电子导电剂对石榴石基固态锂电池循环性能的影响

doi:10.15541/jim20170167

无机材料学报 ›› 2018, Vol. 33 ›› Issue (4): 462-468.DOI: 10.15541/jim20170167 CSTR: 32189.14.10.15541/jim20170167

所属专题：离子电池材料

电子导电剂对石榴石基固态锂电池循环性能的影响

杜付明 1,2, 赵宁 3, 方锐 1,2, 崔忠慧1, 李忆秋1, 郭向欣1

(1. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050; 2. 中国科学院大学, 北京 100049; 3. 青岛大学物理学院, 青岛 266071)

收稿日期:2017-04-12 出版日期:2018-04-30 网络出版日期:2018-03-27
作者简介:杜付明. E-mail: dufuming@student.sic.ac.cn

Influence of Electronic Conducting Additives on Cycle Performance of Garnet-based Solid Lithium Batteries

DU Fu-Ming^1,2, ZHAO Ning³, FANG Rui^1,2, CUI Zhong-Hui¹, LI Yi-Qiu¹, GUO Xiang-Xin¹

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China;
3. College of Physics, Qingdao University, Qingdao 266071, China

Received:2017-04-12 Published:2018-04-30 Online:2018-03-27
About author:Du Fu-Ming(1989-), male, candidate of PhD. E-mail: dufuming@student.sic.ac.cn
Supported by:
National Natural Science Foundation of China (51532002, 51402339);National Basic Research Program of China (2014CB921004);Strategic Priority Research Program of Chinese Academy of Science (XDA09010202);Natural Science Foundation of Shanghai (17ZR1434600)

摘要/Abstract

摘要：

基于石榴石固体电解质的固态锂电池面临着固体电解质和固体电极之间较大的界面阻抗问题, 导致循环性能不佳。为了解决此问题, 本课题组制备并研究了LiNi_1/3Co_1/3Mn_1/3O₂基正极、Li_6.4La₃Zr_1.4Ta_0.6O₁₂陶瓷固体电解质和金属锂负极构成的固态锂电池。在构筑LiNi_1/3Co_1/3Mn_1/3O₂基正极时采用三种不同的导电碳, 研究表明, 与科琴黑和超导炭黑相比, 使用气相生长碳纤维(Vapor Grown Carbon Fiber, VGCF)时, 固态电池有更优异的循环性能。这是因为充电到高电压时, VGCF比另外两种导电剂引起的副反应更少, 从而减少能增加电池内阻的碳酸盐类副产物的形成。这些结果说明电子导电剂的稳定性对固态锂电池的循环性能有重要影响。

关键词: 固态锂电池, 界面阻抗, 石榴石型电解质, 锂负极, 复合正极

Abstract:

Solid state lithium batteries based on garnet-type solid electrolytes face the problem of contact between the solid electrolytes and the solid cathodes, which deteriorates the cycle performance. Aiming to overcome such problem, the solid state batteries with the LiNi_1/3Co_1/3Mn_1/3O₂-based cathodes, the Li_6.4La₃Zr_1.4Ta_0.6O₁₂ ceramic electrolytes, and the lithium metal anodes were studied. For constructing the LiNi_1/3Co_1/3Mn_1/3O₂-based composite cathodes, three-kind carbons were used as electronic conducting additives. It is found that the batteries with cathodes containing vapor grown carbon fibers (VGCFs) show better cycle performance than those with granular Ketjen Black as well as Super P carbons. Analysis indicates that the VGCFs result in less side reaction at high charge potential than do other two electronic additives, leading to reduced carbonates that cause the increase of the internal cell resistance. These results suggest that stability of electronic additives has important influence on cycle performance of solid state lithium batteries.

Key words: solid state lithium batteries, interfacial resistance, garnet electrolytes, lithium anodes, composite cathodes

中图分类号:

TQ174

杜付明, 赵宁, 方锐, 崔忠慧, 李忆秋, 郭向欣. 电子导电剂对石榴石基固态锂电池循环性能的影响[J]. 无机材料学报, 2018, 33(4): 462-468.

DU Fu-Ming, ZHAO Ning, FANG Rui, CUI Zhong-Hui, LI Yi-Qiu, GUO Xiang-Xin. Influence of Electronic Conducting Additives on Cycle Performance of Garnet-based Solid Lithium Batteries[J]. Journal of Inorganic Materials, 2018, 33(4): 462-468.

图/表 4

Fig. 1 (a) Cross-section and (b) plane view SEM images of NCM- based solid state lithium batteries, (c) and (d) EDS mapping of C and S elements in (b), respectively

Fig. 2 The 1st charge-discharge profiles of NCM-based cathode/LLZTO/Li batteries with the composite cathodes (a) excluding and (b) including electronic additives (KB); (c) Comparison of NCM-based solid state batteries with different carbon additives for the 1st charge-discharge profiles and (d) the discharge capacity as a function of cycle number

Fig. 3 EIS of NCM-based cathode/LLZTO/Li batteries with various carbon additives at different states with respect to (a) NCM-KB, (b) NCM-SP, (c) NCM-VGCF, and (d) excluding electronic additivesThe inset in (d) shows the equivalent circuit

Fig. 4 (a) LSV of the carbon electrode/LLZTO/Li cells with KB, SP and VGCF as the component at the scan rate of 0.1 mV/s; (b) The 1st charge profile of the carbon electrode/LLZTO/Li cells for different components at 40 μA/mgc; (c, d) XPS of C1s spectra of the pristine samples and the 1st charged products for the three-kind carbon electrodes, respectively. Carbon electrodes consist of C:LiTFSI:PVdF, and the current density and charge capacity are relative to the mass of carbon materials

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电子导电剂对石榴石基固态锂电池循环性能的影响

Influence of Electronic Conducting Additives on Cycle Performance of Garnet-based Solid Lithium Batteries

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