使用复合树脂隔膜提高锌镍电池的循环性
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摘要
采用环氧树脂、聚酰胺树脂和酚醛树脂粘接聚甲基丙烯酸甲酯粉制备了3种复合树脂隔膜,对其进行吸液性能和离子导电性能测试,并以烧结镍电极为正极、涂覆氧化锌电极为负极组装成锌镍电池进行循环充放电测试。结果表明:3种复合树脂隔膜中添加NaHCO3制备的隔膜综合性能较好,电池循环100次后放电容量基本保持稳定,库仑效率稳定在90%左右,没有发生枝晶短路导致的电池性能衰退。而对比的聚丙烯隔膜电池在20次循环左右即出现了枝晶短路现象,由此表明复合树脂隔膜可有效阻挡枝晶短路、提高锌镍电池的循环性能。
Three kinds of composite resin separators were prepared from epoxy resin, polyamide resin,phenolic resin, and polymethyl methacrylate powder, and their solution absorption performance and ionic conductivity were tested. Zn-Ni batteries were assembled using the three separators with sintered nickel electrode as positive electrode and zinc oxide pasted electrode as negative electrode, and then were conducted cycle charge-discharge tests. The results show that the separator with NaHCO3 has better comprehensive properties. The discharge capacity of the batteries using the three separators basically keep stable after 100 charge-discharge cycles, the coulombic efficiency is around 90%, and the batteries have not occur performance degradation caused by dendrite short circuit. While the battery with polypropylene separator has dendrite short circuit phenomenon caused by zinc dendrite after 20 cycles. It is indicated that these composite resin separators can suppress the short circuit caused by zinc dendrite and improve the cycle performance of Zn-Ni battery.
Three kinds of composite resin separators were prepared from epoxy resin, polyamide resin,phenolic resin, and polymethyl methacrylate powder, and their solution absorption performance and ionic conductivity were tested. Zn-Ni batteries were assembled using the three separators with sintered nickel electrode as positive electrode and zinc oxide pasted electrode as negative electrode, and then were conducted cycle charge-discharge tests. The results show that the separator with NaHCO3 has better comprehensive properties. The discharge capacity of the batteries using the three separators basically keep stable after 100 charge-discharge cycles, the coulombic efficiency is around 90%, and the batteries have not occur performance degradation caused by dendrite short circuit. While the battery with polypropylene separator has dendrite short circuit phenomenon caused by zinc dendrite after 20 cycles. It is indicated that these composite resin separators can suppress the short circuit caused by zinc dendrite and improve the cycle performance of Zn-Ni battery.
引文
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[2] ZHAO Q, HUANG W W, LUO Z Q, et al. High-capacity aqueous zinc batteries using sustainable quinone electrodes[J]. Science Advances,2018,4(3):eaao1761.
[3] GUO X, FANG G Z, ZHANG W Y, et al. Mechanistic insights of Zn2+storage in sodium vanadates[J]. Advanced Energy Materials,2018,https://doi.org/10.1002/aenm.201801819.
[4]曾利辉,杨占红,桑商斌,等.无机缓蚀剂对锌负极性能的影响[J].电池,2007,37(4):289-291.
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[6]高翠琴,罗列超,石建珍,等.有机物添加剂对碱性锌电极的影响[J].武汉大学学报(自然科学版),1999,45(4):427-431.
[7] LIU K L, HE P, BAI H, et al. Effects of dodecyltrimethylammonium bromide surfactant on both corrosion and passivation behaviors of zinc electrodes in alkaline solution[J].Materials Chemistry and Physics,2017,199:73-78.
[8] LAN C J, LEE C Y, CHIN T S. Tetra-alkyl ammonium hydroxides as inhibitors of Zn dendrite in Zn-based secondary batteries[J]. Electrochimica Acta,2007,52(17):5407-5416.
[9] SHIVKUMAR R, PARUTHIMAL G P, VASUDEVAN T, et al. Effect of additives on zinc electrodes in alkaline battery systems[J]. Journal of Power Sources,1995,55(1):53-62.
[10] ZHANG L, CHENG J, YANG Y S, et al. Preliminary study of single flow zinc-nickel battery[J]. Electrochemistry Communications,2007,9:2639-2642.
[11] ZHANG L, CHENG J, YANG Y S, et al. Study of zinc electrodes for single flow zinc/nickel battery application[J].Journal of Power Sources,2008,179(1):381-387.
[12]肖伟,赵丽娜,刘建国,等.一种新型无机涂层锂离子电池隔膜及其制备方法:ZL201310017708.3[P]. 2015-04-08.
[13] RYOU M, LEE D J, LEE J, et al. Lithium-ion batteries:Excellent cycle life of lithium-metal anodes in lithium-ion batteries with mussel-inspired polydopamine-coated separators[J]. Advanced Energy Materials,2012,2(6):645-650.
[14] EUN-HYE K, KEUN-HO C, HYO-JEONG H, et al. Imprintable, bendable, and shape-conformable polymer electrolytes for versatile-shaped lithium-ion batteries[J]. Advanced Materials,2013,25:1395-1400.
[15]翟海潮.实用胶粘剂配方手册[M].北京:化学工业出版社,2007.
[16]刘元刚,唐志远,徐强,等.隔膜对镍氢电池大电流放电性能的影响及特性[J].过程工程学报,2006,6(1):114-119.
[17]王洪,杨驰,谢文峰,等.锂离子电池用陶瓷聚烯烃复合隔膜[J].应用化学,2014,31(7):757-762.
[18]姜红娟,张燕青,吴大勇,等.高性能锂离子电池隔膜的结构设计及其制备与表征[J].高分子学报,2015(11):1271-1279.
[19]郭炳焜,李新海,杨松青.化学电源:电池原理及制造技术[M].长沙:中南大学出版社,2009.
[20]冯辉.二次锌电极及抑制枝晶添加剂的研究[J].郑州大学学报(工学版),2001,22(1):78-80.
[21]王建明,钱亚东.可充锌电极存在的问题及解决途径[J].电池,1999(2):76-80.
[22] YASUMASA I, MICHAEL N, ROBERT P, et al. Gas evolution in a flow-assisted zinc-nickel oxide battery[J]. Journal of Power Sources,2011,196:6583-6587.
[23]倪霞,杨占红,王升威,等.添加剂PAAS对锌镍电池负极性能的影响[J].电池,2010,40(5):262-265.
[24]曾冬青,杨占红,王升威,等.电解液用量及负极添加剂对锌镍电池的影响[J].电池,2010,40(6):306-309.
[2] ZHAO Q, HUANG W W, LUO Z Q, et al. High-capacity aqueous zinc batteries using sustainable quinone electrodes[J]. Science Advances,2018,4(3):eaao1761.
[3] GUO X, FANG G Z, ZHANG W Y, et al. Mechanistic insights of Zn2+storage in sodium vanadates[J]. Advanced Energy Materials,2018,https://doi.org/10.1002/aenm.201801819.
[4]曾利辉,杨占红,桑商斌,等.无机缓蚀剂对锌负极性能的影响[J].电池,2007,37(4):289-291.
[5]张春,王建明,张昭,等.钙添加剂对可充锌电极性能的影响[J].中国有色金属学报,2001,11(5):780-784.
[6]高翠琴,罗列超,石建珍,等.有机物添加剂对碱性锌电极的影响[J].武汉大学学报(自然科学版),1999,45(4):427-431.
[7] LIU K L, HE P, BAI H, et al. Effects of dodecyltrimethylammonium bromide surfactant on both corrosion and passivation behaviors of zinc electrodes in alkaline solution[J].Materials Chemistry and Physics,2017,199:73-78.
[8] LAN C J, LEE C Y, CHIN T S. Tetra-alkyl ammonium hydroxides as inhibitors of Zn dendrite in Zn-based secondary batteries[J]. Electrochimica Acta,2007,52(17):5407-5416.
[9] SHIVKUMAR R, PARUTHIMAL G P, VASUDEVAN T, et al. Effect of additives on zinc electrodes in alkaline battery systems[J]. Journal of Power Sources,1995,55(1):53-62.
[10] ZHANG L, CHENG J, YANG Y S, et al. Preliminary study of single flow zinc-nickel battery[J]. Electrochemistry Communications,2007,9:2639-2642.
[11] ZHANG L, CHENG J, YANG Y S, et al. Study of zinc electrodes for single flow zinc/nickel battery application[J].Journal of Power Sources,2008,179(1):381-387.
[12]肖伟,赵丽娜,刘建国,等.一种新型无机涂层锂离子电池隔膜及其制备方法:ZL201310017708.3[P]. 2015-04-08.
[13] RYOU M, LEE D J, LEE J, et al. Lithium-ion batteries:Excellent cycle life of lithium-metal anodes in lithium-ion batteries with mussel-inspired polydopamine-coated separators[J]. Advanced Energy Materials,2012,2(6):645-650.
[14] EUN-HYE K, KEUN-HO C, HYO-JEONG H, et al. Imprintable, bendable, and shape-conformable polymer electrolytes for versatile-shaped lithium-ion batteries[J]. Advanced Materials,2013,25:1395-1400.
[15]翟海潮.实用胶粘剂配方手册[M].北京:化学工业出版社,2007.
[16]刘元刚,唐志远,徐强,等.隔膜对镍氢电池大电流放电性能的影响及特性[J].过程工程学报,2006,6(1):114-119.
[17]王洪,杨驰,谢文峰,等.锂离子电池用陶瓷聚烯烃复合隔膜[J].应用化学,2014,31(7):757-762.
[18]姜红娟,张燕青,吴大勇,等.高性能锂离子电池隔膜的结构设计及其制备与表征[J].高分子学报,2015(11):1271-1279.
[19]郭炳焜,李新海,杨松青.化学电源:电池原理及制造技术[M].长沙:中南大学出版社,2009.
[20]冯辉.二次锌电极及抑制枝晶添加剂的研究[J].郑州大学学报(工学版),2001,22(1):78-80.
[21]王建明,钱亚东.可充锌电极存在的问题及解决途径[J].电池,1999(2):76-80.
[22] YASUMASA I, MICHAEL N, ROBERT P, et al. Gas evolution in a flow-assisted zinc-nickel oxide battery[J]. Journal of Power Sources,2011,196:6583-6587.
[23]倪霞,杨占红,王升威,等.添加剂PAAS对锌镍电池负极性能的影响[J].电池,2010,40(5):262-265.
[24]曾冬青,杨占红,王升威,等.电解液用量及负极添加剂对锌镍电池的影响[J].电池,2010,40(6):306-309.