Materials Letters 57 (2003) 1759 1764 www.elsevier.

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The effect of fumed silica on the interfacial stability in the polymer gel electrolyte
Yan-bao Fu, Xiao-hua Ma *, Qing-he Yang, Xiang-fu Zong
Department of Materials Science, Fudan University, 220 Handan Road, Shanghai 200433, PR China Received 24 May 2002; accepted 29 May 2002

Abstract Polymer gel electrolyte with addition of fumed silica was prepared by the UV polymerization of methyl methacrylate, oligomer of ethyl glycol dimethacrylate and liquid electrolyte. The effect of fumed silica on the interfacial stability of lithium electrode and polymer gel electrolyte membrane was studied by environmental scanning electron microscopy (ESEM), FTIR and electrochemical AC impedance. The addition of fumed silica has an effect on morphology of polymer gel electrolyte membrane. The silica is interactive with solvent and polymer matrix and it can trap impurities in the polymer gel electrolyte. All of them are beneficial to the interfacial stability, which is confirmed in the AC impedance spectrum. D 2002 Published by Elsevier Science B.V.
Keywords: Polymer gel electrolyte; Interfacial stability; Fumed silica; ESEM; FTIR; AC impedance

1. Introduction Polymer electrolyte, developed at the end of 1970s, has been widely used in solid-state batteries with high specific energy. Among them, the most promising, highly conducting, new-generation polymers are geltype systems, which were obtained by immobilizing solutions of Li salts in organic polymer matrices [1]. Polymer gel electrolytes have a room temperature ionic conductivity in the range of 10 3 S cm 1, which can be compared with liquid electrolyte. However, in the previous research, some results clearly demonstrated that the lithium electrode undergoes

* Corresponding author. Tel.: +86-21-6564-2390; fax: +86-216510-3056. E-mail address: yangjyk@online.sh.cn (X. Ma).

serious passivation in contact with gel electrolyte [2]. The instability of interface would limit the charge transfer reaction at the electrolyte/electrode interface leading to deterioration in the rechargeability of the battery [3]. To decrease the passivation, some researchers used low polar solvents instead of high polar ones and passivation could be improved to some extent by this method [2]. However, the substitute of high polar solvents with low polar ones may lead to the decrease of ionic conductivity, which is not beneficial to its application. In recent years, some inert inorganic fillers were incorporated in the solid polymer electrolyte to improve the interfacial stability between lithium electrode and polymer electrolyte and the effect is obvious. Croce et al. [4] have reported the interfacial resistance of Li/PEO20LiBF4 + Ceramic/Li changed from 150 (freshly prepared) to 200 V/cm2 (stored for 40 days). The interfacial resistance of the

0167-577X/02/$ - see front matter D 2002 Published by Elsevier Science B.V. PII: S 0 1 6 7 - 5 7 7 X ( 0 2 ) 0 1 0 6 5 - 0

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counterpart free of ceramic was 1000 V/cm2 after the cell was stored only for 8 days. The addition of ceramic filler was quite effective to reduce the interfacial resistance for the solid polymer electrolyte without solvent. Compared with the solid polymer electrolyte, the research on the interfacial stability was rare for the addition of ceramic filler to the polymer gel electrolyte. In this paper, to improve the electrochemical stability, the chemically crosslinked polymer gel electrolyte was prepared with the addition of various amounts of fumed silica.

placed in the work chamber of ESEM instrument without pretreatment, such as frozen by liquid nitrogen and then evacuated and dried. The FTIR measurements were made using a Nicolet 550 Series II IR spectrometer in the region of 4000 400 cm 1. The interfacial stability between a lithium metal electrode and the prepared PGE was evaluated by monitoring the AC impedance of symmetric Li/PGE/ Li cells. The AC impedance measurements were performed using a Solartron 1260 impedance/gain phase analyzer in the frequency range 1 MHz 0.1 Hz.

2. Experimental The chemically crosslinked polymer gel electrolyte with fumed silica was prepared by the UV-radiated polymerization of mixture of monomer (methyl methacrylate, Aldrich), crosslinker (oligomer of ethyl glycol dimethacrylate, Mn f 575, Aldrich), liquid electrolyte [LiClO4/EC/PC, 1M, EC/PC = 1:1(weight ratio), Merck], Initiator (Iracure 184, Ciba-Gagi) and fumed silica (Cabot, TS-530). The synthesis procedure is shown in Fig. 1. The required quantity of monomer, crosslinker and liquid electrolyte were mixed together. The initiator and various amounts of silica were added into the mixture. Then, the suspension was stirred until the silica dispersed in the mixture uniformly. The mixture was dipped onto nonwoven fabrics and exposed under the UV light. The polymer gel electrolyte membrane was obtained. The morphology of polymer gel electrolyte was observed by environmental scanning electron microscopy (ESEM), which was carried out on Philips XL30 ESEM. Compared with SEM, ESEM could more truly reflect the morphology and distribution of composition of the PGE membrane. The working condition of ESEM instrument need not be in the vacuum condition, so the PGE membrane can be directly

3. Results and discussion 3.1. The ESEM studies of polymer gel electrolyte ESEM micrographs of polymer gel electrolytes with varied contents of fumed silica are shown in Fig. 2. From Fig. 2a c, the amounts of fumed silica increased, which are 0, 2 and 5 wt.%, respectively. It can be seen in Fig. 2a that the surface of the polymer gel electrolyte membrane is coarse and there exist large cavities among polymer backbones. The liquid electrolyte is mainly stored in the large cavities. Due to the coarse surface of the polymer gel electrolyte membrane, it is not contacted tightly with lithium electrode. This effect would increase the interfacial resistance between polymer gel electrolyte and lithium electrode. The existence of large cavities is not beneficial to the interfacial stability, because the liquid electrolyte is easy to meet with lithium electrode directly. With the addition of fumed silica, the surface of polymer gel electrolyte membrane became wrinkled and the cavities became small, as shown in Fig. 2b. This effect could be attributed to the fact that the silica absorbed large amounts of liquid electrolyte that surrounded the polymer backbone originally. When the amount of silica further increased, the surface of polymer gel

Fig. 1. The synthesis procedure of polymer gel electrolyte membranes.

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Fig. 3. FTIR spectra of liquid electrolyte (LiClO4/EC/PC) with various amounts of fumed silica.

that the addition of nanoparticles is helpful to the formation of micropores. This effect was also observed in the PVC-based polymer electrolyte film [5]. The fine surface is helpful to form the tight contact between polymer gel electrolyte membrane and lithium electrode. From the analysis of morphology, it may be concluded that the addition of fumed silica is beneficial to the interfacial stability between polymer gel electrolyte and lithium electrode. 3.2. FTIR spectroscopy studies FTIR spectra were recorded in the absorbance mode. Fig. 3 shows the FTIR spectra of LiClO4/EC/ PC (free of fumed silica), LiClO4/EC/PC (2% fumed

Fig. 2. The ESEM imagines of PGE membranes with various amounts of fumed silica. (a) Free of silica, (b) 2% silica, (c) 5% silica.

electrolyte membrane became finer and micropores appeared in the polymer matrix, which is shown in Fig. 2c. The size of the micropores was about 5 Am. According to this phenomenon, it could be considered

Fig. 4. FTIR spectra of polymer gel electrolyte with various amounts of fumed silica.

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Fig. 5. The CjO stretching vibrational band for different samples. (a) PGE free of silica, (b) PGE 2% silica, (c) PGE 5% silica.

vibration and deformation vibration, respectively [6]. In the samples, H O H are produced from the impurities. Thus, it can be said that the addition of fumed silica could trap the impurities in the electrolyte. The FTIR spectra of PGE (free silica), PGE (2% silica) and PGE (5% silica) were shown in Fig. 4. The peaks in the region of 1900 1700 cm 1 are assigned to CjO stretching vibration in the polymer matrix, EC and PC [7]. The other strong peaks in the region of 1300 1000 cm 1 assigned to CUO stretching vibration in the polymer matrix, EC, PC and fumed silica [8]. From Fig. 4, it was observed that the addition of silica had an effect on the CjO stretching vibrational band. The peak could be well resolved into three components as shown in Fig. 5. The area percent of each component to the total peak was calculated and the results listed in Table 1. From the results, it can seen that the position of each component changed little for different samples, but the intensity of each one changed obviously. The addition of silica caused an increase in the intensity of the component peak at 1728 cm 1 and a decrease at 1800 cm 1. The change should be attributed to the interaction between silica and CjO. It also took on some change for the shape of CUO stretching vibrational band in the region of 1300 1000 cm 1. However, there is vibrational band in this region for pure fumed silica. Thus, it is not clear if there is an interaction between silica and CUO or not. In the previous research, it was reported that the interfacial passive layer between lithium electrode and electrolyte was mainly produced by the reaction of Li with CjO in the polymer gel electrolyte [9]. Because there is an interaction between CjO and silica, the reaction of Li and CjO would weaken with the addition of silica in the PGE, which is beneficial to the interfacial stability.

silica), LiClO4/EC/PC (5% fumed silica) and fumed silica. From Fig. 3, it can be seen that in the spectrum of LiClO4/EC/PC (free of fumed silica), the absorption peak of 3600 cm 1 is strong, and there is a small peak in the region of 1640 cm 1. With the addition of fumed silica, the peak of 3600 cm 1 weakened gradually and the peak of 1640 cm 1 disappeared. The two peaks correspond to H O H stretching

Table 1 The information of CjO stretching band after peak resolve Sample Center of component peak (cm 1) Area percent of component peak (%)

Peak 1 Peak 2 Peak 3 Peak 1 Peak 2 Peak 3 PGE (0% silica) 1727.2 1775.5 1805.4 17.8 PGE (2% silica) 1728.3 1775.6 1805.4 27.2 PGE (5% silica) 1728.2 1775.7 1805.2 55.2 7.5 7.4 5.7 74.7 65.4 39.1

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3.3. The interfacial stability studies by AC impedance To investigate the interfacial behavior between the polymer gel electrolyte and the lithium electrode, AC impedance spectroscopy was used. The time evolution of the impedance response was monitored for Li/ polymer gel electrolyte/Li cells at open circuit for several days. Fig. 6 shows change of the AC impedance diagrams with time evolution. From Fig. 6, it can be observed that the related impedance spectrum is composed of a distorted semicircle in the middlefrequency range and a spur in the low-frequency region. It reveals a progressive expansion of the middle-frequency semicircle in the impedance spectrum. The progressive expansion of the middle-frequency semicircle is mainly caused by a passive layer produced when the lithium electrode contacted with polymer gel electrolyte [2]. Using the software attached in the instrument, it is possible to separate the various impedance parameters that contribute to determine the responses in the AC impedance spectrum. Thus, the interfacial resistance was obtained. The time evolution of the interfacial resistance was given in Fig. 7 for polymer gel electrolytes with various amounts of fumed silica. From Fig. 7, it can be seen that the interfacial resistance of sample without fumed silica increased largely with time and it stopped increasing after the cell stored for about 1000 h. For samples with addition of fumed silica, the interfacial resistance increased in the initial

Fig. 7. Time evolution at 25 jC of the interfacial resistance Ri of the lithium electrode in PGE.

Fig. 6. Impedance spectra of a Li APGEA Li cell at different storage time at 298 K under open circuit conditions.

time and the maximum value is much less than that of sample without fumed silica. With the content of silica in the polymer gel electrolyte increasing, the improvement of interfacial resistance became obvious. Unfortunately, in this research, the maximum amounts of fumed silica is 5%; if the amounts increased, the mixture of liquid electrolyte, monomer, crosslinker and fumed silica was not in the state of liquid and it was not polymerized by UV radiation. Thus, the effect of silica on the interfacial stability could not be investigated when its content is more than 5% in the polymer gel electrolyte in this research. However, from the present research, it can also be said that the addition of fumed silica improved the interfacial stability between lithium electrode and polymer gel electrolyte. In the previous research, the enhancement of interfacial stability with the addition of inorganic filler was considered such that the inorganic filler could trap the impurities and water in the polymer electrolyte, then prevented them from reacting with lithium electrode [10]. This effect of silica was also confirmed in our research from the above analysis of FTIR. According to the observation of ESEM and analysis of FTIR in our research, it was thought that the addition of fumed silica not only traps impurities and water, but also has an effect on the morphology of the PGE membrane and the reaction of lithium electrode and PGE. From above analysis of morphology by ESEM, it was known that the addition of fumed silica made the cavities among the polymer backbones become small and the surface of PGE

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membrane become fine. Both of them made the PGE contact tightly with lithium electrode and decreased the liquid electrolyte to meet the lithium electrode directly. From the analysis of FTIR, it was considered that there exist interactions between silica and carbonyl base, which weakened the reaction of lithium and carbonyl base. Thus, the addition of fumed silica in the PGE improved the interfacial stability between PGE and lithium electrode.

Acknowledgements The authors would like to acknowledge the financial support from Educational Ministry of China and Science and Technology Committee of Shanghai, PR China (no. 02dz11001).

References
[1] F. Croce, F. Gerace, G. Dautzenberg, et al., Electrochim. Acta 39 (1994) 2187. [2] L.A. Dominey, in: G. Pistoia (Ed.), Lithium BatteriesNew Materials, Developments and Perspectives, Elsevier, Amsterdam, 1994, p. 137, Chapter 4. [3] R. Yazami, M. Deschamps, J. Power Sources 54 (1995) 411. [4] F. Croce, L. Persi, F. Ronci, et al., Nanocomposite polymer electrolytes and their impact on the lithium battery technology [J], Solid State Ionics 135 (2000) 47 52. [5] N.-S. Choi, J.-K. Park, Electrochim. Acta 46 (2001) 1453 1459. [6] B. Crawford, D. Swanson, in: E.G. Brame, J.G. Grasselli (Eds.), Infrared and Raman Spectroscopy, Marcel Dekker, New York, 1976, p. 23, Chap. 1. [7] A. Richard, R. Nyquist, O. Kagel, in: E.G. Brame, J.G. Grasselli (Eds.), Infrared and Raman Spectroscopy, Marcel Dekker, New York, 1976, p. 465, Chap. 6. [8] S.C. Brown, A.B. Harvey, in: E.G. Brame, J.G. Grasselli (Eds.), Infrared and Raman Spectroscopy, Marcel Dekker, New York, 1976, p. 888, Chap. 12. [9] W. Xu, K.S. Siow, Z. Gao, et al., Solid State Ionics 112 (1998) 1 8. [10] K.H. Lee, Y.G. Lee, J.K. Park, et al., Solid State Ionics 133 (2000) 257 263.

4. Conclusion The effect of fumed silica on the interfacial stability of polymer gel electrolyte membrane and lithium electrode was investigated. The addition of fumed silica is quite effective to stabilize the interface. The improvement can be attributed to three factors. The first is that the addition of fumed silica changed the morphology of the PGE membrane, which made the PGE membrane contact tightly with lithium electrode and decreased the chance of direct meeting of solvent and lithium electrode. The second is that the fumed silica can trap the impurities in the PGE, such as water, and prevent them from reacting at the interface. The last one is that there exist some interaction between the fumed silica and other compositions of the PGE, especially the interaction between silica and carbonyl base, which blocked PGE reacting with lithium electrode.