硅酸盐学报

g-C₃N₄在钠硫电池中锚定和催化作用的第一性原理计算

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任乃青 ¹ , 姜艳微 ¹ , 王牧茜 ¹ , 吴亮 ² , 王立锋 ¹ , 殷逸臣 ¹

硅酸盐学报 | 研究论文 2025,53(4): 924-930

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硅酸盐学报 |研究论文 2025 , 53 (4) : 924 -930

g-C₃N₄在钠硫电池中锚定和催化作用的第一性原理计算

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任乃青¹, 姜艳微¹, 王牧茜¹, 吴亮², 王立锋¹, 殷逸臣¹

作者信息

^1．中国矿业大学，材料与物理学院，江苏徐州 221116

^2．兰州交通大学，数理学院，兰州 730070

通讯作者:

任乃青（1996—），女，博士，副教授；

王立锋（1997—），男，博士，副教授；

殷逸臣（1995—），男，博士，教授。

作者简介:

任乃青（1996—），女，博士，副教授。

Analyzing Anchoring and Catalytic Properties of g-C₃N₄ for Na-S Batteries via First-Principles

Naiqing REN¹, Yanwei JIANG¹, Muqian WANG¹, Liang WU², Lifeng WANG¹, Yichen YIN¹

Affiliations

^1.School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China

^2.School of Mathematics and Physics, Lanzhou Jiaotong University, Lanzhou 730070, China

Corresponding Author:

REN Naiqing (1996-), female, Ph.D., Associate Professor. E-mail: rennq@cumt.edu.cn;

WANG Lifeng (1997-), male, Ph.D., Associate Professor. wlifeng@cumt.edu.cn;

YIN Yichen (1995-), male, Ph.D., Professor. yyc@cumt.edu.cn

REN Naiqing (1996-), female, Ph.D., Associate Professor. E-mail: rennq@cumt.edu.cn

出版时间: 2025-04-20 doi: 10.14062/j.issn.0454-5648.20240758

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摘要

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近年来，室温钠硫（RT Na-S）电池因具有能量密度高、原材料丰富等优势，受到了广泛的关注。然而，RT Na-S电池的实际应用面临着硫正极多硫化钠（NaPSs）的溶解穿梭及缓慢的氧化还原反应动力学等巨大挑战。为开发合适的催化剂，抑制NaPSs穿梭并加快其转化，采用基于密度泛函理论的第一性原理计算，研究了NaPSs在石墨相氮化碳（g-C₃N₄）表面的吸附行为，通过计算吸附能、电荷转移，得到了吸附在g-C₃N₄表面的不同NaPSs的构型，并通过态密度分析了g-C₃N₄与NaPSs之间的相互作用。结果表明：g-C₃N₄对NaPSs具有高的吸附能（-4.69~-2.29 eV），表现出很强的化学相互作用。g-C₃N₄表面吸附NaPSs后还会导致电子的重新排布，带隙减小，电子电导提高，有利于NaPSs还原过程中的电子转移。此外，NaPSs在g-C₃N₄表面的转化反应的决速步能垒仅为0.70 eV，表现出对NaPSs良好的催化转化作用。此工作为g-C₃N₄应用于RT Na-S电池正极催化剂提供了理论基础。

关键词

室温钠硫电池 / 第一性原理计算 / 石墨相氮化碳 / 电子结构 / 转化反应动力学

Abstract

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Introduction

Room-temperature sodium-sulfur (RT Na-S) batteries, as one of effective candidates for next-generation high-energy-density battery systems, have the advantages of high theoretical energy density (i.e., 1274 W·h·kg^-1), high elemental abundance (i.e., S and Na) and low cost. However, the practical application of RT Na-S batteries is restricted due to the poor electronic conductivity of sulfur, sluggish reaction kinetics, and sodium polysulfides (NaPSs) shuttle effect. The related studies are performed on cathode materials of RT Na-S batteries. Among various materials, two-dimensional layered materials have attracted extensive attention due to their unique structures and physicochemical properties, showing a substantial promise for applications. Compared to conventional experimental research methods, first-principles computational techniques can assist in designing novel high-performance electrode materials in atomic and electronic scales. This paper was thus to investigate g-C₃N₄ as a catalyst for RT Na-S batteries based on the first-principles calculation methods. In addition, the chemical interactions between g-C₃N₄ and NaPSs, electronic structure, and reaction energy barriers were also analyzed.

Methods

Density functional theory (DFT) calculations were carried out by a software named Vienna ab initio simulation package (VASP). The exchange-correlation energy was described using the Perdew-Burke-Ernzerhof (PBE) functional within the framework of the generalized gradient approximation (GGA). A plane-wave cutoff energy of 500 eV was chosen. A vacuum layer larger than 20Å was used in the calculations to avoid the interlayer interactions. The convergence of energy and force criteria on the atoms were set to be 10^-5 eV and 0.02 eV·Å^-1, respectively. The DFT-D3 method was used to calculate the long-range van der Waals interactions. The 3×3×1 and 4×4×1 Monkhorst-Pack K-points were set in the first Brillouin zone for geometric optimization and calculation of density of states (DOS), respectively. The adsorption energy of NaPSs adsorbed on g-C₃N₄ monolayer was calculated by

E_ads = E_{g-C₃N₄/NaPSs} - E_g-C₃N₄ - E_NaPSs (1)

where E_{g-C₃N₄/NaPSs}, E_g-C₃N₄ and E_g-C₃N₄ are the calculated total energies of g-C₃N₄ monolayer with adsorption of NaPSs, g-C₃N₄ before adsorption, and isolated NaPSs. The differential charge density was calculated by

Δρ = ρ_{g-C₃N₄/NaPSs} - ρ_g-C₃N₄ - ρ_NaPSs (2)

where ρ_{g-C₃N₄/NaPSs}, ρ_g-C₃N₄ and ρ_NaPSs are the calculated electron densities of g-C₃N₄ monolayer with adsorption of NaPSs, g-C₃N₄ monolayer, and isolated NaPSs.

Results and discussion

The g-C₃N₄ studied belongs to a hexagonal crystal system, where C and N atoms are bonded in sp² hybridized configuration, forming a conjugated π-electron structure. The density of states (DOS) of g-C₃N₄ monolayer shows semiconductor characteristics with a band gap of 1.12 eV. The adsorption energy is a fundamental criterion for assessing whether a material can anchor polysulfides. The adsorption energies of NaPSs and S₈ on the g-C₃N₄ surface were calculated, and all the values range from -1.0 eV to -5.0 eV, indicating that g-C₃N₄ can be ideal candidates for anchoring NaPSs. The analysis of DOS and differential charge density of these adsorption systems shows that electron transfer occurs through Na-S and Na-N bonds and the band gap decreases, compared to the pristine g-C₃N₄ (except S₈ adsorption system), facilitating electron transfer and providing electrons for the redox processes of NaPSs. The Gibbs free energy calculation for the entire discharge process reveals that the energy barrier of the rate-determining step is only 0.70 eV. These results emphasize a pivotal role played by the g-C₃N₄ in accelerating the conversion of NaPSs.

Conclusions

Based on first-principles calculations, we systematically investigated the anchoring and catalytic behavior of g-C₃N₄ toward NaPSs. The results showed that g-C₃N₄ could have a great potential as a sulfur host and catalytic material for RT Na-S batteries. g-C₃N₄ had an anchoring effect on NaPSs, contributing to improved battery cycle life. g-C₃N₄ could effectively capture NaPSs from the electrolytes, suppressing the shuttle effect. And g-C₃N₄ accelerated the conversion kinetics of NaPSs, enhancing sulfur utilization. All these findings could underscore an immense potential of g-C₃N₄ in the design of RT Na-S battery cathodes.

Key words

room-temperature sodium-sulfur battery / first-principles calculations / g-C₃N₄ / electronic structure / conversion reaction kinetics

引用本文

任乃青, 姜艳微, 王牧茜, 吴亮, 王立锋, 殷逸臣. g-C₃N₄在钠硫电池中锚定和催化作用的第一性原理计算. 硅酸盐学报, 2025 , 53 (4) : 924 -930 . DOI: 10.14062/j.issn.0454-5648.20240758

Naiqing REN, Yanwei JIANG, Muqian WANG, Liang WU, Lifeng WANG, Yichen YIN. Analyzing Anchoring and Catalytic Properties of g-C₃N₄ for Na-S Batteries via First-Principles[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (4) : 924 -930 . DOI: 10.14062/j.issn.0454-5648.20240758

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中国矿业大学人才引进资助项目

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2025年第53卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240758

接收时间：2024-11-28
首发时间：2026-10-22
出版时间：2025-04-20

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收稿日期：2024-11-28
修回日期：2024-12-09

基金

中国矿业大学人才引进资助项目

作者信息

^1．中国矿业大学，材料与物理学院，江苏徐州 221116

^2．兰州交通大学，数理学院，兰州 730070

通讯作者:

任乃青（1996—），女，博士，副教授；

王立锋（1997—），男，博士，副教授；

殷逸臣（1995—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240758

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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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