LiNi_(1-x-y)Co_xMn_yO_2正极材料的制备与电化学性能
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摘要
LiNi_(1-x-y)Co_xMn_yO_2正极材料作为最有商业化前途的锂离子电池正极材料,近年来成为研究者关注的焦点。但目前针对该材料合成工艺的研究还较少。对LiNi_(0.8)Co_(0.15)Mn_(0.05)O_2开展了不同的烧结工艺研究,并对制备出的正极材料进行了表征和性能测试。研究发现在0.1C (电池容量额定值)倍率下充放电比容量为200mA·h·g~(-1)左右,在1C倍率循环100次下,480℃@3h+780℃@5h和500℃@5h+780℃@10h两种烧结工艺下容量保持率分别为94%和86%,说明用这两种工艺制备的正极材料的综合性能最优。
As the most promising commercial lithium-ion battery,the LiNi_(1-x-y)Co_xMn_yO_2 cathode have become the focus of researchers in recent years.However,there are less researches on the synthetic process of this material.This paper discusses various sintering processes of LiNi_(0.8)Co_(0.15)Mn_(0.05)O_2,and the characterization and electrochemical performances testing of the prepared cathode materials.The research shows that the material has higher specific capacity(about 200 mA·h·g~(-1))at 0.1 C(Cis battery capacity rating value)chargingdischarging rate.At 1 Cand 100 times of charging-discharging,the capacity retention ratios of 480 ℃@3 h +780℃@5 hand 500℃@5 h+780℃@10 hsintering processes are 94%and 86%,respectively,which illustrates the synthetical properties of the cathode materials prepared by these two processes are optimal.
As the most promising commercial lithium-ion battery,the LiNi_(1-x-y)Co_xMn_yO_2 cathode have become the focus of researchers in recent years.However,there are less researches on the synthetic process of this material.This paper discusses various sintering processes of LiNi_(0.8)Co_(0.15)Mn_(0.05)O_2,and the characterization and electrochemical performances testing of the prepared cathode materials.The research shows that the material has higher specific capacity(about 200 mA·h·g~(-1))at 0.1 C(Cis battery capacity rating value)chargingdischarging rate.At 1 Cand 100 times of charging-discharging,the capacity retention ratios of 480 ℃@3 h +780℃@5 hand 500℃@5 h+780℃@10 hsintering processes are 94%and 86%,respectively,which illustrates the synthetical properties of the cathode materials prepared by these two processes are optimal.
引文
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[19]翟静,赵敏寿,沙鸥,等.锂离子电池正极材料Li3V2(PO4)3的研究进展[J].稀有金属材料与工程,2010,39(7):1311-1316.(Zhai Jing,Zhao Minshou,Sha Ou,et al.Research progress in cathode material Li3V2(PO4)3for Li-ion batteries.Rare Metal Materials and Engineering,2010,39(7):1311-1316)
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[21]李龙.锂离子电池镍钴锰三元正极材料的合成与改性研究[D].北京:清华大学,2012:1-54.(Li Long.Synthesis and modification of LiN-ixCoyMnzO2cathode material for lithium battery.Beijing:Tsinghua University,2012:1-54)
[22]阮泽文.LiNi(1-x-y)CoxAlyO2高镍三元正极材料的制备及改性研究[D].哈尔滨:哈尔滨工业大学,2016:1-81.(Ruan Zewen.Synthesis and modification of LiNi1-x-yCoxAlyO2nickel rich cathode materials.Harbin:Harbin Institute of Technology,2016:1-81)
[23]艾灵,毛丽萍,李世友,等.三元正极材料LiNi0.6Co0.2Mn0.2O2制备及改性方法进展[J].化工新型材料,2018,46(5):11-15.(Ai Ling,Mao Liping,Li Shiyou,et al.Progress on the preparation and modification of LiNi0.6Co0.2Mn0.2O2ternary anode material.New Chemical Materials,2018,46(5):11-15)
[24]李尚津.锂离子电池三元正极材料LiNi0.5Co0.2Mn0.3O2的制备与改性[D].南宁:广西大学:2017:1-47.(Li Shangjin.Preparation and modification of LiNi0.5Co0.2Mn0.3O2of the lithium ion battery.Nanning:Guangxi University,2017:1-47)
[25]路乃群,王存国,王静强,等.锂离子电池三元正极材料LiNi1/3Co1/3Mn1/3O2的制备方法及其改性研究进展[J].化工科技,2018,26(6):58-63.(Lu Naiqun,Wang Cunguo,Wang Jingqiang,et al.Development of the ternary cathode material LiNi1/3Co1/3Mn1/3O2and its modification for lithium ion batteries.Science&Technology in Chemical Industry,2018,26(6):58-63)
[26]Wolff-Goodrich S,Lin F,Markus I M,et al.Tailoring the surface properties of LiNi0.4Mn0.4Co0.2O2by titanium substitution for improved high voltage cycling performance[J].Physical Chemistry Chemical Physics,2015,17(34):21778-21781.
[27]王义飞,武行兵,王双双,等.三元正极材料LiNi1-x-yCoxAlyO的研究进展[J].电池,2017,47(2):112-115.(Wang Yifei,Wu Xingbing,Wang Shuangshuang,et al.Research progress in ternary cathode materials LiNi1-x-yCoxAlyO2.Battery Bimonthly,2017,47(2):112-115)
[2]Li Yangxing,Wan Chunrong,Wu Yuping,et al.Synthesis and characterization of ultrafine LiCoO2powders by a spray-drying method[J].Journal of Power Sources,2000,85(2):294-298.
[3]Armand M,Tarascon J M.Building better batteries[J].Nature,2008,451:652-657.
[4]庞春会,吴川,吴锋,等.锂离子电池纳米正极材料合成方法研究进展[J].硅酸盐学报,2012,40(2):247-255.(Pang Chunhui,Wu Chuan,Wu Feng,et al.Development on synthesis methods for nano-materials of cathode for lithium ion battery.Journal of the Chinese Ceramic Society,2012,40(2):247-255)
[5]Patil A,Patil V,Shin D W,et al.Issue and challenges facing rechargeable thin film lithium batteries[J].Mater Res Bull,2008,43:1913-1942.
[6]Shukla A K,Kumar T P.Materials for next-generation lithium batteries[J].Curr Sci,2008,94:314-331.
[7]Hassoun J,Kim J H,Lee D J.A contribution to the progress of high energy batteries:A metal-free,lithium-ion,silicon-sulfur battery[J].Journal of Power Sources,2012,202:308-313.
[8]邹邦坤,丁楚雄,陈春华.锂离子电池三元正极材料的研究进展[J].中国科学:化学,2014,44(7):1104-1115.(Zou Bangkun,Ding Chuxiong,Chen Chunhua.Research progress in ternary cathode materials Li(Ni,Co,Mn)O2for lithium ion batteries.Scientia Sinica Chimica,2014,44(7):1104-1115)
[9]黄可龙,王兆翔,刘素琴.锂离子电池原理与关键技术[M].北京:化学工业出版社,2008:1-10.(Huang Kelong,Wang Zhaoxiang,Liu Suqin.Principle and key technology of lithium ion battery.Beijing:Chemical Industry Press,2008:1-10)
[10]马璨,吕迎春,李泓.锂离子电池基础科学问题(Ⅶ)-正极材料[J].储能科学与技术,2014,3(1):53-65.(Ma Can,LüYingchun,Li Hong.Fundamental scientific aspects of lithium batteries(Ⅶ)-positive electrode materials.Energy Storage Science and Technology,2014,3(1):53-65)
[11]章福平,纪勇,李安东,等.锂离子电池正极材料研究的新动向和挑战[J].化学通报,2011,74(10):891.(Zhang Fuping,Ji Yong,Li Andong,et al.Progresses and challenges in studies on cathodic materials of Li-ion battery.Chemistry,2011,74(10):891)
[12]王昭.锂离子电池富锂锰基三元正极材料的研究[D].北京:北京理工大学,2015:1-189.(Wang Zhao.Studies on Li-excess Mn-based Li1.2Mn0.54Ni0.13Co0.13O2as cathode materials for lithium batteries.Beijing:Beijing Institute of Technology,2015:1-189)
[13]周燕芳,钟辉.锂离子电池正极材料的研究进展[J].材料开发与应用,2003,18(2):34-38.(Zhou Yanfang,Zhong Hui.Research progress in positive electrode materials for lithium ion battery.Development and Application of Materials,2003,18(2):34-38)
[14]Muto S S,Tatsumi K S,Kojima Y J,et al.Effect of Mg-doping on the degradation of LiNiO2-based cathode materials by combined spectroscopic methods[J].Power Sources,2012,205:449-455.
[15]Cui Y L,Bao W J,Yuan Z,et al.Comparison of different soft chemical routes synthesis of submicro-LiMn2O4and their influence on its electrochemical properties[J].Solid State Electrochemistry,2012,16(4):1551-1559.
[16]周文彩,李金洪,姜晓谦.磷酸铁锂制备工艺及研究进展[J].硅酸盐通报,2010,29(1):134-146.(Zhou Wencai,Li Jinhong,Jiang Xiaoqian.Preparation and research progress of LiFePO4cathode material.Bulletin of the Chinese Ceramic Society,2010,29(1):134-146)
[17]张新龙,胡国荣,彭忠东,等.锂离子电池正极材料LiFePO4的研究进展[J].电池,2003,33(4):252-254.(Zhang Xinlong,Hu Guorong,Peng Zhongdong,et al.Development of LiFePO4as cathode material of Li-ion battery.Battery Bimonthly,2003,33(4):252-254)
[18]沙鸥,赵敏寿,翟静,等.锂离子电池新型正极材料LiFePO4的研究进展[J].稀有金属材料与工程,2009,38(11):252-254.(Sha Ou,Zhao Minshou,Zhai Jing,et al.Research progress on LiFePO4-A new type of cathode materials for lithium-ion battery.Rare Metal Materials and Engineering,2009,38(11):252-254)
[19]翟静,赵敏寿,沙鸥,等.锂离子电池正极材料Li3V2(PO4)3的研究进展[J].稀有金属材料与工程,2010,39(7):1311-1316.(Zhai Jing,Zhao Minshou,Sha Ou,et al.Research progress in cathode material Li3V2(PO4)3for Li-ion batteries.Rare Metal Materials and Engineering,2010,39(7):1311-1316)
[20]Li Y J,Hong L,Wu F.Preparation of Li3V2(PO4)3cathode material for power Li-ion batteries[J].Progress in Chemistry,2012,24(1):47-53.
[21]李龙.锂离子电池镍钴锰三元正极材料的合成与改性研究[D].北京:清华大学,2012:1-54.(Li Long.Synthesis and modification of LiN-ixCoyMnzO2cathode material for lithium battery.Beijing:Tsinghua University,2012:1-54)
[22]阮泽文.LiNi(1-x-y)CoxAlyO2高镍三元正极材料的制备及改性研究[D].哈尔滨:哈尔滨工业大学,2016:1-81.(Ruan Zewen.Synthesis and modification of LiNi1-x-yCoxAlyO2nickel rich cathode materials.Harbin:Harbin Institute of Technology,2016:1-81)
[23]艾灵,毛丽萍,李世友,等.三元正极材料LiNi0.6Co0.2Mn0.2O2制备及改性方法进展[J].化工新型材料,2018,46(5):11-15.(Ai Ling,Mao Liping,Li Shiyou,et al.Progress on the preparation and modification of LiNi0.6Co0.2Mn0.2O2ternary anode material.New Chemical Materials,2018,46(5):11-15)
[24]李尚津.锂离子电池三元正极材料LiNi0.5Co0.2Mn0.3O2的制备与改性[D].南宁:广西大学:2017:1-47.(Li Shangjin.Preparation and modification of LiNi0.5Co0.2Mn0.3O2of the lithium ion battery.Nanning:Guangxi University,2017:1-47)
[25]路乃群,王存国,王静强,等.锂离子电池三元正极材料LiNi1/3Co1/3Mn1/3O2的制备方法及其改性研究进展[J].化工科技,2018,26(6):58-63.(Lu Naiqun,Wang Cunguo,Wang Jingqiang,et al.Development of the ternary cathode material LiNi1/3Co1/3Mn1/3O2and its modification for lithium ion batteries.Science&Technology in Chemical Industry,2018,26(6):58-63)
[26]Wolff-Goodrich S,Lin F,Markus I M,et al.Tailoring the surface properties of LiNi0.4Mn0.4Co0.2O2by titanium substitution for improved high voltage cycling performance[J].Physical Chemistry Chemical Physics,2015,17(34):21778-21781.
[27]王义飞,武行兵,王双双,等.三元正极材料LiNi1-x-yCoxAlyO的研究进展[J].电池,2017,47(2):112-115.(Wang Yifei,Wu Xingbing,Wang Shuangshuang,et al.Research progress in ternary cathode materials LiNi1-x-yCoxAlyO2.Battery Bimonthly,2017,47(2):112-115)