硫功能化M2N型MXene的钠离子多层吸附性能增强机制

doi:10.11949/0438-1157.20250366

化工学报 ›› 2025, Vol. 76 ›› Issue (12): 6729-6738.DOI: 10.11949/0438-1157.20250366

• 材料化学工程与纳米技术 • 上一篇下一篇

硫功能化M₂N型MXene的钠离子多层吸附性能增强机制

曹宇¹^,²(), 杜心宇¹^,², 高昂¹^,², 梁康¹^,², 蔡永茂³(), 逄金波⁴, 周静¹^,⁵()

^1.现代电力系统仿真控制与绿色电能新技术教育部重点实验室（东北电力大学），吉林吉林 132012
^2.东北电力大学电气工程学院，吉林吉林 132012
^3.东北电力大学理学院，吉林吉林 132012
^4.济南大学前沿交叉科学研究院，山东济南 250022
^5.东北电力大学化学工程学院，吉林吉林 132012

收稿日期:2025-04-09 修回日期:2025-05-04 出版日期:2025-12-31 发布日期:2026-01-23
通讯作者: 蔡永茂,周静
作者简介:曹宇（1986—），男，博士，教授，ycao@neepu.edu.cn
基金资助:
国家自然科学基金项目(52172185);吉林市科技创新发展计划项目(20230103006)

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

Yu CAO¹^,²(), Xinyu DU¹^,², Ang GAO¹^,², Kang LIANG¹^,², Yongmao CAI³(), Jinbo PANG⁴, Jing ZHOU¹^,⁵()

^1.Key Laboratory of Modern Power System Simulation and Control & Renewable Energy Technologies (Northeast Electric Power University), Ministry of Education, Jilin 132012, Jilin, China
^2.School of Electrical Engineering, Northeast Electric Power University, Jilin 132012, Jilin, China
^3.School of Science, Northeast Electric Power University, Jilin 132012, Jilin, China
^4.Institute of Frontier and Interdisciplinary Science, University of Jinan, Jinan 250022, Shandong, China
^5.School of Chemical Engineering, Northeast Electric Power University, Jilin 132012, Jilin, China

Received:2025-04-09 Revised:2025-05-04 Online:2025-12-31 Published:2026-01-23
Contact: Yongmao CAI, Jing ZHOU

摘要/Abstract

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

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

中图分类号:

TQ 152

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.

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.

图/表 8

图1 晶体结构图

Fig.1 Crystal structure diagrams

表1 M2N和M2NS2晶体结构具体参数

Table 1 Specific parameters of the crystal structures of M2N and M2NS2

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

表2 MXene的平均吸附能及迁移路径以及相应的迁移能垒

Table 2 Average adsorption energy and migration paths of MXene， as well as the corresponding migration energy barriers

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

图2 差分电荷密度图（等值面能级设定为0.0010 e/Bohr3，黄色和浅蓝色分别表示电荷的累积与消耗）

Fig.2 Differential charge density diagrams (The isosurface energy level is set to 0.0010 e/Bohr3, yellow and light blue respectively represent the accumulation and consumption of charges)

图3 不同MXene的ELF图

Fig.3 ELF diagrams of different MXenes

图4 迁移路径和迁移能垒

Fig.4 Migration paths and migration energy barriers

图5 吸附在Sc2NS2表面上的Na离子层

Fig.5 The Na+ ion layer adsorbed on the Sc2NS2 surface

图6 开路电压与理论容量

Fig.6 Open-circuit voltage and theoretical capacity

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硫功能化M₂N型MXene的钠离子多层吸附性能增强机制

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

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