the shift of the
(002) peak to smaller 2Θ values (Figure 4b).
Similarly, the Raman spectra of the spherical particles were
characterized by an increased magnitude of the signal at 1250−
1400 cm−1 (D-band), which is usually attributed to structural
disorder. Higher defectiveness, as seen from the larger d spacing
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Figure 4. Characterization of the crystalline perfection of various
graphite materials. (a) X-ray diffraction patterns of sonicated graphite
flakes before and after charging at a rate of 50 mA g−1 to a capacity of
132 mAh g−1. (b and c) XRD and Raman spectroscopy measurements
of the pristine graphite flakes before and after their processing by
sonication into smaller flakes. For comparison, data for the potato-
shaped particles, prepared in house by knife-milling of the pristine
flakes or obtained from the commercial source, are also shown.
and more intense Raman D-band (Figure 4b,c), might be the
key factor that explains why the commercial potato-shaped
particles exhibit the lowest charge-storage capacities for AlCl4−
ions (in agreement with the data from ref 45). Overall, despite
the fact that intercalation of both Li+ and AlCl4− ions into
graphite occurs through the edges,70 bending and folding of the
layers as well as atomic and crystalline disorder appear to be
much stronger negative factors for the insertion of larger AlCl4−
ions.
Spectroscopic Evidence of the Incorporation of AlCl4−
Ions into Graphite. The conclusion that AlCl4− species
intercalate into graphite was corroborated thus far not only by
XRD measurements but also by X-ray photoelectron (XPS),
Auger electron (AES), and X-ray absorption (XAS) spectros-
copy measurements.15,27,28,41,43,45 Herein, we present another
direct spectroscopic probe of the fate of Al species using
solution- and solid-state 27Al NMR measurements. For these
measurements, small graphite flakes were charged at 50 mA g−1
up to 2.45 V and then washed from the ionic liquid using
tetrachloromethane (CCl4) as an oxidatively stable solvent
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capable of removing the ionic liquid. Retention of the charged
state was confirmed by the observation of the same XRD
pattern after the washing step (Figure S5). Importantly, other
solvents that can solubilize the ionic liquid, such as acetonitrile,
methanol, toluene, pentane, tetrahydrofuran, hexane, and
trichloroethylene, expectedly reduced the graphite framework
[i.e., chemically discharged (see further details in Figure S6)].
The 13C NMR spectra showed the absence of CCl4 and
EMIMCl signals after the washing and drying procedures
(Figure S7). The 27Al solid-state NMR spectra of the charged
and washed graphite (Figure 5) exhibited a single peak at 103
Figure 5. 27Al solid-state NMR spectra of charged (blue) and
noncharged (black) small flakes of graphite particles. The noncharged
particles were prepared by impregnation with the AlCl3:EMIMCl
electrolyte, followed by washing with CCl4.
ppm, confirming AlCl4− as the single or dominant form of Al
species that intercalated. This assignment was further
corroborated by a comparison with literature values for Al
chloride-based ionic liquids71,72 and by the 27Al NMR
measurements of our reference solutions of acidic (r = 2)
and neutral (r = 1) AlCl3:EMIMCl melts (see Figures S8 and
S9 for further discussions). In another reference measurement
using 27Al solid-state NMR, no signal was detected on graphite
flakes that were simply immersed in the electrolyte overnight
and washed with CCl4 (Figure 5).
■ CONCLUSIONS
We have examined the electrochemical behavior of AlCl3−
graphite batteries, employing natural graphite flakes in
powdered form as cathodes. We found that the electrochemical
oxidation of the graphite network is accompanied by the
intercalation of AlCl4− ions, as evidenced by 27Al NMR
spectroscopy. The major factors governing the efficient uptake
of AlCl4− ions are the flake morphologies of the graphite
particles and the high atomistic structural quality of these
particles. The highest capacities of ≤150 mAh g−1 were
obtained with sonicated natural graphite flakes. Considering
that this battery is not a “rocking-chair” system, we have
focused on the question of the practically achievable energy
densities. The liquid phase of this battery was estimated to be a
capacity-limiting liquid anode, which means that the energy
density is primarily determined by the concentration of the
electroactive species in the ionic liquid rather than by the
cathodic capacity of the graphite. AlCl3−graphite batteries were
characterized by high energy efficiencies of ≤91% and by high
power densities (rate capabilities) of 489 W kg−1 at the full
DOI: 10.1021/acs.chemmater.7b01060
Chem. Mater. 2017, 29, 4484−4492
Chemistry of Materials
charge. Increasing the AlCl3:EMIMCl ratio to 2:1 and using
graphite flakes as an anode, we reached an energy density of 62
Wh kg−1, which is on par with major stationary battery
technologies. Our analysis shows that these energy densities are
difficult to further improve, and we anticipate a practical limit of
70−80 Wh kg−1. On one side, the AlCl3:EMIMCl ratio at r = 2
already contains 64.5 wt % AlCl3. Higher contents of AlCl3 will
be difficult to realize. As an upper bound to this content limit,
we took the proton instead of the EMIM+ cation in Figure 1b,
which yielded 88 wt % AlCl3. On the other side, graphitic
capacities of >150 mAh g−1 would have a marginal effect on the
overall energy density. We suggest that future work should
focus on the other issues associated with this technology, one
being the incompatibility of most metallic current collectors
with the corrosive AlCl3-based ionic liquids. Even gold slowly
dissolves in AlCl3:EMIMCl ionic liquid when electrochemically
polarized up to 2.5 V versus Al. Thus far, only tungsten and
molybdenum have been identified as electrochemically stable
current collectors in such batteries. These metals do not fulfill
the criterion of high natural abundance, when compared to the
abundance of the other components of the AlCl3−graphite
battery or to Li ions. There is a pressing need to identify
current collectors made of alternative alloys or compounds
comprising elements of higher natural abundance and available
at low manufacturing costs.
■
EXPERIMENTAL SECTION
Chemicals and Battery Components. Pristine graphite flakes
(99.9%, ∼10 mesh, Alfa Aesar), spherical graphite powder (AE 104L,
TIMCAL), 1-ethyl-3-methylimidazolium chloride (EMIMCl, 99%,
Iolitec), AlCl3 (99%, granules, Acros), Al foil (MTI Corp.), a W plate
(Bocheng Molybdenum Co., Ltd), a glassy carbon plate (Good-
Fellow), and a glass microfiber separator (GF/D, catalog no. 1823-
257, Whatman) were used as received.
Preparation of Electrolytes. Ionic liquid electrolytes based on
EMIMCl were prepared by slowly mixing EMIMCl solid powder and
AlCl3 granules in an argon-filled glovebox. During mixing, a highly
isothermal reaction occurs, eventually forming a light-yellow liquid.
Subsequently, the ionic liquid electrolyte was treated with Al foil at
150 °C for 6 h until a nearly colorless liquid was seen.
Sonication of Pristine Graphite Flakes. Pristine graphite flakes
(0.2 g) were placed into a 4 mL glass vial, and the vial was filled with
3.5 mL of ethanol and sonicated for 30 min using a model HD2200
Sonopuls ultrasonic homogenizer operated at 30% power. The
resulting smaller flakes were washed three times with ethanol and
dried under vacuum at 80 °C for 12 h.
Knife-Milling of Pristine Graphite Flakes (spheroidization).
Pristine graphite flakes (10 g) were placed in a kitchen blender (Betty
Bossi from Fust MixFIT) and knife-milled for 30 min. During the
milling, a nitrogen flow was added to the container to cause more
efficient stirring of the flakes. The knife-milled graphite particles were
dried under vacuum at 80 °C for 12 h.
Assembly and Testing of AlCl3−Graphite Batteries. All
graphite samples were dried at 200 °C under vacuum overnight. No
binders or solvents were used for the preparation of the electrodes.
Homemade plastic cells were assembled in an argon-filled glovebox
(<1 ppm O2, <1 ppm H2O) using three layers of a glass-fiber separator
soaked with AlCl3:EMIMCl ionic liquid (Figure S2). Aluminum foil
served as both the reference and counter electrodes. A tungsten plate
was used as the cathodic current collector. Graphitic material (10 mg
over ∼1 cm2) was homogeneously distributed on the surface of the
glass-fiber separator before it was covered with the tungsten current
collector. These cells were cycled between 0.01 and 2.45 V on an
MPG2 multichannel workstation (Bio-Logic). A CCCV protocol was
used at 1.92 and 2.07 V until the current dropped to 10% of the initial
value.
4490
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Assembly and Testing of Li-Ion Batteries. The same plastic
cells, separators, and graphite loadings (≥10 mg cm−2) were utilized.
LiPF6 (1 M) in ethylene carbonate and dimethyl carbonate (1:1 vol %)
was used as the Li electrolyte, and metallic Li foils were used as the
counter and reference electrodes.
Structural Characterization of Graphite Particles. Scanning
electron microscopy (SEM) images were obtained with a model M400
SEM microscope. The XRD patterns were recorded using a Bruker
AXS D8 Advance X-ray diffractometer with Ni-filtered (2 mm
thickness) Cu Kα radiation (λ = 1.5406 Å) operating at 40 kV and 40
mA. Each sample was run at least twice using silicon as the internal
standard. For ex situ X-ray diffraction (XRD) studies, fully charged
graphite flakes were removed from the cell inside the glovebox and
washed with dried CCl4. To isolate them from the atmosphere, the
charged graphite samples were sealed between Scotch tape and
exposed to the air shortly prior to the XRD measurements. The sizes
of the potato- and flake-shaped graphite particles were determined by a
small-angle light scattering (SALS) instrument, Mastersizer 2000
(Malvern). The sample was diluted with anhydrous ethanol without
being filtered. Raman spectroscopy measurements were performed on
a high-resolution confocal Raman microscope (Ntegra Spectra, NT-
MDT) equipped with a 632.8 nm HeNe laser at an incident power of
1.7 mW for excitation at room temperature. Nitrogen adsorption
isotherms were measured at 77 K between 10−3 and 100 kPa using a
fully computerized Micromeritics ASAP 2020 instrument. Surface
areas were calculated by the Brunauer−Emmett−Teller (BET)
method between P/P0 values of 0.005 and 1. Prior to the
measurements, samples were degassed under vacuum (10−1 mbar) at
473 K for 12 h using a Micromeritics VacPrep 061 Sample Degas
System.
NMR Spectroscopy Measurements. All solid-state NMR spectra
were recorded on a Bruker 16.4 T NMR spectrometer equipped with
an Avance III console and a double-resonance 2.5 mm solid-state
probe head. Solution-state NMR spectra were recorded on a Bruker
11.7 T spectrometer equipped with a PABBO gradient field three-
channel liquid-state probe head for 5 mm NMR tubes. Experiments
were performed at room temperature without spinning. Chemical
shifts were referenced to Al(NO3)3 in D2O (27Al) and Si(CH3)4 (13C).
The numbers of transients were 1024 for the 27Al NMR spectra and
10240 for the 13C NMR spectra. A classical Hahn-echo pulse sequence
was used for the 27Al spectra, and a simple 30°-one-pulse excitation
sequence was used for the 13C NMR spectra. All spectra were recorded
without decoupling. The recycle delay was set to 2 s, the echo delay to
0.2 ms, and the pulse length for a 90° flip angle to 3.4 μs for the 27Al
NMR spectra. A recycle delay of 2 s was used with a pulse length for a
30° flip angle of 1.1 μs for the 13C NMR spectra. The number of
transients for the solution-state NMR spectra varied from 1 to 16 scans
for 27Al NMR and from 64 to 128 for the 13C spectra. The 27Al and
13
C 90° solution-state excitation pulse lengths were 9.5 and 9.8 μs,
respectively. During the acquisition of the solution-state NMR spectra,
decoupling was performed using a waltz16 sequence while a recycle
delay of 2 s was applied.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.7b01060.
Additional electrochemical, XRD, Raman, BET, and
NMR data and photos of the cell used for electro-
chemical measurements (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: mvkovalenko@ethz.ch.
ORCID
Shutao Wang: 0000-0002-1689-2272
DOI: 10.1021/acs.chemmater.7b01060
Chem. Mater. 2017, 29, 4484−4492
Chemistry of Materials
Maksym V. Kovalenko: 0000-0002-6396-8938
Author Contributions
§
K.V.K. and S.W. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We thank Dr. Frank Krumeich for assistance with SEM
measurements, Dr. Michael Wörle for assistance with XRD
measurements, Mr. Alberto Cingolani and Mrs. Lu Jin for
assistance with SALS, and Mr. Feng Shao for assistance with
Raman measurements. This work was financially supported by
the Swiss Federal Commission for Technology and Innovation
(CTI) through the CTI Swiss Competence Centers for Energy
Research (SCCER, “Heat and Electricity Storage”) and by the
Competence Center for Energy and Mobility (CCEM, Project
SLIB).
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