储能科学与技术2024,Vol.13Issue(3) :742-748.DOI:10.19799/j.cnki.2095-4239.2023.0741

Al-Y-Zr原位共掺杂提高4.53V钴酸锂正极材料的循环性能

Improving the cycling performance of LiCoO2 at 4.53 V via in situ co-doping of Al-Y-Zr

胡大林 任潘利 张昌明 杨明阳 卢周广
储能科学与技术2024,Vol.13Issue(3) :742-748.DOI:10.19799/j.cnki.2095-4239.2023.0741

Al-Y-Zr原位共掺杂提高4.53V钴酸锂正极材料的循环性能

Improving the cycling performance of LiCoO2 at 4.53 V via in situ co-doping of Al-Y-Zr

胡大林 1任潘利 1张昌明 1杨明阳 2卢周广2
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作者信息

  • 1. 南科大材料系-豪鹏科技新能源联合实验室,深圳市豪鹏科技股份有限公司,广东深圳 518111
  • 2. 南科大材料系-豪鹏科技新能源联合实验室,深圳市界面材料界面科学与工程应用重点实验室,南方科技大学材料科学与工程系,广东深圳 518055
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摘要

钴酸锂是一种成功实现商业化的锂离子电池正极材料,但其实际的容量远低于其理论容量(274mAh/g).提高钴酸锂的充电截止电压能够有效提高其放电容量,但钴酸锂在高压条件下结构不稳定性,导致其循环寿命明显降低.本工作提出一种Al-Y-Zr原位共掺杂的策略,以提高钴酸锂在4.53V的循环性能.通过将Al-Y-Zr掺杂的Co3O4、Li2CO3、MgO按一定化学计量比称取并混合均匀后,采用高温固相法合成LiCo(1-a-b-c-d)AlaZrbYcMgdO2正极材料,并探究了原位共掺杂对高电压钴酸锂循环性能的影响.X射线衍射(XRD)表明掺杂前后晶体均为六方相层状结构,扫描电镜(SEM)说明了掺杂元素对晶体颗粒粒径的调控作用.循环前后的电化学阻抗谱(EIS)表明,Al-Y和Al-Y-Zr共掺杂能有效抑制循环过程中电荷转移阻抗(Rct)的增长.扣式电池及软包电池测试结果都表明Al-Y和Al-Y-Zr前驱体共掺杂能够显著提升循环性能,后者提升更明显.本研究有助于推动高电压钴酸锂正极的应用,为高比能量锂离子电池技术的研发提供实验依据.

Abstract

The LiCoO2 is a commercially successful lithium-ion battery cathode material;however,its actual capacity falls short of its theoretical capacity(274 mAh/g).Increasing the charging cutoff voltage can boost discharge capacity;however,the instability of LiCoO2 under high voltage compromises its cycle life.This study aims to introduce an in situ co-doping strategy with Al-Y-Zr to enhance the cycling performance of LiCoO2 at 4.53 V.The LiCo(1-a-b-c-d)AlaZrbYcMgdO2 cathode material was synthesized using a high-temperature solid-phase method by mixing Al-Y-Zr-doped Co3O4,Li2CO3,and MgO in a specific stoichiometric ratio.The impact of in situ co-doping on high-voltage LiCoO2's cycling performance was investigated.X-ray diffraction revealed a hexagonal layered crystal structure before and after doping,whereas scanning electron microscopy confirmed the regulation of crystal particle size by the doping elements.Electrochemical impedance spectroscopy demonstrated that the co-doping of Al-Y and Al-Y-Zr effectively inhibits growth of Rct value during cycle testing.Test results from coin and pouch cells showed that in situ co-doping substantially improves the cycling performance,with the latter displaying substantial pronounced enhancement.This study contributes to advancing the application of high-voltage lithium cobalt oxide cathodes.In addition,it provides an experimental foundation for research and development in high-specific-energy lithium-ion battery technology.

关键词

锂离子电池/钴酸锂/高电压/共掺杂/循环性能

Key words

Li ion batteries/LiCoO2/high voltage/co-doping/cyclic performance

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基金项目

国家自然科学基金(U22A20439)

深圳市基础研究重点项目(JCYJ20220818100418040)

出版年

2024
储能科学与技术
化学工业出版社

储能科学与技术

CSTPCDCSCD北大核心
影响因子:0.852
ISSN:2095-4239
参考文献量13
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