Abstract
In this work, a special structural poly(acrylonitrile) (PAN)-based microporous membrane for lithium-ion batteries is prepared from PAN emulsion by simple casting and extracting techniques. It is found that the microporous membrane is fabricated by PAN particles with uniform size (about 580 nm), and a lot of micropores exist among the particles. The Gurley number of the microporous membrane obviously depends on the amount of additive but the porosity does not. The PAN-based microporous membrane is activated by non-aqueous liquid electrolyte to form microporous gel electrolyte (MGE), and its ionic conductivity increases with the decrease of the Gurley number. The resulting MGE shows typical thermal shut-down action because of the swelling–incorporating behaviors of PAN-based particles by the help of the solvent of liquid electrolyte at high temperature. In addition, the electrochemical stability window of the MGE can extend to 5.5 V vs. Li+/Li. The test cell using MGE as separator shows high initial discharge capacity (143 mAh g-1 based on LiCoO2) and high capacity retention ratio (around 94.8% at the 50th cycle). Generally, the special structural microporous membrane is promisingly used to prepare high-safety lithium-ion batteries.
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Wang HP, Huang H, Wunder SL (2000) Novel microporous poly(vinylidene fluoride) blend electrolytes for lithium-ion batteries. J Electrochem Soc 147:2853–2861
Lee YM, Kim JW, Choi NS, Lee JA, Seol WH, Park JK (2005) Novel porous separator based on PVdF and PE non-woven matrix for rechargeable lithium batteries. J Power Sourc 139:235–241
Ko JM, Min BG, Kim DW, Ryu KS, Kim KM, Lee YG, Chang SH (2004) Thin-film type Li-ion battery, using a polyethylene separator grafted with glycidyl methacrylate. Electrochim Acta 50:367–370
Kim JY, Lee Y, Lim DY (2009) Plasma-modified polyethylene membrane as a separator for lithium-ion polymer battery. Electrochim Acta 54:3714–3719
Choi NS, Lee YG, Park JK, Ko JM (2001) Preparation and electrochemcial characteristics of plasticized polymer electrolytes based upon a P(VdF-co-HFP)/PVAc blend. Electrochim Acta 46:1581–1586
Zhang SS, Xu K, Foster DL, Ervin MH, Jow TR (2004) Microporous gel electrolyte Li-ion battery. J Power Sourc 125:114–118
Yamamoto T, Hara T, Segawa K, Honda K, Akashi H (2007) 4.4 V lithium-ion polymer batteries with a chemical stable gel electrolyte. J Power Sourc 174:1036–1040
Min HS, Ko JM, Kim DW (2003) Preparation and characterization of porous polyacrylonitrile membranes for lithium-ion polymer batteries. J Power Sourc 119–121:469–472
Subramania A, Kalyana Sundaram NT, Rohini Priya A, Gangadharan R, Vasudevan T (2005) Preparation of a microporous gel polymer electrolyte with a novel preferential polymer dissolution process for Li-ion batteries. J Appl Polym Sci 98:1891–1896
Pu W, He X, Wang L, Tian Z, Jiang C, Wan C (2006) Preparation of P(AN-MMA) microporous membrane for Li-ion batteries by phase inversion. J Membr Sci 280:6–9
Tian Z, He X, Pu W, Wan C, Jiang C (2006) Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries. Electrochim Acta 52:688–693
Wu G, Yang HY, Chen HZ, Yuan F, Yang LG, Wang M, Fu RJ (2007) Novel porous polymer electrolyte based on polyacrylonitrile. Mater Chem Phys 104:284–287
Zhou DY, Wang GZ, Li WS, Li GL, Tan CL, Rao MM, Liao YH (2008) Preparation and performances of porous polyacrylonitrile-methyl methacrylate membrane for lithium-ion batteries. J Power Sourc 184:477–480
Rao MM, Liu JS, Li WS, Liang Y, Liao YH, Zhao LZ (2009) Performance improvement of poly(acrylonitrile-vinyl acetate) by activation of poly(methyl methacrylate). J Power Sourc 189:711–715
Pu W, He X, Wang L, Tian Z, Jiang C, Wan C (2008) Preparation of P(AN-MMA) gel electrolyte for Li-ion batteries. Ionics 14:27–31
Tarascona JM, Gozdz AS, Schmutz C, Shokoohi F, Warren PC (1996) Performance of Bellcore’s plastic rechargeable Li-ion batteries. Solid State Ionics 86–88:49–54
Boudin F, Andrieu X, Jehoulet C, Olsen II (1999) Microporous PVdF gel for lithium-ion batteries. J Power Sourc 81–82:804–807
Kim DW, Sun YK (2001) Electrochemical characterization of gel polymer electrolytes prepared with porous membranes. J Power Sourc 102:41–45
Manuel Stephan A, Saito Y (2002) Ionic conductivity and diffusion coefficient studies of PVdF-HFP polymer electrolytes prepared using phase inversion technique. Solid State Ionics 148:475–481
Magistris A, Quartarone E, Mustarelli P, Saito Y, Kataoka H (2002) PVDF-based porous polymer electrolytes for lithium batteries. Solid State Ionics 152–153:347–354
Manuel Stephan A, Teeters D (2003) Characterization of PVdF-HFP polymer membranes prepared by phase inversion techniques I. Morphology and charge–discharge studies. Electrochim Acta 48:2143–2148
Zhang SS, Xu K, Foster DL, Ervin MH, Jow TR (2004) Microporous gel electrolyte Li-ion battery. J Power Sourc 125:114–118
Kim JR, Choi SW, Jo SM, Lee WS, Kim BC (2004) Electrospun PVdF-based fibrous polymer electrolytes for lithium ion polymer batteries. Electrochim Acta 50:69–75
Cui ZY, Xu YY, Zhu LP, Wang JY, Zhu BK (2009) Investigation on PVDF-HFP microporous membranes prepared by TIPS process and their application as polymer electrolytes for lithium ion batteries. Ionics 15:469–476
Manuel Stephan A (2006) Review on gel polymer electrolytes for lithium batteries. Euro Polym J 42:21–42
Kalyana Sundaram NT, Subramania A (2007) Microstructure of PVdF-co-HFP based electrolyte prepared by preferential polymer dissolution process. J Membr Sci 289:1–6
Li W, Xu L, Luo D, Wu H, Tu J, Yang M (2007) A composite microporous gel polymer electrolyte prepared by ultra-violet cross-linking. Euro Polym J 43:522–528
Zhang HP, Zhang P, Li GC, Wu YP, Sun DL (2009) A porous poly(vinylidene fluoride) gel electrolyte for lithium ion batteries prepared by using salicylic acid as a foaming agent. J Power Sourc 189:594–598
Gopalan AI, Santhosh P, Manesh KM, Nho JH, Kim SH, Hwang CG, Lee KP (2008) Development of electrospun PVdF-PAN membrane-based polymer electrolytes for lithium batteries. J Membr Sci 325:683–693
Kim JK, Cheruvally G, Li X, Ahn JH, Kim KW, Ahn HJ (2008) Preparation and electrochemical characterization of electrospun, microporous membrane-based composite polymer electrolytes for lithium batteries. J Power Sourc 178:815–820
Gnana Kumar G, Nahm KS, Nimma Elizabeth R (2008) Electrochemical properties of porous PVdF-HFP membranes prepared with different nonsolvents. J Membr Sci 325:117–124
Hwang YJ, Jeong SK, Nahm KS, Manuel Stephan A (2007) Electrochemical studies on poly(vinylidene fluoride-hexafluoropropylene) membranes prepared by phase inversion method. Euro Polym J 43:65–71
Djian D, Alloin F, Martinet S, Lignier H (2009) Macroporous poly(vinylidene fluoride) membrane as a separator for lithium-ion batteries with high charge rate capacity. J Power Sourc 187:57–580
Ji GL, Zhu BK, Cui ZY, Zhang CF, Xu YY (2007) PVDF porous matrix with controlled microstructure prepared by TIPS process as polymer electrolyte for lithium ion battery. Polymer 48:6415–6425
Pasquier AD, Disma F, Bowner T, Gozdz AS, Amatucci G, Tarascon JM (1998) Differential scanning calorimetry study of the reactivity of carbon anodes in plastic Li-ion batteries. J Electrochem Soc 145:472–477
Maledi H, Deng G, Anari A, Howard J (1999) Thermal stability studies of Li-ion cells and components. J Electrochem Soc 146:3224–3229
Zhang SS, Jow TR (2002) Study of poly(acrylonitrile-methyl methacrylate) as binder for graphite anode and LiMn2O4 cathode of Li-ion batteries. J Power Sourc 109:422–426
Grabanov AV, Sazanov YN (2008) Polyacrylonitrile: carbonization problems. Russ J Appl Chem 81:919–932
Costache MC, Jiang DD, Wilkie CA (2005) Thermal degradation of ethylene-vinyl acetate coplymer nanocomposites. Polymer 46:6947–6958
Amaral FA, Dalmolin C, Canobre SC, Bocchi N, Rocha-Filho RC, Biaggio SR (2007) Electrochemical and physical properties of poly(acrylonitrile)/poly(vinyl acetate)-based gel electrolytes for lithium ion batteries. J Power Sourc 164:379–385
Whittingham MS (2004) Lithium batteries and cathode materials. Chem Rev 104:4271–4301
Acknowledgment
The authors gratefully acknowledge the supports of National High-Tech Research & Development Program of China (863 program, NO. 2009AA03Z231) and Chengdu Zhongke Laifang Energy and Technology Co. LTD.
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Huai, Y., Gao, J., Deng, Z. et al. Preparation and characterization of a special structural poly(acrylonitrile)-based microporous membrane for lithium-ion batteries. Ionics 16, 603–611 (2010). https://doi.org/10.1007/s11581-010-0431-4
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DOI: https://doi.org/10.1007/s11581-010-0431-4