无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ
新能源电池材料

4.6 V高电压钴酸锂正极材料Al-Zn共掺杂研究

  • 刘娟 ,
  • 蒋庆来 ,
  • 张月异
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  • 长沙职业技术学院,湖南 长沙 410217
刘娟(1979— ),女,硕士,讲师,研究方向为新能源汽车技术;E-mail:juanliu197910@163.com

收稿日期: 2024-03-04

  网络出版日期: 2024-04-28

基金资助

湖南省科技厅自然科学基金项目(2023JJ60268)

Study on Al-Zn co-doping of 4.6 V high voltage lithium cobalt oxide cathode materials

  • LIU Juan ,
  • JIANG Qinglai ,
  • ZHANG Yueyi
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  • Changsha Vocational and Technical College,Changsha 410217,China

Received date: 2024-03-04

  Online published: 2024-04-28

摘要

钴酸锂具有高达274 mA·h/g的理论容量,是最早商业化的锂离子电池正极材料之一。然而,钴酸锂层状结构在高电压下的不稳定性使其实际充电电压很难超过4.45 V(vs.Li),这大大限制了其容量发挥。针对上述问题,采用小半径铝离子与大半径锌离子共掺杂的方法来提升钴酸锂正极材料在高电压下的结构稳定性。通过高分辨透射电子显微镜及X射线衍射证明了Al-Zn共掺杂可增大钴酸锂晶面间距;扫描电镜-元素分布分析证明了Al-Zn的均匀掺杂;电化学阻抗谱证明了共掺杂对界面副反应的抑制作用。结果表明,通过调控晶体结构和界面副反应,可以有效增强高电压下钴酸锂的电化学稳定性。通过软包金属锂电池的组装发现,Al-Zn共掺杂的钴酸锂正极材料在4.6 V充电截止电压、0.2C倍率下,充放电比容量可达218.8 mA·h/g,循环600次后容量保持率可达83.3%,且其综合电化学性能远高于铝掺杂及未改性的钴酸锂正极材料。

本文引用格式

刘娟 , 蒋庆来 , 张月异 . 4.6 V高电压钴酸锂正极材料Al-Zn共掺杂研究[J]. 无机盐工业, 2024 , 56(11) : 59 -64 . DOI: 10.19964/j.issn.1006-4990.2024-0115

Abstract

Lithium cobalt oxide has a theoretical capacity of up to 274 mA·h/g and it is one of the earliest commercialized cathode materials for lithium-ion batteries.However,the instability of the layered structure of lithium cobalt oxide at high voltage makes it difficult for its actual charging voltage to exceed 4.45 V(vs.Li),thus greatly limiting its capacity.In response to the above problems,the method of co-doping with small-radius aluminum ions and large-radius zinc ions was used to improve the structural stability of lithium cobalt oxide cathode materials at high voltage.High-resolution transmission electron microscopy and X-ray diffraction proved that Al-Zn co-doping could increase the interplanar spacing of lithium cobalt oxide.The scanning electron microscopy-element distribution analysis proved the uniform doping of Al-Zn.And the electrochemical impedance spectroscopy proved the inhibitory effect of co-doping on interfacial side reactions.The results showed that the electrochemical stability of lithium cobalt oxide at high voltage could be effectively enhanced by regulating the crystal structure and interfacial side reactions.Through the assembly of soft-pack metal lithium batteries,it was found that the Al-Zn co-doped lithium cobalt oxide cathode material has a charge and discharge specific capacity of 218.8 mA·h/g at a charge cut-off voltage of 4.6 V and a rate of 0.2C.The capacity retention rate could reach 83.3% after 600 cycles,and its comprehensive electrochemical performance was much higher than that of aluminum-doped and unmodified lithium cobalt oxide cathode materials.

参考文献

1 XU Shaomao, HU Liangbing.Towards a high-performance garnet-based solid-state Li metal battery:A perspective on recent advan-ces[J].Journal of Power Sources2020472:228571 .
2 LIU Chaofeng, NEALE Z G, CAO Guozhong.Understanding electrochemical potentials of cathode materials in rechargeable batteries[J].Materials Today201619(2):109-123.
3 刘卓钦,周晓崇,莫梁君.硼酸锂包覆改性尖晶石锰酸锂的研究[J].无机盐工业202254(9):90-95.
  LIU Zhuoqin, ZHOU Xiaochong, MO Liangjun.Study on modification of spinel lithium manganate coated with lithium borate[J].Inorganic Chemicals Industry202254(9):90-95.
4 WHITTINGHAM M S.Ultimate limits to intercalation reactions for lithium batteries[J].Chemical Reviews2014114(23):11414-11443.
5 ZHANG Xueqiang, CHENG Xinbing, ZHANG Qiang.Nanostructured energy materials for electrochemical energy conversion and storage:A review[J].Journal of Energy Chemistry201625(6):967-984.
6 WANG Kai, WAN Jiajia, XIANG Yuxuan,et al.Recent advances and historical developments of high voltage lithium cobalt oxide materials for rechargeable Li-ion batteries[J].Journal of Power Sources2020460:228062.
7 QIAN Jiawei, LIU Lei, YANG Jixiang,et al.Electrochemical surface passivation of LiCoO2 particles at ultrahigh voltage and its applications in lithium-based batteries[J].Nature Communications20189(1):4918.
8 YOON M, DONG Yanhao, YOO Y,et al.Unveiling nickel chemistry in stabilizing high-voltage cobalt-rich cathodes for lithium-ion batteries[J].Advanced Functional Materials202030(6):1907903.
9 PENG Linfeng, REN Haotian, ZHANG Junzhao,et al.LiNbO3-coated LiNi0.7Co0.1Mn0.2O2 and chlorine-rich argyrodite enabling high-performance solid-state batteries under different temperatur-es[J].Energy Storage Materials202143:53-61.
10 OHTA S, KOMAGATA S, SEKI J,et al.All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing[J].Journal of Power Sources2013238:53-56.
11 CADY C W, GARDNER G, MARON Z O,et al.Tuning the electrocatalytic water oxidation properties of AB2O4 spinel nanocrystals:A(Li,Mg,Zn) and B(Mn,Co) site variants of LiMn2O4 [J].ACS Catalysis20155(6):3403-3410.
12 HAN Fudong, ZHU Yizhou, HE Xingfeng,et al.Electrochemical stability of Li10GeP2S12 and Li7La3Zr2O12 solid electrolytes[J].Advanced Energy Materials20166(8):1501590.
13 GAO Aolei, SUN Zhenhua, LI Shaopeng,et al.The mechanism of manganese dissolution on Li1.6Mn1.6O4 ion sieves with HCl[J].Dalton Transactions201847(11):3864-3871.
14 ZHU Zhi, YU Daiwei, SHI Zhe,et al.Gradient-morph LiCoO2 sin-gle crystals with stabilized energy density above3 400 W·h/L[J].Energy & Environmental Science,2020,13(6):1865-1878.
15 LI Xiaona, LIANG Jianwen, CHEN Ning,et al.Water-mediated synthesis of a superionic halide solid electrolyte[J].Angewandte Chemie201958(46):16427-16432.
16 JIN Congrui.Comment on “multiphase,multiscale chemomechanics at extreme low temperatures:Battery electrodes for operation in a wide temperature range”[J].Advanced Energy Materials202212(25):2200686.
17 ZHAO Ning, KHOKHAR W, BI Zhijie,et al.Solid garnet batteries[J].Joule20193(5):1190-1199.
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