硅酸盐学报

混合金属协同助力钠离子电池硫化物负极实现超大电流密度下的长循环稳定性

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杨林 ¹ , 黄思鸣 ¹ , 马竟雄 ¹ , 冯元龙 ¹ , 代文静 ¹ , 周颖宁 ¹ , 秦秋石 ¹ , 李阳光 ¹ , 王明珊 ¹^,²

硅酸盐学报 | 研究论文 2025,53(7): 2001-2012

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硅酸盐学报 |研究论文 2025 , 53 (7) : 2001 -2012

混合金属协同助力钠离子电池硫化物负极实现超大电流密度下的长循环稳定性

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杨林¹, 黄思鸣¹, 马竟雄¹, 冯元龙¹, 代文静¹, 周颖宁¹, 秦秋石¹, 李阳光¹, 王明珊¹^,²

作者信息

^1．西南石油大学新能源与材料学院，成都 610500

^2．油气藏地质及开发工程全国重点实验室，成都 610500

通讯作者:

王明珊（1986—），女，博士，教授。

作者简介:

杨林（1997—），男，硕士研究生。

Mixed-Metal Synergies Enables Sodium-Ion Battery Sulfide Anodes to Achieve Long Cycle Stability at Ultra-High Currents Density

Lin YANG¹, Siming HUANG¹, Jingxiong MA¹, Yuanlong FENG¹, Wenjing DAI¹, Yingning ZHOU¹, Qinshi QIN¹, Yangguang LI¹, Mingshan WANG¹^,²

Affiliations

^1.School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China

^2.State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Chengdu 610500, China

Corresponding Author:

WANG Mingshan (1986-), female, Ph.D., Professor. E-mail: ustbwangmingshan@163.com

YANG Lin (1997-), male, Master candidate. E-mail: yanglin12082022@163.com

出版时间: 2025-07-20 doi: 10.14062/j.issn.0454-5648.20240793

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摘要

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为了改进单金属硫化物循环性能较差，不满足大电流充放电的缺点，选用Fe、Co、Ni、Cu、Sn金属离子，通过共沉淀法和高温煅烧硫化成功制备了一种混合金属硫化物NiS/Cu₂（Fe, Co, Ni）SnS₄/碳纳米管复合材料。在充放电过程中，多重金属离子还原成金属单质，促进了离子和电子的传输，抑制了电池极化。Fe、Co、Ni、Cu、Sn金属可以作为活性催化中心以及导电位点增强电池稳定性和倍率性能。NiS和Cu₂（Fe, Co, Ni）SnS₄之间的异质界面形成了一个内置电场，促进了电化学反应动力学。此外，碳纳米管的引入作为材料间的桥梁，提供了电子传输路径，维持了材料的结构稳定性。对所制备的材料进行储钠性能研究，在5 A·g^-1的电流密度下循环1000圈后，放电比容量为626 mA·h·g^-1，并且在20 A·g^-1超大电流密度下循环8000圈之后，还具有399 mA·h·g^-1的放电比容量。NiS/Cu₂（Fe, Co, Ni）SnS₄/CNT混合金属硫化物负极在大电流密度下展现了优异的电化学性能，解决了金属硫化物导电性差的缺点，为混合金属硫化物负极材料的研究和改性提供了新的视角和思路。

关键词

混合金属硫化物 / 负极 / 钠离子电池 / 超大电流密度

Abstract

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Introduction

It is critical for large-scale energy storage to develop sodium-ion batteries (SIBs) due to their cost-effectiveness and abundant sodium resources. However, some challenges like sluggish kinetics from large Na⁺ radii and poor structural stability of electrode materials hinder their practical application. Transition metal sulfides (TMS) like SnS, NiS, and FeS exhibit high theoretical capacities, but suffer from some intrinsic drawbacks (i.e., low conductivity and severe volume expansion during cycling). To address these limitations, this study was to propose a novel strategy, i.e., designing a mixed-metal sulfide composite of (NiS/Cu₂(Fe,Co,Ni)SnS₄/CNT) with heterointerfaces and multi-metal synergy. The integration of Fe, Co, Ni, Cu, and Sn could enhance electronic/ionic transport, mitigate volume changes, and leverage catalytic effects of transition metals. Carbon nanotube (CNT) were introduced to further improve conductivity and structural integrity. This mixed-metal sulfide composite exhibited the excellent performance at a ultra-high current density.

Methods

The composite was synthesized via a co-precipitation method and a subsequent high-temperature sulfidation. For NiS/Cu₂(Fe,Co,Ni)SnS₄/CNT, stoichiometric amounts of FeSO₄, CoSO₄, NiSO₄, CuSO₄, and SnSO₄ were dissolved and co-precipitated with NaOH. The CNT slurry was ultrasonically dispersed and incorporated into the precursor. After sulfidation with thioacetamide in N₂ at 500 ℃, the final product was obtained. NiS/CNT (control sample) followed the similar process using only NiSO₄. The crystallinity, morphology, and elemental states of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). To evaluate their kinetics, rate capability and cycling stability, CR2032 half-cells assembled with Na metal counter electrodes were tested by cyclic voltammetry (CV), constant-current charge/discharge test, galvanostatic intermittent titration (GITT) and electrochemical impedance spectroscopy (EIS), respectively.

Results and discussion

The results show that the complex consists of Cu₂(Fe,Co,Ni)SnS₄ and NiS biphasic phases, and the heterogeneous interfaces exist, which are confirmed by high-resolution transmission electron microscopy (HRTEM). The built-in electric field at the heterogeneous interface accelerates the charge transfer, and the multimetal synergy (Fe/Co/Ni/Cu/Sn) provides abundant catalytic sites and reduces the Na⁺ diffusion barrier (i.e., 32% reduction in the diffusion barrier according to density-functional theory calculations). The three-dimensional conductive network constructed by the CNTs inhibits the volume expansion efficiently (i.e., the thickness of the electrodes increases by only 37.9% after cycling, which is significantly lower than that of the NiS/CNT). For the electrochemical performance, NiS/Cu₂(Fe, Co, Ni)SnS₄/CNT exhibits an excellent high rate charge/discharge performance and a long cycle stability, and still maintains a discharge specific capacity of 626 mA·h·g^-1 after 1000 cycles at a current density of 5 A·g^-1, and 399 mA·h·g^-1 after 8000 cycles at an ultra-high current density of 20 A·g^-1. Capacitive-dominated storage and enhanced Na⁺ diffusivity outperform monometallic NiS/CNT. The TEM images and CV indicate a reversible phase transition between sulfide and Na₂S, thus validating the reaction mechanism.

Conclusions

The built-in electric field formed by the heterogeneous interface and the synergistic effect of polymetallic cations could enhance the ion and charge transfer rate, and the reduction of polymetallic ions to metal monomers facilitated the ion and electron transport during the charging and discharging process, effectively suppressing the polysulfide shuttling phenomenon, thus decreasing the polarization of the battery. The introduction of carbon nanotubes provided electron transport paths, which further enhanced the structural stability of the material. This study could have a great potential of mixed metal sulfides for application in anode materials for sodium-ion batteries.

Key words

mixed metal sulfides / anode / sodium-ion battery / ultra-high current density

引用本文

杨林, 黄思鸣, 马竟雄, 冯元龙, 代文静, 周颖宁, 秦秋石, 李阳光, 王明珊. 混合金属协同助力钠离子电池硫化物负极实现超大电流密度下的长循环稳定性. 硅酸盐学报, 2025 , 53 (7) : 2001 -2012 . DOI: 10.14062/j.issn.0454-5648.20240793

Lin YANG, Siming HUANG, Jingxiong MA, Yuanlong FENG, Wenjing DAI, Yingning ZHOU, Qinshi QIN, Yangguang LI, Mingshan WANG. Mixed-Metal Synergies Enables Sodium-Ion Battery Sulfide Anodes to Achieve Long Cycle Stability at Ultra-High Currents Density[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (7) : 2001 -2012 . DOI: 10.14062/j.issn.0454-5648.20240793

基金

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国家自然科学基金面上项目(52072322)
四川省科技计划项目重点研发项目(2025YFHZ0172; 2024ZDZX0033)

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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.0454-5648.20240793

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

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出版历史

收稿日期：2024-12-12
修回日期：2025-01-13

基金

国家自然科学基金面上项目(52072322)

四川省科技计划项目重点研发项目(2025YFHZ0172; 2024ZDZX0033)

作者信息

^1．西南石油大学新能源与材料学院，成都 610500

^2．油气藏地质及开发工程全国重点实验室，成都 610500

通讯作者:

王明珊（1986—），女，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240793

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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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