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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.
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E (U)
J. Electrochem. Soc., Vol. 141, No. 7, July 1994 The Electrochemical Society, Inc.
L73
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J. Electrochem. Soc.,
L74
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
%
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
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
[1]
[2]
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-
..........................................
-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
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J. Electrochem. Soc., Vol. 141, No. 7, July 1994 9 The Electrochemical Society, Inc.
L76
9.
10.
11.
12.
13.
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.
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.
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