一种用于长寿命水系锌锰电池的海藻酸钠/二氧化硅准凝胶复合电解质

doi:10.15541/jim20190473

无机材料学报 ›› 2020, Vol. 35 ›› Issue (8): 909-915.DOI: 10.15541/jim20190473 CSTR: 32189.14.10.15541/jim20190473

所属专题：能源材料论文精选(二)：超级电容器与储能电池(2020)

一种用于长寿命水系锌锰电池的海藻酸钠/二氧化硅准凝胶复合电解质

李雪渊^1,²(),王宏刚^1,³,田柱¹,朱建辉²,刘影²,贾兰¹,尤东江²,李向明²,康利涛²()

1.太原理工大学材料科学与工程学院, 太原 030024
2.烟台大学环境与材料工程学院, 烟台 264005
3.潍柴动力股份有限公司, 潍坊 261001

收稿日期:2019-09-16 修回日期:2019-11-21 出版日期:2020-08-20 网络出版日期:2019-12-29
作者简介:李雪渊(1993–), 男, 硕士研究生. E-mail: 343610098@qq.com
LI Xueyuan(1993–), male, Master candidate. E-mail: 343610098@qq.com
基金资助:
国家自然科学基金(51502194);国家自然科学基金(21606191);山东省重大基础研究计划(ZR2018ZC1459);烟台市自然科学基金(2019XDHZ87)

A Quasi-gel SiO₂/Sodium Alginate (SA) Composite Electrolyte for Long-life Zinc-manganese Aqueous Batteries

LI Xueyuan^1,²(),WANG Honggang^1,³,TIAN Zhu¹,ZHU Jianhui²,LIU Ying²,JIA Lan¹,YOU Dongjiang²,LI Xiangming²,KANG Litao²()

1. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2. School of Environmental and Material Engineering, Yantai University, Yantai 264005, China
3. Weichai Power Co., Ltd., Weifang 261001, China

Received:2019-09-16 Revised:2019-11-21 Published:2020-08-20 Online:2019-12-29
Supported by:
National Natural Science Foundation of China(51502194);National Natural Science Foundation of China(21606191);Major Basic Research Plan of Shandong Province(ZR2018ZC1459);Yantai Natural Science Foundation(2019XDHZ87)

摘要/Abstract

摘要：

锌锰(Zn-MnO₂)电池具有高安全性、高环保性、高性价比的优点, 适用于大规模储能电池。然而, 金属锌负极在充放电中会因为“尖端效应”而产生锌枝晶, 造成电池容量衰减甚至短路失效。本研究通过添加亲水性纳米二氧化硅(SiO₂)和海藻酸钠(SA)将电解质转化为准凝胶电解质, 有效抑制了锌负极表面的枝晶生长, 以及由之造成的Zn-MnO₂电池性能衰减。恒流充放电测试结果表明, 采用准凝胶电解质的Zn-MnO₂电池在1800次循环后容量保留率可达78%, 而使用普通电解质的Zn-MnO₂电池在1000次循环后容量已基本衰减为0。进一步探究准凝胶电解质对锌沉积行为的影响, 发现准凝胶电解质的三维网络结构可以提高锌离子分布的均匀性, 降低电池容量衰减速度与失效风险。

关键词: 锌锰电池, 锌枝晶, 准凝胶电解质, 海藻酸钠, 二氧化硅

Abstract:

Zinc-manganese (Zn/MnO₂) batteries with outstanding advantages of high operation safety, high environmental benignity and high cost performance, is suitable for the application of large-scale energy storage battery. However, the uncontrolled growth of zinc dendrites on the metal zinc anode during charge-discharge cycling causes serious problems such as quick capacity decrease and short circuit failure. In this study, the aqueous electrolyte was converted into a composite quasi-gel electrolyte by adding hydrophilic nano-silica (SiO₂) and sodium alginate (SA), which effectively inhibits the dendrite growth of the surface of the zinc negative electrode and the capacity degradation of the Zn-MnO₂ battery. Galvanostatic charge-discharge tests showed that the Zn/MnO₂ battery with composite gel electrolyte achieves a capacity retention of 78% after 1800 cycles, while the capacity of Zn/MnO₂ battery using ordinary electrolyte almost fails after 1000 cycles. The three-dimensional network structure of the gel electrolyte can improve the distribution uniformity of zinc ion in electrolyte, reduce the capacity decay rate and failure risk of the batteries.

Key words: zinc-manganese battery, zinc dendrite, quasi-gel electrolyte, sodium alginate, silica

中图分类号:

TM911

李雪渊,王宏刚,田柱,朱建辉,刘影,贾兰,尤东江,李向明,康利涛. 一种用于长寿命水系锌锰电池的海藻酸钠/二氧化硅准凝胶复合电解质[J]. 无机材料学报, 2020, 35(8): 909-915.

LI Xueyuan,WANG Honggang,TIAN Zhu,ZHU Jianhui,LIU Ying,JIA Lan,YOU Dongjiang,LI Xiangming,KANG Litao. A Quasi-gel SiO₂/Sodium Alginate (SA) Composite Electrolyte for Long-life Zinc-manganese Aqueous Batteries[J]. Journal of Inorganic Materials, 2020, 35(8): 909-915.

图/表 14

图1 不同电解质的光学照片(a~c)和不同添加剂在水中分散并冷冻干燥后的SEM照片(d~f)

Fig. 1 Optical photographs of different electrolytes (a-c) and SEM images of freeze-dried additives from their aqueous dispersions (d-f)

图2 不同电解质的傅里叶变换红外光谱图(a)和热重曲线(b)

Fig. 2 FT-IR spectra (a) and TGA curves (b) of different electrolytes

图3 采用不同电解质的Zn-Zn对称电池的恒电流充放电曲线(a~b)以及在1 mA?cm-2电流密度下循环50圈后锌电极的SEM照片(c~f)

Fig. 3 Galvanostatic charge/discharge curves of Zn-Zn symmetric cells in different electrolytes (a-b), and SEM images of Zn electrodes after 50 cycles at 1 mA?cm-2 (c-f)

图4 采用不同电解质的Zn-MnO2电池的循环伏安曲线(a)和恒电流充放电曲线(b)

Fig. 4 CV (a) and galvanostatic charge/discharge curves (b) of Zn-MnO2 batteries with different electrolytes

图5 使用不同电解质的Zn-MnO2电池在0.5(a)和1 A?g-1(b)电流密度下循环稳定性曲线; 在1 A?g-1循环100次后锌负极的横截面SEM照片(c~f)

Fig. 5 Cycling performance of Zn-MnO2 batteries using different electrolytes at 0.5 (a) and 1 A?g-1 (b); Cross sectional SEM images of zinc electrodes after 100 cycles at 1 A?g-1 (c-f)

图6 采用不同电解质的Zn-MnO2电池的倍率性能

Fig. 6 Rate performance of Zn-MnO2 batteries with different electrolytes

图7 采用不同电解质的Zn-MnO2电池的电化学阻抗图谱(a)以及100次循环后锌负极的XRD图谱(b)

Fig. 7 EIS plots of Zn-MnO2 battery with different electrolytes (a) and XRD patterns of Zn anode after 100 cycles (b)

图8 SA/SiO2准凝胶电解质抑制锌枝晶生长机理示意图

Fig. 8 Schematic illustration showing the Zn dendrite depressing mechanism of the SA/SiO2 quasi-gel electrolyte

图S1 压制在两片泡沫镍中间的海藻酸钠粉末在循环伏安测试前后的光学照片

Fig. S1 Optical image of sodium alginate powder pressed between two pieces of nickel foams before and after cyclic voltammetry test

图S2 SiO2和SA电极的循环伏安曲线

Fig. S2 Cyclic voltammetry curves of SiO2 and SA electrodes

图S3 使用不同电解质的Zn-MnO2电池100次充放电循环后的锌负极SEM照片

Fig. S3 SEM images of zinc electrodes for Zn-MnO2 batteries after 100 charge/discharge cycles in different electrolytes

图S4 采用滤纸隔膜和玻璃纤维隔膜的Zn-MnO2电池容量变化曲线

Fig. S4 Capacity evolution of Zn-MnO2 batteries with a filter paper or glass fiber separator

图S5 采用不同电解质的Zn-MnO2电池的恒流充放电曲线

Fig. S5 Charge and discharge curves of Zn-MnO2 batteries with different electrolytes

图S6 在不同电解质中锌沉积过电位测试

Fig. S6 Overpotential measurement of electrodeposited zinc in different electrolytes

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一种用于长寿命水系锌锰电池的海藻酸钠/二氧化硅准凝胶复合电解质

A Quasi-gel SiO₂/Sodium Alginate (SA) Composite Electrolyte for Long-life Zinc-manganese Aqueous Batteries

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一种用于长寿命水系锌锰电池的海藻酸钠/二氧化硅准凝胶复合电解质

A Quasi-gel SiO2/Sodium Alginate (SA) Composite Electrolyte for Long-life Zinc-manganese Aqueous Batteries

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A Quasi-gel SiO₂/Sodium Alginate (SA) Composite Electrolyte for Long-life Zinc-manganese Aqueous Batteries