基于分级共沉淀法制备锂离子电池LiNi0.5Co0.2Mn0.3O2正极材料

doi:10.11949/j.issn.0438-1157.20160974

化工学报 ›› 2017, Vol. 68 ›› Issue (3): 1239-1246.DOI: 10.11949/j.issn.0438-1157.20160974

• 材料化学工程与纳米技术 • 上一篇下一篇

基于分级共沉淀法制备锂离子电池LiNi_0.5Co_0.2Mn_0.3O₂正极材料

夏青, 赵俊豪, 王凯, 李昇, 郭冰, 田院, 杨则恒, 张卫新

合肥工业大学化学与化工学院, 安徽合肥 230009

收稿日期:2016-07-11 修回日期:2016-11-02 出版日期:2017-03-05 发布日期:2017-03-05
通讯作者: 张卫新,wxzhang@hfut.edu.cn
基金资助:
国家自然科学基金项目（91534102，21271058）；安徽省科技攻关项目（1501021013）；合肥工业大学智能制造技术研究院项目（IMICZ2015104）。

Synthesis and characterization of LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials by stepwise co-precipitation

XIA Qing, ZHAO Junhao, WANG Kai, LI Sheng, GUO Bing, TIAN Yuan, YANG Zeheng, ZHANG Weixin

School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, Anhui, China

Received:2016-07-11 Revised:2016-11-02 Online:2017-03-05 Published:2017-03-05
Contact: 10.11949/j.issn.0438-1157.20160974
Supported by:
supported by the National Natural Science Foundation of China (91534102,21271058),the Science and Technology Project of Anhui Province (1501021013) and the Intelligent Manufacturing Institute of Hefei University of Technology (IMICZ2015104).

摘要/Abstract

摘要：

通过分级共沉淀（分级进料）方法，结合高温热处理合成了金属元素（Ni，Mn）浓度从中心到表面呈梯度分布（中心富Ni，表面富Mn）的球形三元正极材料LiNi_0.5Co_0.2Mn_0.3O₂。利用X射线衍射（XRD）、场发射扫描电镜（FESEM）、能谱仪（EDS）和电感耦合等离子质谱仪（ICP-MS）等表征了所制备材料的成分、形貌和元素分布。通过恒流充放电和循环伏安、交流阻抗等方法对材料的电化学性能进行测试。结果表明，与传统的一级共沉淀方法相比，分级共沉淀所制备材料展现出更高的倍率性能（20 C放电比容量为104.1 mAh·g^-1）、循环保持率（0.5 C循环200次容量保持率为95.8%）和快速充放电性能（20 C/20 C放电比容量为85.4 mAh·g^-1）。这种分级进料制备技术可以有效提高共沉淀法制备锂离子电池三元正极材料的电化学性能。

关键词: 锂离子电池, 分级共沉淀, 合成, 化学反应, 梯度分布, 电化学

Abstract:

A stepwise co-precipitation route (precipitation with different ratios of Ni, Mn elements in three steps)has been adopted to synthesize the precursor of LiNi_0.5Co_0.2Mn_0.3(OH)₂, which was mixed with Li₂CO₃ afterwards in a certain proportion. After post-heat treatment, the obtained LiNi_0.5Co_0.2Mn_0.3O₂ spherical cathode materials exhibit a gradient element distribution (nickel-rich in centre and manganese-rich around surface). The structure, morphology and chemical composition of the samples were characterized by X-Ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive Spectrometer (EDS) and Inductively Coupled Plasma Mass Spectrometry(ICP-MS), respectively. The electrochemical performances of the as-prepared LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials were studied by galvanostatic charge/discharge measurements, Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). The testing results show that the materials derived from stepwise co-precipitation exhibit higher rate capability (104.1 mAh·g^-1 at 20 C), better cycle performance (with capacity retention of 95.8% after 200 cycles at 0.5 C) and more efficient fast charge and discharge performance (85.4 mAh·g^-1 at 20 C/20 C), compared with the counterparts obtained from the conventional co-precipitation. In summary, this stepwise co-precipitation strategy is extremely promising for the preparation of LiNi_0.5Co_0.2Mn_0.3O₂ electrode materials with enhanced electrochemical performances.

Key words: Lithium-ion battery, stepwise co-precipitation, synthesis, chemical reaction, gradient distribution, electrochemistry

中图分类号:

TQ150.1

夏青, 赵俊豪, 王凯, 李昇, 郭冰, 田院, 杨则恒, 张卫新. 基于分级共沉淀法制备锂离子电池LiNi_0.5Co_0.2Mn_0.3O₂正极材料[J]. 化工学报, 2017, 68(3): 1239-1246.

XIA Qing, ZHAO Junhao, WANG Kai, LI Sheng, GUO Bing, TIAN Yuan, YANG Zeheng, ZHANG Weixin. Synthesis and characterization of LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials by stepwise co-precipitation[J]. CIESC Journal, 2017, 68(3): 1239-1246.

参考文献 30

[1]	ARMAND M, TARASCON J M. Building better batteries[J]. Nat., 2008, 451(7179):652-657.
[2]	LIU W, OH P, LIU X, et al. Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries[J]. Angew. Chem. Int. Ed., 2015, 54(15):4440-4457.
[3]	田从学, 张昭, 侯隽, 等. 非化学计量比尖晶石型锂离子电池正极材料的合成与表征[J]. 化工学报, 2006, 57(4):937-942. TIAN C X, ZHANG Z, HOU J, et al. Synthesis and characterization of non stoichiometric spinel as anode for rechargeable lithium ion battery[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(4):937-942.
[4]	MA G, Li S, ZHANG W X, et al. A general and mild approach to controllable preparation of manganese-base micro-and nanostructured bars for high performance lithium-ion batteries[J]. Angew. Chem. Int. Ed., 2016, 128:21-30.
[5]	LIU Z, YU A, LEE J Y. Synthesis and characterization of LiNi1-x-yCoxMnyO2 as the cathode materials of secondary lithium batteries[J]. J. Power Sources, 1999, s81/s82(9):416-419.
[6]	JUNG S K, GWON H, HONG J, et al. Understanding the degradation mechanisms of LiNi0.5Co0.2Mn0.3O2 cathode material in lithium ion batteries[J]. Adv. Energy Mater., 2014, 4(1):94-98.
[7]	HE Y S, MA Z F, LIAO X Z, et al. Synthesis and characterization of submicron-sized LiNi1/3Co1/3Mn1/3O2 by a simple self-propagating solid-state metathesis method[J]. J. Power Sources, 2007, 163(2):1053-1058.
[8]	LI L J, LI X H, WANG Z X, et al. Synthesis of LiNi0.8Co0.1Mn0.1O2 cathode material by chloride co-precipitation method[J]. Trans. Nonferrous Met. Soc., China, 2010, 20:s279-s282.
[9]	FU H Q, ZHANG X Y, HUANG H, et al. Conductivity property of polyaniline synthesized by emulsion polymerization[J]. J. Chem. Ind. Eng., 2005, 56(9):1790-1793.
[10]	LEE M H, KANG Y J, MYUNG S T, et al. Synthetic optimization of Li[Ni1/3Co1/3Mn1/3] O2 via co-precipitation[J]. Electrochim. Acta, 2004, 50(4):939-948.
[11]	MANTHIRA A, KNIGHT J C, MYUNG S T, et al. Nickel-rich and lithium-lich layered oxide cathodes:progress and perspectives[J]. Adv. Energy Mater., 2016, 6(1). DOI:10.1002/aenm.201501010. http://onlinelibrary.wiley.com/doi/10.1002/aenm.201501010/full
[12]	WRIGHT R B, CHRISTOPHERSEN J P, MOTLOCH C G, et al. Power fade and capacity fade resulting from cycle-life testing of advanced technology development program lithium-ion batteries[J]. J. Power Sources, 2003, 119/120/121(3):865-869.
[13]	WOO S U, PARK B C, YOON C S, et al. Improvement of electrochemical performances of Li[Ni0.8Co0.1Mn0.1] O2 cathode materials by fluorine substitution[J]. J. Electrochem. Soc., 2007, 154(7):A649-A655.
[14]	SUN Y K, LEE B R, NOH H J, et al. A novel concentration-gradient Li[Ni0.83Co0.07Mn0.10] O2 cathode material for high-energy lithium batteries[J]. J. Mater. Chem., 2011, 21(27):10108-10112.
[15]	NOH M, CHO J. Optimized synthetic conditions of LiNi0.5Co0.2Mn0.3O2 cathode materials for high rate lithium batteries via co-precipitation method[J]. J. Electrochem. Soc., 2012, 160(1):A105-A111.
[16]	LI X, QIU K, GAO Y, et al. High potential performance of cerium-doped LiNi0.5Co0.2Mn0.3O2 cathode material for Li-ion battery[J]. J. Mater. Sci., 2015, 50(7):2914-2920.
[17]	YANG Z H, LU J B, BIAN D C, et al. Stepwise co-precipitation to synthesize LiNi1/3Co1/3Mn1/3O2 one-dimensional hierarchical structure for lithium ion batteries[J]. J. Power Sources, 2014, 272:144-151.
[18]	OHZUKU T, MAKIMURA Y. Layered lithium insertion material of LiCoNiO2 for lithium-ion batteries[J]. Chem. Lett., 2001, (7):642-643.
[19]	KIM J M, CHUNG H T. Role of transition metals in layered Li[Ni,Co,Mn]O2 under electrochemical operation[J]. Electrochim. Acta, 2004, 49(21):3573-3580.
[20]	王亮, 何雨石, 张晓鸣, 等. 微波共沉淀法制备锂离子电池正极材料LiNi0.8Co0.2O2[J]. 化工学报, 2007, 58(4):1048-1052. WANG L, HE Y S, ZHANG X M, et al. Preparation and electrochemical properties of LiNi0.8Co0.2O2 cathode material by microwave coprecipitation method[J]. Journal of Chemical Industry and Engineering (China), 2007, 58(4):1048-1052.
[21]	OHZUKU T, UETA A, NAGAYAMA M, et al. Comparative study of LiCoO2, LiNiCoO2 and LiNiO2 for 4 volt secondary lithium cells[J]. Electrochim. Acta, 1993, 38(9):1159-1167.
[22]	HUANG Z D, LIU X M, OH S W, et al. Microscopically porous, interconnected single crystal LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries[J]. J. Mater. Chem., 2011, 21(29):10777-10784.
[23]	LU J, PENG Q, WANG W Y, et al. Nanoscale coating of LiMO2(M=Ni, Co, Mn) nanobelts with Li+-conductive Li2TiO3:toward better rate capabilities for Li-ion batteries[J]. J. Am. Chem. Soc., 2013, 135(5):1649-1652.
[24]	LIN F, NORDLUND D, LI Y, et al. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries[J]. Nat. Energy, 2016, 1(1). DOI:10.1038/nenergy.2015.4. http://www.nature.com/articles/nenergy20154
[25]	SUN Y K, MYUNG S T, PARK B C, et al. High-energy cathode material for long-life and safe lithium batteries[J]. Nat. Mater., 2009, 8(4):320-324.
[26]	SUN Y K, CHEN Z H, NOH H J, et al. Nanostructured high-energy cathode materials for advanced lithium batteries[J]. Nat. Mater., 2012, 11(11):942-947.
[27]	YI T F, FANG Z K, XIE Y, et al. Synthesis of LiNi0.5Mn1.5O4 cathode with excellent fast charge-discharge performance for lithium-ion battery[J]. Electrochim. Acta, 2014, 147(147):250-256.
[28]	KONAROVA M, TANIGUCHI I. Synthesis of carbon-coated LiFePO4 nanoparticles with high rate performance in lithium secondary batteries[J]. J. Power Sources, 2010, 195(11):3661-3667.
[29]	SHAJU K M, RAO G V S, CHOWDARI B V R. Influence of Li-ion kinetics in the cathodic performance of layered Li(Ni1/3Co1/3Mn1/3)O2[J]. J. Electrochem. Soc., 2003, 151(9):A1324-A1332.
[30]	LI J, CAO C, XU X, et al. LiNi1/3Co1/3Mn1/3O2 hollow nano-micro hierarchical microspheres with enhanced performances as cathodes for lithium-ion batteries[J]. J. Mater. Chem. A, 2013, 1(38):11848-11852.

基于分级共沉淀法制备锂离子电池LiNi_0.5Co_0.2Mn_0.3O₂正极材料

Synthesis and characterization of LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials by stepwise co-precipitation

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王琪, 张斌, 张晓昕, 武虎建, 战海涛, 王涛. 氯铝酸-三乙胺离子液体/P₂O₅催化合成伊索克酸和2-乙基蒽醌[J]. 化工学报, 2023, 74(S1): 245-249.
[2]	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.
[3]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[4]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[5]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[6]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[7]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[8]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[9]	何晓崐, 刘锐, 薛园, 左然. MOCVD生长AlN单晶薄膜的气相和表面化学反应综述[J]. 化工学报, 2023, 74(7): 2800-2813.
[10]	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.
[11]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[12]	张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.
[13]	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.
[14]	李彬, 徐正虎, 姜爽, 张天永. 双氧水催化氧化法清洁高效合成促进剂CBS[J]. 化工学报, 2023, 74(7): 2919-2925.
[15]	张谭, 刘光, 李晋平, 孙予罕. Ru基氮还原电催化剂性能调控策略[J]. 化工学报, 2023, 74(6): 2264-2280.