球磨法制备锂离子液流电池石墨负极浆料的性能研究

doi:10.11868/j.issn.1001-4381.2016.000751

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摘要

采用球磨法制备锂离子液流电池所用的石墨负极浆料，并对石墨负极浆料的颗粒形貌、电导率、比容量性能及循环性能进行研究。结果表明：导电添加剂的加入有助于提高电极浆料的悬浮稳定性；球磨过程可以降低石墨和导电添加剂混合粉体的电阻率，球料比达到5：1时即可实现较好的球磨效果，但球料比不宜过高，否则会造成石墨材料层状结构的破坏，影响电极浆料性能的稳定性。提高石墨和导电添加剂的含量可以在电极浆料中形成稳定的导电网络结构，使可逆比容量提高；在保证电极浆料可流动的情况下，可逆比容量可大于40mAh/g。石墨负极浆料的容量损失主要发生在首次充放电过程中，随着循环次数的增加，容量损耗的速率降低，第5次循环以后容量趋于稳定。

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关键词 ：锂离子液流电池, 石墨, 负极浆料, 球磨

Abstract：

Graphite anode slurry of lithium-ion flow battery was prepared by the method of ball milling. The morphology, conductivity, specific capacity and cycle performance of graphite anode slurry were studied. Results show that the addition of conductive carbon material can improve the suspension stability of the electrode slurry; the ball milling process can not only improve the suspension stability but also reduce the resistivity of the mixed powders of graphite and conductive carbon materials, the ball milling effect is satisfactory when the mass ratio of the balls and the solid particles is 5:1, but too high ratio of the milling ball and the solid materials can destroy the layer structure of the graphite and affect the stability of the slurry. Increasing the fraction of the graphite and conductive carbon materials can form stable electrical network structure in the slurry and improve the reversible capacity; at the premise of keeping the flowability of the electrode slurry, the reversible specific capacity can be more than 40mAh/g. The capacity loss of graphite anode slurry mainly occurs in the first charging-discharging process, as the increase of the cycles, the capacity loss rate decreases, the capacity goes stable after 5 cycles.

Key words： lithium-ion flow battery graphite anode slurry ball milling

收稿日期: 2016-06-20 出版日期: 2018-02-01

中图分类号:

TM912.9

基金资助:国家自然科学基金项目(51477170);北京市科技计划项目(Z161100000416001)

通讯作者: 陈永翀 E-mail: ycchen@mail.iee.ac.cn

作者简介: 陈永翀(1975-), 男, 教授, 研究方向为储能技术, 联系地址:北京市海淀区中关村北二条6号中国科学院电工研究所储能技术研究组(100190), E-mail: ycchen@mail.iee.ac.cn

引用本文:

冯彩梅, 巩宇, 陈永翀, 刘丹丹, 张萍. 球磨法制备锂离子液流电池石墨负极浆料的性能研究[J]. 材料工程, 2018, 46(2): 1-8.
Cai-mei FENG, Yu GONG, Yong-chong CHEN, Dan-dan LIU, Ping ZHANG. Performance Study of Graphite Anode Slurry in Lithium-ion Flow Battery by Ball Milling. Journal of Materials Engineering, 2018, 46(2): 1-8.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2016.000751 或 http://jme.biam.ac.cn/CN/Y2018/V46/I2/1

Fig.1 不同导电添加剂材料含量的浆料沉降体积随时间的变化

Fig.2 颗粒形貌图 (a)石墨颗粒；(b)导电添加剂

Fig.3 石墨浆料静置2天后的实物图 (a)搅拌法；(b)球磨法

Fig.4 不同球料比制备浆料中颗粒的SEM图 (a)2:1；(b)5:1；(c)10:1；(d)15:1；(e)20:1

Table 1 不同球料比制备粉体材料的电导率

Fig.5 导电添加剂在石墨颗粒之间形成的桥联结构

Fig.6 不同球料比制备电极材料的放电比容量

Fig.7 石墨负极浆料充放电测试结果 (a)石墨3%，导电剂0.3%；(b)石墨15%，导电剂0.6%

Fig.8 不同配比石墨负极浆料的可逆比容量

Fig.9 石墨负极浆料循环性能测试

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