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

参考文献 30

[1]	YAO XIA-YIN, LIU DENG, WANG CHUN-SHENG, et al. Nano Letters. Nano Letters, 2016, 16(11): 7148-7154.
[2]	XU XIAO-XIONG, WEN ZHAO-YIN.Glass and glass-ceramics solid electrolytes for lithium-ion battery.Journal of Inorganic Materials, 2005, 20(1): 21-26.
[3]	ZHANG JIAN-JUN, ZHAO JIANG-HUI, YUE LI-PING, et al. Advanced Energy Materials. Advanced Energy Materials, 2015, 5(24): 1401408.
[4]	ZENG XIAN-XIANG, YIN YA-XIA, LI NIAN-WU, et al. Reshaping lithium plating/stripping behavior via bifunctional polymer electrolyte for room-temperature solid Li metal batteries. Journal of the American Chemical Society, 2016, 138(49): 15825-15828.
[5]	ZHENG YUE-LEI, CHEN REN-JIE, WU FENG, et al. Journal of Inorganic Materials. Journal of Inorganic Materials, 2013, 28(11): 1172-1180.
[6]	YADA CHIHIRO, OHMORI AKIHIRO, IDE KAZUTO, et al. Advanced Energy Materials. Advanced Energy Materials, 2014, 4(9): 1301416.
[7]	MURUGAN RAMASWAMY, THANGADURAI VENKATARAMAN, WEPPNER WERNER.Fast lithium ion conduction in garnet-type Li7La3Zr2O12.Angewandte Chemie-International Edition, 2007, 46(41): 7778-7781.
[8]	LIU CAI, WEN ZHAO-YIN, RUI KUN.High ion conductivity in garnet-type F-doped Li7La3Zr2O12.Journal of Inorganic Materials, 2015, 30(9): 995-1000.
[9]	HUANG MIAN, SHOJI MAO, SHEN YANG, et al. Preparation and electrochemical properties of Zr-site substituted Li7La3(Zr2-xMx)O12, 2014, 261: 206-211.
[10]	WU JIAN-FANG, CHEN EN-YI, YU YAO, et al. Gallium-doped Li7La3Zr2O12 garnet-type electrolytes with high lithium-ion conductivity. ACS Applied Materials & Interfaces, 2017, 9(2): 1542-1552.
[11]	TSAI CHIH-LONG, RODDATIS VLADIMIR, CHANDRAN C VINOD, et al. Li7La3Zr2O12 interface modification for Li dendrite prevention. ACS Applied Materials & Interfaces, 2016, 8(16): 10617-10626.
[12]	YAO XIA-YIN, HUANG BING-XIN, YIN JING-YUN, et al. Chinese Physics B. Chinese Physics B, 2016, 25(1): 018802.
[13]	LUO WEI, GONG YUN-HUI, ZHU YI-ZHOU, et al. Journal of the American Chemical Society. Journal of the American Chemical Society, 2016, 138(37): 12258-12262.
[14]	CHENG LEI, CHEN WEI, KUNZ MARTIN, et al. ACS Applied Materials & Interfaces. ACS Applied Materials & Interfaces, 2015, 7(3): 2073-2081.
[15]	HAN XIAO-GANG, GONG YUN-HUI, FU KUN (KELVIN), et al. Nature Materials. Nature Materials, 2016, 16(5): 572.
[16]	OHTA SHINGO, KOMAGATA SHOGO, SEKI JUNTARO, et al. All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing. Journal of Power Sources, 2013, 238: 53-56.
[17]	OHTA SHINGO, SEKI JUNTARO, YAGI YUSUKE, et al. Journal of Power Sources. Journal of Power Sources, 2014, 265: 40-44.
[18]	LIU TING, REN YAO-YU, SHEN YANG, et al. Achieving high capacity in bulk-type solid-state lithium ion battery based on Li6.75La3Zr1.75Ta0.25O12 electrolyte: interfacial resistance. Journal of Power Sources, 2016, 324: 349-357.
[19]	KIM KI-HYUN, IRIYAMA YASUTOSHI, YAMAMOTO KAZUO, et al. Characterization of the interface between LiCoO2 and Li7La3Zr2O12 in an all-solid-state rechargeable lithium battery. Journal of Power Sources, 2011, 196(2): 764-767.
[20]	PARK KYUSUNG, YU BYEONG-CHUL, JUNG JI-WON, et al. Electrochemical nature of the cathode interface for a solid-state lithium-ion battery: interface between LiCoO2 and garnet- Li7La3Zr2O12. Chemistry of Materials, 2016, 28(21): 8051-8059.
[21]	VAN DEN BROEK JAN, AFYON SEMIH, RUPP JENNIFER L M. Interface-engineered all-solid-state Li-ion batteries based on garnet-type fast Li+ conductors.Advanced Energy Materials, 2016, 6(19): 1600736.
[22]	DU FU-MING, ZHAO NING, LI YI-QIU, et al. Journal of Power Sources. Journal of Power Sources, 2015, 300: 24-28.
[23]	OKADA KAZUYA, MACHIDA NOBUYA, NAITO MUNEYUKI, et al. Preparation and electrochemical properties of LiAlO2-coated Li(Ni1/3Mn1/3Co1/3)O2 for all-solid-state batteries. Solid State Ionics, 2014, 255: 120-127.
[24]	SAKUDA ATSUSHI, TAKEUCHI TOMONARI, KOBAYASHI HIRONORI.Electrode morphology in all-solid-state lithium secondary batteries consisting of LiNi1/3Mn1/3Co1/3O2 and Li2S-P2S5 solid electrolytes.Solid State Ionics, 2016, 285: 112-117.
[25]	HAN FU-DONG, ZHU YI-ZHOU Z, HE XING-FENG, et al. Electrochemical stability of Li10GeP2S12 and Li7La3Zr2O12 solid electrolytes. Advanced Energy Materials, 2016, 6(8): 1501590.
[26]	JALEM R, MORISHITA Y, OKAJIMA T, et al. Journal of Materials Chemistry A. Journal of Materials Chemistry A, 2016, 4(37): 14371-14379.
[27]	YOUNESI REZA, CHRISTIANSEN ANE-SÆLLAND, SCIPIONI ROBERTO, et al. Journal of the Electrochemical Society. Journal of the Electrochemical Society, 2015, 162(7): A1289-A1296.
[28]	QUINLAN RONALD A, LU YI-CHUN, YANG SHAO-HORN, et al. XPS studies of surface chemistry changes of LiNi0.5Mn0.5O2 electrodes during high-voltage cycling. Journal of the Electrochemical Society, 2013, 160(4): A669-A677.
[29]	YOUNESI REZA, HAHLIN MARIA, ROBERTS MATTHEW, et al. The SEI layer formed on lithium metal in the presence of oxygen: a seldom considered component in the development of the Li-O2 battery. Journal of Power Sources, 2013, 225: 40-45.
[30]	ZHENG JIAN-MING, XIAO JIE, XU WU, et al. Journal of Power Sources. Journal of Power Sources, 2013, 227: 211-217.

编辑推荐 0

Metrics

阅读次数

全文

1759

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	22	0	0	1737

来源	本网站	其他网站

次数	1247	512
比例	71%	29%

摘要

1069

最新录用	在线预览	正式出版

0	0	1069

来源	本网站	其他网站

次数	367	702
比例	34%	66%

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

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 4

参考文献 30

相关文章 6

编辑推荐 0

Metrics

本文评价

[1]	谭淑雨, 刘晓宁, 毕志杰, 万勇, 郭向欣. 正极包覆与界面修饰: 双策略改善聚氧化乙烯固态电解质对高电压正极稳定性[J]. 无机材料学报, 2023, 38(12): 1466-1474.
[2]	夏求应, 孙硕, 昝峰, 徐璟, 夏晖. 非晶LiSiON薄膜电解质的全固态薄膜锂电池性能[J]. 无机材料学报, 2022, 37(2): 230-236.
[3]	李栋, 雷超, 赖华, 刘小林, 姚文俐, 梁彤祥, 钟盛文. 全固态锂离子电池正极与石榴石型固体电解质界面的研究进展[J]. 无机材料学报, 2019, 34(7): 694-702.
[4]	陈飞彪, 王英男, 吴伯荣, 熊云奎, 廖维林, 吴锋, 孙喆. 锂硫电池石墨烯/硫复合正极材料的制备及其电化学性能[J]. 无机材料学报, 2014, 29(6): 627-632.
[5]	陈威, 彭文杰, 王志兴. 复合正极材料LiFePO₄/Al/C的制备及性能研究[J]. 无机材料学报, 2012, 27(10): 1030-1034.
[6]	郑俊超,李新海,王志兴,覃东棉,郭华军,彭文杰. 锂离子电池复合正极材料xLiFePO₄·yLi₃V₂(PO₄)₃的制备与性能研究[J]. 无机材料学报, 2009, 24(1): 143-146.