锂电池研究中的X射线多晶衍射实验与分析方法综述

doi:10.12028/j.issn.2095-4239.2018.0212

储能科学与技术 ›› 2019, Vol. 8 ›› Issue (3): 443-467.doi: 10.12028/j.issn.2095-4239.2018.0212

锂电池研究中的X射线多晶衍射实验与分析方法综述

张杰男¹, 汪君洋¹, 吕迎春², 禹习谦^1,3, 李泓^1,3

1 中国科学院物理研究所, 北京 100190;
2 上海大学材料基因组工程研究院, 上海 200444;
3 天目湖先进储能技术研究院有限公司, 江苏溧阳 213300

收稿日期:2018-10-20 修回日期:2019-02-20 出版日期:2019-05-01 发布日期:2019-03-13
通讯作者: 禹习谦,研究员,研究方向为高能量密度锂离子电池与固态锂电池材料设计,二次电池材料与器件先进表征及锂电池失效分析与逆向分析,E-mail:xyu@iphy.ac.cn
作者简介:张杰男(1990-),男,博士,研究方向为锂离子电池层状正极材料及锂电池失效分析,E-mail:jnzhang@iphy.ac.cn
基金资助:
国家重点研发计划新能源汽车重点专项（2016YFB0100100）及中国科学院战略性先导科技专项（XDA09010000）。

Experimental measurement and analysis methods of polycrystalline X-ray diffraction for lithium batteries

ZHANG Jienan¹, WANG Junyang¹, LÜ Yingchun², YU Xiqian^1,3, LI Hong^1,3

1 Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China;
2 Materials Genome Institution of Shanghai University, Shanghai 200444, China;
3 Tianmu Lake Institute of Advanced Energy Storage Technologies Co., Ltd, Liyang 213300, Jiangsu, China

Received:2018-10-20 Revised:2019-02-20 Online:2019-05-01 Published:2019-03-13

摘要/Abstract

摘要： X射线多晶衍射技术是研究晶体结构的重要手段，通过对衍射数据的分析，能够得到材料的晶胞参数、原子占位、晶粒大小、晶粒取向、应力分布等信息，对研究材料结构与性能之间的关系具有重要意义。在锂离子电池研究领域，X射线衍射技术广泛应用于材料合成、电芯检测及失效分析中的物相检测，极大地推动了电池材料的进步与发展。本文主要介绍了X射线多晶衍射基本原理与实验方法、测试过程常用参数设置、数据处理与结构精修方法，并结合实例介绍了X射线衍射技术在研究锂离子电池材料结构演化、反应机制、安全性能等方面的应用。

关键词: X射线衍射, 多晶分析, 测试方法, 锂电池

Abstract: Polycrystalline X-ray diffraction is an important tool to study the crystal structure of the material. Through analysis of the diffraction data, the structural parameters, e.g. lattice parameters, atomic site, grain size, grain orientation and stress distribution, can be retrieved, providing crucial information for studying relationship between structure and performance. This review briefly introduces the fundamental principles and experimental measurement methods and the commonly used Rietveld refinement method of polycrystalline X-ray diffraction. The applications of polycrystalline X-ray diffraction on study of lithium batteries are also discussed.

Key words: X-ray diffraction, polycrystalline analysis, measurement method, lithium batteries

中图分类号:

O636

张杰男, 汪君洋, 吕迎春, 禹习谦, 李泓. 锂电池研究中的X射线多晶衍射实验与分析方法综述[J]. 储能科学与技术, 2019, 8(3): 443-467.

ZHANG Jienan, WANG Junyang, Lyu Yingchun, YU Xiqian, LI Hong. Experimental measurement and analysis methods of polycrystalline X-ray diffraction for lithium batteries[J]. Energy Storage Science and Technology, 2019, 8(3): 443-467.

参考文献

[1] CELESTE A REISS, KHARCHENKO A, GATESHKI M. On the use of laboratory X-ray diffraction equipment for pair distribution function (PDF) studies[J]. Zeitschrift für Kristallographie Crystalline Materials, 2012, 227:257-261.
[2] YAMADA A, IWANE N, HARADA Y, et al. Lithium iron borates as high-capacity battery electrodes[J]. Adv. Mater., 2010, 22:3583-3587.
[3] YU X Q, HE Y, SUN J P, et al. Nanocrystalline MnO thin film anode for lithium ion batteries with low overpotential[J]. Electrochem. Commun., 2009, 11:791-794.
[4] CHUPAS P J, CHAPMAN K W, KURTZ C, et al. A versatile sample-environment cell for non-ambient X-ray scattering experiments[J]. J. Appl. Crystallogr., 2008, 41:822-824.
[5] 梁敬魁. 粉末衍射法测定晶体结构(第二版)[M]. 北京:科学出版社, 2011. LIANG Jingkui. Determination of crystal structures by powder diffraction method (2nd Edition)[M]. Beijing:Science Press, 2011.
[6] 郑振环, 李强. X射线多晶衍射数据Rietveld精修及GSAS软件入门[M]. 北京:中国建材工业出版社, 2016. ZHENG Zhenhuan, LI Qiang. Rietveld refinement of X-ray polycrystalline diffraction data and introduction of GSAS software[M]. Beijing:China Buliding Materials Press, 2016.
[7] MACGLASHAN G S, ANDREEV Y G, BRUCE P G. Structure of the polymer electrolyte poly(ethylene oxide)₆:LiAsF₆[J]. Nature, 1999, 398:792-794.
[8] WANG L, XU H, YAN N, et al. Exploring Brønsted acids confined in the 10-ring channels of the zeolite ferrierite[J]. CrystEngComm., 2018, 20:699-702.
[9] GORELIK T E, SCHMIDT M U, KOLB U,et al. Total-scattering pair-distribution function of organic material from powder electron diffraction data[J]. Microsc. Microanal, 2015, 21:459-471.
[10] BLIDBERG A, GUSTAFSSON T, TENGSTEDT C,et al. Monitoring Li_xFeSO₄F (x=1, 0.5, 0) phase distributions in operando to determine reaction homogeneity in porous battery electrodes[J]. Chem. Mater., 2017, 29:7159-7169.
[11] SCHERF L M, HATTENDORFF J, BUCHBERGER I, et al. Electrochemical synthesis of the allotrope allo-Ge and investigations on its use as an anode material[J]. J. Mater. Chem. A, 2017, 5:11179-11187.
[12] RENMAN V, HU S, ERIKSSON R, et al. Ni₃Sb₄O₆F₆ and its electrochemical behavior toward lithium-A combination of conversion and alloying reactions[J]. Chem. Mater., 2016, 28:6520-6527.
[13] TOBY B H. R factors in Rietveld analysis:How good is good enough?[J]. Powder Diffr., 2006, 21:67-70.
[14] LEE E S, NAM K W, HU E, et al. Influence of cation ordering and lattice distortion on the charge-Discharge behavior of LiMn_1.5Ni_0.5O₄ spinel between 50 and 20 V[J]. Chem. Mater., 2012, 24:3610-3620.
[15] BAK S M, SHADIKE Z, LIN R, et al. In situ/operando synchrotron-based X-ray techniques for lithium-ion battery research[J]. NPG Asia Materials, 2018:563-580.
[16] 王其钰, 褚赓, 张杰男, 等. 锂离子扣式电池的组装, 充放电测量和数据分析[J]. 储能科学与技术, 2018, 7(2):327-344. WANG Qiyu, CHU Geng, ZHANG Jienan, et al. The assembly, charge-discharge performance measurement and data analysis of lithium-ion button cell[J]. Energy Storage Science and Technology, 2018, 7(2):327-344.
[17] 张杰男. 高电压钴酸锂的失效分析与改性研究[D]. 北京:中国科学院物理研究所, 2018. ZHANG Jienan. Failure analysis and modification research of high voltage LiCoO₃[D]. Beijing:Institute of Physics, Chinese Academy of Sciences, 2018.
[18] NAM K W, BAK S M, HU E, et al. Combining in situ synchrotron X-ray diffraction and absorption techniques with transmission electron microscopy to study the origin of thermal instability in overcharged cathode materials for lithium-ion batteries[J]. Adv. Funct. Mater., 2013, 23:1047-1063.
[19] MOHANTY D, KALNAUS S, MEISNER R A, et al. Structural transformation of a lithium-rich Li₁₂Co_0.1Mn_0.55Ni_0.15O₂ cathode during high voltage cycling resolved by in situ X-ray diffraction[J]. J. Power Sources, 2013, 229:239-248.
[20] LERICHE J B, HAMELET S, SHU J, et al. An electrochemical cell for operando study of lithium batteries using synchrotron radiation[J]. J. Electrochem. Soc., 2010, 157:A606-A610.
[21] ROBERTS M R, MADSEN A, NICKLIN C, et al. Direct observation of active material concentration gradients and crystallinity breakdown in LiFePO₄ electrodes during charge/discharge cycling of lithium batteries[J]. J. Phys. Chem. C, 2014, 118:6548-6557.
[22] WANG X J, CHEN H Y, YU X Q, et al. A new in situ synchrotron X-ray diffraction technique to study the chemical delithiation of LiFePO₄[J]. Chem. Commun., 2011, 47:7170-7172.
[23] LI Y, XU R, REN Y, et al. Synthesis of full concentration gradient cathode studied by high energy X-ray diffraction[J]. Nano Energy, 2016, 19:522-531.
[24] GAO J, SHI S, XIAO R, LI H. Synthesis and ionic transport mechanisms of α-LiAlO₂[J]. Solid State Ionics, 2016, 286:122-134.
[25] LIU Q, GAO M R, LIU Y, et al. Quantifying the nucleation and growth kinetics of microwave nanochemistry enabled by in situ high-energy X-ray scattering[J]. Nano Lett., 2016, 16:715-720.
[26] CHEN J, BAI J, CHEN H, et al. In situ hydrothermal synthesis of LiFePO₄ studied by synchrotron X-ray diffraction[J]. The Journal of Physical Chemistry Letters, 2011, 2:1874-1878.
[27] CRAVILLON J, SCHRÖDER C A, BUX H, et al. Formate modulated solvothermal synthesis of ZIF-8 investigated using time-resolved in situ X-ray diffraction and scanning electron microscopy[J]. CrystEngComm., 2012, 14:492-498.
[28] 高健, 吕迎春, 李泓. 锂电池基础科学问题(Ⅲ)-相图与相变[J]. 储能科学与技术, 2013, 2(3):250-266. GAO Jian, LV Yingchun, LI Hong. Fundamental scientific aspects of lithium batteries (Ⅲ)-Phase transition and phase diagram[J].Energy Storage Science and Technology, 2013, 2(3):250-266.
[29] LUO C, MARTIN M. Stability and defect structure of spinels Li_1+xMn_2-xO_4-δ:In situ investigations on the stability field of the spinel phase[J]. J. Mater. Sci., 2007, 42:1955-1964.
[30] DELACOURT C, POIZOT P, TARASCON J M, et al. The existence of a temperature-driven solid solution in Li_xFePO₄ for 0≤ x ≤ 1[J]. Nat. Mater., 2005, 4:254-260.
[31] 高健, 吕迎春, 李泓. 锂电池基础科学问题(Ⅳ)-相图与相变(2)[J]. 储能科学与技术, 2013, 2(4):383-401. GAO Jian, LV Yingchun, LI Hong. Fundamental scientific aspects of lithium batteries (IV)-Phase transition and phase diagram (2)[J]. Energy Storage Science and Technology, 2013, 2(4):383-401.
[32] LYU Y, HU E, XIAO D, et al. Correlations between transition metal chemistry, local structure and global structure in Li₂Ru_0.5Mn_0.5O₃ investigated in a wide voltage window[J]. Chemistry of Materials, 2017:9053-9065.
[33] LYU Y, ZHAO N, HU E, et al. Probing reversible multielectron transfer and structure evolution of Li_1.2Cr_0.4Mn_0.4O₂ cathode material for Li-ion batteries in a voltage range of 10-48V[J]. Chemistry of Materials, 2015, 27:5238-5252.
[34] SU N, LYU Y, GU R, GUO B. Al₂O₃ coated Li_1.2Ni_0.2Mn_0.2Ru_0.4O₂ as cathode material for Li-ion batteries[J]. J. Alloys Compd., 2018, 741:398-403.
[35] GIBOT P, CASAS-CABANAS M, LAFFONT L, et al. Room-temperature single-phase Li insertion/extraction in nanoscale Li_xFePO₄[J]. Nat. Mater., 2008, 7:741-747.
[36] OMENYA F, MILLER J K, FANG J, et al. Single-phase lithiation and delithiation of simferite compounds Li(Mg,Mn,Fe)PO₄[J]. Chem. Mater., 2014, 26:6206-6212.
[37] ORIKASA Y, MAEDA T, KOYAMA Y, et al. Direct observation of a metastable crystal phase of Li_xFePO₄ under electrochemical phase transition[J]. J. Am. Chem. Soc., 2013, 135:5497-5500.
[38] ZHOU Y N, YUE J L, HU E, et al. High-rate charging induced intermediate phases and structural changes of layer-structured cathode for lithium-ion batteries[J]. Adv. Energy Mater., 2016, 6:doi:10.1002/aenm.201600597.
[39] ORIKASA Y, MAEDA T, KOYAMA Y, et al. Transient phase change in two phase reaction between LiFePO₄ and FePO₄ under battery operation[J]. Chem. Mater., 2013, 25:1032-1039.
[40] LIU H, STROBRIDGE F C, BORKIEWICZ O J, et al. Capturing metastable structures during high-rate cycling of LiFePO₄ nanoparticle electrodes[J]. Science, 2014, 344:doi:10.1126/science. 1252817.
[41] BAK S M, NAM K W, CHANG W, et al. Correlating structural changes and gas evolution during the thermal decomposition of charged Li_xNi₀₈Co₀₁₅Al₀₀₅O₂ cathode materials[J]. Chem. Mater., 2013, 25:337-351.>0.4Mn_0.4O₂ Cathode Material for Li-Ion Batteries in a Voltage Range of 1.0–4.8 V[J]. Chemistry of Materials, 27 (2015) 5238-5252.
[34] N. Su, Y. Lyu, R. Gu, B. Guo, Al2O3 coated Li_1.2Ni_0.2Mn_0.2Ru_0.4O₂ as cathode material for Li-ion batteries[J]. J. Alloys Compd., 741 (2018) 398-403.
[35] P. Gibot, M. Casas-Cabanas, L. Laffont, S. Levasseur, P. Carlach, S. Hamelet, J.-M. Tarascon, C. Masquelier, Room-temperature single-phase Li insertion/extraction in nanoscale Li_(x)FePO₍₄₎ [J]. Nat. Mater., 7 (2008) 741-747.
[36] F. Omenya, J.K. Miller, J. Fang, B. Wen, R. Zhang, Q. Wang, N.A. Chernova, M.S. Whittingham, Single-Phase Lithiation and Delithiation of Simferite Compounds Li(Mg,Mn,Fe)PO₄[J]. Chem. Mater., 26 (2014) 6206-6212.
[37] Y. Orikasa, T. Maeda, Y. Koyama, et al. Direct observation of a metastable crystal phase of Li_xFePO₄ under electrochemical phase transition[J]. J. Am. Chem. Soc., 135 (2013) 5497-5500.
[38] ZHOU Y N, YUE J L, HU E, et al, High‐Rate Charging induced intermediate phases and structural changes of layer‐structured cathode for lithium-ion batteries[J]. Adv. Energy Mater., 2016, 6: 1600597.
[39] ORIKASA Y, MAEDA T, KOYAMA Y, et al. Transient phase change in two phase reaction between LiFePO₄ and FePO₄ under battery operation[J]. Chem. Mater., 2013, 25: 1032-1039.
[40] LIU H, STROBRIDGE F C, BORKIEWICZ O J, et al. Capturing metastable structures during high-rate cycling of LiFePO₄ nanoparticle electrodes[J]. Science, 2014, 344: 1252817.
[41] BAK S M, NAM K W, CHANG W, et al. Correlating structural changes and gas evolution during the thermal decomposition of charged Li_xNi_0.8Co_0.15Al_0.05O₂ cathode materials[J]. Chem. Mater., 2013, 25: 337-351.

锂电池研究中的X射线多晶衍射实验与分析方法综述

Experimental measurement and analysis methods of polycrystalline X-ray diffraction for lithium batteries

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