Enhanced sodium-ion multilayer adsorption performance of sulfur-functionalized M2N-type Mxene

doi:10.11949/0438-1157.20250366

Abstract

Abstract:

Based on density functional theory (DFT), the effects of sulfur (S) functionalization on the structural stability, electronic properties and sodium storage performance of M₂N MXene (M=Sc, Ti, V, Zr, Nb) were systematically investigated. The results demonstrate that sulfur functionalization significantly enhances multilayer adsorption capacity by inducing charge redistribution and strengthening sodium ion adsorption. Specifically, the theoretical capacities of Sc₂NS₂ and Zr₂NS₂ reach 968 mAh/g and 617 mAh/g, respectively, substantially exceeding those of non-functionalized Sc₂N (515 mAh/g) and conventional hard carbon materials (300—400 mAh/g). The migration energy barriers of S-functionalized M₂NS₂ materials (e.g, 0.168 eV for Sc₂NS₂and 0.165 eV for Zr₂NS₂) are notably lower than those of hard carbon (0.25 eV). Differential charge density and electron localization function (ELF) analyses reveal that sulfur incorporation enhances charge transfer between sodium ions and the material surface, as well as localized electronic interactions, thereby providing additional active sites for multilayer adsorption. This work establishes a theoretical foundation for designing high-capacity, fast-charging sodium-ion battery anodes and highlights the promising application potential of S-functionalized M₂N-type MXenes in energy storage systems.

Key words: sodium-ion batteries, MXene, sulfur functionalization, density functional theory, theoretical capacity, nanomaterials, simulation, kinetics

摘要：

基于密度泛函理论（DFT），系统探究了硫（S）功能化对M₂N型MXene（M=Sc、Ti、V、Zr、Nb）结构稳定性、电子性质及储钠性能的影响。结果表明，硫功能化通过诱导电荷重分布并增强钠离子的吸附强度，显著提升了多层吸附能力。其中，Sc₂NS₂和Zr₂NS₂的理论容量分别达到968 mAh/g和617 mAh/g，远高于未功能化的Sc₂N（理论容量为515 mAh/g）及传统硬碳材料（理论容量为300~400 mAh/g）。硫功能化后的M₂NS₂材料的迁移能垒（如Sc₂NS₂为0.168 eV，Zr₂NS₂为0.165 eV）显著低于硬碳的迁移能垒（0.25 eV）。差分电荷密度与电子局域函数（electron localization function，ELF）分析表明，硫的引入增强了钠离子与材料表面的电荷转移及局域化电子相互作用，为多层吸附提供了更多活性位点。该研究为高容量、快充放钠电负极的设计提供了理论依据，凸显了硫功能化M₂N型MXene在储能领域的应用潜力。

关键词: 钠离子电池, MXene, 硫功能化, 密度泛函理论, 理论容量, 纳米材料, 模拟, 动力学

CLC Number:

TQ 152

Yu CAO, Xinyu DU, Ang GAO, Kang LIANG, Yongmao CAI, Jinbo PANG, Jing ZHOU. Enhanced sodium-ion multilayer adsorption performance of sulfur-functionalized M₂N-type Mxene[J]. CIESC Journal, 2025, 76(12): 6729-6738.

曹宇, 杜心宇, 高昂, 梁康, 蔡永茂, 逄金波, 周静. 硫功能化M₂N型MXene的钠离子多层吸附性能增强机制[J]. 化工学报, 2025, 76(12): 6729-6738.

Figures/Tables 8

References 40

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晶体	晶格常数/Å	键长/Å		厚度/Å
晶体	晶格常数/Å	M—N	M—S	厚度/Å
Sc₂N	3.15	2.20	—	2.47
Sc₂NS₂	3.30	2.28	2.52	5.87
Ti₂N	2.96	2.06	—	2.31
Ti₂NS₂	3.16	2.16	2.39	5.43
V₂N	2.89	1.96	—	2.09
V₂NS₂	3.05	2.04	2.36	5.25
Zr₂N	3.22	2.24	—	2.51
Zr₂NS₂	3.42	2.36	2.53	5.73
Nb₂N	3.12	2.12	—	2.26
Nb₂NS₂	3.28	2.21	2.48	5.50

晶体	晶格常数/Å	键长/Å		厚度/Å
晶体	晶格常数/Å	M—N	M—S	厚度/Å
Sc₂N	3.15	2.20	—	2.47
Sc₂NS₂	3.30	2.28	2.52	5.87
Ti₂N	2.96	2.06	—	2.31
Ti₂NS₂	3.16	2.16	2.39	5.43
V₂N	2.89	1.96	—	2.09
V₂NS₂	3.05	2.04	2.36	5.25
Zr₂N	3.22	2.24	—	2.51
Zr₂NS₂	3.42	2.36	2.53	5.73
Nb₂N	3.12	2.12	—	2.26
Nb₂NS₂	3.28	2.21	2.48	5.50

项目	未功能化MXene					硫功能化MXene
项目	Sc₂N	Ti₂N	V₂N	Zr₂N	Nb₂N	Sc₂NS₂	Ti₂NS₂	V₂NS₂	Zr₂NS₂	Nb₂NS₂
第一层平均吸附能/eV	-0.38	-0.41	-0.35	-0.51	-0.49	-1.26	-0.60	-0.08	-0.78	-0.20
第二层平均吸附能/eV	0.05	0.20	0.26	0.02	0.07	-0.07	-0.01	0.14	-0.12	0.001
第三层平均吸附能/eV	—	—	—	—	—	-0.02	0.14	—	-0.05	—
迁移路径	N-N	N-N	N-N	N-N	N-N	N-N	N-N	M1-M1	N-N	M1-M1
迁移能垒/eV	0.012	0.006	0.010	0.012	0.044	0.168	0.142	0.114	0.165	0.099

项目	未功能化MXene					硫功能化MXene
项目	Sc₂N	Ti₂N	V₂N	Zr₂N	Nb₂N	Sc₂NS₂	Ti₂NS₂	V₂NS₂	Zr₂NS₂	Nb₂NS₂
第一层平均吸附能/eV	-0.38	-0.41	-0.35	-0.51	-0.49	-1.26	-0.60	-0.08	-0.78	-0.20
第二层平均吸附能/eV	0.05	0.20	0.26	0.02	0.07	-0.07	-0.01	0.14	-0.12	0.001
第三层平均吸附能/eV	—	—	—	—	—	-0.02	0.14	—	-0.05	—
迁移路径	N-N	N-N	N-N	N-N	N-N	N-N	N-N	M1-M1	N-N	M1-M1
迁移能垒/eV	0.012	0.006	0.010	0.012	0.044	0.168	0.142	0.114	0.165	0.099

Enhanced sodium-ion multilayer adsorption performance of sulfur-functionalized M₂N-type Mxene

硫功能化M₂N型MXene的钠离子多层吸附性能增强机制

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