硅酸盐学报

反钙钛矿型X₃OBH₄（X=Li, Na）的电化学稳定性和离子输运的第一性原理计算

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刘波 ¹ , 钟微 ¹ , 蒋达国 ¹ , 伍冬兰 ¹ , 方成 ¹ , 肖志鹏 ¹ , 施思齐 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): 1873-1884

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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) : 1873 -1884

反钙钛矿型X₃OBH₄（X=Li, Na）的电化学稳定性和离子输运的第一性原理计算

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刘波¹, 钟微¹, 蒋达国¹, 伍冬兰¹, 方成¹, 肖志鹏¹, 施思齐²

作者信息

^1．井冈山大学数理学院，江西吉安 343009

^2．上海大学材料科学与工程学院，上海 200444

通讯作者:

刘波（1990—），男，博士，副教授；

施思齐（1978—），男，博士，教授。

作者简介:

刘波（1990—），男，博士，副教授。

First Principles Calculation on Electrochemical Stability and Ion Transport of Antiperovskite Type X₃OBH₄ (X=Li, Na)

Bo LIU¹, Wei ZHONG¹, Daguo JIANG¹, Donglan WU¹, Cheng FANG¹, Zhipeng XIAO¹, Siqi SHI²

Affiliations

^1.College of Mathematics and Physics, Jinggangshan University, Ji'an 343009, Jiangxi, China

^2.School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China

Corresponding Author:

LIU Bo (1990-), male, Ph.D., Associate Professor. E-mail: liubo@jgsu.edu.cn;

SHI Siqi (1978-), male, Ph.D., Professor. sqshi@shu.edu.cn

LIU Bo (1990-), male, Ph.D, Associnate Professor. E-mail: liubo@jgsu.edu.cn

出版时间: 2025-07-20 doi: 10.14062/j.issn.0454-5648.20250003

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摘要

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基于簇阴离子的反钙钛矿超离子导体由于其在可充电电池固态电解质中的应用前景而引起了人们的兴趣。但是，对其安全性和稳定性至关重要的热力学性能关注甚少。采用第一性原理计算系统地研究了反钙钛矿型X₃OBH₄（X=Li, Na）材料的电子结构、相稳定性、电化学稳定性、界面兼容性、机械性能和离子输运性质。计算结果表明，X₃OBH₄（X=Li, Na）在0 K下是热力学亚稳态且宽带隙的电子绝缘体，其在高压下是不稳定的。然而，相应的分解产物XBH₄（X=Li, Na）具有宽的电化学稳定窗口，可以保护固态电解质。此外，X₃OBH₄（X=Li, Na）的低迁移势垒分别为0.34 eV和0.35 eV，室温离子电导率可达10^-4 S/cm。超卤素的旋转促进了锂/钠离子的运动，从而提高了其离子电导率。这些发现为进一步设计高性能固态电解质提供了理论指导。

关键词

反钙钛矿固态电解质 / 电化学稳定性 / 离子输运 / 第一性原理计算

Abstract

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Introduction

Compared with organic lithium-ion batteries, all-solid-state batteries are expected to improve battery safety and energy density simultaneously. They have attracted extensive attention. The ideal solid electrolyte material should have the basic properties of electronic insulation, wide electrochemical window, good interface compatibility and high ionic conductivity. Many types of solid electrolyte materials are reported, including oxides, sulfides, halides, borohydrides and phosphates, each of which has advantages and disadvantages. For instance, lithium-based halide and sulfide solid electrolytes have a high ionic conductivity but a narrow electrochemical window, and they are unstable to lithium metal negatives. The interface compatibility between oxide solid electrolyte and electrode is poor, and lithium dendrites grow rapidly along the grain boundary in oxide solid electrolyte. To further develop all-solid-state batteries with a higher energy density, a longer cycle life and a higher safety, solid electrolyte materials with excellent comprehensive performance must be designed. Anti-perovskite superionic conductors based on cluster anions have attracted much attention due to their potential applications in solid electrolytes for rechargeable batteries. However, little theoretical studies on the phase stability, electrochemical stability and interface compatibility of anti-perovskite X₃OBH₄(X=Li, Na) materials have been reported yet. In this work, the electronic structure, phase stability, electrochemical stability, interface compatibility, mechanical properties and ion transport properties of anti-perovskite X₃OBH₄(X=Li, Na) materials were systematically investigated via first-principles calculation.

Methods

All the calculations were performed based on density functional theory (DFT) by a projector augmented wave method, as implemented in the Vienna ab initio Simulation Package (VASP). The generalized gradient approximation (GGA) with Perdew-Burke-Ernzerhof (PBE) was applied to treat the electronic exchange-correlation interactions. The cutoff energy was set to 520 eV. The crystal structure was fully relaxed until the convergence criteria for each atomic force and energy were less than 0.02 eV/Å and 10^-5 eV, respectively. Based on electrochemical energy storage materials design platform (bmaterials.cn), the phase stability and interfacial stability (including electrochemical and chemical stability) of X₃OBH₄(X=Li, Na) were evaluated.

Results and discussion

The results show that X₃OBH₄(X=Li, Na) is a thermodynamically metastable and wide-band insulator at 0 K, which is unstable at a high pressure. Based on the energy calculated by DFT, the phase diagrams of Na-NaBH₄-O₂ and Li-LiBH₄-O₂ are constructed, respectively, and the calculated E_hull of Li₃OBH₄ and Na₃OBH₄ is 52.4 meV/atom and 110.7 meV/atom, respectively. X₃OBH₄(X=Li, Na) is thermodynamically unstable at 0 K. Since the E_hull value is relatively small, it is possible to stabilize the compound through the regulation of external conditions such as high temperature, high pressure and high entropy. Based on the lithium (sodium) giant potential phase diagram of the constructed X-O-B-H quaternary system, the voltage distribution and phase equilibrium of X₃OBH₄(X=Li, Na) in the process of lithiation/delithiation are calculated by DFT. The electrochemical window range of X₃OBH₄(X=Li, Na) is 0.53-0.93 V and 0-0.41 V, respectively. The corresponding decomposition product XBH₄(X=Li, Na) has a wide electrochemical stability window, which can protect the solid electrolyte. The calculated moduli of B, E and G of X₃OBH₄ (X=Li, Na) are greater than those of lithium (sodium) metal or even Li₃PS₄ electrolyte, indicating that X₃OBH₄ (X=Li, Na) can effectively block the growth of lithium (sodium) dendrites and has a good mechanical contact at the electrode/solid electrolyte interface. In addition, the low migration barriers of X₃OBH₄(X=Li, Na) are 0.34 eV and 0.35 eV, respectively, and the ionic conductivity at room temperature can reach 10^-4 S/cm. The rotation of the superhalogen promotes the movement of the lithium/sodium ions, thereby increasing their ionic conductivity.

Conclusions

The electronic properties, phase stability, electrochemical stability, chemical stability, mechanical properties and ion transport mechanism of the anti-perovskite type X₃OBH₄(X=Li, Na) were systematically investigated via first-principles calculation. The results showed that the crystal structure of X₃OBH₄(X=Li, Na) could be a metastable electronic insulator with a wide band gap. Under electrochemical oxidation conditions, X₃OBH₄(X=Li, Na) could be thermodynamically unstable and easily oxidized at relatively high voltages. However, the decomposition products could form a protective layer at the interface, preventing the electrolyte from further reacting and providing an improved electrochemical stability. In addition, X₃OBH₄(X=Li, Na) also had a good interface compatibility with typical cathode materials. The calculated mechanical properties indicated that X₃OBH₄(X=Li, Na) was brittle. However, their relatively large shear modulus indicated that they could be stable for lithium/sodium metal dendrites growth. By CI-NEB calculation, X₃OBH₄(X=Li, Na) showed a low migration barrier. In summary, these theoretical results could favor to better understand the thermodynamic and kinetic processes of X₃OBH₄(X=Li, Na), and provide a theoretical guidance for the development of high-performance solid electrolytes.

Key words

antiperovskite solid electrolyte / electrochemical stability / ion transport / first principles calculations

引用本文

刘波, 钟微, 蒋达国, 伍冬兰, 方成, 肖志鹏, 施思齐. 反钙钛矿型X₃OBH₄（X=Li, Na）的电化学稳定性和离子输运的第一性原理计算. 硅酸盐学报, 2025 , 53 (7) : 1873 -1884 . DOI: 10.14062/j.issn.0454-5648.20250003

Bo LIU, Wei ZHONG, Daguo JIANG, Donglan WU, Cheng FANG, Zhipeng XIAO, Siqi SHI. First Principles Calculation on Electrochemical Stability and Ion Transport of Antiperovskite Type X₃OBH₄ (X=Li, Na)[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (7) : 1873 -1884 . DOI: 10.14062/j.issn.0454-5648.20250003

基金

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国家自然科学基金(12464032)
江西省自然科学基金(20232 BAB201032)

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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.0454-5648.20250003

接收时间：2025-01-02
首发时间：2026-10-21
出版时间：2025-07-20

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收稿日期：2025-01-02
修回日期：2025-02-19

基金

国家自然科学基金(12464032)

江西省自然科学基金(20232 BAB201032)

作者信息

^1．井冈山大学数理学院，江西吉安 343009

^2．上海大学材料科学与工程学院，上海 200444

通讯作者:

刘波（1990—），男，博士，副教授；

施思齐（1978—），男，博士，教授。

参考文献

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250003

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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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