PEO类聚合物基体的改性及其高性能电解质材料研究的新进展
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摘要
聚氧化乙烯(PEO)是聚合物电解质传统的基体材料,它最大的优势在于在不添加任何增塑剂的情况下,可以与锂盐形成稳定的络合物,但PEO易于结晶,使离子电导率降低。研究表明:采用共混、接枝、共聚、交联以及与无机物复合等方法对PEO进行改性,可以进一步提高此类聚合物电解质的性能。重点对PEO类聚合物基体的改性及其高性能固体聚合物电解质材料研究的新进展进行介绍,并对其研究前景做了展望。
Polyethylene oxide(PEO)is a traditional matrix material of polymer electrolyte.Its greatest advantage lies in forming a stable lithium salt complex without any plasticizing agent.But the easy crystallization characteristic of PEO leads to decline of ionic conductivity.Previous studies confirmed the effectiveness of modifying PEO matrix to improve the properties of the polymer electrolytes,by using blending,grafting,copolymerization,crosslinking,and forming composite with inorganic compounds.In this paper,we provide a general description about the latest progress on modification of PEO polymer matrix and its high-performance solid polymer electrolyte materials,and give brief prospects on the future research.
Polyethylene oxide(PEO)is a traditional matrix material of polymer electrolyte.Its greatest advantage lies in forming a stable lithium salt complex without any plasticizing agent.But the easy crystallization characteristic of PEO leads to decline of ionic conductivity.Previous studies confirmed the effectiveness of modifying PEO matrix to improve the properties of the polymer electrolytes,by using blending,grafting,copolymerization,crosslinking,and forming composite with inorganic compounds.In this paper,we provide a general description about the latest progress on modification of PEO polymer matrix and its high-performance solid polymer electrolyte materials,and give brief prospects on the future research.
引文
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2 Armand M B,Chabagno J M,Duclot M J,et al.Fast ion transport in solids[M].New York:Elsevier,1979
3 Gorecki W,Jeannin M,Belorizky E,et al.Physical properties of solid polymer electrolyte PEO(LiTFSI)complexes[J].J Phys:Condens Matter,1995,34(7):6823
4 Meyer W H.Polymer electrolytes for lithium-ion batteries[J].Adv Mater,1998,10(6):439
5 Scrosati B,Croce F,Panero S.Progress in lithium polymer battery R&D[J].J Power Sources,2001,100(1-2):93
6 Zheng T,Zhou Q,Li Q,et al.A new branched copolyether-based polymer electrolyte for lithium batteries[J].Solid State Ionics,2014,259:9
7 Chen Wei,Zhang Yihe.Application and research progress of PEObased solid polymer electrolyte for lithium battery[J].Eng Plastics Appl,2010,38(6):89(in Chinese)陈伟,张以河.锂电池用PEO基固态聚合物电解质研究进展及应用[J].工程塑料应用,2010,38(6):89
8 Prasanth R,Aravindan V,Srinivasan M.Novel polymer electrolyte based on cob-web electrospum multi component polymer blend of polyacrylonitrile/poly(methyl methacrylate)/polystyrene for lithium ion batteries—Preparation and electrochemical characterization[J].J Power Sources,2012,202:299
9 Wieczorek W,Such K,Florjanczyk Z,et al.Application of acrylic polymers in blend-based polymeric electrolytes[J].Electrochimica Acta,1992,37(9):1565
10 Barteau K P,Wolffs M,Lynd N A,et al.Allyl glycidyl ether-based polymer electrolytes for room temperature lithium batteries[J].Macromolecules,2013,46(22):8988
11 Rochow E G.Silicon and silicones[M].Berlin:Springer-Verlag,1987:99
12 Li Y J,Wu F,Chao H R,et al.A new composite polymer electrolyte based on poly(ethyleneoxide)/polysiloxane/BMImTFSI/organomontmorillonite[J].Chinese Chem Lett,2013,24(1):70
13 Reddeppa N,Sharma A K,Rao V V R N,et al.Preparation and characterization of pure and KBr doped polymer blend(PVC/PEO)electrolyte thin films[J].Microelectronic Eng,2013,112:57
14 Lee Sung-IJ,Schoner M,Peng H,et al.Correlations between ion conductivity and polymer dynamics in hyperbranched poly(ethylene oxide)electrolytes for lithium-ion batteries[J].Chem Mater,2011,23(11):2685
15 Pan Chunyue.Preparation of PPALi and PEO based solid polymer electrolytes using composite-in-situ method[D].Changsha:Central South University,2006(in Chinese)潘春跃.原位复合法制备PAALi基与PEO基固态聚合物电解质[D].长沙:中南大学,2006
16 Luo Weixin,Liu Yuping,Yang Shuyan,et al.Synthesis and conduction mechanism of comb-like polymethacrylate solid polymer electrolytes[J].Acta Polym Sin,2014(1):63(in Chinese)骆伟新,刘煜平,杨树颜,等.新型梳状聚甲基丙烯酸酯固态聚合物电解质的制备及导电性能研究[J].高分子学报,2014(1):63
17 Aihara Y,Kuratomi J,Bando T,et al.Investigation on solvent-free solid polymer electrolytes for advanced lithium batteries and their performance[J].J Power Sources,2003,114:96
18 Aihara Y,Hayaizu K,Sugimoto K,et al.Ion diffusion mechanisms in the cross-linked poly(ether)doped with LiN(CF3SO2)2[J].J Power Sources,2001,97-98:628
19 Kuratomi J,Igughi T,Bando T,et al.Development of solid polymer lithium secondary batteries[J].J Power Sources,2001,97-98:801
20 Tang Zhiyuan,Wang Zhanliang.Poly(ethylene oxide)polymer electrolyte[J].Polym Mater Sci Eng,2003(2):48(in Chinese)唐致远,王占良.PEO基聚合物电解质[J].高分子材料科学与工程,2003(2):48
21 Ji J,Keen J,Zhong W H.Simultaneous improvement in ionic conductivity and mechanical properties of multi-functional block-copolymer modified solid polymer electrolytes for lithium ion batteries[J].J Power Sources,2011,196(23):10163
22 Chiu C Y,Hsu W H,Yen Y J,et al.Miscibility behavior and interaction mechanism of polymer electrolytes comprising LiClO4 and MPEG-block-PCL copolymers[J].Macromolecules,2005,38(15):6640
23 Shu Yuanhong,Jiang Tao.Progress in grafting modification of PVDF[J].Chinese J Colloid Polym,2011,29:184
24 Li Ming.Study on preparation and properties of nitrile rubber based gel polymer electrolytes plasticized with ionic liquids[D].Shanghai:Shanghai Jiao Tong University,2011(in Chinese)李明.离子液体改性丁腈橡胶制备凝胶聚合物电解质的研究[D].上海:上海交通大学,2011
25 Kang Y,Lee J,et al.Ionic conductivity and electrochemical properties of cross-linked solid polymer electrolyte using star-shaped siloxane acrylate[J].J Power Sources,2007,165(1):92
26 Armand M B,Chabagno J M,Duclot M J.Fast ion transport in solids[M].USA,New York:North-Holland,1979:131
27 Choi N S,Park J K.A comparative study of coordination between host polymers and Li+ions in UV-cured gel polymer electrolytes[J].Solid State Ionics,2009,180(20-22):1204
28 Han Pengfei.Study of metal-organic frameworks and cross-linked electrolyte for all-solid-state lithium ion batteries[D].Changsha:Central South University,2014(in Chinese)韩鹏飞.全固态锂离子电池用金属有机框架及交联型电解质的研究[D].长沙:中南大学,2014
29 Weston J E,Steele B C.Effects of inert fillers on the mechanical and electrochemical properties of lithium salt PEO polymer electrolytes[J].Solid State Ionics,1982,7:75
30 Sun H Y,Sohn H J,Yamamoto O,et al.Enhanced iithium-ion transport in PEO-based composite polymer electrolytes with ferroelectric BaTiO3[J].J Electrochem Soc,1999,146(5):1672
31 Sun H Y,Takeda Y,Imanishi N,et al.Ferroelectric materials as a ceramic filler in solid composite polyethylene oxide-based electrolytes[J].J Electrochem Soc,2000,147(7):2462
32 Angulakshmi N,Nahm K S,Nair J R,et al.Cycling profile of MgAl2O4-incorporated composite electrolytes composed of PEO and LiPF6for lithium polymer batteries[J].Electrochimica Acta,2013,90:179
33 Angulakhsmi N,Thomas S,Nair J R,et al.Cycling profile of innovative nanochitin-incorporated poly(ethylene oxide)based electrolytes for lithium batteries[J].J Power Sources,2013,228:294
34 Xi Jingyu,Qiu Xinping,Zhu Wentao,et al.PEO-LiClO4-ZSM5composite polymer electrolyte I.Electrochemical study[J].Science in China Ser B Chemistry,2005,35(6):478(in Chinese)席靖宇,邱新平,朱文涛,等.PEO-LiClO4-ZSM5复合聚合物电解质[J].中国科学B辑化学,2005,35(6):478
35 Samad Y A,Asghar A,Hashaikeh R.Electrospun cellulose/PEO fiber mats as a solid polymer electrolytes for Li ion batteries[J].Renewable Energy,2013,56:90
36 Chakrabarti A,Juilfs A,Filler R,et al.Novel PEO-based dendronized polymers for lithium ion batteries[J].Solid State Ionics,2010,181(21):982
37 Deng F,Wang X,He D,et al.Microporous polymer electrolyte based on PVDF/PEO star polymer blends for lithium ion batteries[J].J Membr Sci,2015,491:82
2 Armand M B,Chabagno J M,Duclot M J,et al.Fast ion transport in solids[M].New York:Elsevier,1979
3 Gorecki W,Jeannin M,Belorizky E,et al.Physical properties of solid polymer electrolyte PEO(LiTFSI)complexes[J].J Phys:Condens Matter,1995,34(7):6823
4 Meyer W H.Polymer electrolytes for lithium-ion batteries[J].Adv Mater,1998,10(6):439
5 Scrosati B,Croce F,Panero S.Progress in lithium polymer battery R&D[J].J Power Sources,2001,100(1-2):93
6 Zheng T,Zhou Q,Li Q,et al.A new branched copolyether-based polymer electrolyte for lithium batteries[J].Solid State Ionics,2014,259:9
7 Chen Wei,Zhang Yihe.Application and research progress of PEObased solid polymer electrolyte for lithium battery[J].Eng Plastics Appl,2010,38(6):89(in Chinese)陈伟,张以河.锂电池用PEO基固态聚合物电解质研究进展及应用[J].工程塑料应用,2010,38(6):89
8 Prasanth R,Aravindan V,Srinivasan M.Novel polymer electrolyte based on cob-web electrospum multi component polymer blend of polyacrylonitrile/poly(methyl methacrylate)/polystyrene for lithium ion batteries—Preparation and electrochemical characterization[J].J Power Sources,2012,202:299
9 Wieczorek W,Such K,Florjanczyk Z,et al.Application of acrylic polymers in blend-based polymeric electrolytes[J].Electrochimica Acta,1992,37(9):1565
10 Barteau K P,Wolffs M,Lynd N A,et al.Allyl glycidyl ether-based polymer electrolytes for room temperature lithium batteries[J].Macromolecules,2013,46(22):8988
11 Rochow E G.Silicon and silicones[M].Berlin:Springer-Verlag,1987:99
12 Li Y J,Wu F,Chao H R,et al.A new composite polymer electrolyte based on poly(ethyleneoxide)/polysiloxane/BMImTFSI/organomontmorillonite[J].Chinese Chem Lett,2013,24(1):70
13 Reddeppa N,Sharma A K,Rao V V R N,et al.Preparation and characterization of pure and KBr doped polymer blend(PVC/PEO)electrolyte thin films[J].Microelectronic Eng,2013,112:57
14 Lee Sung-IJ,Schoner M,Peng H,et al.Correlations between ion conductivity and polymer dynamics in hyperbranched poly(ethylene oxide)electrolytes for lithium-ion batteries[J].Chem Mater,2011,23(11):2685
15 Pan Chunyue.Preparation of PPALi and PEO based solid polymer electrolytes using composite-in-situ method[D].Changsha:Central South University,2006(in Chinese)潘春跃.原位复合法制备PAALi基与PEO基固态聚合物电解质[D].长沙:中南大学,2006
16 Luo Weixin,Liu Yuping,Yang Shuyan,et al.Synthesis and conduction mechanism of comb-like polymethacrylate solid polymer electrolytes[J].Acta Polym Sin,2014(1):63(in Chinese)骆伟新,刘煜平,杨树颜,等.新型梳状聚甲基丙烯酸酯固态聚合物电解质的制备及导电性能研究[J].高分子学报,2014(1):63
17 Aihara Y,Kuratomi J,Bando T,et al.Investigation on solvent-free solid polymer electrolytes for advanced lithium batteries and their performance[J].J Power Sources,2003,114:96
18 Aihara Y,Hayaizu K,Sugimoto K,et al.Ion diffusion mechanisms in the cross-linked poly(ether)doped with LiN(CF3SO2)2[J].J Power Sources,2001,97-98:628
19 Kuratomi J,Igughi T,Bando T,et al.Development of solid polymer lithium secondary batteries[J].J Power Sources,2001,97-98:801
20 Tang Zhiyuan,Wang Zhanliang.Poly(ethylene oxide)polymer electrolyte[J].Polym Mater Sci Eng,2003(2):48(in Chinese)唐致远,王占良.PEO基聚合物电解质[J].高分子材料科学与工程,2003(2):48
21 Ji J,Keen J,Zhong W H.Simultaneous improvement in ionic conductivity and mechanical properties of multi-functional block-copolymer modified solid polymer electrolytes for lithium ion batteries[J].J Power Sources,2011,196(23):10163
22 Chiu C Y,Hsu W H,Yen Y J,et al.Miscibility behavior and interaction mechanism of polymer electrolytes comprising LiClO4 and MPEG-block-PCL copolymers[J].Macromolecules,2005,38(15):6640
23 Shu Yuanhong,Jiang Tao.Progress in grafting modification of PVDF[J].Chinese J Colloid Polym,2011,29:184
24 Li Ming.Study on preparation and properties of nitrile rubber based gel polymer electrolytes plasticized with ionic liquids[D].Shanghai:Shanghai Jiao Tong University,2011(in Chinese)李明.离子液体改性丁腈橡胶制备凝胶聚合物电解质的研究[D].上海:上海交通大学,2011
25 Kang Y,Lee J,et al.Ionic conductivity and electrochemical properties of cross-linked solid polymer electrolyte using star-shaped siloxane acrylate[J].J Power Sources,2007,165(1):92
26 Armand M B,Chabagno J M,Duclot M J.Fast ion transport in solids[M].USA,New York:North-Holland,1979:131
27 Choi N S,Park J K.A comparative study of coordination between host polymers and Li+ions in UV-cured gel polymer electrolytes[J].Solid State Ionics,2009,180(20-22):1204
28 Han Pengfei.Study of metal-organic frameworks and cross-linked electrolyte for all-solid-state lithium ion batteries[D].Changsha:Central South University,2014(in Chinese)韩鹏飞.全固态锂离子电池用金属有机框架及交联型电解质的研究[D].长沙:中南大学,2014
29 Weston J E,Steele B C.Effects of inert fillers on the mechanical and electrochemical properties of lithium salt PEO polymer electrolytes[J].Solid State Ionics,1982,7:75
30 Sun H Y,Sohn H J,Yamamoto O,et al.Enhanced iithium-ion transport in PEO-based composite polymer electrolytes with ferroelectric BaTiO3[J].J Electrochem Soc,1999,146(5):1672
31 Sun H Y,Takeda Y,Imanishi N,et al.Ferroelectric materials as a ceramic filler in solid composite polyethylene oxide-based electrolytes[J].J Electrochem Soc,2000,147(7):2462
32 Angulakshmi N,Nahm K S,Nair J R,et al.Cycling profile of MgAl2O4-incorporated composite electrolytes composed of PEO and LiPF6for lithium polymer batteries[J].Electrochimica Acta,2013,90:179
33 Angulakhsmi N,Thomas S,Nair J R,et al.Cycling profile of innovative nanochitin-incorporated poly(ethylene oxide)based electrolytes for lithium batteries[J].J Power Sources,2013,228:294
34 Xi Jingyu,Qiu Xinping,Zhu Wentao,et al.PEO-LiClO4-ZSM5composite polymer electrolyte I.Electrochemical study[J].Science in China Ser B Chemistry,2005,35(6):478(in Chinese)席靖宇,邱新平,朱文涛,等.PEO-LiClO4-ZSM5复合聚合物电解质[J].中国科学B辑化学,2005,35(6):478
35 Samad Y A,Asghar A,Hashaikeh R.Electrospun cellulose/PEO fiber mats as a solid polymer electrolytes for Li ion batteries[J].Renewable Energy,2013,56:90
36 Chakrabarti A,Juilfs A,Filler R,et al.Novel PEO-based dendronized polymers for lithium ion batteries[J].Solid State Ionics,2010,181(21):982
37 Deng F,Wang X,He D,et al.Microporous polymer electrolyte based on PVDF/PEO star polymer blends for lithium ion batteries[J].J Membr Sci,2015,491:82