基于聚乙二醇链段杂化固体电解质的初步研究
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摘要
本文设计合成了两种不同的聚合物固体电解质：聚乙二醇／SiO_2固体电解质和聚乙二醇单甲醚／SiO_2固体电解质。用红外光谱、扫描电镜、透射电镜、X射线衍射、热重—差热等测试方法对固体电解质膜进行表征。用DDS—11A型离子电导率仪对固体电解质膜进行离子电导率测量。
对聚乙二醇／SiO_2电解质膜，正硅酸乙酯水解产生的无机SiO_2粒子通过化学键的作用与聚合物基体结合形成了交联结构，使得聚合物电解质具有比较好的热稳定性。随温度升高，固体电解质的离子电导率出现最大值。离子电导率与PEG与HDI的比值有关，当两者比值为1：2时，离子电导率最高。离子电导率随着固体电解质中聚乙二醇链段长度增加而出现最大值，此时链段长度为800。
前驱体和正硅酸乙酯(TEOS)在酸性条件下水解得到聚乙二醇单甲醚／SiO_2电解质溶液的SiO_2，粒径范围比较大，并形成了外层为聚合物，内层为SiO_2的具有核壳结构的粒子，正硅酸乙酯加入量越多，则其粒子容易发生团聚。正硅酸乙酯在酸性条件下水解形成无机SiO_2粒子后，得到的固体电解质膜呈非晶态，无机SiO_2破坏了聚合物的结晶。离子电导率随着温度升高而增加，因为温度升高有利于离子迁移。离子电导率随固体电解质中聚乙二醇单甲醚分子链段增加而增加。随着TEOS加入量增多，离子导电率增加，但是过量的TEOS会导致离子电导率下降。在不加入TEOS情况下，锂离子也可能通过Si-O-Si键中的氧来传递，离子电导率较大。随着高氯酸锂用量的增加，离子电导率出现最大值，此时高氯酸锂与聚乙二醇单甲醚中EO单元摩尔比为1：5。
In this dissertation,two kinds of Poly(ethylene glycol)/SiO2 solid electrolyte and methoxy Poly(ethylene glycol)/Si02 solid electrolyte were designed and sythesized. The structure of hybrid solid electrolytes were characterized by FT-IR, SEM, TEM. XRD, TG-DSC etc.. The ionic conductivity(σ ) of the solid electrolyte membrane was measured with Model DDS-11A conductor.
For Poly(ethylene glycol)/SiO2 solid electrolyte membrane , Polymer solid electrolyte membrane had good heat resistance because inorganic SiO2 particles had a chemical bond with the polymer, σ showed a maximum conductivity with increasing of temperature, σ reached the highest at PEG/HDI of 1:2. The hybrid solid electrolyte showed a maximum value when the segments of Poly(ethylene glycol) were 800.
The diameter distribution of core-shell SiO2 particles in the acid environment synthesized by sol-gel reaction were not uniformly. If the amount of TEOS used was abundant, SiO2 particles aggregated. SiO2 particles destroyed the crystallization of polymer,and the membrane was amorphous, σ increased as temperature rised, because the Li+ could move easily, σ rised with the rising of segments of methoxy Poly(ethylene glycol) . σ rised when the amount of TEOS increased, but too much TEOS added result in a lower conductivity. Without TEOS, σ was relatively higher for Li+ might transmit through oxygen in Si-O-Si bond. Conductivity rised with the increasing of [Li+]/[EO] till the proportion of [Li+]/[EO] was 1:5.
对聚乙二醇／SiO_2电解质膜，正硅酸乙酯水解产生的无机SiO_2粒子通过化学键的作用与聚合物基体结合形成了交联结构，使得聚合物电解质具有比较好的热稳定性。随温度升高，固体电解质的离子电导率出现最大值。离子电导率与PEG与HDI的比值有关，当两者比值为1：2时，离子电导率最高。离子电导率随着固体电解质中聚乙二醇链段长度增加而出现最大值，此时链段长度为800。
前驱体和正硅酸乙酯(TEOS)在酸性条件下水解得到聚乙二醇单甲醚／SiO_2电解质溶液的SiO_2，粒径范围比较大，并形成了外层为聚合物，内层为SiO_2的具有核壳结构的粒子，正硅酸乙酯加入量越多，则其粒子容易发生团聚。正硅酸乙酯在酸性条件下水解形成无机SiO_2粒子后，得到的固体电解质膜呈非晶态，无机SiO_2破坏了聚合物的结晶。离子电导率随着温度升高而增加，因为温度升高有利于离子迁移。离子电导率随固体电解质中聚乙二醇单甲醚分子链段增加而增加。随着TEOS加入量增多，离子导电率增加，但是过量的TEOS会导致离子电导率下降。在不加入TEOS情况下，锂离子也可能通过Si-O-Si键中的氧来传递，离子电导率较大。随着高氯酸锂用量的增加，离子电导率出现最大值，此时高氯酸锂与聚乙二醇单甲醚中EO单元摩尔比为1：5。
In this dissertation,two kinds of Poly(ethylene glycol)/SiO2 solid electrolyte and methoxy Poly(ethylene glycol)/Si02 solid electrolyte were designed and sythesized. The structure of hybrid solid electrolytes were characterized by FT-IR, SEM, TEM. XRD, TG-DSC etc.. The ionic conductivity(σ ) of the solid electrolyte membrane was measured with Model DDS-11A conductor.
For Poly(ethylene glycol)/SiO2 solid electrolyte membrane , Polymer solid electrolyte membrane had good heat resistance because inorganic SiO2 particles had a chemical bond with the polymer, σ showed a maximum conductivity with increasing of temperature, σ reached the highest at PEG/HDI of 1:2. The hybrid solid electrolyte showed a maximum value when the segments of Poly(ethylene glycol) were 800.
The diameter distribution of core-shell SiO2 particles in the acid environment synthesized by sol-gel reaction were not uniformly. If the amount of TEOS used was abundant, SiO2 particles aggregated. SiO2 particles destroyed the crystallization of polymer,and the membrane was amorphous, σ increased as temperature rised, because the Li+ could move easily, σ rised with the rising of segments of methoxy Poly(ethylene glycol) . σ rised when the amount of TEOS increased, but too much TEOS added result in a lower conductivity. Without TEOS, σ was relatively higher for Li+ might transmit through oxygen in Si-O-Si bond. Conductivity rised with the increasing of [Li+]/[EO] till the proportion of [Li+]/[EO] was 1:5.
引文
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[13] 土田英俊，户捣直树等编，方世壁译．高分子络合物的电子功能．1992：111～129
[14] Hou X P, Siow K S. Polymer electrolytes based on acrylonitrile-butadienestyrene Copolymer. Solid State Electro-chemistry
[15] Appetecchi G B,Groce F.Power Sources. 1997,66:77～82
[16] Song J Y, Wang Y Y.Power Sources,1999,77 1:183～197
[17] Killis A,Lenest J F, Gandini A. Solid State Ionics.1984,14:231～237
[18] 倪建龙，林青云，王佛松．高分子学报．1992，10：585～588
[19] 汪国杰，周震淘，潘慧铭．高分子材料科学与工程．2001，5：78～81
[20] Reiche A,Tubke J,Sabder B.Solid State Ionics. 1996,85:121
[21] Misha R,Baskaran N,Ramakrishan P A.Solid State Ionics. 1998,112:261～273
[22] 余春晴，黄海燕，吴益华．电源技术．2000，3：139-140
[23] 侯欣平，张肇熙，夏笃炜．高分子材料科学与工程．1996，2：119～122
[24] Gozdz A S,Tarascon J M,Waren P C.USP,1995,5:418
[25] Kwawiec W.Power Sources.1995,54:310～315
[26] 于明昕，石桥，周啸．高分子学报．2002，1：38～42
[27] Sun H Y, Sohn H J. Electrochemica soc.1999,146(5):1672～1674
[28] Matsuo,Kuwano.Solid state ionics. 1995,79:295～299
[29] Y.Liu,J Y Lee,L.Hong.In situ preparation of poly(ethylene oxide)-SiO_2 composite polymer electrolytes.Power sources.2004,129:303～311
[30] Peter P. Chu, M. Jaipal Reddy.Sm_2O_3 composite PEO solid polymer electrolyte.Power sourses.2003,115:288～294
[31] Th. Joykumar Singh, S.V. Bhat.Increased lithium-ion conductivity in (PEG)_(46)LiCIO_4 solid polymer electrolyte with -Al_2O_3 nanoparticles. Power sourses. 2004,129:280～287
[32] Qi Li, Takahito Itoha, Nobuyuki Imanishi, Atsushi Hirano,Yasuo Takeda, Osamu Yamamoto.All solid lithium polymer batteries with a novel composite polymer electrolyte. Solid State Ionics.2003,159:97～109
[33] Graham S, Macglashan, Yurig, Andreev & Peter Gbruce. Nature. 1999, 398:792～794
[34] Zlatka Gadjourova, David P.Nature.2002,412:520～523
[35] 周宁琳编．有机硅聚合物导论．科学出版社，2000，5
[36] 章基凯主编．有机硅材料．中国物资出版社，1999，10
[37] 王家芳，章文贡．溶胶-凝胶法合成有机／无机杂化材料进展——1组分间以化学键作用的有机／无机杂化材料．高分子通报．2001，2：60～67
[38] 胡春圃．含某些碱金属盐的互穿聚合物网络的离子导电性．高分子材料科学与工程．1990，3：50～54
[39] 含方鹏飞，李光远，汪溶．NaI的环氧树脂-PEO互穿网络高分子固体电解质的离子电导研究．功能高分子学报．1998，3：71～75
[40] 卢翠红，潘春秋．聚合物电解质离子电导率的影响因素．材料导报．2003，4：58～60
[41] S-L Chen.Preparation of monosize silica spheres and their crystalline stack。Colloids and Surfaces.1998, 142:59～63
[42] 陈小泉，古国榜．W／O微乳体系酸催化水解硅酸乙酯合成单分散酸性超微二氧化硅．现代化工．2002，3：26～30
[43] 许佩新，谢文明，陈治中．聚(丙烯酸-丙烯酰胺)-碱金属盐复合物的离子电导性．高分子材料科学与工程，1999，15，23～25
[2] Wright P V.Polymer.1975,7:319
[3] Armand M B,Chabagno J M ,Duclot. Amsterdam(Elsevier). 1979:131
[4] 吴伯荣，苏兰英．高分子材料科学与工程．1997,6：128～131
[5] Quatarone E,Tomasic. Electrochimica Acta. 1998,43:1435～1439
[6] Stallworth P E,Greenbaum S G.Electrochimica Acta. 1995,40:2137～2140
[7] Guyomard D T, Tarascon J M.Highvoltage stable liquid electrolyte for Lil_(1-x)Mn_2O_4/Carbon rocking-chair lithium batteries.Power Sources. 1995,54:92～98
[8] Guan J G, Yuan R Z,Xie H Q.Study on conductivity of two kinds of cross-linked polyether solid electrolytes and electroheological properties of anhydrous suspensions based on them.Polymer. 1998,5307～5313
[9] Xu W, Zhang X Z,Deng Z H.Solid State Ionics.1998,111(3～4):219
[10] Alan V, Chadwick.Nature.2000,408:925～926
[11] Murata K.Electrochimica,Acta. 1995,40:2177～2184
[12] Baudry P, Lascauds,Majastre H. Power Source. 1997,68:432～435
[13] 土田英俊，户捣直树等编，方世壁译．高分子络合物的电子功能．1992：111～129
[14] Hou X P, Siow K S. Polymer electrolytes based on acrylonitrile-butadienestyrene Copolymer. Solid State Electro-chemistry
[15] Appetecchi G B,Groce F.Power Sources. 1997,66:77～82
[16] Song J Y, Wang Y Y.Power Sources,1999,77 1:183～197
[17] Killis A,Lenest J F, Gandini A. Solid State Ionics.1984,14:231～237
[18] 倪建龙，林青云，王佛松．高分子学报．1992，10：585～588
[19] 汪国杰，周震淘，潘慧铭．高分子材料科学与工程．2001，5：78～81
[20] Reiche A,Tubke J,Sabder B.Solid State Ionics. 1996,85:121
[21] Misha R,Baskaran N,Ramakrishan P A.Solid State Ionics. 1998,112:261～273
[22] 余春晴，黄海燕，吴益华．电源技术．2000，3：139-140
[23] 侯欣平，张肇熙，夏笃炜．高分子材料科学与工程．1996，2：119～122
[24] Gozdz A S,Tarascon J M,Waren P C.USP,1995,5:418
[25] Kwawiec W.Power Sources.1995,54:310～315
[26] 于明昕，石桥，周啸．高分子学报．2002，1：38～42
[27] Sun H Y, Sohn H J. Electrochemica soc.1999,146(5):1672～1674
[28] Matsuo,Kuwano.Solid state ionics. 1995,79:295～299
[29] Y.Liu,J Y Lee,L.Hong.In situ preparation of poly(ethylene oxide)-SiO_2 composite polymer electrolytes.Power sources.2004,129:303～311
[30] Peter P. Chu, M. Jaipal Reddy.Sm_2O_3 composite PEO solid polymer electrolyte.Power sourses.2003,115:288～294
[31] Th. Joykumar Singh, S.V. Bhat.Increased lithium-ion conductivity in (PEG)_(46)LiCIO_4 solid polymer electrolyte with -Al_2O_3 nanoparticles. Power sourses. 2004,129:280～287
[32] Qi Li, Takahito Itoha, Nobuyuki Imanishi, Atsushi Hirano,Yasuo Takeda, Osamu Yamamoto.All solid lithium polymer batteries with a novel composite polymer electrolyte. Solid State Ionics.2003,159:97～109
[33] Graham S, Macglashan, Yurig, Andreev & Peter Gbruce. Nature. 1999, 398:792～794
[34] Zlatka Gadjourova, David P.Nature.2002,412:520～523
[35] 周宁琳编．有机硅聚合物导论．科学出版社，2000，5
[36] 章基凯主编．有机硅材料．中国物资出版社，1999，10
[37] 王家芳，章文贡．溶胶-凝胶法合成有机／无机杂化材料进展——1组分间以化学键作用的有机／无机杂化材料．高分子通报．2001，2：60～67
[38] 胡春圃．含某些碱金属盐的互穿聚合物网络的离子导电性．高分子材料科学与工程．1990，3：50～54
[39] 含方鹏飞，李光远，汪溶．NaI的环氧树脂-PEO互穿网络高分子固体电解质的离子电导研究．功能高分子学报．1998，3：71～75
[40] 卢翠红，潘春秋．聚合物电解质离子电导率的影响因素．材料导报．2003，4：58～60
[41] S-L Chen.Preparation of monosize silica spheres and their crystalline stack。Colloids and Surfaces.1998, 142:59～63
[42] 陈小泉，古国榜．W／O微乳体系酸催化水解硅酸乙酯合成单分散酸性超微二氧化硅．现代化工．2002，3：26～30
[43] 许佩新，谢文明，陈治中．聚(丙烯酸-丙烯酰胺)-碱金属盐复合物的离子电导性．高分子材料科学与工程，1999，15，23～25