Effects of Alkyl Chain in Imidazolium-Type Room-Temperature

Ionic Liquids as Lithium Secondary Battery Electrolytes

Shiro Seki,
a,z
Yuichi Mita,
a,
*
Hiroyuki Tokuda,
b
Yasutaka Ohno,
a
Yo Kobayashi,
a,
*
Akira Usami,
a
Masayoshi Watanabe,
b,
*
Nobuyuki Terada,
a
and
Hajime Miyashiro
a
a
Materials Science Research Laboratory, Central Research Institute of Electric Power Industry,
2-11-1, Iwado-kita, Komae, Tokyo 201-8511, Japan
b
Department of Chemistry and Biotechnology, Yokohama National University, 79-5 Tokiwadai,
Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan
Lithium secondary batteries that use a room-temperature ionic liquid as an electrolyte were investigated for the purpose of
realizing high-safe batteries. For the improvement of stability under charge/discharge operation with electrodes, we focused
attention on a series of 1-alkyl-3-methyl-imidazolium bistriuoromethane sulfonylimide. The temperature dependence of ionic
conductivity and battery charge-discharge performance were examined by changing the alkyl chain lengths: -methyl/-ethyl/-butyl/-
hexyl/-octyl. According to the results, the effects of extending the alkyl chain were conrmed in, for example, the increase in
carrier ion number, and the improvement of battery charge-discharge performance characteristics.
2007 The Electrochemical Society. DOI: 10.1149/1.2768168 All rights reserved.
Manuscript submitted May 8, 2007; revised manuscript received July 6, 2007. Available electronically August 3, 2007.
With the establishment of new ways of using electric power in
Japan, such as all-electric homes, heat pump water heaters commer-
cial name: Eco Cute, large-scale energy storage devices for storing
electric power at the household level electric-load leveling systems
are expected to be realized.
1
Not only can savings in electrical bills
be achieved by the use of cheaper late-evening electric power during
the daytime, but also positive effects for useful applications such as
emergency power supplies and uninterruptible power sources can be
expected in a time of disaster. Lithium secondary batteries have a
higher energy density per unit volume and weight compared with
other battery systems,
2
and the wide range of application elds is
strongly desired, from consumer equipment applications such as cel-
lular phones and notebook-type personal computers to high-power
power supplies such as those in electric vehicles.
3,4
For this reason,
we have recently been promoting the research and development of
very safe lithium secondary batteries that use room-temperature
ionic liquids
5
or solid polymers
6-8
as electrolyte materials instead of
conventional ammable organic electrolyte solutions. In particular,
room-temperature ionic liquids have received considerable attention
because the newly developed third liquid differs from water and
organic solvent,
9,10
and they are considered to be one candidate
for new battery electrolytes of large-scale and safe electric storage
devices. Since the room-temperature ionic liquids are organic salts
that consist only of cations positive ions and anions negative
ions, they show relatively low volatility, low combustibility, high
thermal stability, and relatively high ionic conductivity, and are very
attractive materials for consideration as new electrolytes. For ex-
ample, as for room-temperature ionic liquids geared toward energy
conversion and storage, their applications for use as safe electro-
lytes in electric double-layer capacitors,
11,12
fuel cells,
13
dye-
synthesized solar cells,
14,15
lithium secondary batteries,
16,17
and
actuators,
18
among others, have been examined. Also, the optimiza-
tion of cell preparation conditions long charge/discharge cycle life
using a quaternary-ammonium cation based room-temperature ionic
liquid,
19
the protection of the cathode/electrolyte interface high
voltage, high capacity by using a stable ZrO
2
layer at the LiCoO
2
cathode surface,
20
and the development of high-stability room-
temperature ionic liquids prepared by substituting the chemically
stable protective group at the second position of the imidazolium
cation,
21
among others,
22
have so far been reported as methods of
improving battery characteristics. However, simple 1,3-alkyl imida-
zolium cation-based room-temperature ionic liquids are most com-
monly used because of their relatively easy synthesis. In this report,
to improve the performance of lithium secondary batteries that use
1,3-alkyl imidazolium cation-based room-temperature ionic
liquids,
23
we examined the molecular design of various room-
temperature ionic liquids. In particular, to promote charge delocal-
ization in the imidazolium cation ring and to control the three-
dimensional attack at the second position of the imidazolium cation
ring, room-temperature ionic liquids that lengthened the alkyl chains
in the rst position third position were examined.
Experimental
Five types of room-temperature ionic liquids with various
lengths of alkyl chains in the rst position third position of the
imidazolium cation ring, mmimCF
3
SO
2

2
N methyl, emim
CF
3
SO
2

2
N ethyl, bmimCF
3
SO
2

2
N butyl, hmim
CF
3
SO
2

2
N hexyl, and omimCF
3
SO
2

2
N octyl shown in
Fig. 1 were synthesized, respectively, according to previous
reports.
22
First, all room-temperature ionic liquids were dried in a
vacuum chamber at 323 K for more than 24 h, and stored in a dry-
argon-lled glove box O
2
0.4 ppm, H
2
O 0.1 ppm, Miwa
MFG Co., Ltd.. Next, the room-temperature ionic liquid-lithium
salt LiNCF
3
SO
2

2
, Kishida Chemical battery grade, dried in a
vacuum chamber at room temperature and stored in a dry-argon-
lled glove box mixed electrolytes were prepared by dissolving a
* Electrochemical Society Active Member.
z
E-mail: s-seki@criepi.denken.or.jp
Figure 1. Chemical structures of mmimCF
3
SO
2

2
N, emim
CF
3
SO
2

2
N, bmimCF
3
SO
2

2
N, hmimCF
3
SO
2

2
N, and omim
CF
3
SO
2

2
N.
Electrochemical and Solid-State Letters, 10 10 A237-A240 2007
1099-0062/2007/1010/A237/4/$20.00 The Electrochemical Society
A237
ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 150.65.7.77 Downloaded on 2013-04-18 to IP
given amount concentration: 0.32 mol kg
1
of LiNCF
3
SO
2

2
into
the room-temperature ionic liquids, and stored at room temperature
in the glove box.
The battery performance was investigated using LiCoO
2
cathoderoom-temperature ionic liquid-LiNCF
3
SO
2

2
mixed
electrolytelithium metal anode cells. The cathode sheets were pre-
pared from LiCoO
2
85 wt % as a cathode active material, acety-
lene black 9 wt %, Denka as an eletrically conductive additive,
and polyvinylidene uoride PVdF, 6 wt %, Kureha Chemical,
N-methylpyrrolidone solution as a binder polymer. These constitu-
ent materials were thoroughly agitated together in a homogenizer for
20 min. The obtained paste was applied to an aluminum current
collector using an automatic applicator at 353 K for more than 12 h.
After drying the coated paste, the cathode sheet was compressed to
increase packing density for the improvement of the electrical con-
ductivity. The dried cathode sheet, a separator, the room-temperature
ionic liquid-LiNCF
3
SO
2

2
mixed electrolyte and the lithium metal
anode were encapsulated into 2032-type coin cells. For favorable
penetration of the electrolyte into the pressed cathode sheet, thermal
aging of the prepared battery was performed at 333 K for more than
12 h.
The temperature dependences of the ionic conductivities of
various room-temperature ionic liquid-LiNCF
3
SO
2

2
mixed elec-
trolytes were measured in SUS stainless steelelectrolyteSUS
cells and determined by the complex impedance method, using an ac
impedance analyzer Princeton Applied Research, PARSTAT-2263,
200 kHz to 50 mHz; impressed voltage: 10 mV between 353 and
233 K at 10 K intervals with cooling.
Charge-discharge cycle tests of the batteries were performed at
3.04.2 V vs Li/Li
+
V at a current density of 0.05 mA cm
2
1/8
C at 303 K constant current chargeconstant current discharge,
Hokuto Denko HJ-1010mSM8A.
Results and Discussion
Figure 2 shows the temperature dependence Arrhenius plots of
ionic conductivity for the mmimCF
3
SO
2

2
N, emim
CF
3
SO
2

2
N, bmimCF
3
SO
2

2
N, hmimCF
3
SO
2

2
N, and
omimCF
3
SO
2

2
NLiNCF
3
SO
2

2
mixed electrolytes used in
this study. The Arrehenius-type temperature dependences of for all
electrolytes in this study exhibited convex curved proles, following
the WilliamsLandelFerry or VogelTammanFulcher VTF
behavior. Although mmimCF
3
SO
2

2
NLiNCF
3
SO
2

2
and
emimCF
3
SO
2

2
NLiNCF
3
SO
2

2
mixed electrolytes exhibited
close values throughout the entire temperature range in this study,
largely decareases monotonically with increasing alkyl length of the
imidazolium cation. These trends are similar to the case of the neat
room-temperature ionic liquid systems.
23
They correlate to the order
of the viscosity values and the self-diffusion coefcients on the basis
of pulsed-gradient spin-echo nuclear magnetic resonance in the case
of bulk room-temperature ionic liquid systems, and the microscopic
ionic mobility room-temperature ionic liquid cations, NCF
3
SO
2

2
anions, and lithium cations might be similarly reected even if
LiNCF
3
SO
2

2
was added into room-temperature ionic liquids.
In this research, the temperature dependences of the ionic con-
ductivities of all electrolyte systems showed convex curved proles,
and they are analyzed using the VTF equation
24,25
= AT
1/2
expB/T T
0
1
where A parameter is a pre-exponential constant proportional to the
number of carrier ions in this study, room-temperature ionic liquid
cations, TFSI anions, and lithium cations in the case of extremely
high temperatures, B parameter is the pseudo-activation energy for
ionic conduction expressed in temperature units, and T
0
is the ideal
glass transition temperature. Figure 3 shows the relationships be-
tween best-t VTF equation parameters obtained from ionic conduc-
tivity data with error bars and the alkyl carbon numbers of the ve
types of room-temperature ionic liquidLiNSO
2
CF
3

2
mixture
electrolytes a: A parameter, b: B parameter, c: T
0
. A param-
eters and B parameters monotonically increased, whereas T
0
monotonically decreased, with increasing length of the alkyl chain.
In a previous report, the density values of imidazolium cation-based
Figure 2. Arrhenius plots of the ionic conductivities of the ve types of
room-temperature ionic liquid-LiNSO
2
CF
3

2
mixture electrolytes.
Figure 3. VTF equation = AT
1/2
expB/T T
0
parameters for
ionic conductivity data for the ve types of room-temperature ionic liquid-
LiNSO
2
CF
3

2
mixture electrolytes a: A parameter, b: B parameter, c:
T
0
.
A238 Electrochemical and Solid-State Letters, 10 10 A237-A240 2007 A238
ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 150.65.7.77 Downloaded on 2013-04-18 to IP
room-temperature ionic liquids follow the order mmim
CF
3
SO
2

2
N emimCF
3
SO
2

2
N bmimCF
3
SO
2

2
N
hmimCF
3
SO
2

2
N omimCF
3
SO
2

2
N in the tempera-
ture range of 288313 K. Although an increase of density indicates
the increased afnity of the molecules, A parameters can increase as
the alkyl chain extends as a result of the formation of space for the
added lithium cations and for the entry of CF
3
SO
2

2
N anions into
the vacant space. In other words, an increase of ion content per
each unit volume has been suggested. The increase in B parameter
accompanying LiNCF
3
SO
2

2
concentration can explain the de-
creasing tendency of the ionic conductivity in the low-temperature
region. On the other hand, T
0
showed a different tendency from that
of neat room-temperature ionic liquid systems.
23
In this study, the
concentration of the dissolved LiNCF
3
SO
2

2
is constant at
0.32 mol kg
1
, and the molar ratio of LiNCF
3
SO
2

2
to room-
temperature ionic liquid increases with alkyl chain length. More-
over, in particular, LiNCF
3
SO
2

2
might not inuence the alkyl part
in the imidazolium cation ring. Therefore, it is thought that the in-
teraction between imidazolium cations and lithium cations became
small with increasing length of the alkyl chain. Of course, lithium
cations most likely have a very weak interaction with the imidazo-
lium cations no matter what the alkyl chain length, and the lithium
cations will be strongly interacting with the anions for all of the
electrolytes.
Because the ionic conductivity of all electrolytes was higher than
10
3
S cm
1
303 K, the characteristics of the electrolytes for actual
lithium secondary batteries were examined. Figure 4 shows the
cycle number dependences of the cathode-limited discharge capaci-
ties a and the Coulombic efciencies b of the LiCoO
2
cathoderoom-temperature ionic liquidLiNCF
3
SO
2

2
mixed
electrolytelithium metal anode cells with various room-temperature
ionic liquids. The initial discharge capacities of all the electrolyte
systems except the mmim cation were approximately
135 mAh g
1
which is close to the theoretical capacity of Li
x
CoO
2
0.5 x 1; between 3.0 and 4.2 V. The cycle performance of
the battery was improved with the extension of the alkyl chain
length of the imidazolium cation ring, in particular when the alkyl
chain is longer than butyl contains more than 4 carbon atoms. For
example, hmim and omim cation room-temperature ionic liquid
electrolyte systems maintained a high capacity retention over
110 mAh g
1
after 100 charge/discharge cycles. The Coulombic
efciency, calculated from the charge capacity and discharge capac-
ity, was also improved with the extension of the alkyl chain length
in the imidazolium cation ring, as well as in case of using second
position substituted imidazolium cation.
21
In other words, these re-
sults suggest that side reactions at electrode / electrolyte interfaces
probably, reductive decomposition at lithium metal anode de-
creased with the extension of the alkyl chain length due to formation
of stable interfaces, for example, solid electrolyte interface SEI.
For example, in order to overcome the problem of insufcient sta-
bility with lithium metal electrode, proposal of the quaternary pip-
eridinium cation-based room-temperature ionic liquids
26-28
or appli-
cations of the stable SEI forming room-temperature ionic liquid
29
and additive
30
have been reported. Of course, the possibility of the
SEI formation by all ionic species cations and anions should not be
neglected
31-33
at the present stage. On the other hand, in neat room-
temperature ionic liquid systems, with increasing number of carbon
atoms in the alkyl chain, the van der Waals inductive forces among
alkyl chains of imidazolium cations were increased.
23
For example,
recently, Lopes and Pdua have reported the formation of mi-
crophase intramolecular separation as the length of the alkyl chain
increases using computer simulations.
34
In particular, they reported
the aggregation formation of the alkyl chains in nonpolar domain
charge delocalization in the imidazolium cation ring, in the case of
the alkyl chain is longer than butyl. That is, the separation of hydro-
philic part and hydrophobic part might be promoted i.e., intramo-
lecular phase dissociation might promote hydrophobic nature. Not
only a single-molecular order charge delocalization of the imidazo-
lium ring and control of the attack at the second position by the
steric barrier, but also a multimolecular order for example, a small
amount of moisture control due to a phase separation of the room-
temperature ionic liquids structure might be affected by the alkyl
chain length of the imidazolium cation ring.
Conclusion
Rechargeable lithium batteries were fabricated using the ve
kinds of 1,3-alkyl imidazolium cation alkyl: methyloctyl based
room-temperature ionic liquids, and their battery properties were
investigated. The results are summarized as follows:
1. Ionic conductivity of room-temperature ionic liquidlithium
salt mixed electrolytes lithium salt concentration: 0.32 mol kg
1

was higher than 10

3
S cm
1
at 303 K in all room-temperature ionic
liquid systems. Ionic conductivity decreases monotonically with in-
creasing alkyl length carbon atom numbers of the imidazolium
cation of the room-temperature ionic liquids.
2. Charge/discharge cycle performances of the battery have been
improved with the extension of the alkyl chain length of the imida-
zolium cation ring, in particular when the alkyl chain is more than
butyl. For example, high capacity retention over 110 mAh g
1
af-
ter 100 cycles were realized when the alkyl chain is longer than
hexyl contains more than 6 carbon atoms.
Central Research Institute of Electric Power Industry assisted in meeting
the publication costs of this article.
References
1. http://www.tepco.co.jp/en/related/rd/products/index-e.html
2. J.-M. Tarascon and M. Armand, Nature (London), 414, 359 2001.
3. K. Takei, K. Ishihara, K. Kumai, T. Iwahori, K. Miyake, T. Nakatsu, N. Terada, and
N. Arai, J. Power Sources, 119121, 887 2003.
4. J. Arai, T. Yamaki, S. Yamauchi, T. Yuasa, T. Maeshima, T. Sakai, M. Koseki, and
T. Horiba, J. Power Sources, 146, 788 2005.
5. S. Seki, Y. Ohno, Y. Kobayashi, H. Miyashiro, A. Usami, Y. Mita, H. Tokuda, M.
Watanabe, K. Hayamizu, S. Tsuzuki, M. Hattori, and N. Terada, J. Electrochem.
Soc., 154, A173 2007.
6. S. Seki, Y. Kobayashi, H. Miyashiro, Y. Mita, and T. Iwahori, Chem. Mater., 17,
2041 2005.
7. Y. Kobayashi, S. Seki, M. Tabuchi, H. Miyashiro, Y. Mita, and T. Iwahori, J.
Electrochem. Soc., 152, A1985 2005.
8. S. Seki, Y. Kobayashi, H. Miyashiro, A. Usami, Y. Mita, and N. Terada, J. Elec-
trochem. Soc., 153, A1073 2006.
Figure 4. Cycle-life performances for LiCoO
2
cathodeimidazolium cation
based room-temperature ionic liquid-LiNSO
2
CF
3

2
mixture electro-
lytelithium metal anode cells: a discharge capacity and b Coulombic
efciency.
A239 Electrochemical and Solid-State Letters, 10 10 A237-A240 2007 A239
ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 150.65.7.77 Downloaded on 2013-04-18 to IP
9. T. Welton, Chem. Rev. (Washington, D.C.), 99, 2071 1999.
10. P. Wassersheild and W. Keim, Angew. Chem., Int. Ed., 39, 3772 2000.
11. T. Sato, G. Masuda, and K. Takagi, Electrochim. Acta, 49, 3603 2004.
12. M. Ue, M. Takeda, A. Toriumi, A. Kominato, R. Hagiwara, and Y. Ito, J. Electro-
chem. Soc., 150, A499 2003.
13. A. Noda, M. A. B. H. Susan, K. Kudo, S. Mitsushima, K. Hayamizu, and M.
Watanabe, J. Phys. Chem. B, 107, 4024 2003.
14. P. Wang, S. M. Zakeeruddin, J.-E. Moser, R. Humphry-Baker, and M. Gratzel, J.
Am. Chem. Soc., 126, 7164 2004.
15. K. Kato, T. Kado, S. Tanaka, A. Okazaki, and S. Hayase, J. Electrochem. Soc.,
153, A626 2006.
16. M. Ishikawa, T. Sugimoto, M. Kikuta, E. Ishiko, and M. Kono, J. Power Sources,
162, 658 2006.
17. H. Matsumoto, H. Sakaebe, K. Tatsumi, M. Kikuta, E. Ishiko, and M. Kono, J.
Power Sources, 160, 1308 2006.
18. H. N. Randriamahazaka, C. Plesse, D. Teyssi and C. Chevrot, Electrochem. Com-
mun., 5, 613 2003.
19. S. Seki, Y. Kobayashi, H. Miyashiro, Y. Ohno, Y. Mita, A. Usami, N. Terada, and
M. Watanabe, Electrochem. Solid-State Lett., 8, A577 2005.
20. S. Seki, Y. Kobayashi, H. Miyashiro, Y. Ohno, A. Usami, Y. Mita, M. Watanabe,
and N. Terada, Chem. Commun. (Cambridge), 2006, 544.
21. S. Seki, Y. Kobayashi, H. Miyashiro, Y. Ohno, A. Usami, Y. Mita, N. Kihira, M.
Watanabe, and N. Terada, J. Phys. Chem. B, 110, 10228 2006.
22. K. Hayashi, Y. Nemoto, K. Akuto, and Y. Sakurai, J. Power Sources, 146, 689
2005.
23. H. Tokuda, K. Hayamizu, K. Ishii, M. A. B. H. Susan and M. Watanabe, J. Phys.
Chem. B, 109, 6103 2005.
24. H. Vogel, Phys. Z., 22, 645 1921.
25. G. S. Fulcher, J. Am. Ceram. Soc., 8, 339 1923.
26. H. Sakaebe and H. Matsumoto, Electrochem. Commun., 5, 594 2003.
27. H. Matsumoto, H. Sakaebe, and K. Tatsumi, J. Power Sources, 146, 45 2005.
28. H. Sakaebe, H. Matsumoto, and K. Tatsumi, J. Power Sources, 146, 693 2005.
29. M. Egashira, M. Nakagawa, I. Watanabe, S. Okada, and J. Yamaki, J. Power
Sources, 146, 685 2005.
30. J. Xu, J. Yang, Y. NuLi, J. Wang, and Z. Zhang, J. Power Sources, 160, 621
2006.
31. D. Aurbach, J. Power Sources, 89, 206 2000.
32. P. C. Howlett, N. Brack, A. F. Hollenkamp, M. Forsyth, and D. R. MacFarlane, J.
Electrochem. Soc., 153, A595 2006.
33. F. Endres and S. Z. E. Abedin, Phys. Chem. Chem. Phys., 8, 2101 2006.
34. J. N. A. C. Lopes and A. A. H. Pdua, J. Phys. Chem. B, 110, 3330 2006.
A240 Electrochemical and Solid-State Letters, 10 10 A237-A240 2007 A240
ecsdl.org/site/terms_use address. Redistribution subject to ECS license or copyright; see 150.65.7.77 Downloaded on 2013-04-18 to IP