Synthesis and characterization of LiNi0.5Co0.2Mn0.3O2 cathode materials by stepwise co-precipitation

doi:10.11949/j.issn.0438-1157.20160974

Abstract

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

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

CLC Number:

TQ150.1

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.

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.

References 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.

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

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

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