ELECTROCHEMICAL SOCIETY LETTERS

Dual Intercalating Molten Electrolyte Batteries

Richard T. Carlin,* Hugh C. De Long,* Joan Fuller, and Paul C. Trulove*
Frank J. Seller Research Laboratory, United States Air Force Academy, Colorado 80840-6272

ABSTRACT
The reductive and oxidative intercalation of ions into graphite from room-temperature and low temperature molten salts is demonstrated. For this investigation, the molten salts use 1-ethyl-3-methylimidazolium (EMI +) or 1,2-dimethyl-3-propylimidazolium (DMPI +) as the
cation and AICI4, BF~, PF6, CF3SO~, or C6H5CO~as the anion. In a two-electrode battery configuration, the molten salt electrolyte provides
both the cation and anion which are intercalated into the graphite anode and cathode, respectively. A cell employing a (DMPI)(AICI4)
electrolyte and two graphite rod electrodes achieved an open-circuit voltage of 3.5 V and a cycling efficiency of 85%.
Batteries employing a lithium/carbon intercalation anode and a
transition metal oxide lithium intercalation cathode, Le., rockingchair batteries, have been the subject of substantial research efforts throughout the world. 1 The many improvements (reliability,
safety, environmental, and economic) offered by the rocking-chair
battery over other rechargeable batteries comes primarily from the
use of a carbon or graphite anode. The cathodes in these batteries
still use transition metal oxides of manganese, nickel, or cobalt
which are more expensive, less desirable environmentally, and
more synthetically demanding than the carbon anode, In addition,
the liquid electrolytes in these batteries consist of lithium salts
dissolved in a mixture of organic carbonates or ethers which require
rigorous purification. Therefore, the rocking-chair battery requires
the synthesis, purification, and assemblage of multiple active
components.
We report here a battery concept and initial demonstration that
employs a single molten salt to function as the electrolyte, the
cation graphite intercalate source, and the anion graphite intercalate source. The systems discussed here use room-temperature or
low melting molten salts composed of a substituted imidazolium
cation and an inorganic or organic anion. The molten salt serves in
a multifunctional capacity leading to a battery configuration requir* ElectrochemicalSocietyActive Member.

30.00

_1

ing only two active materials, the molten salt and graphite. Because
molten salts provide both the cations and the anions for the graphite
intercalation processes, we have termed these systems dual intercalating molten electrolyte (DIME) batteries.

Experimental
The organic chlorides 1-ethyl-3-methylimidazolium chloride
(EMIC) and 1,2-dimethyl-3-propylimidazolium chloride (DMPIC)
were prepared as previously described. 2,3 The room-temperature
1:1 chloroaluminate molten salts were prepared by combining
equal molar quantities of sublimed AICI3 with the appropriate organic chloride inside a Vacuum Atmosphere glove box under He
with an 02 4- H20 concentration of <5 ppm. The air and water stable
room-temperature molten salts (EMI)(BF4), (EMI)(CF3SO3), and
(EMI)(C6HsCO2) were prepared by reacting the appropriate acid
with excess solid Ag20 in water followed by addition of an equal
molar quantity of EMIC. The resulting solution was filtered to remove solid AgCI and Ag20 and rotoevaporated to provide the ionic
liquid product which was further dried at ca. 120C under vacuum.
The air- and water-stable salt (EMI)(PFs) (mp = 58-60C) was
prepared by direct addition of equal molar quantities of HPFe and
EMIC in water. The desired salt was collected by filtration and dried
at ca. 120C under vacuum.

jl

_
;,:

,,t

20.00

,,:'--

A/

/_
/s

10,00
E
u

$
u

0.000

/o

-10, 00

Fig. 1. Staircase cyclic voltammograms in (EMI)(AICI4)

showing (.4) reductive intercalation of EMI into graphite,
(B) reduction of EMI + at GC,
(C) oxidative intercalation of
AICI; into graphite, and (D) oxidation of AICI~ at GC. Scan
rate is 50 mV s -1 for all curves.

-20.00

I
3. 000

2.000

1.000

I
0.900

I
- 1.. 0 0 0

I
-2.000

E (U)

J. Electrochem. Soc., Vol. 141, No. 7, July 1994 The Electrochemical Society, Inc.

L73

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J. Electrochem. Soc.,

L74

Vol. 141, No. 7, July 1994 9 The Electrochemical Society, Inc.

Table I. Anion and cation intercalation into graphite using molten salt electrolytes.
Charging time is 30 min unless stated otherwise, All potentials are referenced to AI in a 1.5:1.0 chloroaluminate melt,
Molten salt
electrolyte

Intercalating
ion

T
(~

/Chacgm_2)
(mA

Ech=ge

(EMI)(AICI4)

EMI +
EMI ~
AICI4
AICI~

24
24
24
24

1
2
1
2

- 1.64
- 1.69
+ 1.93
+2.01

1
2
1
2

1.47
1.50
+ 1.6
+ 1.6

59
65
41
64

(DM PI)(AICI4)

DMPI +
DMPI
DMPI +
AICIZ
AICI~
AICI4

30
30
30
30
30
30

1
1
1
1
1
1

- 1.70
- 1.70
-1.70
+ 2.15
+2.15
+2.15

1
0.5
0.25
1
0.5
0.25

- 1.25
- 1.36
-1.35
+ 1.50
+ 1.60
+ 1.60

60
100
94
64
86
76

(EMI)(BF4)

EMI b
BF~ b

24
24

6
1

-- 1.89
+2.33

6
1

-- 1.30
+ 1.50

33
55

(EMI)(PF6)

EMI +
PF~

90
90

5
5

-2.4
+2.0

5
5

- 1.4
+1.3

21
23

(EMI)(CF3SOa) ~

CF3SO3
CF3SO3

40
40

1
1

+ 1.8
+ 1.9

1
0.5

+ 1.3
+ 1.3

9
14

(EMI)(C6HsCO2) d

EMI +
EMI +

70
70

0.5
0.5

-2.0
-2.0

0.5
0.25

1.7
-1.8

50
45

(V)

I~s c

E~isoha,ge

mg-e2)

(V)

Efficiency
%

Charging time = 60 min.

b Charging time = 10 min.
~ EMI + graphite intercalate is unstable in this melt.
d C6HsCO2 is oxidized before the graphite oxidative intercalation process.

All electrochemical experiments were performed in a Vacuum

Atmosphere glove box under He using an EG&G Princeton Applied
Research Company (PARC) Model 273 potentiostat/galvanostat
controlled with the EG&G PARC 270 software package. The
graphite working electrode was a high purity spectroscopic grade
graphite rod with a 3 mm diameter (Union Carbide). The graphite
rod was pretreated by heating at 400~ for several hours in air and
cooling under vacuum in the glove box antechamber. A known
length, generally 1 cm, of the graphite rod was immersed in the
electrolyte to allow calculation of the working electrode area. In the
chloroaluminate melt studies, the reference and counterelectrodes
consisted of AI wires placed in separate fritted tubes containing
either a 1.5:1.0 melt with the same organic cation (reference electrode) or the analyte melt (counterelectrode). For the other melts,
the reference and counterelectrodes consisted of platinum wires
inserted into separate fritted tubes containing the analyte melt. The
platinum quasi-reference electrode potential was converted to the
AI wire reference potential by recognizing that the EMI reduction

at glassy carbon (GC) occurs at - 2 . 2 V vs. AI in a 1.5:1.0 chloroaluminate melt. Therefore, for melts with a Pt quasi-reference electrode, the EMI reduction potential at a GC electrode (0.071 cm 2
from Bioanalytical Systems) was measured and set to - 2 . 2 V on
the potential scale.

Results

and

Discussion

Staircase cyclic voltammograms for the reductive and oxidative

intercalation of graphite in the room-temperature molten salt
(EMI)(AICI4) are compared to staircase cyclic voltammograms at a
GC electrode in Fig. 1. The graphite electrochemical intercalation
processes shown in Fig. 1A and C occur well within the electrochemical limits of the melt which, at GC, are found at - 2 . 2 and
+2.5 V and correspond to EMI + reduction (Fig. 1B) and AICI~
oxidation (Fig. 1 D), respectively. The electrochemical process at
- 1 . 5 V in Fig. 1A involves the intercalation (forward scan) and
deintercalation (reverse scan) of EMI into the graphite lattice. To
our knowledge, this is the first report of imidazolium intercalation

4.000

3,080

Fig. 2. Chronapotentiometrlc
curves
at
graphite
in
(DMPI)(AICI4) showing (A) DMPI
intercalation (! mA cm -2) and
deintercalatian (0.25 mA cm-2),
(B) AICI4 intercalation (1 mA
cm 2) and deintercalatian (0.25
mA cm-2), and (C) cell charging
and discharging (both 1 mA
cm-2).

2.900
l.Bgg

8.080
--1. BOO

m2.000

0. 800

1.80B

E.ggO

3.000

4.B80

5.888

6.BBO

?.Bg8

(ks)

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L75

J. Electrochem. Soc., Vol. 141, No. 7, July 1994 9 The Electrochemical Society, Inc.
Table II. Performance parameters for DIME cells.
Molten salt
electrolyte

T
(~

Eopen

tcharge

/charge

Echarge

(V)

(min)

(mA cm z)

(V)

(mA cm z)

(DMPI)(AICI4)
(EMI)(AICI4)

30
24

3.52
3.54

60
20

1
1

3.72
3.67

1
0.5

into graphite; although, quaternary ammonium intercalation has

been well established. 4-6 The electrochemical process at +1.8 in
Fig. 1D probably involves the intercalation and deintercalation of
AICI~- into the graphite lattice. Although it has been proposed that
graphite oxidation in this melt involves intercalation of CI2, 7 the
potential of the oxidative intercalation (0.6 V negative of AICI~- oxidation to CI2) and the lack of known stable chlorine intercalates
points toward the formation of an AICI4 intercalation compound
instead. 8 Numerous chloroaluminate and other metal halide intercalation compounds are known. 5'6 Therefore, the proposed electrochemical intercalation processes in Fig. 1 can be written
EMI + xC +-e- ~ (EMI)Cx

[1]

AICI4 + yC <-> Cy(AICI4) + e-

[2]

Additional evidence that electrochemical intercalation reactions

are occurring at the graphite electrode is provided by the observed
exfoliation of the graphite electrodes after repeated charge and
discharge cycles. 6 Exfoliation is also observed for the intercalation
reactions discussed below using nonchloroaluminate melts. The
degree of exfoliation is dependent on the depth of charge and the
history of the electrode. This observation, combined with the differences in behavior at graphite vs. GC, are reasonable evidence of
intercalation.
The intercalation processes in reactions 1 and 2 were studied
using chronopotentiometry, and results for the (EMI)(AICI4) melt are
presented as the first set of entries in Table I. Average charge
(intercalation) and discharge (deintercalation) potentials at various
current densities are also provided. The cycling efficiencies, defined as % efficiency = discharge coulombs/charge coulombs x
100, are only approximately 60% for both graphite intercalation
processes in this melt. The EMI intercalate is unstable and decomposes in a few minutes on standing at open circuit. The decomposition may involve reaction of the relatively acidic C-2 proton with
the negatively charged graphite lattice) This is supported by the
high cycling efficiencies observed for the reductive intercalation of
the DMPI* cation (second set of entries in Table l) in which the C-2
proton has been replaced by a methyl group.
Chronopotentiometric charging and discharging curves for
graphite in (DMPI)(AICI4) are shown in Fig. 2A and B, respectively.
The deintercalation process for DMPI + has a high efficiency, 94%,
and a flat potential profile. From the discharge potentials for the two
couples, we may construct a battery with a voltage of approximately 3 V using only two graphite electrodes. Such a cell was
constructed by inserting two 3 mm graphite rod electrodes into the
melt. Using the potentiostat in a two-electrode configuration,

0.5

0
EMI+

t
DMPI+

I
AICI4-

2.92
3.22

Efficiency
(%)
85
44

charge and discharge curves for this cell were collected. The resulting curves are shown in Fig. 2C, and the cell performance parameters are summarized in Table I1. The small spikes on the discharge
curve are current interrupts used to measure the open-circuit potential at various times during discharge. The net cell reaction can
be written
DMPI + + AICl4 + (x + y)C 4-->(DMPI)Cx + Cy(AICI4)

[3]

A similar cell configuration was tested for the (EMI)(AICI4) melt, and
these results are also presented in Table II. Both cells exhibit similar
potential behavior including an open-circuit potential of 3.5 V immediately after charging; however, the (EMI)(AICI4) cycling efficiency
is much lower due to the instability of the EMI intercalate. In
reaction 3, the cations and anions for both electrochemical intercalation reactions are provided by the molten salt electrolyte, Le., the
cell operates as a DIME battery.
Our laboratory has been exploring the electrochemical and physical properties of new room-temperature and low temperature
molten salts employing the EMI cation. 1~Most of these new melts
are air and moisture stable, unlike melts containing AICIz. Although
these melts use the EMI cation and, therefore, are not ideal DIME
battery candidates, they do provide a means to study the intercalation and deintercalation reaction of numerous anions. The results
for several such melts are provided in the remainder of Table I.
Reversible graphite intercalates of anions formed by electrochemical oxidation in organic solvents containing the appropriate salt
have been reported previously and proposed as battery
cathodes. 6'11'12However, the use of an organic solvent can lead to
co-intercalation of solvent molecules which may hinder the capacity
of an intercalate electrode,s The discharge potentials for numerous
experiments are plotted in Fig. 3 for the various ions listed in
Table I. All potentials have been referenced to the potential of an AI
wire immersed in a 1.5:1.0 AICI3:EMIC melt. Based on Fig. 3, we
may construct other DIME cells with discharge voltages of approximately 3 V.
Currently, we are investigating the reversibility, capacity, and
structure of the graphite intercalates formed in these moffen salts
as a function of several parameters. In particular, it is well known
that the type of graphite or carbon used plays a significant role in
the formation of the intercalation compound. 5'6'~3The rate and capacity of the intercalation processes are dependent on numerous
parameters including carbon structure, temperature, and electrode
history. The cycling efficiency of the experiments discussed above
remained relatively constant after numerous cycles, as long as
excessive exfoliation of the graphite rod electrodes was avoided.

Conclusion

BF4-

Acknowledgment

I
PF6-

CF3SO3-

..........................................

This work was supported by the Air Force Office of Scientific

Research.
Manuscript submitted Jan. 18, 1994; revised manuscript received April 7, 1994.

-1
-1.5

Edi~oharge
(V)

A single-room temperature or low temperature molten salt electrolyte can be used to provide the intercalating ions for a rechargeable electrochemical cell using a graphite anode and cathode. This
DIME battery has many practical advantages including (i) inexpensive graphite electrodes are used, (ii) only a single molten salt must
be synthesized and purified, (iii) no organic solvents are required,
(iv) the battery can be assembled in the discharged states, and (v)
all components have low toxicity.

1.5

-0.5

/discharge

-I ....

! ...............................

-2

Fig. 3. Graphite discharge (deintercalation) potentials for

molten salt cations and anions,

The Frank J. Seller Research Laboratory assisted in meeting the

publication costs of this article.
REFERENCES
1. J. M. Tarascon and D. Guyomard, Electrochim. Acta, 38, 1221
(1992).
2. J. S. Wilkes, L. A. Levinsky, R. A. Wilson, and C. L. Hussey,
Inorg. Chem., 21, 1263 (1982).

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J. Electrochem. Soc., Vol. 141, No. 7, July 1994 9 The Electrochemical Society, Inc.

L76

3. P. R. Gifford and J. B. Palimisano, This Journal, 134, 610

(1987).
4. J. O. Besenhard and H. P. Fritz, ibid., 53, 329 (1974).
5. R. Setton, in Graphite Intercalation Compounds h Structure
and Dynamics, H. Zabel and S. A. Solin, Editors, p. 305,
Springer Verlag, Berlin (1990).
6. K. Kinoshita, Carbon, Electrochemical and Physiochemical
Properties, John Wiley & Sons, Inc., New York (1988).
7. P. R. Gifford and J. B. Palmisano, This Journal, 135, 650
(1988).
8. H. Selig and L. B. Ebert, in Advances in Inorganic Chemistry

9.
10.
11.
12.
13.

and Radiochemistry, Vot. 23, H. J. Emeleus and A. G.

Sharpe, Editors, p. 281, Academic Press, Inc., Orlando, FL
(1980).
J. L. Wong and J. H. Keck, Jr., J. Org. Chem., 39, 2398 (1974).
J. Fuller, R. T. Carlin, H. C. De Long, and D. Haworth, J. Chem.
Soc., Chem. Commun., p. 299 (1994).
F. Beck, H. Junge, and H. Krohn, Electrochim. Act& 26, 799
(1981).
M. Armand and P. Touzain, Mat. Sci. Eng., 31,319 (1977).
J. R. Dahn, A. K. Sleigh, H. Shi, J. N. Reimers, Q. Zhong, and
B. M Way, Electrochim. Acta, 38, 1191 (1993).

A 3 Volt Lithium Manganese Oxide Cathode for

Rechargeable Lithium Batteries
Haitao Huang and Peter G. Bruce*
Centre for Electrochemical and Materials Sciences (CEMS), School of Chemistry, University of Saint Andrews,
Saint Andrews, Fife KY16 9ST, Scotland

ABSTRACT
A new 3 volt lithium manganese oxide cathode, LiMnzO4m for lithium batteries has been prepared by a solution-based route that can
be carried out in air unlike previous sol-gel processes. The addition of carbon to the solution during preparation yields a material with a
significantly enhanced cycling performance. Cycling at discharge and charge current densities of 1 and 0.5 mA cm -2, respectively
(corresponding to a discharge rate of C/2), and between 3.7 and 2.0 V yields a capacity of 90 mA hg -1 after 300 cycles for the material
prepared using carbon. This represents an enhancement of the discharge capacity of 50% on the 300th cycle when compared with the same
material without carbon.

As a result of their high gravimetric and volumetric energy densities, rechargeable lithium batteries are under intensive development worldwide. It is envisaged that they will find applications in
consumer electronic products and as a power source for electric
traction. Systems based on both lithium metal and carbon anodes
are being investigated, they require, respectively, cathodes with
potentials of 3 and 4 V vs. Li
A commercial system of the latter
type based on lithium cobalt oxide is already marketed by the Sony
Corporation.~ Of the candidate cathodes presently being considered for systems under development, those based on manganese
oxides are considerably cheaper and less toxic compared with their
rivals which are based on Co, Ni, or V oxides. Several lithium
manganese oxides have been investigated as 3 V cathodes including the spinel LiMn204 and other spinel-related materials, e.g.,
Li2Mn409 and Li4MnsO~2 as well as CDMO which consists of a
mixture of h'/13MnO2and lithiated spinel.25 Early studies on materials prepared by solid-state reaction at high temperatures yielded
highly stoichiometric materials which exhibited poor cycling performance. Later materials were prepared by low temperature routes
often involving sol-gel processes to improve on the cycling behavior.e9 A main challenge in developing a rechargeable lithium battery is to prepare a manganese oxide-based cathode which can be
cycled many times with excellent capacity retention at relatively
high current densities and to deep discharge. Here we present
cycling results for a defect lithium manganese oxide spinel,
LiMn204.1, which is prepared by a new solution route involving the
use of carbon powders; this route has been patented,t~ The incorporation of carbon during the synthesis results in a significant improvement in the cycling performance of these materials. Further,
the solution preparation can be carried out in air, unlike sol-gel
methods which are based on the use of LiOH.

Synthesis and Characterization of

Active Material
Mn(CHsCOO)2 94HzO(Aldrich 99+%) was added to a solution of
Li2CO3 (BDH, 99.5%) in distilled water. Sufficient manganese(ll)
acetate was used to yield a 2:1 mote ratio of manganese to lithium.
A small amount of carbon (less than 1% by weight of
Mn(CH~COO)2 94H20 was introduced into the mixture which was
9 ElectrochemicalSociety Active Member.

then subjected to vigorous stirring. A precipitate formed, the remaining water being removed first by rotary evaporation at 85~
followed by drying in air at 200~ for 4 days. To study the influence
of carbon on the properties of the electrodes some materials were
prepared exactly as described above but without the addition of
carbon during the synthesis. The resulting powders were analyzed
by x-ray diffraction (XRD) using a Philips dfffraetometer operating
with Cu-K~ radiation. The powder patterns for materials with and
without carbon are similar (Fig. 1). Both exhibit broad peaks which
are indicative of a small particle size. The patterns are consistent
with a spinel structure although the peak widths preclude an accurate determination of their positions and hence detailed comparison
of their lattice parameters. There is no evidence of any additional
peaks in the x-ray patterns arising from other phases. The oxidation
states of the lithium manganese oxide spinels were determined by
a sequence of redox titrations involving the MnO4/Mn 2+ and Fe3+/
Fe2+ couples and based on the procedure described by Vetter and
Jeager.1~ This process yielded a composition LiMn~O44 for both
materials, this is indicative of a defect spinel with a higher average
oxidation state than the stoichiometric LiMn204 prepared at high
temperatures.

Cell Assembly and Testing

Composite cathodes were fabricated by dry mixing the lithium
manganese oxides, carbon black and polytetrafluoroethylene
(PTFE) in the weight ratios 80:13:7. The mixtures were pressed
onto aluminum grids, typically with a loading of 16 mg cm -2, and the
entire assembly was then dried under a vacuum at 80~ for 12 h.
The three electrode cells were constructed from the composite
cathode, lithium metal reference, and counterelectrodes. The electrolyte consisted of a 1M solution of LiAsF8 (LITHCO) dissolved in
propylene carbonate (Aldrich 99+%). The salt was used as received but the propylene carbonate (PC) was rigorously purified
using a Fischer HMS 500 C distillation apparatus with 90 theoretical
plates. The electrolyte was soaked into Whatman GF/F filter pads
which acted as separators between the electrodes. All manipulations of air-sensitive materials as welt as the celI assembly were
carried out in an MBraun argon-filled glove box from which H~O and
02 are continuously removed.
By introducing a third (reference) electrode into the cell, cycling
of the composite cathode may be carried out in isolation, Le., with-

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