热处理时间对锂电池正极材料Cr8O21的影响

doi:10.13208/j.electrochem.210121

电化学（中英文） ›› 2021, Vol. 27 ›› Issue (6): 689-697. doi: 10.13208/j.electrochem.210121

热处理时间对锂电池正极材料Cr₈O₂₁的影响

滕久康¹, 王庆杰¹^,^*(), 张亮¹, 张红梅¹, 陈晓涛¹, 张鹏², 赵金保²^,³

1.贵州梅岭电源有限公司,特种化学电源国家重点实验室,贵州遵义 563003
2.厦门大学能源学院,福建厦门361102
3.厦门大学化学化工学院,固体表面物理化学国家重点实验室,新能源汽车动力电源技术国家地方联合工程实验室,福建厦门 361005

收稿日期:2021-01-25 修回日期:2021-04-14 出版日期:2021-12-28 发布日期:2021-05-04
通讯作者: 王庆杰 E-mail:wqj3401@163.com
基金资助:
贵州省科技计划项目(20202Y057)

Influence of Heat Treatment Time on Cathode Material Cr₈O₂₁ for Lithium Battery

Jiu-Kang Teng¹, Qing-Jie Wang¹^,^*(), Liang Zhang¹, Hong-Mei Zhang¹, Xiao-Tao Chen¹, Peng Zhang², Jin-Bao Zhao²^,³

1. Guizhou Meiling Power Sources Co. Ltd, State Key Laboratory of Advanced Chemical Power Sources,Zunyi 563003, Guizhou, China
2. College of Energy & School of Energy Research, Xiamen University,Xiamen 361102, Fujian, China
3. State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Centre of Chemistry for Energy Materials, State-Province Joint Engineering Laboratory of Power Source Technology for New Energy Vehicle, Engineering Research Center of Electrochemical Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2021-01-25 Revised:2021-04-14 Published:2021-12-28 Online:2021-05-04
Contact: Qing-Jie Wang E-mail:wqj3401@163.com

摘要/Abstract

摘要：

本文以CrO₃为原料,采用高温固相法制备锂电池用正极材料Cr₈O₂₁,系统研究了热处理时间对Cr₈O₂₁结构、电化学性能的影响。采用TGA、XRD、SEM、EDS、ICP、EIS和恒流放电技术对制备的铬氧化物的物相及电化学性能进行研究。结果表明,延长热处理时间有利于提升材料的电化学性能。且不同的热处理时间对材料的电化学性能有重要影响。热处理时间为48 h得到的材料性能优异,在恒放电电流0.05 mA下,材料克比容量达到383.26 mAh·g^-1,克比能量达到1153.83 mWh·g^-1,平均放电电压3.01 V。

关键词: 锂电池, 正极材料, Cr₈O₂₁, 铬氧化物, 热处理时间

Abstract:

Chromium oxide (Cr₈O₂₁) cathode material for lithium batteries was synthesized by thermal decomposition of chromium trioxide (CrO₃) at high temperature. The electrochemical properties of chromium oxide depended on the time and temperature during the heat treatment. Pure phase chromium oxide was prepared, and the effects of heat treatment time on the structures and electrochemical properties of Cr₈O₂₁ were systematically studied. The first discharge mechanism of chromium oxide in lithium batteries was explored, and the results were similar to that in lithium-sulfur batteries. The crystal phases and electrochemical properties of the prepared chromium oxide were analyzed by TGA, XRD, SEM, EDS, ICP, EIS techniques and constant current discharge measurement. The results show that heat treatment time had an important impact. Extending the heat treatment time was beneficial to improve the electrochemical properties of the material. The less the amount of residual CrO₃, the better the electrochemical performance. The severe oxidation reaction between CrO₃ and the electrolyte caused the electrode to be corroded. The material obtained in 48 h exhibited excellent performance, complete crystallization, good morphology, and low electrochemical impedance. At a constant discharge current of 0.05 mA, the specific capacity of the material reached 383.26 mAh·g^-1 with the specific energy of 1153.83 mWh·g^-1 and the average discharge voltage of 3.01 V. This study provides an effective way to prepare pure phase chromium oxide and proves its potential application in the field of lithium batteries.

Key words: lithium battery, cathode material, Cr₈O₂₁, chromium oxide, heat treatment time

滕久康, 王庆杰, 张亮, 张红梅, 陈晓涛, 张鹏, 赵金保. 热处理时间对锂电池正极材料Cr₈O₂₁的影响[J]. 电化学（中英文）, 2021, 27(6): 689-697.

Jiu-Kang Teng, Qing-Jie Wang, Liang Zhang, Hong-Mei Zhang, Xiao-Tao Chen, Peng Zhang, Jin-Bao Zhao. Influence of Heat Treatment Time on Cathode Material Cr₈O₂₁ for Lithium Battery[J]. Journal of Electrochemistry, 2021, 27(6): 689-697.

图/表 15

表1

图1

图2

图3

图4

表2

表3

图5

图6

表4

表5

表6

表7

图7

图8

参考文献 14

[1]	Yuan Z Z(袁中直), Liu J C(刘金成), Lü Z Z(吕正中), Zhu Y(祝媛), Pu F(卜芳). Technical progress and future of lithium primary batteries[J]. J. Power Sources (Chinese)(电源技术), 2019, 5(43): 735-738.
[2]	Besenhard J O, Schollhorn R. Chromium oxides as cathodes for secondary high energy density lithium batteries[J]. J. Electrochem. Soc., 1977, 124(7): 968-971. doi: 10.1149/1.2133510 URL
[3]	Takeda Y, Kanno R, Tsuji Y, Yamamoto O, Taguch H. Chromium oxides as cathodes for lithium cells[J]. J. Power Sources, 1983, 9: 325-328. doi: 10.1016/0378-7753(83)87034-7 URL
[4]	Li T(李婷), Qian J F(钱江峰), Cao Y L(曹余良), Yang H X(杨汉西), Ai X P(艾新平). Electrochemical performance of Li₁-_xM_xFePO₄ cathode materials synthesized by polymer pyrolysis route[J]. J. Electrochem.(电化学), 2007, 13(2): 136-139.
[5]	Xiao J(肖婕), Zhan H(詹晖), Zhou Y H(周运鸿). Synjournal and electrochemical behavior of layered-structure LiMn₁-_xCr_xO₂[J]. J. Electrochem.(电化学), 2004, 10(3): 324-329.
[6]	Desilvestro J, Haas O. Metal oxide cathode materials for electrochemical energy storage: a review[J]. J. Electrochem. Soc., 1990, 137(1): 5C-22C. doi: 10.1149/1.2086438 URL
[7]	Liu J Y(刘建勇), Li H(李泓), Wang Z X(王兆翔), Huang X J(黄学杰). Study on preparation and performance of chromium oxide cathode material for secondary lithium battery[A]. Soild State Ionics, 2004: 57-59.
[8]	Feng X Y, Ding N, Wang L, Ma X H, Li Y M, Chen C H. Synjournal and reversible lithium storage of Cr₂O₅ as a new high energy density cathode material for rechargeable lithium batteries[J]. J. Power Sources, 2013, 222: 184-187. doi: 10.1016/j.jpowsour.2012.08.061 URL
[9]	Ramaraja P R, Ramadass P, Bala S H, Branko N P. Synjournal, characterization and cycling performance of novel chromium oxide cathode materials for lithium batteries[J]. J. Power Sources, 2003, 124: 155-162. doi: 10.1016/S0378-7753(03)00612-8 URL
[10]	Liu J Y, Wang Z X, Li H, Huang X J. Synjournal and characterization of Cr₈O₂₁ as cathode material for rechargeable lithium batteries[J]. Solid State Ionics, 2006, 177: 2675-2678. doi: 10.1016/j.ssi.2006.05.017 URL
[11]	Liu D X(刘东旭). Preparation and electrochemical performance studies of chromium oxide as cathode materials for lithium batteries[D]. Harbin: Harbin Institute of Technology(哈尔滨工业大学), 2019.
[12]	Yamamoto O, Takeda Y, Kanno R, Oyabe Y, Shinya Y. Amorphous chromium oxide; a new lithium battery cathode[J]. J. Power Sources, 1987, 20(1): 151-156. doi: 10.1016/0378-7753(87)80105-2 URL
[13]	Feng G X, Li L F, Liu J Y, Liu N, Li H, Yang X Q, Huang X J, Chen L Q. Enhanced electrochemical lithium storage activity of LiCrO₂ by size effect[J]. J. Mater. Chem., 2009, 19: 2993-2998. doi: 10.1039/b817624h URL
[14]	Zhuang Q C(庄全超), Xu S D(徐守冬), Qiu X Y(邱祥云), Cui Y L(崔永丽), Fang L(方亮), Sun S G(孙世刚). Diagnosis of electrochemical impedance spectroscopy in lithium ion batteries[J]. Prog. Chem.(化学进展), 2010, 22(6): 1044-1057.

Material number	Heating temperature/°C	Heating time/h
A-2	270	2
A-6	270	6
A-12	270	12
A-24	270	24
A-48	270	48

Element	Atomic percent/%	Mass percent/%
Cr	27.9	55.59
O	72.1	44.41

Material number	Specific capacity/(mAh·g^-1)	Specific energy/(mWh·g^-1)	Average voltage/V
A-2	256.67	765.67	2.97
A-6	271.26	812.86	3.00
A-12	304.28	919.04	3.00
A-24	352.90	1074.71	3.00
A-48	383.26	1153.83	3.01

Material number	Specific capacity/(mAh·g^-1)	Specific energy/(mWh·g^-1)	Average voltage/V
A-2	246.50	729.64	3.02
A-6	243.17	715.26	2.99
A-12	283.03	839.97	2.98
A-24	340.91	994.99	2.95
A-48	346.17	1017.86	2.95

Material number	Specific capacity/(mAh·g^-1)	Average voltage/V
A-2	207.73	2.90
A-6	222.01	2.86
A-12	258.43	2.85
A-24	252.72	2.89
A-48	280.32	2.82

热处理时间对锂电池正极材料Cr₈O₂₁的影响

Influence of Heat Treatment Time on Cathode Material Cr₈O₂₁ for Lithium Battery

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 15

参考文献 14

相关文章 15

Metrics

Material number	Specific capacity/(mAh·g^-1)	Average voltage/V
A-2	92.75	2.64
A-6	144.23	2.79
A-12	183.30	2.70
A-24	213.18	2.77
A-48	227.32	2.76

[1]	侯博文, 何龙, 冯旭宁, 张伟峰, 王莉, 何向明. 胺类添加剂对NCM811‖SiC电池热失控抑制效果研究[J]. 电化学（中英文）, 2023, 29(8): 2211141-.
[2]	胡炳文, 李超, 耿福山, 沈明. 金属离子电池中的磁共振：从核磁共振(NMR)到电子顺磁共振(EPR)[J]. 电化学（中英文）, 2022, 28(2): 2108421-.
[3]	骆晨旭, 师晨光, 余志远, 黄令, 孙世刚. 富锂锰基层状正极材料的合成及其首周过充下的结构演化[J]. 电化学（中英文）, 2022, 28(1): 2006131-.
[4]	王存, 张维江, 何腾飞, 雷博, 史尤杰, 郑耀东, 罗伟林, 蒋方明. NCA三元锂离子电池分荷电状态循环的热特性和容量衰退研究[J]. 电化学（中英文）, 2020, 26(6): 777-788.
[5]	王佳, 黄秋安, 李伟恒, 王娟, 庄全超, 张久俊. 电化学阻抗谱弛豫时间分布基础[J]. 电化学（中英文）, 2020, 26(5): 607-627.
[6]	王杜丹, 王非, 翟欢欢, 李玉鹏, 杨纳川, 陈康华. 富锂层状正极材料Li₂MnO₃的表面改性及其电化学性能研究[J]. 电化学（中英文）, 2020, 26(2): 289-297.
[7]	王非, 翟欢欢, 王杜丹, 李玉鹏, 陈康华. Sn-Cl共掺杂的锂离子正极材料Li₂MnO₃的结构及电化学性能研究[J]. 电化学（中英文）, 2020, 26(1): 148-155.
[8]	黄云辉. 钴酸锂正极材料与锂离子电池的发展 ——2019年诺贝尔化学奖解读[J]. 电化学（中英文）, 2019, 25(5): 609-613.
[9]	王凡凡, 刘晓斌, 陈龙, 陈程成, 刘永畅, 范丽珍. 室温钠离子电池关键材料研究进展[J]. 电化学（中英文）, 2019, 25(1): 55-76.
[10]	赵一博, 刘蕙蕙, 陈松良, 薄首行. 先进成像技术在全固态锂电池关键问题研究中的应用[J]. 电化学（中英文）, 2019, 25(1): 17-30.
[11]	谢永纯，王成，蒋芳，杨洋，苏静，龙云飞，文衍宣. 钠锰比对Na_xMnO₂的性能和钠离子脱嵌过程的影响[J]. 电化学（中英文）, 2018, 24(4): 375-384.
[12]	关小云，洪朝钰，朱建平，王伟立，李益孝，杨勇. 高首效富镍正极材料LiNi_0.6Co_0.2Mn_0.2O₂的合成及电化学性能研究[J]. 电化学（中英文）, 2018, 24(1): 56-62.
[13]	魏雪霞，黄嘉祺，刘施阳，程璇，张颖. 不同羧酸对钒改性硅酸铁锂结构性能的影响[J]. 电化学（中英文）, 2018, 24(1): 72-80.
[14]	胡燚，何湘柱, 邓忠德，孔令涌，尚伟丽. 锂离子电池正极材料LiNi _0.5Co_0.2Mn _0.3O₂和LiNi_0.5Co _0.2Mn _0.3O₂/LiFePO₄容量衰减原因分析[J]. 电化学（中英文）, 2017, 23(6): 675-683.
[15]	张广瑞，胡利强，张宝珠. 一种新型的碳复合钼掺杂的钒氧化物纳米线钠离子电池正极材料[J]. 电化学（中英文）, 2017, 23(4): 456-465.