高电压镍锰酸锂正极材料的合成与电化学机理  

Synthesis and electrochemical mechanism of high voltage lithium nickel manganate cathode materials

作　　者：李美萱 成建凤 黄国勇 徐盛明 郁丰善[1,4] 翁雅青 曹才放[6] 温嘉玮[1] 王俊莲 王春霞 顾斌涛[5] 张袁华[2] 刘斌 王才平 潘剑明 徐泽良 王翀 王珂 LI Meixuan;CHENG Jianfeng;HUANG Guoyong;XU Shengming;YU Fengshan;WENG Yaqing;CAO Caifang;WEN Jiawei;WANG Junlian;WANG Chunxia;GU Bintao;ZHANG Yuanhua;LIU Bin;WANG Caiping;PAN Jianming;XU Zeliang;WANG Chong;WANG Ke(College of New Energy and Materials,China University of Petroleum,Beijing 102249,China;Jiangxi Naihua Environmental Protection Technology Co.,Ltd.,Shangrao 334000,Jiangxi,China;Institute of Nuclear and New Energy Technology,Tsinghua University,Beijing 100084,China;Jiangxi Province Junxin Precious Metal Technology Materials Co.,Ltd.,Shangrao 335500,Jiangxi,China;Jiangxi Academy of Sciences,Nanchang 330096,Jiangxi,China;Jiangxi University of Science and Technology,Ganzhou 341000,Jiangxi,China;School of Civil and Resource Engineering,University of Science and Technology Beijing,Beijing 100083,China;Zhejiang Micro General New Catalytic materials Co.,Ltd.,Lishui 323300,Zhejiang,China;Hengfeng Kaiyi Industrial Co.,Ltd.,Shangrao 334300,Jiangxi,China)

机构地区：[1]中国石油大学(北京)新能源与材料学院,北京102249 [2]江西耐华环保科技有限公司,江西上饶334000 [3]清华大学核能与新能源技术研究院,北京100084 [4]江西省君鑫贵金属科技材料有限公司,江西上饶335500 [5]江西省科学院,江西南昌330096 [6]江西理工大学,江西赣州341000 [7]北京科技大学土木与资源工程学院,北京100083 [8]浙江微通催化新材料有限公司,浙江丽水323300 [9]横峰县凯怡实业有限公司,江西上饶334300

出　　处：《化工进展》2024年第9期5086-5094,共9页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(52274307);国家重点研发计划(2021YFC2901100);中国石油大学科学基金(2462021QNX2010);重油加工国家重点实验室(HON-KFKT2022-10)。

摘　　要：尖晶石型镍锰酸锂(Li Ni_(0.5)Mn_(1.5)O_(4))正极材料的工作电压平台为4.7V (vs.Li/Li^(+)),是目前输出电压最高、成本较低且环保的锂离子电池正极材料。本文采用水热法制备了铝掺杂的镍锰酸锂(Li Ni_(0.45)Al_(0.05)Mn_(1.5)O_(4),简称Al@LNMO)样品,并通过密度泛函理论计算研究了掺铝对镍锰酸锂电化学特性的影响。DFT计算结果表明,铝掺杂可以降低镍锰酸锂的带隙,提高其电导率。XRD和FTIR表征证明,合成的Al@LNMO的晶体结构为F3dm。此外,电化学循环测试表明,Al@LNMO在25℃和50℃温度下、1C倍率下的初始比放电容量分别为137.1m Ah/g、138.0m Ah/g;经过100次循环后,其容量保持率分别为82.9%和79.1%;并且,Al@LNMO在50℃下的容量保持率与在25℃下的容量保持率相近。这表明Al@LNMO具有良好的高温稳定性。Spinel-type lithium nickel manganese oxide(LiNi_(0.5)Mn_(1.5)O_(4))cathode material has an operating voltage plateau of 4.7V(vs.Li/Li^(+)),which is environmental-friendly cathode material alternatives for lithium-ion batteries with the highest output voltage and lower cost.In this paper,aluminum-doped lithium nickel manganese oxide(LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4),Al@LNMO)samples were prepared by a hydrothermal method,and the effect of aluminum doping on the electrochemical properties of lithium nickel manganese oxide(LNMO)was investigated by density functional theory(DFT)calculations.According to the results of DFT calculations,aluminum doping could reduce the band gap of LNMO and increase its conductivity.Structural characterization by XRD and FTIR showed that the crystal structure of the synthesized Al@LNMO was F3ˉdm.In addition,electrochemical cycling tests indicated that the initial specific discharge capacities of Al@LNMO were 137.1mAh/g and 138.0mAh/g at 25℃ and 50℃ and a multiplicity of 1C,respectively;and the capacity retention rates were 82.9% and 79.1% after 100 cycles,respectively.Moreover,the capacity retention rate of Al@LNMO at 50℃was similar to that at 25℃.This indicated that Al@LNMO had good high-temperature stability.The results showed that Al@LNMO was a promising high voltage cathode material for lithium-ion batteries.

关 键 词：铝掺杂镍锰酸锂 电化学 复合材料 分子模拟 高电压 

分 类 号：TM911[电气工程—电力电子与电力传动]