Artittcle
Artittcle
Artittcle
Short communication
a r t i c l e i n f o a b s t r a c t
Article history: A copolymer, polyacrylonitrile–methyl methacrylate P(AN–MMA), was synthesized by suspension poly-
Received 12 January 2008 merization with acrylonitrile (AN) and methyl methacrylate (MMA) as monomers. With this copolymer,
Received in revised form 3 May 2008 polymer membrane was prepared by phase inversion. The performances of the polymer were charac-
Accepted 8 May 2008
terized by FTIR, SEM, DSC/TG, EIS and LSV. The copolymer contains CH2 , CN and CO bonds, and shows
Available online 16 May 2008
its thermal stability up to 300 ◦ C. The polymer membrane has a porous structure with an average pore
diameter of 0.5 m. The conductivity of the polymer electrolyte is 1.25 mS cm−1 at room temperature, and
Keywords:
it is electrochemically stable up to 5 V (vs. Li). Using the polymer electrolyte as the gel polymer electrolyte
Suspension polymerization
Gel polymer electrolyte
(GPE), the cell Li/GPE/LiCoO2 shows its cyclic stability as good as the cell with liquid electrolyte.
Conductivity © 2008 Elsevier B.V. All rights reserved.
Lithium-ion battery
0378-7753/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jpowsour.2008.05.027
478 D.Y. Zhou et al. / Journal of Power Sources 184 (2008) 477–480
Fig. 1. FTIR spectra of monomers, AN and MMA, and their copolymer, P(AN–MMA). at 1597 or 1616 cm−1 for C C, indicating that the copolymer main-
tains the main characteristics of the monomers and the monomers
are copolymerized through the breaking of double bonds C C in
the exchange of DMF and water by phase inversion, a substantial
both monomers. It can be expected that the copolymer has good
number of pores were formed in the films. The resulting mem-
strength due to the cross-linking between two monomers and good
branes were washed, rinsed and dried at 60 ◦ C under vacuum for
conductivity due to the existence of strong polarity bonds CN and
24 h, successively, before further processing.
CO.
The P(AN–MMA) polymer electrolytes were prepared by soaking
Fig. 2 presents the TGA and DSC curves of P(AN–MMA) copoly-
the membranes in an electrolyte solution, 1 M LiPF6 in ethylene
mer. There is a large exothermic peak at 300 ◦ C for the DSC curve,
carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC)
which is accompanied by the significant weight loss for TGA curve.
(1:1:1 in mass), for 30 min in an argon-filled glove box (Mikrouna).
These phenomena reflect the decomposition of the copolymer.
The structure and properties of the polymer were characterized
Therefore, the copolymer is thermally stable at the temperature
by Fourier transform infrared (FTIR) (PerkinElmer Spectrograph).
lower than 300 ◦ C, which is better than PMMA and PAN [19]. Appar-
The thermogravimetric analysis (TGA) and differential scanning
ently, the cross-linking between MMA and AN can improve the
calorimetry (DSC) traces were obtained using a NETZSCH simul-
thermal stability of the polymer with single monomer. It can be
taneous TG-DTA/DSC analyser (model STA-449C). The morphology
noted from Fig. 2 that there appears small weight loss at 100–150 ◦ C,
of the polymer membrane was characterized by scanning electron
it may result from the volatilization of solvents remaining in the
microscopy (SEM) (JEOL, JSM-6380LV, JAPAN, at an acceleration
polymer.
voltage of 15 kV). The electrochemical stability was carried out on
Fig. 3 presents the SEM image of P(AN–MMA) membrane pre-
the stainless steel electrode with lithium metal electrode as the
pared by the phase inversion technique. In the phase inversion
reference and counter electrodes by the linear sweep voltamme-
process, the porous membrane is formed by polymer precipitation.
try (LSV) at 2 mV s−1 using Solartron 1260. The ionic conductivity
Usually, copolymer between different monomers forms more uni-
of the polymer electrolyte was measured by the electrochemical
form pores than the polymer with single monomer. It can be found
impedance spectroscopy (EIS) using Solartron 1260 with ac ampli-
from Fig. 3 that the self-supporting membrane has a large number
tude of 10 mV from 100 kHz to 1 Hz. The polymer electrolyte was
of micro-porous pores with an average size of 0.5 m. It is expected
sandwiched between two parallel stainless steel (SS) discs.
To determine the battery performance, 2016 type cell
Li/GPE/LiCoO2 was assembled in the glove box. A positive elec-
trode consisted of LiCoO2 (84 wt.%), acetylene black (8 wt.%) and
poly(vinylidenefluoride) (PVDF) (8 wt.%). LAND-CT2001A lithium-
ion battery testing device (Wuhan Blue Electronic Industry Co., Ltd.)
was used to test the cycle stability of the batteries. The batteries
were charged and discharged with 0.1 C constant current between
3.0 and 4.2 V.
4. Conclusion
polymer electrolyte (GPE), the cell Li/GPE/LiCoO2 shows its good [6] J.D. Jeon, B.W. Cho, S.Y. Kwak, J. Power Sources 143 (2005) 219–226.
cyclic stability as better as the cell with liquid electrolyte. [7] X.L. Yao, S. Xie, C.H. Chen, Q.S. Wang, J.H. Sun, Y.L. Li, S.X. Lu, J. Power Sources
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