聚芳噁二唑磺酸锂聚合物电解质的制备与性能

doi:10.12028/j.issn.2095-4239.2018.0223

储能科学与技术 ›› 2019, Vol. 8 ›› Issue (2): 304-310.doi: 10.12028/j.issn.2095-4239.2018.0223

聚芳噁二唑磺酸锂聚合物电解质的制备与性能

毛建昭, 高慧慧, 薛润萍, 杨晨, 刘鹏清, 徐建军, 陈胜, 姜猛进

四川大学高分子科学与工程学院, 四川成都 610065;四川大学高分子材料工程国家重点实验室, 四川成都 610065

收稿日期:2018-11-13 修回日期:2019-01-04 出版日期:2019-03-01 发布日期:2019-03-01
通讯作者: 姜猛进。E-mail:memoggy@126.com
作者简介:毛建昭(1993-),男,硕士研究生,主要从事聚合物电解质的研究,E-mail:1106756354@qq.com

Preparation and properties of lithium sulfonated polyoxadiazoles electrolyte

MAO Jianzhao, GAO Huihui, XUE Runping, YANG Chen, LIU Pengqing, XU Jianjun, CHEN Sheng, JIANG Mengjin

College of Polymer Science & Engineering, Sichuan University, Chengdu 610065, Sichuan, China;The State Key Laboratory of Polymer Materials and Engineering, Sichuan University, Chengdu 610065, Sichuan, China

Received:2018-11-13 Revised:2019-01-04 Online:2019-03-01 Published:2019-03-01

摘要/Abstract

摘要： 以硫酸肼（HS）、对苯二甲酸（TPA）、4，4'-联苯醚二甲酸（DPE）为单体，发烟硫酸做溶剂和脱水剂一步合成了一系列不同TPA和DPE单体配比的磺化聚芳噁二唑（SPOD），再通过氢氧化锂中和得到聚芳噁二唑磺酸锂（Li-SPOD）聚合物电解质，采用浇铸成膜法制得Li-SPOD电解质膜，研究改变TPA和DPE两种单体配比对Li-SPOD结构及性能的影响。结果表明，几种不同单体配比均能实现在聚合过程中一步得到SPOD，磺酸基团接枝在DPE结构的苯环上，并且可以达到理论接枝量；同时Li-SPOD电解质膜的聚集态结构差异很小；热性能的表现均非常优异，初始热分解温度都在450 ℃以上；力学性能随DPE单体含量的增加稍有下降但依然保持在较高的水平；电导率约为10^-5S/cm级别，随DPE含量增加而逐渐降低；Li-SPOD固态电解质电化学稳定性较好，对锂稳定电化学窗口均在4.0 V以上。

关键词: 聚芳噁二唑磺酸锂, 聚合物电解质, 单离子导体, 磺化聚芳噁二唑

Abstract: A series of sulfonated polyoxadiazoles (SPOD) with different monomer ratios were synthesized by using hydrazine sulfate (HS), terephthalic acid (TPA) and 4,4'-diphenyl ether dicarboxylic acid (DPE) as monomers, fuming sulfuric acid as solvent and dehydrating agent. Then, the SPOD films were obtained by the solution casting method. Finally, the SPOD films were neutralized with lithium hydroxide to form Li-SPOD polymer electrolytes films. The effects of two monomer ratios of TPA and DPE on the structure and properties of Li-SPOD were studied. Results show that SPOD can be obtained with different monomer ratios, and the sulfonic acid group was grafted on the benzene ring of DPE chain segments. The aggregation structure difference among Li-SPOD electrolyte films is small. Their thermal stabilities are excellent, and the initial thermal decomposition temperature are all above 450℃. The mechanical properties of Li-SPOD films decrease slightly with the increase of DPE contents. The conductivities of Li-SPOD electrolyte films are about 10^-5S·cm^-1, and gradually decrease with the increase of DPE content. Their electrochemical stability are good, and the decomposition voltages are all above 4.0 V.

Key words: lithium sulfonated polyoxadiazoles, polymer electrolyte, single ion conductor, sulfonated polyoxadiazoles

中图分类号:

TQ317

毛建昭, 高慧慧, 薛润萍, 杨晨, 刘鹏清, 徐建军, 陈胜, 姜猛进. 聚芳噁二唑磺酸锂聚合物电解质的制备与性能[J]. 储能科学与技术, 2019, 8(2): 304-310.

MAO Jianzhao, GAO Huihui, XUE Runping, YANG Chen, LIU Pengqing, XU Jianjun, CHEN Sheng, JIANG Mengjin. Preparation and properties of lithium sulfonated polyoxadiazoles electrolyte[J]. Energy Storage Science and Technology, 2019, 8(2): 304-310.

参考文献

[1] THACKERAY M M, WOLVERTON C, ISAACS E D. Electrical energy storage for transportation-Approaching the limits of, and going beyond, lithium-ion batteries[J]. Energy & Environmental Science, 2012, 5(7):7854-7863.
[2] 骆蓉, 聂进. 聚磷腈高分子固体电解质研究进展[J]. 功能高分子学报, 2004, 17(1):151-158. LUO Rong, NIE Jin. Recent advances of the solid polymer electolytes based on polyphosphazene[j]. journal of Functional Polymers, 2004, 17(1):151-158.
[3] 董晓臣, 王立. 用于锂离子电池聚合物电解质的组成、结构和性能[J]. 化学进展, 2005, 17(2):70-75. DONG Xiaochen, WANG Li. Compositions, structures and properties of polymer electrolytes for lithium ion battery[J]. Progress in Chemistry, 2005, 17(2):70-75.
[4] 程琥, 李涛, 杨勇. 锂/聚合物电解质电化学固/固界面的研究[J]. 化学进展, 2006, 18(5):26-33. CHEN Hu, LI Tao, YANG Yong. Progress in the study of solid/solid interface between lithium electrode and polymer electrolytes in lithium polymer batteries[j]. Progress in Chemistry, 2006, 18(5):26-33.
[5] 凌志军, 何向明, 李建军, 等. 锂离子聚合物常温固体电解质的研究进展[J]. 化学进展, 2006, 18(4):99-106. LING Zhijun, HE Xiangming, LI Jianjun, et al. Recent advances of all-solid-state polymer electrolyte for Li-Ion batteries[J]. Progress in Chemistry, 2006, 18(4):99-106.
[6] 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):89-92. CHEN Wei, ZHANG Yihe. Application and research progress of PEO-based solid polymer electrolyte for lithium battery[J]. Engineering Plastics Application, 2010, 38(6):89-92.
[7] ARMAND M B, CHABAGNO J M, DUCLOT M J. Poly-ethers as solid electrolytes[C].//Intenational Conference on Fast Ion Transport in Solids, Electrodes and Electrolytes. USA:Lake Geneva, WI. 1979:131-136.
[8] ZHANG J, YANG J, DONG T, et al. Aliphatic polycarbonate-based solid-state polymer electrolytes for advanced lithium batteries:Advances and perspective[J]. Small, 14, 2018:e1800821.
[9] WANG F, HU C, LO S, et al. The investigation of electrochemical properties and ionic motion of functionalized copolymer electrolytes based on polysiloxane[J]. Solid State Ionics, 2009, 180(4/5):405-411.
[10] YOUNG Wenshiue, KUAN Weifan, THOMAS H. Epps Ⅲ. Block copolymer electrolytes for rechargeable lithium batteries[J]. Journal of Polymer Science Part B:Polymer Physics, 2013, 52(1):1-16.
[11] 张恒, 郑丽萍, 聂进,等. 锂单离子导电固态聚合物电解质[J]. 化学进展, 2014, 26(6):1005-1020. ZHANG Heng, ZHEN Liping, NIE Jin, et al. Single lithium-ion conducting solid polymer electrolytes:advances and perspectives[J]. Progress in Chemistry, 2014, 26(6):1005-1020.
[12] GOMES D, ROEDER J, PONCE M L, et al. Characterization of partially sulfonated polyoxadiazoles and oxadiazole-triazole copolymers[J]. Journal of Membrane Science, 2007, 295(1):121-129.
[13] JERUSA R, DOMINIQUE G, MARIELA L, et al. Protonation of sulfonated poly(4,4'phenylether1,3,4-oxadiazole) membranes[J]. macromolecular Chemistry & physics, 2007, 208(5):467-473.
[14] GOMES D, BUDER I, NUNES S P. Sulfonated silica-based electrolyte nanocomposite membranes[J]. Journal of Polymer Science Part B Polymer Physics, 2010, 44(16):2278-2298.
[15] GOMES D, ROEDER J, PONCE M L, et al. Single-step synthesis of sulfonated polyoxadiazoles and their use as proton conducting membranes[J]. Journal of Power Sources, 2008, 175(1):49-59.
[16] HAMCIUC C, HAMCIUC E, BRUMA M, et al. New aromatic polyethers containing phenylquinoxaline and 1,3,4-oxadiazole rings[J]. Polymer, 2001, 42(14):5955-5961.
[17] YAN X, Li Z, Zhou W, et al. Study of the thermal decomposition and flame-retardant mechanism of sulfonated polyoxadiazole fibers[J]. Journal of Thermal Analysis & Calorimetry, 2016, 126(3):1-11.

聚芳噁二唑磺酸锂聚合物电解质的制备与性能

Preparation and properties of lithium sulfonated polyoxadiazoles electrolyte

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