高镍系三元层状氧化物正极材料容量衰减机理的研究进展

doi:10.15541/jim20160255

摘要/Abstract

摘要：

高镍系三元层状氧化物正极材料因其高比容量、低廉的价格以及较好的环境友好性而受到广泛关注, 但是其固有的一些缺点, 如循环过程中结构稳定性差、高温稳定性差以及储存性能差等极大地限制了其在各领域的广泛应用。本文着重总结并讨论近年来对高镍系三元层状氧化物正极材料循环过程容量衰减机理的研究进展, 并对高镍系三元层状氧化物正极材料的进一步改性作了简要的展望。

关键词: 高镍系氧化物, 三元层状氧化物, 正极材料, 衰减机理, 循环稳定性, 综述

Abstract:

Owing to advantages of high specific capacity, low cost and environmental friendliness, high-nickel ternary layered oxide cathode materials have received much attention and have been extensively studied over the past ten years. However, its further application is hindered by its structural instability during the cycling, thermal instability and poor storage properties. In order to provide references to tackle the problems that high nickel ternary layered oxide cathode materials faces, the degradation mechanisms of high-nickel ternary layered oxide cathode materials during cycling was summarized and discussed in this review. The degradation mechanisms are categorized as two major factors. One is thermodynamic factors including cation disorder as well as surface reactions, and the other is kinetic factors comprising of micro-cracks formation as well as rearrangement of conductive materials. The modification strategies corresponding to the major mechanisms and the research focusing on initial irreversible capacity loss are also briefly introduced.

Key words: high-nickel oxide, ternary layered oxide, cathode material, degradation mechanisms, cycling stability, review

中图分类号:

TM912

李想, 葛武杰, 王昊, 瞿美臻. 高镍系三元层状氧化物正极材料容量衰减机理的研究进展[J]. 无机材料学报, 2017, 32(2): 113-121.

LI Xiang, GE Wu-Jie, WANG Hao, QU Mei-Zhen. Research Progress on the Capacity Fading Mechanisms of High-Nickel Ternary Layered Oxide Cathode Materials[J]. Journal of Inorganic Materials, 2017, 32(2): 113-121.

图/表 9

图1 循环10次以后NCA晶界处的高分辨率扫描透射电镜图像[16]

Fig. 1 High-resolution STEM image of LiNi0.8Co0.15Al0.05O2 at a grain boundary layer after ten cycles [16]

图2 正极材料表面支柱层示意图[17]

Fig. 2 Schematic view of the layered cathode material with a pillar layer at the surface[17]

图3 Li层空间示意图 [22]

Fig. 3 Schematic representation of the inter-slab space[22](a) In the LixNi1+zO2 system, the oxidation of the Ni2+ ions during the cycling induces a local collapse of the inter-slab space which makes lithium diffusion and re-intercalation difficult; (b) The LixNi1-yMgO2 system, the electrochemically inactive Mg2+ ions do not hinder lithium diffusion since their size is very close to that of the Li+ ion

图4 氧缺陷对结构不稳定性的影响[25]

Fig. 4 Influence of oxygen defect on structural instabilities[25]

图5 NCA在(a)首次循环和(b)10次循环后的扫描透射电镜图像[16]

Fig. 5 STEM images of LiNi0.8Co0.15Al0.05O2 after (a) first cycle and (b) ten-cycles[16]

图6 (a)经过锂化的正极颗粒界面透射电镜图显示单个一次颗粒中成排的纳米结构, (b)单个纳米片的电子衍射图像显示晶胞的c轴垂直于片的基本面[43]

Fig. 6 (a) TEM image of cross-section of lithiated particle showing the aligned nanostructure inside a single particle, (b) Electron diffraction pattern on a single nanoplate showing that the c axis (in R3?m space) is perpendicular to the basal plane of the plate[43]

图7 5 μm×5 μm区域内LiNi0.8Co0.15Al0.05O2表面导电性(右边)和形貌(左边)的电流响应原子力显微镜图(接触电压1.0 V) [45]

Fig. 7 CSAFM images of surface conductance (right-hand panel) and topography (left-hand panel) of a 5×5 μm region of the composite LiNi0.8Co0.15Al0.05O2 cathode surface at 1.0 V tip-sample voltage difference[45](a) Virgin cell; (b) Cathode from the cell which lost 34% of power

图8 原位XRD和质谱联用分析结果示意图[52]

Fig. 8 Schematic of the results from in situ TR-XRD with MS analysis[52]

图 9 高镍系层状氧化物正极材料容量衰减机理示意图

Fig. 9 Schematic of capacity fading mechanism of high-nickel layered cathode materials

参考文献 54

[1]	LIU W, OH P, LIU X E, Nickel-Rich layered lithium transition-metal oxide for high-energy lithium-ion batteries.Angewandte Chemie International Edition, 2015, 54: 4440-4457.
[2]	YUAN RONG-ZHONG, QU MEI-ZHEN, YU ZUO-LONG.Thermal stability of nickel-based lithium transition metal oxides as the cathode materials for lithium-ion batteries. Journal of Inorganic Materials, 2003, 18(5): 973-979.
[3]	LI X L, KANG F Y, SHEN W C,et al. Improvement of structural stability and electrochemical activity of a cathode material LiNi0.7Co0.3O2 by chlorine doping. Electrochimica Acta, 2007, 53(4): 1761-1765.
[4]	WOO S W, MYUNG S T, BANG H, et al. Improvement of electrochemical and thermal properties of LiNi0.8Co0.1Mn0.1O2 positive electrode materials by multiple metal (Al, Mg) substitution. Electrochimica Acta, 2009, 54(15): 3851-3856.
[5]	MUTO S, TATSUMI K, KOJIMA Y,et al. Effect of Mg-doping on the degradation of LiNiO2-based cathode materials by combined spectroscopic methods. Journal of Power Sources, 2012, 205: 449-455.
[6]	LIU W M, HU G R, DU K,et al. Surface coating of LiNi0.8Co0.15Al0.05O2 with LiCoO2 by a molten salt method. Surface and Coating Technology, 2013, 216: 267-272.
[7]	XIONG X H, WANG Z X, YAN G C, et al. Role of V2O5 coating on LiNiO2-based materials for lithium ion battery. Journal of Power Sources, 2014, 245: 183-193.
[8]	HUANG B, LI X H, WANG Z X,et al. Enhanced electrochemical performance in LiNi0.8Co0.15Al0.05O2 cathode material: Resulting from Mn-surface-modification using a facile oxidizing-coating method. Materials Letters, 2014, 115: 49-52.
[9]	XIA SHU-BIAO, ZHANG YING-JIE, DONG PENG, et al. CeO2 surface modification to improve cycle and storage performance on lithium ion battery cathode material LiNi0.8Co0.15Al0.05O2. Chin. Journal of Inorganic Chemistry, 2014, 30(3): 529-535.
[10]	JU S H, KANG I S, LEE Y S,et al. Improvement of the cycling performance of LiNi0.6Co0.2Mn0.2O2 cathode active materials by a dual-conductive polymer coating. ACS Applied Materials and Interfaces, 2014, 6(4): 2546-2552.
[11]	LEE S H, YOON C S, KHALIL A,et al. Improvement of long-term cycling performance of Li(Ni0.8Co0.15Al0.05)O2 by AlF3 coating . Journal of Power Sources, 2013, 234: 201-207.
[12]	YANG H Z, LIU P X, CHEN Q L,et al. Fabrication and characteristics of high-capacity LiNi0.8Co0.15Al0.05O2 with monodisperse yolk-shell spherical precursors by a facile method . RSC Advances, 2014, 4: 35522-35527.
[13]	WU N T, WU H, YUAN W,et al. Facile synthesis of one-dimensional LiNi0.8Co0.15Al0.05O2 microrods as advanced cathode materials for lithium ion batteries. Journal of Materials Chemistry A, 2015, 3: 13648-13652.
[14]	YE NAI-QING, LIU CHANG-JIU, SHEN SHANG-YUE.Drawbacks and improve ways of LINiO2 as a cathode material for lithium ion batteries.Journal of Inorganic Materials, 2004, 19(6): 1217-1224.
[15]	LIN F, DENNIS N, LI Y Y,et al. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries. Nature Energy, 2016, 1: 15004.
[16]	MAKIMURA Y, ZHENG S J, IKUHARA Y C,et al. Microstructural observation of LiNi0.8Co0.15Al0.05O2 after charge and discharge by scanning transmission electron microscopy. Journal of The Electrochemical Society, 2012, 159(7): A1070-A1073.
[17]	CHO Y H, OH P, CHO J.A new type of protective surface layer for high-capacity Ni-based cathode materials: nanoscaled surface pillaring layer.Nano Letters, 2013, 13: 1145-1152.
[18]	KIM H J, KIM M G, JEONG H Y,et al. A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles. Nano Letters, 2015, 15: 2111-2119.
[19]	KONDO H, TAKEUCHI Y, SASAKI T,et al. Effects of Mg-substitution in Li(Ni,Co,Al)O2 positive electrode materials on the crystal structure and battery performance. Journal of Power Sources. 2007, 174(2): 1131-1136.
[20]	SATHIYAMOORTHI R, SHAKKTHIVEL P, RAMALAKSHMI S,et al. Influence of Mg doping on the performance of LiNiO2 matrix ceramic nanoparticles in high-voltage lithium-ion cells. Journal of Power Sources. 2007, 171(2): 922-927.
[21]	HUANG B, LI X, WANG Z,et al. Synthesis of Mg-doped LiNi0.8Co0.15Al0.05O2 oxide and its electrochemical behavior in high-voltage lithium-ion batteries. Ceramics International, 2014, 40: 13223-13230.
[22]	POUILLERIE C, CROGUENNEC L, BIENSAN P,et al. Synthesis and characterization of new LiNi1-yMgyO2 positive electrode materials for lithium-ion batteries. Journal of The Electrochemical Society, 2000, 147: 2061-2067.
[23]	WU F, TIAN J, SU Y F,et al. Effect of Ni2+ content on lithium/nickel disorder for Ni-rich cathode materials. ACS Appl. Mater. Interfaces, 2015, 7: 7702-7708.
[24]	CHEN Z Z, YUAN X J, WEN M S,et al. Preparation of LiNi0.80Co0.15Al0.05O2 cathode material via Li-rich method. Energy Storage Science and Technology, 2014, 3(6): 620-623.
[25]	BI Y J, YANG W C, DU R,et al. Correlation of oxygen non-stoichiometry to the instabilities and electrochemical performance of LiNi0.8Co0.1Mn0.1O2 utilized in lithium ion battery. Journal of Power Sources, 2015, 283: 211-218.
[26]	LI X, XIE Z W, LIU W J,et al. Effects of fluorine doping on structure, surface chemistry, and electrochemical performance of LiNi0.8Co0.15Al0.05O2. Electrochimica Acta, 2015, 174: 1122-1130.
[27]	ZHUANG G R V, CHEN G Y, SHIM J,et al. Li2CO3 in LiNi0.8Co0.15Al0.05O2 cathodes and its effects on capacity and power. Journal of Power Sources, 2004, 134(2): 293-297.
[28]	LIU W M, HU G R, DU K,et al. Enhanced storage property of LiNi0.8Co0.15Al0.05O2 coated with LiCoO2. Journal of Power Sources, 2013, 230: 201-206.
[29]	ZHU L, LIU Y, WU W Y,et al. Surface fluorinated LiNi0.8Co0.15Al0.05O2 as a positive electrode material for lithium ion batteries. Journal of Materials Chemistry A, 2015, 3: 15156-15162.
[30]	XIONG X H, WANG Z X, YUE P,et al. Washing effects on electrochemical performance and storage characteristics of LiNi0.8Co0.1Mn0.1O2 as cathode material for lithium-ion batteries. Journal of Power Sources, 2013, 222: 318-325.
[31]	ZHENG X B, LI X H, WANG Z X,et al. Investigation and improvement on the electrochemical performance and storage characteristics of LiNiO2-based materials for lithium ion battery. Electrochimica Acta, 2016, 191: 832.
[32]	BI Y J, WANG T, LIU M,et al. Stability of Li2CO3 in cathode of lithium ion battery and its influence on electrochemical performance. RSC Advances, 2016, 6: 19233-19237.
[33]	DOKKO K, NISHIZAWA M, HORIKOSHI S,et al. In situ observation of LiNiO2 single-particle fracture during Li-ion extraction and insertion. Electrochemical and Solid-State Letters, 2000, 3(3): 125-127.
[34]	ROBERT R, BÜNZLI C,BERG E J,et al.Activation mechanism of LiNi0.8Co0.15Al0.05O2: surface and bulk operando electrochemical, differential electrochemical mass spectrometry, and X ray diffraction analyses. Chemistry of Materials, 2015, 27: 526-536.
[35]	ITOU Y, UKYO Y.Performance of LiNiCoO2 materials for advanced lithium-ion batteries.Journal of Power Sources, 2005, 146(1/2): 39-44.
[36]	ZHENG S J, HUANG R, MAKIMURA Y,et al. Microstructural changes in LiNi0.8Co0.15Al0.05O2 positive electrode material during the first cycle .Journal of The Electrochemical Society, 2011, 158(4): A357-A362.
[37]	WATANABE S, KINOSHIRA M, HASOKAWA T,et al. Capacity fade of LiAlyNi1-x-yCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (surface analysis of LiAlyNi1-x-yCoxO2 cathode after cycle tests in restricted depth of discharge ranges). Journal of Power Sources, 2014, 258: 210-217.
[38]	MAKIMURA Y, ZHENG S J, IKUHARA Y,et al. Microstructural observation of LiNi0.8Co0.15Al0.05O2 after charge and discharge by scanning transmission electron microscopy. Journal of The Electrochemical Society, 2012, 159(7): A1070-A1073.
[39]	NOH H J, YOUN S, YOON C S,et al. Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2(x=1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries. Journal of Power Sources, 2013, 233: 121-130.
[40]	OHZUKU T, UEDA A, NAGAYAMA M.Electrochemistry and structural chemistry of LiNiO2 (R-3m) for 4 V secondary lithium cells.Journal of The Electrochemical Society, 1993, 140: 1862-1870.
[41]	YANG X Q, SUN X, MCBREEN J.Structural changes and thermal stability: In situ X-ray diffraction studies of a new cathode material LiMg0.125Ti0.125Ni0.75O2.Electrochemical Communications, 2000, 2: 733-737.
[42]	SUN Y K, CHEN Z H, NOH H J, et al. Nanostructured high-energy cathode materials for advanced lithium batteries. Nature Materials, 2012, 11: 942-947.
[43]	LEE E J, CHEN Z H, NOH H J,et al. Development of microstrain in aged lithium transition metal oxides. Nano Letters, 2014, 14: 4873-4880.
[44]	YANG J, XIA Y Y.Suppressing the phase transition of the layered Ni-rich oxide cathode during high-voltage cycling by introducing low-content Li2MnO3.ACS Applied Materials and Interfaces, 2016, 8(2): 1297-1308.
[45]	KOSTECKI R, MCLARNON F.Local-probe studies of degradation of composite LiNi0.8Co0.15Al0.05O2 cathodes in high-power Lithium-ion cells.Electrochemical and Solid-State Letters, 2004, 7(10): A380-A383.
[46]	KOSTECKI R, MCLARNON F.Degradation of LiNi0.8Co0.2O2 cathode surfaces in high-power lithium-ion batteries.Electrochemical and Solid-State Letters, 2002, 5(7): A164-A166.
[47]	KOSTECKI R, LEI J L, MCLARNON F,et al. Diagnostic evaluation of detrimental phenomena in high-power lithium-ion batteries. Journal of The Electrochemical Society, 2006, 153(4): A669-A672.
[48]	LEI J L, MCLARNON F, KOSTECKI R,et al. In situ Raman microscopy of individual LiNi0.8Co0.15Al0.05O2 particles in a Li-ion battery composite cathode. Journal of Physical Chemistry B, 2005, 109(2): 952-957.
[49]	SASAKI T, NONAKA T, OKA H,et al. Capacity-fading mechanisms of LiNiO2-based lithium-ion batteries I. Analysis by electrochemical and spectroscopic examination. Journal of The Electrochemical Society, 2009, 156(4): A289-A293.
[50]	MUTO S, SASANO Y, TATSUMI K,et al. Capacity-fading mechanisms of LiNiO2-based lithium-ion batteries II. Diagnostic analysis by electron microscopy and spectroscopy. Journal of The Electrochemical Society, 2009, 156(5): A371-A377.
[51]	KOJIMA Y, MUTO S, TATSUMI K,et al. Degradation analysis of a Ni-based layered positive-electrode active material cycled at elevated temperatures studied by scanning transmission electron microscopy and electron energy-loss spectroscopy. Journal of Power Sources, 2011, 196: 7721-7727.
[52]	BAK S M, NAM K W, CHANG W Y,et al. Correlating structural changes and gas evolution during the thermal decomposition of charged LixNi0.8Co0.15Al0.05O2 cathode materials. Chemistry of Materials, 2013, 25: 337-351.
[53]	WU L J, NAM K W, WANG X J,et al. Structural origin of overcharge-induced thermal instability of Ni-containing layered-cathodes for high-energy-density lithium batteries. Chemistry of Materials, 2011, 23: 3953-3960.
[54]	SHIM J, KOSTECKI R, RICHARDSON T,et al. Electrochemical analysis for cycle performance and capacity fading of a lithium-ion battery cycled at elevated temperature. Journal of Power Sources, 2002, 112: 222-230.