X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用

doi:10.15541/jim20220331

无机材料学报 ›› 2023, Vol. 38 ›› Issue (6): 589-605.DOI: 10.15541/jim20220331

• 综述 • 下一篇

X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用

杨卓(), 卢勇, 赵庆, 陈军()

南开大学化学学院, 先进能源材料化学教育部重点实验室, 新能源转化与存储交叉科学中心, 天津 300071

收稿日期:2022-06-14 修回日期:2022-12-28 出版日期:2023-01-11 网络出版日期:2023-01-11
通讯作者: 陈军，教授. E-mail: chenabc@nankai.edu.cn
作者简介:杨卓(1993-), 男, 博士研究生. E-mail: yzhuo94@outlook.com.
基金资助:
国家自然科学基金(22121005);国家自然科学基金(22109075);国家自然科学基金(22020102002);国家自然科学基金(21835004)

X-ray Diffraction Rietveld Refinement and Its Application in Cathode Materials for Lithium-ion Batteries

YANG Zhuo(), LU Yong, ZHAO Qing, CHEN Jun()

Renewable Energy Conversion and Storage Center (RECAST), Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

Received:2022-06-14 Revised:2022-12-28 Published:2023-01-11 Online:2023-01-11
Contact: CHEN Jun, professor. E-mail: chenabc@nankai.edu.cn
About author:YANG Zhuo (1993-), male, PhD candidate. E-mail: yzhuo94@outlook.com.
Supported by:
National Natural Science Foundation of China(22121005);National Natural Science Foundation of China(22109075);National Natural Science Foundation of China(22020102002);National Natural Science Foundation of China(21835004)

摘要/Abstract

摘要：

2022年是X射线衍射(XRD)发现的110周年。XRD Rietveld精修作为材料结构分析的重要手段, 在建立材料“构-效”关系方面发挥着重要的作用。正极材料是锂离子电池的重要组成部分, 深入理解其晶体结构及原子分布规律有助于推动锂离子电池正极材料的发展。本文简要介绍了XRD Rietveld结构精修及其在锂离子电池正极材料中的应用, 围绕几类典型正极材料, 重点讨论了Rietveld结构精修在正极材料的合成、退化衰减及结构改性中的应用和研究进展。XRD Rietveld精修可以得到物相比例、晶胞参数、关键原子占比、原子坐标等结构信息, 对开发高性能锂离子电池正极材料具有重要的指导意义。最后, 本文展望了X射线衍射技术在锂电正极材料结构研究中的机遇与挑战。

关键词: X射线衍射, Rietveld精修, 锂离子电池, 正极材料, 综述

Abstract:

2022 marks the 110th anniversary of X-ray diffraction (XRD), which is a powerful technique used to find out the nature of materials. Rietveld refinement method, as an important means of extracting material structure information, plays a significant role in establishing the relationship between structure and performance of materials. Cathode materials are a vital part of lithium-ion batteries (LIBs). In-depth understanding of their crystal structure and atomic distribution is extremely helpful to promote the development of cathode materials for LIBs. Cathode materials for LIBs are generally the hosts of lithium. Studies on lithium occupation and transfer are inseparable from a deep understanding of its structural characteristics. This review summarizes XRD Rietveld structure refinement and its application in cathode materials for LIBs. XRD Rietveld structure refinement in synthesis, degradation, and structural modification of cathode materials are analyzed by using several types of typical cathode materials as examples. XRD Rietveld method could provide useful structural information of the cathode materials, including phase ratio in composite and crystallographic parameters (e.g., cell parameters, key atomic occupation, and atomic coordinates). Therefore, exploring structure of cathode materials assisted with XRD Rietveld refinement method is of great significance for the development of high-performance cathode materials for LIBs. Finally, the opportunities and challenges in the field of X-ray diffraction technology in detecting structure of cathode materials for LIBs are prospected.

Key words: X-ray diffraction, Rietveld refinement, lithium-ion battery, cathode material, review

中图分类号:

TQ174

杨卓, 卢勇, 赵庆, 陈军. X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用[J]. 无机材料学报, 2023, 38(6): 589-605.

YANG Zhuo, LU Yong, ZHAO Qing, CHEN Jun. X-ray Diffraction Rietveld Refinement and Its Application in Cathode Materials for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2023, 38(6): 589-605.

图/表 18

图1 X射线衍射谱图的影响因素

Fig. 1 Influencing factors of X-ray diffraction patterns

图2 原位X射线衍射装置示意图[20-21]

表1 常见的锂离子电池正极材料的结构及性能[24⇓⇓⇓-28]

Table 1 Structures and properties of common cathode materials for lithium-ion batteries[24⇓⇓⇓-28]

Cathode material	Crystal structure	Space group	Cell parameter	Atom site		Theoretical specific capacity/(mAh·g^-1)	Working voltage/ V (vs. Li⁺/Li)
LiFePO₄	Olivine	Pnma	a≠b≠c	Li	4a	170	3.4
				Fe	4c
				O	4c/8d
LiMn₂O₄	Spinel	Fd-3m	a=b=c	Li	8a	148	4
				Mn	16d
				O	32e
LiCoO₂	Layer	R-3m	a=b≠c	Li	3a	274	3.9
				Co	3b
				O	6c
LiNi_xCo_y(Mn/Al)_1-_x_-_yO₂	Layer	R-3m	a=b≠c	Li	3a	273-285	3.8
				Ni/Co/Mn/Al	3b
				O	6c
xLi₂MnO₃·(1-x)LiMO₂ (0<x<1, M=Ni, Co, Mn)	Layer	R-3m+ C2/m	a=b≠c	Li	2b/2c/4h	273-350	3.8
				Mn	4g
				O	4i/4j

图3 正极材料晶体结构示意图[25⇓⇓-28]

Fig. 3 Schematic diagram of the crystal structures of cathode materials[25⇓⇓-28] (a) LiMPO4 (M=Fe, Mn)(© 2021, IOP Publishing)[25]; (b) LiMn2O4 (© 2022, MDPI)[26]; (c) LiMO2 (M=Ni, Co, Mn, Al) (© 2021, Elsevier Ltd.)[27]; (d) xLi2MnO3·(1-x)LiMO2 (M=Ni, Co, Mn) (© 2022, Springer Nature)[28] Colorful figures are available on website

图4 XRD Rietveld精修在锂离子电池正极材料中的应用

Fig. 4 Application of XRD Rietveld refinement in cathode materials for lithium-ion batteries

图5 LiNi0.8Co0.2O2合成过程中的结构演化[41]

Fig. 5 Structural evolution during high temperature synthesis of LiNi0.8Co0.2O2 (© 2017, Wiley-VCH)[41] (a) Concentration of the phases Ni(Co)O, Li2CO3, and LiNi0.8Co0.2O2 at different temperatures; (b) Ratio unit cell parameters (c/a), (c) content of Li+ occupying the 3a sites (Li sites), and (d) Ni-O and Li-O bond lengths as a function of temperature; (e) Schematic diagram of the structural evolution and variation of the interlayer distances of the Li and Ni(Co) slabs during the synthesis of LiNi0.8Co0.2O2. 1 Å=0.1 nm. Colorful figures are available on website

图6 正极材料LiNi0.6Co0.2Mn0.2O2的合成过程温度分辨XRD表征结果[43]

Fig. 6 Temperature-resolved XRD characterization of synthesis process of cathode material LiNi0.6Co0.2Mn0.2O2 (© 2021, Wiley-VCH)[43] (a) In situ XRD patterns of the mixture of Ni0.6Co0.2Mn0.2(OH)2 and LiOH·H2O during heating and (c) corresponding weight fractions of different phases as a function of temperature; (b) 3D profiles of in situ XRD patterns, corresponding (d) evolution of phase fraction and (f) lattice parameters of the samples as a function of heating temperature starting from mixture of the Ni0.6Co0.2Mn0.2CO3 and LiOH·H2O; (e) Schematic illustration of structural evolution during synthesis of LiNi0.6Co0.2Mn0.2O2; In (a, b), the subscripts T1, T2 and R represent Ni0.6Co0.2Mn0.2(OH)2 (P-3m1, T1 phase), LiNi0.6Co0.2Mn0.2O2 (R-3m, T2 phase) and the rock-salt-type, respectively. 1 Å=0.1 nm Colorful figures are available on website

图7 LiNi1/3Mn1/3Co1/3O2(NCM111)的微波水热合成原位XRD表征结果[44]

Fig. 7 In-situ XRD characterization of microwave (MW) hydrothermal synthesis of NCM111(© 2020, AAAS) [44] (a) Schematic illustration of the experimental setup specialized for fast synchrotron X-ray probing of the microwave hydrothermal synthesis; (b) Time resolved synchrotron XRD patterns during MW hydrothermal synthesis of NCM111; (c) Lattice parameter c of the Ni1/3Co1/3Mn1/3(OH)2 precursor (green) as a function of temperature during solid-state synthesis (black), hydrothermal synthesis (blue), and MW hydrothermal synthesis (red). 1 Å=0.1 nm. Colorful figures are available on website

图8 高镍正极LiNi0.8Co0.1Mn0.1O2的充放电原位XRD表征结果[49]

Fig. 8 In situ XRD characterization of Ni-rich cathode LiNi0.8Co0.1Mn0.1O2(NCM811) during charge-discharge (© 2015, ECS)[49] (a) In-situ XRD patterns of NCM811 cycled between 3.0-4.4 V at a rate of C/100 for two cycles; (b) Cell parameters c and a as functions of specific capacity and cell potential; (c) XRD refinement patterns, corresponding cell parameters and Li/Ni occupation information of fresh NCM811 electrode and the recovered electrodes that cycled 200 times to 4.1, 4.2, 4.3 and 4.4 V, respectively. 1 Å=0.1 nm; Ch: Charged; DisCh: Discharged. Colorful figures are available on website

图9 Li1.2Ni0.13Co0.13Mn0.54O2的充放电原位同步辐射XRD表征结果[54]

Fig. 9 In-situ XRD characterization of Li1.2Ni0.13Co0.13Mn0.54O2 during charge-discharge process (© 2021, Springer Nature)[54] (a) Charge-discharge curve and corresponding contour plot of XRD pattern during the 201st cycle with the colour red to blue representing the decreasing peak intensity; (b, c) Lattice parameters (c and V) as functions of potential during the 1st and 201st cycles after the electrode activated at a rate of 0.1C. 1 Å=0.1 nm. Colorful figures are available on website

图10 LiNi0.8Co0.1Mn0.1O2正极材料的充放电原位XRD Rietveld精修结果[57]

Fig. 10 In-situ XRD Rietveld refinement results of LiNi0.8Co0.1Mn0.1O2 cathode materials during charge and discharge process (© 2022, ECS)[57] (a, d) Lattice parameters a; (b, e) Lattice parameters c; (c, f) Unit cell volumes. 1 Å=0.1 nm. Colorful figures are available on website

表2 LiFePO4和LiFe0.95M0.05PO4的结构精修结果[62]

Sample	Doped atomic radius/nm	Displace ion radius/nm	Lattice constant/nm	Lattice volume/nm³	Interatomic distance/nm	Reliability factor
LFP	r_Fe = 0.172	r_Fe2+ = 0.074	a=1.031634 b=0.600129 c=0.469139	0.29045	Li-O₁:0.21664 Li-O₂:0.20901 Li-O₃:0.21651 Li-O:0.214050	R_wp= 7.72% R_p=5.63% χ²= 2.794
LFMgP	r_Mg = 0.172	r_Mg2+ = 0.065	a=1.031583 b=0.600035 c=0.469090	0.29036	Li-O₁:0.21712 Li-O₂:0.21041 Li-O₃:0.21665 Li-O:0.214720	R_wp= 9.32% R_p= 6.79% χ²= 2.878
LFAlP	r_Al = 0.182	r_Al3+ = 0.050	a=1.032204 b=0.600358 c=0.469072	0.29068	Li-O₁:0.21670 Li-O₂:0.21001 Li-O₃:0.21747 Li-O:0.214730	R_wp= 9.14% R_p= 6.60% χ²= 2.989
LFNiP	r_Ni = 0.162	r_Ni2+ = 0.072	a=1.031083 b=0.599820 c=0.468923	0.29001	Li-O₁:0.21734 Li-O₂:0.20863 Li-O₃:0.21586 Li-O:0.213950	R_wp= 8.26% R_p= 6.12% χ²= 2.929
LFVP	r_V = 0.192	r_V3+ = 0.074	a=1.032223 b=0.600494 c=0.469485	0.291	Li-O₁:0.21864 Li-O₂:0.21074 Li-O₃:0.21794 Li-O:0.215770	R_wp= 9.86% R_p= 7.15% χ²= 2.426

图11 LiFePO4改性前后XRD精修结果[63]

Fig. 11 XRD Rietveld refinement results of LiFePO4 before and after modification (© 2021, RSC)[63] (a, b) XRD Rietveld refinement patterns of (a) LFP/C and (b) LFP/C-YF-2; (c, d) Schematic diagrams of change in Li-O bond length of (c) LFP/C and (d) LFP/C-YF-2. 1 Å=0.1 nm. Colorful figures are available on website

表3 XRD精修得到LiFePO4改性前后的晶胞参数[63]

Sample	a/nm	b/nm	c/nm	V/nm³
LFP/C	1.03229	0.60061	0.46941	0.29104
LFP/C-YF-1	1.03054	0.59985	0.46903	0.28994
LFP/C-YF-2	1.03082	0.59977	0.46874	0.28980
LFP/C-YF-3	1.03069	0.59989	0.46892	0.28994

表4 Al、Ti、Mg共掺杂LiCoO2及纯LiCoO2的XRD结构精修结果[64]

Atom	Site	z	Occupancy	U_iso
Li^a	3a	0	1.000	0.014(6)
Co^a	3b	0.50000	1.000	0.023(8)
O^a	6c	0.2300(6)	1.000	0.049(1)
Li^b	3a	0	0.98(1)	0.020(1)
Mg^b	3a	0	0.01(9)	0.020(1)
Co^b	3b	0.50000	0.99(7)	0.001(2)
Al^b	3b	0.50000	0.002(0)	0.001(2)
Ti^b	3b	0.50000	0.001(0)	0.001(2)
O^b	6c	0.2476(3)	1.000	0.068(5)

图12 Li(Li0.2Ni0.2Mn0.6)O2正极材料的XRD结构精修结果[66]

Fig. 12 XRD Rietveld refinement results of Li(Li0.2Ni0.2Mn0.6)O2 cathode materials (© 2022, Wiley-VCH)[66] (a, b) Experimental XRD patterns and Rietveld refinement results of (a) LLNMO-PC and (b) LLNMO-SC; (c, d) Changes of lattice parameters (a, b, c, and V) for (c) LLNMO-PC and (d) LLNMO-SC electrodes during charge and discharge 1 Å=0.1 nm. Colorful figures are available on website

表5 Al掺杂LiMn2O4的XRD结构精修结果[69]

Formula	Calculated				Experimental
Formula	a/nm	b/nm	c/nm	V/nm³	a/nm	V/nm³
Li₈Mn₁₆O₃₂	0.886205	0.886205	0.886205	0.695990	-	-
Li₈Mn₁₅AlO₃₂	0.826725	0.826725	0.826725	0.567617	0.82507	0.561658
Li₈Mn₁₄Al₂O₃₂	0.831493	0.831493	0.799071	0.552416	0.82466	0.560821
Li₈Mn₁₃Al₃O₃₂	0.814375	0.826337	0.820583	0.551780	0.82110	0.553590

图13 复相正极材料的XRD精修图谱

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X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用

X-ray Diffraction Rietveld Refinement and Its Application in Cathode Materials for Lithium-ion Batteries

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