Cr掺杂对富锂锰基正极材料Li1.2Ni0.2Mn0.6O2结构和电化学性能的影响

doi:10.11949/j.issn.0438-1157.20160875

化工学报 ›› 2017, Vol. 68 ›› Issue (1): 398-407.DOI: 10.11949/j.issn.0438-1157.20160875

• 材料化学工程与纳米技术 • 上一篇下一篇

Cr掺杂对富锂锰基正极材料Li_1.2Ni_0.2Mn_0.6O₂结构和电化学性能的影响

张志强, 征圣全, 王起亮, 窦爱春, 苏明如, 刘云建

江苏大学材料科学与工程学院, 江苏镇江 212013

收稿日期:2016-06-27 修回日期:2016-10-18 出版日期:2017-01-05 发布日期:2017-01-05
通讯作者: 刘云建
基金资助:
国家自然科学基金项目（51304081）；江苏省自然科学基金项目（BK20140581，BK20150506，BK20140558）。

Effects of Cr-doping on structure and electrochemical performance of lithiumand manganese-rich cathode materials Li_1.2Ni_0.2Mn_0.6O₂

ZHANG Zhiqiang, ZHENG Shengquan, WANG Qiliang, DOU Aichun, SU Mingru, LIU Yunjian

College of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China

Received:2016-06-27 Revised:2016-10-18 Online:2017-01-05 Published:2017-01-05
Contact: 10.11949/j.issn.0438-1157.20160875
Supported by:
supported by the National Natural Science Foundation of China (51304081) and the Natural Science Foundation of Jiangsu Province (BK20140581, BK20150506, BK20140558).

摘要/Abstract

摘要：

采用共沉淀-高温固相合成法制备锂离子电池正极材料Li_1.2Ni_0.2Mn_0.2-x/2Mn_0.6-x/2Cr_xO₂（x=0，0.04，0.08，0.12）。利用X射线衍射（XRD）、扫描电镜（SEM）、恒电流充放电测试和电化学交流阻抗谱（EIS）对掺杂不同Cr含量的正极材料的结构、形貌和电化学性能进行分析测试。结果表明：制备出的Li_1.2Ni_0.2Mn_0.2-x/2Mn_0.6-x/2Cr_xO₂正极材料均具备层状固溶体结构。Cr掺杂不会改变材料的结构，而且能够有效抑制循环过程中材料由层状向尖晶石结构转变的过程。当Cr的掺杂量为8%（即x=0.08）时，得到的正极材料Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂具有最好的电化学性能。0.1C的首次放电比容量由未掺杂的230.4 mA·h·g^-1增加到246.6 mA·h·g^-1，在0.2C电流下50次循环后的容量保持率由93.5%提高至95.36%，5C的放电比容量由91.5 mA·h·g^-1增加到104.2 mA·h·g^-1。而且x=0.08时制备的样品具有最小的电荷转移阻抗。

关键词: 锂离子电池, 正极材料, 富锂锰基, Li_1.2Ni_0.2Mn_0.6O₂, Cr掺杂

Abstract:

Lithium-ion battery cathode materials Li_1.2Ni_0.2Mn_0.2-x/2Mn_0.6-x/2Cr_xO₂(x=0, 0.04, 0.08, 0.12) were synthesized by co-precipitation and high temperature solid state reaction.The structure, morphology and electrochemical properties of cathode material, which was doped with different amounts of Cr, were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), galvanostatic charge-discharge testing and electrochemical impedance spectroscopy(EIS).The results show that the cathode materials Li_1.2Ni_0.2Mn_0.2-x/2Mn_0.6-x/2Cr_xO₂ display the layered structure of solid solution.Cr-doping does not change the material structure, and stabilizes the host layered structure by prohibiting the speed of spinel structure formation during cycling.Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ has the best electrochemical properties.The first discharge specific capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 246.6 mA·h·g^-1at 0.1C, while Li_1.2Ni_0.2Mn_0.6O₂ is 230.4 mA·h·g^-1.The capacity retaining ratio is improved from 93.5% to 95.36% after 50 cycles at 0.2C.The discharge capacity of Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ is 104.2 mA·h·g^-1 at 5C, while that of pristine is about 91.5 mA·h·g^-1.EIS results show that Li_1.2Ni_0.16Mn_0.56Cr_0.08O₂ has the lowest charge transfer impedance.

Key words: lithium-ion battery, cathode material, lithium-and manganese-rich, Li_1.2Ni_0.2Mn_0.6O₂, Cr-doping

中图分类号:

TM912.9

张志强, 征圣全, 王起亮, 窦爱春, 苏明如, 刘云建. Cr掺杂对富锂锰基正极材料Li_1.2Ni_0.2Mn_0.6O₂结构和电化学性能的影响[J]. 化工学报, 2017, 68(1): 398-407.

ZHANG Zhiqiang, ZHENG Shengquan, WANG Qiliang, DOU Aichun, SU Mingru, LIU Yunjian. Effects of Cr-doping on structure and electrochemical performance of lithiumand manganese-rich cathode materials Li_1.2Ni_0.2Mn_0.6O₂[J]. CIESC Journal, 2017, 68(1): 398-407.

参考文献 26

[1]	CHUNG S Y, BLOKING J T, CHIANG Y M. Electronically conductive phospho-olivines as lithium storage electrodes[J]. Nature Materials, 2003, 1(2):123-128.
[2]	NUMATA K, SAKAKI C, YAMANAKA S. Synthesis of solid solutions in a system of LiCoO2-Li2MnO3 for cathode materials of secondary lithium batteries[J]. Chem. Lett., 1997, 1997(8):725-726.
[3]	THACKERAY M M, JOHNSON C S, AMINE K, et al. Lithium metal oxide electrodes for lithium cells and batteries:US 6677082[P]. 2004-01-13.
[4]	KIM D H, KANG S H, BALASUBRAMANIAN M, et al. High-energy and high-power Li-rich nickel manganese oxide electrode materials[J]. Electrochem. Commun., 2010, 12(8):1618-1621.
[5]	KOENIGJR G M, BELHAROUAK I, WU H M, et al. Hollow lithiated metal oxide particles as lithium-ion battery cathode materials[J]. Electrochim. Acta, 2011, 56(8):1426-1431.
[6]	陈来, 陈实, 胡道中, 等. 不同组分下富锂正极材料xLi2MnO3·(1-x)LiNi0.5Mn0.5O2(x=0.1~0.8)的晶体结构与电化学性能[J]. 物理化学学报, 2014, 30(3):467-475. CHEN L, CHEN S, HU D Z, et al. Crystal structure and electrochemical performance of lithium-rich cathode materials xLi2MnO3·(1-x)LiNi0.5Mn0.5O2(x=0.1-0.8)[J]. Acta Physico-Chimica Sinica, 2014, 30(3):467-475.
[7]	SONG B, LAI M O, LU L. Influence of Ru substitution on Li-rich 0.55Li2MnO3·0.45LiNi1/3Co1/3Mn1/3 cathode for Li-ion batteries[J]. Electrochimica Acta, 2012, 80(1):187-195
[8]	ARMSTRONG A R, HOLZAPFEL M, NOVAK P, et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2[J]. Journal of the American Chemical Society, 2006, 128(26):8694-8698.
[9]	HONG Y S, PARK Y J, RYU K S. Synthesis and electrochemical properties of nanocrystalline Li[NixLi(1-2x)/3Mn(2-x)/3]O2 prepared by a simple combustion method[J]. Journal of Materials Chemistry, 2004, 14(9):1424-1429.
[10]	HUANG X K, ZHANG Q S, CHANG H T, et al. Hydrothermal synthesis of nanosized LiMnO2-Li2MnO3 compounds and their electrochemical performances[J]. Journal of the Electrochemical Society, 2009, 156(3):162-168.
[11]	VENKATRAMAN S, CHOI J, MANTHIRAM A. Factors influencing the chemical lithium extraction rate from layered LiNi1-y-zCoyMnzO2 cathodes[J]. Electrochemistry Communications, 2004, 6(8):832-837.
[12]	DOU S, WANG W. Synthesis and electrochemical properties of layered LiNi0.5-xMn0.5-xCo2xO2 for lithium-ion battery from nickel manganese cobalt oxide precursor[J]. Solid State Electrochemical, 2010, 15(2):399-404.
[13]	ZHANG J M, ZHANG Z R, WU X B, et al. The effects of AlF3 coating on the performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 positive electrode material for lithium-ion battery[J]. Journal of the Electrochemical Society, 2008, 155(10):775-782.
[14]	WU Y, VADIVEL MURUGAN A, MANTHIRAM A. Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode by AlPO4 [J]. Journal of the Electrochemical Society, 2008, 155(9):635-641.
[15]	KANG Y J, KIM J H, LEE S W, et al. The effect of Al(OH)3 coating on the Li[Li0.2Ni0.2Mn0.6]O2 cathode material for lithium secondary battery[J]. Electrochimica Acta, 2005, 50(24):4784-4791.
[16]	王伟东, 仇卫华, 丁倩倩, 等. 锂离子电池三元材料——工艺技术及生产应用[M]. 北京:化学工业出版社, 2015:30-35. WANG W D, QIU W H, DING Q Q, et al. Nickel Cobalt Manganese Based Cathode Materials for Li-ion Batteries Technology Production and Application[M]. Beijing:Chemical Industry Press, 2015:30-35.
[17]	朱伟雄. 裡离子电池富锂锰基LiLi0.2Ni0.2Mn0.6O2正极材料的制备及改性研究[D]. 长沙:中南大学, 2013:40-49. ZHU W X. Preparation and modification of Li-rich Mn-based LiLi0.2Ni0.2Mn0.6O2 cathode materials for Li-ion batteries[D]. Changsha:Central South University, 2013:40-49.
[18]	LIU Y J, GAO Y Y, DOU A C. Influence of Li content on the structure and electrochemical performance of Li1+xNi0.25Mn0.75O2.25+x/2 cathode for Li-ion battery[J]. Journal of Power Sources, 2014, 248:679-684.
[19]	FU F, HUANG Y Y, WU P, et al. Controlled synthesis of lithium-rich layered Li1.2Mn0.56Ni0.12Co0.12O2 oxide with tunable morphology and structure as cathode material for lithium-ion batteries by solvo/hydrothermal methods[J]. Journal of Alloys and Compounds, 2015, 618:673-678.
[20]	赵煜娟, 岳影影, 孙玉成, 等纳米材料Li1.2Ni0.2Mn0.6O2的合成及性能研究[J]. 电池, 2014, 44(4):198-201. ZHAO Y J, YUE Y Y, SUN Y C, et al. The study on synthesis of nano Li1.2Ni0.2Mn0.6O2 material and its electrochemical performance[J]. Battery Bimonthly, 2014, 44(4):198-201.
[21]	PARK S H, KANG S H, JOHNSON C S, et al. Lithium-manganese-nickel-oxide electrodes with integrated layered-spinel structures for lithium batteries[J]. Electrochemistry Communications, 2007, 56(9):262-268.
[22]	刘云建, 王亚平, 刘三兵, 等. LiNi0.2Li0.2Mn0.6O2正极材料的合成与碳包覆[J]. 中南大学学报(自然科学版), 2013, 44(2):482-486. LIU Y J, WANG Y P, LIU S B, et al. Synthesized and carbon-coating of LiNi0.2Li0.2Mn0.6O2 cathodes[J]. Journal of Central South University (Science and Technology), 2013, 44(2):482-486.
[23]	SONG B H, ZHOU C F, WANG H L, et al. Advances in sustain stable voltage of Cr-doped Li-rich layered cathodes for lithium ion batteries[J]. Journal of the Electrochemical Society, 2014, 161(10):A1723-A1730.
[24]	YI T F, SHU J, ZHU Y R, et al. Structure and electrochemical performance of Li4Ti5O12-coated LiMn1.4Ni0.4Cr0.2O4 spinel as 5 V materials[J]. Electrochemistry Communications, 2009, 11(1):91-94.
[25]	KANG S H, JOHNSON C S, VAUGHEY J T, et al. The effects of acid treatment on the electrochemical properties of 0.5Li2MnO3·0.5LiNi0.44Co0.25Mn0.31O2 electrodes in lithium cells[J]. Journal of Electrochemical Society, 2006, 153(6):A1186-A1192.
[26]	LU Z H, CHEN Z H, DAHN J R. Lack of cation clustering in Li[NixLi1/3-2x/3Mn2/3-x/3]O2(0≤x≤1/2) and Li[CrxLi(1-x)/3Mn(2-2x)/3]O2(0

Cr掺杂对富锂锰基正极材料Li_1.2Ni_0.2Mn_0.6O₂结构和电化学性能的影响

Effects of Cr-doping on structure and electrochemical performance of lithiumand manganese-rich cathode materials Li_1.2Ni_0.2Mn_0.6O₂

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	康飞, 吕伟光, 巨锋, 孙峙. 废锂离子电池放电路径与评价研究[J]. 化工学报, 2023, 74(9): 3903-3911.
[2]	王志龙, 杨烨, 赵真真, 田涛, 赵桐, 崔亚辉. 搅拌时间和混合顺序对锂离子电池正极浆料分散特性的影响[J]. 化工学报, 2023, 74(7): 3127-3138.
[3]	葛加丽, 管图祥, 邱新民, 吴健, 沈丽明, 暴宁钟. 垂直多孔碳包覆的FeF₃正极的构筑及储锂性能研究[J]. 化工学报, 2023, 74(7): 3058-3067.
[4]	李靖, 沈聪浩, 郭大亮, 李静, 沙力争, 童欣. 木质素基碳纤维复合材料在储能元件中的应用研究进展[J]. 化工学报, 2023, 74(6): 2322-2334.
[5]	肖忠良, 尹碧露, 宋刘斌, 匡尹杰, 赵亭亭, 刘成, 袁荣耀. 废旧锂离子电池回收工艺研究进展及其安全风险分析[J]. 化工学报, 2023, 74(4): 1446-1456.
[6]	杜江龙, 杨雯棋, 黄凯, 练成, 刘洪来. 复合相变材料/空冷复合式锂离子电池模块散热性能[J]. 化工学报, 2023, 74(2): 674-689.
[7]	程伟江, 汪何琦, 高翔, 李娜, 马赛男. 锂离子电池硅基负极电解液成膜添加剂的研究进展[J]. 化工学报, 2023, 74(2): 571-584.
[8]	钟磊, 邱学青, 张文礼. 木质素衍生炭在碱金属离子电池负极中的研究进展[J]. 化工学报, 2022, 73(8): 3369-3380.
[9]	胡华坤, 薛文东, 霍思达, 李勇, 蒋朋. 锂离子电池电解液SEI成膜添加剂的研究进展[J]. 化工学报, 2022, 73(4): 1436-1454.
[10]	杨伟, 王昱杰, 方凯斌, 邹汉波, 陈胜洲, 刘自力. Co-Mn比例调控对LiNi_0.8Co_0.10-_y Mn_0.05+_y Al_0.05O₂材料性能影响探究[J]. 化工学报, 2022, 73(12): 5615-5624.
[11]	王朋朋, 贾洋刚, 邵霞, 程婕, 冒爱琴, 檀杰, 方道来. K⁺掺杂尖晶石型（Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2）₃O₄高熵氧化物负极材料制备与储锂性能研究[J]. 化工学报, 2022, 73(12): 5625-5637.
[12]	贾理男, 杜一博, 郭邦军, 张希. 基于硫化物电解质的全固态锂离子电池负极研究进展[J]. 化工学报, 2022, 73(12): 5289-5304.
[13]	宋刘斌, 王怡萱, 匡尹杰, 夏宇博, 肖忠良. 钠离子电池中关键材料及技术的发展与前景[J]. 化工学报, 2022, 73(11): 4814-4825.
[14]	周弋惟, 陈卓, 徐建鸿. 湿法冶金回收废旧锂电池正极材料的研究进展[J]. 化工学报, 2022, 73(1): 85-96.
[15]	王慧艳, 陈怡沁, 周静红, 曹约强, 周兴贵. 锂离子电池正极涂层孔隙结构优化的数值模拟[J]. 化工学报, 2022, 73(1): 376-383.