硅酸盐学报

卤化物固体电解质Li₃InCl₆的基本特性及Li离子迁移机理的第一性原理计算

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仇家豪 ¹ , 苏蕾 ¹ , 张佳颖 ¹ , 吴木生 ¹^,² , 孙宝珍 ¹ , 欧阳楚英 ¹^,²

硅酸盐学报 | 电化学储能材料计算与设计专题—研究论文 2025,53(7): 1831-1843

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硅酸盐学报 |电化学储能材料计算与设计专题—研究论文 2025 , 53 (7) : 1831 -1843

卤化物固体电解质Li₃InCl₆的基本特性及Li离子迁移机理的第一性原理计算

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仇家豪¹, 苏蕾¹, 张佳颖¹, 吴木生¹^,², 孙宝珍¹, 欧阳楚英¹^,²

作者信息

^1．江西师范大学物理与通信电子学院，计算材料物理实验室，南昌 330022

^2．宁德时代创新实验室，福建宁德 352100

通讯作者:

吴木生（1979—），男，博士，副教授。

作者简介:

仇家豪（1996—），男，硕士研究生。

First-Principles Study on Basic Properties and Li-Ion Migration Mechanism of Halide Solid Electrolyte Li₃InCl₆

Jiahao QIU¹, Lei SU¹, Jiaying ZHANG¹, Musheng WU¹^,², Baozhen SUN¹, Chuying OUYANG¹^,²

Affiliations

^1.School of Physics and Communication Electronics, Computational Materials Physics Laboratory, Jiangxi Normal University, Nanchang 330022, China

^2.21C Innovation Laboratory, Contemporary Amperex Technology Ltd.(21C LAB), Ningde 352100, Fujian, China

Corresponding Author:

WU Musheng (1979-), male, Ph.D., Associate Professor. E-mail: smwu@jxnu.edu.cn

QIU Jiahao (1996-), male, Master candidate. E-mail: qiujiahao0913@163.com

出版时间: 2025-07-20 doi: 10.14062/j.issn.0454-5648.20240840

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摘要

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全固态锂离子电池被认为是解决目前商用锂离子电池能量密度和安全性问题的理想替代品。符合实际需求的固体电解质材料的开发是其应用的关键。最近，以Li₃InCl₆为代表的卤化物快离子导体由于展现出优异的性能，成为倍受人们关注的一类极具潜力的新型固体电解质。然而，与Li₃InCl₆应用密切相关的一些问题仍不清楚，比如绝缘性、力学和热特性等，尤其是高离子电导率的本质原因。利用第一性原理计算系统揭示了Li₃InCl₆的电子结构与热力学等基本物理特性和锂离子迁移机理。研究结果发现，Li₃InCl₆具有4.71 eV的宽带隙，低的弹性模量和高的Pugh比（2.09），优于同类卤化物Li₃YCl₆和Li₃YBr₆，表明其具有大的理论电化学窗口及杰出的机械特性。另外，通过对其缺陷类型的深入研究，发现缺陷既具有0.24 eV的低形成能，又具有0.26 eV的锂空位迁移势垒，表明是Li₃InCl₆材料的主导缺陷类型，并且锂空位是主导的载流子。这些结果为Li₃InCl₆材料的改善及应用提供了理论依据。

关键词

全固态锂离子电池 / 卤化物固体电解质 / 物理特性 / 迁移机理 / 第一性原理计算

Abstract

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Introduction

Lithium-ion batteries are currently the most widely used secondary batteries, extensively applied in electric vehicles, laptops, and smartphones. However, commercial lithium-ion batteries generally use flammable organic solvents, which pose safety issues such as leakage and self-ignition. As the demand for higher energy density grows in fields like aerospace and electric vehicles, the existing commercial lithium-ion batteries cannot available. All-solid-state lithium-ion batteries (ASSLBs) with a high energy density and a good safety become one of the ideal alternatives to address the issues of the existing lithium-ion batteries. However, the bottleneck for ASSLB applications is the lack of solid electrolyte (SE) materials with a high ionic conductivity and a good stability simultaneously. Recently, a novel class of revived ternary halide SEs represented by Li₃InCl₆ (LInC) has attracted much attention due to their high room temperature ionic conductivity, high oxidative stability, compatibility with high voltage cathodes, and particularly high humidity stability. However, there are still some application-related issues regarding LIC that remain unclear, such as mechanical and thermal properties, especially the Li-ion migration mechanisms. First-principles calculations can reveal the underlying mechanisms in an atomic scale, compared to experimental methods. This paper was to evaluate the fundamental physical properties required for LInC as a SE material and reveal the main factors for high ionic conductivity, thus providing methods for the improvement and application of LIC SE. The geometric and electric structure, mechanical and thermal properties, defect chemistry, and Li-ion migration mechanism of LIC were investigated, and the findings indicated that LIC could be used as a promising SE material for ASSLBs.

Methods

In this work, all the calculations were performed by first-principles methods based on density functional theory (DFT) implementing in a software named VASP (Vienna Ab initio Simulation Package). The interaction between ion cores and valence electrons was described by Projector-Augmented Wave (PAW) with a plane wave cutoff energy of 640 eV. The exchange-correlation functional was described by the Perdew-Burke-Ernzerhof (PBE) functional within the Generalized Gradient Approximation (GGA). During geometry relaxation, the numerical integration over the Brillouin zone was performed by the Monkhorst-Pack method with a k-point grid of 3×2×3; for electronic structure calculations, the grid is 5×3×5, and a Gaussian smearing was applied to the Fermi level with a width of 0.2 eV. The electronic structure and band structure of the system were calculated by hybrid density functionals based on the Heyd-Scuseria-Ernzerhof (HSE06) method. All atoms within the unit cell were fully relaxed with a convergence criterion of 10^-5 eV/atom, and the interatomic forces were less than 0.01 eV/Å. In addition, for the calculation of defects and Li ion migration barriers, a supercell of 2×1×2 was also constructed, containing 24 Li, 8 In, and 48 Cl atoms. The Climb Image Nudged Elastic Band (CI-NEB) method was used to search for the migration path of Li⁺ and to calculate the migration barrier.

Results and discussion

We modeled LInC crystal based on the XRD experimental data. LInC unit cell with C2/m space group exhibits the lattice constants (i.e., a = 6.63 Å, b = 11.34 Å, c = 6.46 Å, α = γ = 90°, and β = 112.0°), which are in good agreement with the experimental data. All Cl atoms fully occupy the 4i and 8j Wyckoff sites, In atoms partially occupy the 4g site within the plane (001), and Li atoms fully occupy the 4h and 2d sites within the plane (002). The band structure illustrates LIC with a bandgap of 4.71 eV, indicating a great theoretical electrochemical window. Furthermore, DFT calculations demonstrate that LInC possesses low elastic moduli with B=14.71 GPa, G=7.05 GPa, and E=18.24 GPa, which is smaller than those of Li₁₀GeP₂S₁₂ (LGPS) and Li₃YCl₆ (LYC), and exhibits a high Pugh ratio (i.e., B/G=2.09), indicating its favorable mechanical properties and ductility. LInC can be suitable as a solid electrolyte for all-solid-state batteries. The defect chemistry and Li-ion migration of LInC show that although isolated with a formation energy of -1.43 eV can form spontaneously, migration barriers as high as 0.48 eV indicates that the contribution of to the conductivity of LInC is negligible. Similarly, despite presenting a low migration barrier of 0.17 eV in ab plane, isolated has a high formation energy of 4.75 eV, indicating a negligible contribution to conductivity of bulk LInC. For four considered neutral defect pairs, the defect formation energies and Li-ion migration barriers follow an order of and , respectively. The results indicate that Frenkel defect pair is the dominant defect type, playing a critical role in the high ionic conductivity of LInC. The contribution of and defect pairs to the ionic conductivity of LInC bulk is also not negligible. This work provides valuable insights for evaluating LInC as SE material, and elucidates some dominant factors for a high ionic conductivity of LInC.

Conclusions

This work systematically investigated the basic properties and Li-ion migration mechanisms of LInC by first-principles calculation methods. The results showed that LInC had high theoretical electrochemical window as well as good mechanical property and ductility. Furthermore, the Frenkel defect pair with the low formation energy of 0.24 eV presented a low migration barrier of 0.26 eV, confirming that it could be the dominant defect type in LInC, and Li vacancies were the predominant carriers in LInC bulk. The findings of this work could provide a theoretical basis for the modification and application of LInC materials.

Key words

all-solid-state lithium-ion batteries / halide solid electrolytes / physical property / migration mechanism / first-principles calculations

引用本文

仇家豪, 苏蕾, 张佳颖, 吴木生, 孙宝珍, 欧阳楚英. 卤化物固体电解质Li₃InCl₆的基本特性及Li离子迁移机理的第一性原理计算. 硅酸盐学报, 2025 , 53 (7) : 1831 -1843 . DOI: 10.14062/j.issn.0454-5648.20240840

Jiahao QIU, Lei SU, Jiaying ZHANG, Musheng WU, Baozhen SUN, Chuying OUYANG. First-Principles Study on Basic Properties and Li-Ion Migration Mechanism of Halide Solid Electrolyte Li₃InCl₆[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (7) : 1831 -1843 . DOI: 10.14062/j.issn.0454-5648.20240840

基金

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国家自然科学基金(464029; 12174162和12364026)
江西省自然科学基金(20232BAB201030; 20232BAB201038)
宁德时代创新实验室开放基金资助(21C-OP-202306)

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2025年第53卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240840

接收时间：2024-12-30
首发时间：2026-10-21
出版时间：2025-07-20

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收稿日期：2024-12-30
修回日期：2025-01-13

基金

国家自然科学基金(464029; 12174162和12364026)

江西省自然科学基金(20232BAB201030; 20232BAB201038)

宁德时代创新实验室开放基金资助(21C-OP-202306)

作者信息

^1．江西师范大学物理与通信电子学院，计算材料物理实验室，南昌 330022

^2．宁德时代创新实验室，福建宁德 352100

通讯作者:

吴木生（1979—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240840

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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