.
Angewandte
Communications
DOI: 10.1002/anie.201302586
Lithium batteries
Quasi-Solid-State Rechargeable Lithium-Ion Batteries with
a Calix[4]quinone Cathode and Gel Polymer Electrolyte**
Weiwei Huang, Zhiqiang Zhu, Lijiang Wang, Shiwen Wang, Hao Li, Zhanliang Tao, Jifu Shi,
Lunhui Guan, and Jun Chen*
Rechargeable lithium-ion batteries (LIBs), which are cur-
rently based on the exchange of Li/Li between a graphite
cyclability has been obtained for tetracyanoquinodimethane
(TCNQ)-based all-solid-state cells with a silica room-temper-
ature ionic liquid (RTIL) composite quasi-solid electrolyte.
+
[6a]
(
Li C ) anode and an inorganic lithium-transition-metal-
x
6
oxide cathode, have been widely used in portable electron-
More recently, by using the same electrolyte, a capacity of
[
1]
À1
ics. However, the further application of LIBs in the areas of
large-capacity and high-power electronics, electrical vehicles,
and smart grids is still limited. Critical issues are the low
capacity, low energy/power density, short life, high cost, and
low safety of the batteries. Among various strategies, one
interesting approach is to find redox-active organic materials
approximately 300 mAhg
540 Whkg has been achieved by 2,5-dihydroxy benzoqui-
none (DHBQ)-based solid-state cells.
with a power density of
À1
[
6b]
Wrightꢀs group discovered the ionic conductivity of
poly(ethylene oxide) (PEO) doped with alkali-metal salt
[
7]
complexes in 1973. Armand and co-workers studied poly-
mer electrolyte used for solid-state electrochemical devices
[
2]
with high capacities and low cost. Recently, carbonyl
À1
[8]
organic compounds, such as Li C O (C = 589 mAhg )
a few years later. Although this system offers very low ionic
2
2
6
theo
À1
À8
À1
[9]
and pyrene-4,5,9,10-tetraone (Ctheo = 409 mAhg ) have been
considered as promising materials for the cathode of LIBs
primarily owing to their high theoretical gravimetric capaci-
conductivity (ca. 10 Scm at room temperature), it
stimulated the study of gel polymer electrolyte (GPE),
which displays a much higher conductivity through the
introduction of an organic aprotic dipolar solvent into the
polymer matrix. To date, a series of polymer hosts, such as
PEO, poly(propylene oxide) (PPO), poly(acrylonitrile)
(PAN), poly(methyl methacrylate) (PMMA), poly(vinyl
chloride) (PVC), poly(vinylidene fluoride) (PVdF), and
poly(vinylidene fluoride hexafluoro propylene) (PVdF-
[
2b,3]
ties.
However, the electrochemical performance of those
materials as the cathode of LIBs was always poor because
they suffer from severe solubility in liquid organic electrolyte.
As an attempt to solve this problem, it is found that grafting
a soluble active “monomer” organic molecule to an insoluble
[4]
inactive substrate, such as SiO helps. However, the tested
2
[
10]
molecule, which is a quinone derivative of calix[4]arene, only
HFP) have been developed.
Among various polymer
À1
has a low theoretical capacity (189 mAhg ). Moreover, since
matrices, PEO-based polymers are the most thoroughly
studied because the CH CH O unit in the PEO chain has
the ion conduction and transport in electrolyte is so important
2
2
[
5]
+
in electrochemical energy conversion and storage, the
solubility problem of organic materials in electrolyte has
been effectively mitigated by accommodating soluble qui-
a good solvating ability with respect to Li ions and the
polymer chain segments are highly mobile.
[
9,11]
As a low-
molecular weight polyether, poly(ethylene glycol) (PEG)
which offers similar advantages has been investigated in
[
6]
nonic cathode materials in quasi-solid-state cells. For
À1
[12]
example, a capacity exceeding 200 mAhg with excellent
LIBs. Our group reported a poly(methacrylate) (PMA)/
PEG-based GPE as the electrolyte of dye-sensitized solar
cells (DSSCs), which shows satisfactory ionic conductivity
that is benefited from its ability of entrapping large numbers
of liquid electrolyte. The question arises how about PMA/
PEG-based GPE as the electrolyte of organic LIBs when
[
+]
[+]
[
*] Dr. W. Huang, Dr. Z. Zhu, Dr. L. Wang, Dr. S. Wang, H. Li,
Prof. Dr. Z. Tao, Prof. Dr. J. Chen
[
13]
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of
Education), College of Chemistry; Synergetic Innovation Center of
Chemical Science and Engineering, Nankai University
Tianjin 300071 (China)
using a traditional LIB electrolyte, such as LiClO in dimethyl
4
sulfoxide (DMSO) to replace the DSSCs liquid electrolyte,
E-mail: chenabc@nankai.edu.cn
such as LiI and I , in a mixed solution of ethylene carbonate
2
Prof. Dr. J. Shi
(EC) and propylene carbonate (PC)). Herein, we report the
Key Lab Renewable Energy & Gas Hydrate, Inst Energy Convers,
Chinese Academy of Sciences
Guangzhou 510640 (China)
extension of a PMA/PEG-based GPE loading LiClO4 in
DMSO for organic LIBs using a high capacity carbonyl
compound calix[4]quinone (C H O , C4Q, Ctheo
=
2
8
16
8
Prof. Dr. L. Guan
State Key Laboratory of Structural Chemistry, Fujian Institute of
Research on the Structure of Matter Chinese Academy of Sciences
À1
4
46 mAhg ) as the cathode with desirable electrochemical
À1
performance (a capacity of ca. 380 mAhg has been main-
tained after 100 cycles at 0.2C charge/discharge rate).
Fujian 350002 (China)
+
Figure 1a shows the fabrication process of the PMA/
PEG-based GPE. The synthesis details are described in the
Experimental Section. Figure 1b,c show photographs of the
as-prepared PAM/PEG hybrid and PMA/PEG-based GPE
[
] These authors contributed equally to this work.
[
**] This work was supported by Programs of National 973
(
2011CB935900), NSFC (21231005), and 111 Project (B12015).
with LiClO /DMSO loading, both are a homogeneous semi-
4
9
162
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2013, 52, 9162 –9166