硅酸盐学报

铁负载酸活化蒙脱石制备硅/硅化铁纳米复合材料及其储锂性能

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杜静 ¹^,²^,³ , 李向军 ⁴ , 谢捷洋 ¹^,²^,³ , 韦寿淑 ¹^,²^,³ , 熊涛 ¹^,²^,³ , 何诗雅 ¹^,²^,³ , 陈情泽 ¹^,²^,³ , 朱润良 ¹^,²^,³

硅酸盐学报 | 研究论文 2024,52(10): 3252-3262

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硅酸盐学报 |研究论文 2024 , 52 (10) : 3252 -3262

铁负载酸活化蒙脱石制备硅/硅化铁纳米复合材料及其储锂性能

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杜静¹^,²^,³, 李向军⁴, 谢捷洋¹^,²^,³, 韦寿淑¹^,²^,³, 熊涛¹^,²^,³, 何诗雅¹^,²^,³, 陈情泽¹^,²^,³, 朱润良¹^,²^,³

作者信息

^1．中国科学院广州地球化学研究所中国科学院矿物学与成矿学重点实验室/广东省矿物物理与材料研究开发重点实验室，广州 510640

^2．中国科学院深地科学卓越创新中心，广州 510640

^3．中国科学院大学，北京 100049

^4．惠州市鼎元新能源科技有限公司，广东惠州 516227

通讯作者:

陈情泽（1991—），男，博士，副研究员。

作者简介:

杜静（1996—），女，博士研究生；

李向军（1986—），男，硕士。

Iron Silicide/Silicon Nanomaterials Derived from Iron/Acid-Montmorillonite for High Performance Lithium-Ion Battery Anode

Jing DU¹^,²^,³, Xiangjun LI⁴, Jieyang XIE¹^,²^,³, Shoushu WEI¹^,²^,³, Tao XIONG¹^,²^,³, Shiya HE¹^,²^,³, Qingze CHEN¹^,²^,³, Runliang ZHU¹^,²^,³

Affiliations

^1.CAS Key Laboratory of Mineralogy and Metallogeny/Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry, Chinese Academy of Science, Guangzhou 510640, China

^2.CAS Center for Excellence in Deep Earth Science, Guangzhou 510640, China

^3.University of Chinese Academy of Sciences, Beijing 100049, China

^4.Huizhou Dingyuan New Energy Technology Company Limited, Huizhou 516227, Guangdong, China

Corresponding Author:

CHEN Qingze (1991-), male, Ph.D., Associate Professor. E-mail: chenqingze@gig.ac.cn

DU Jing (1996-), female, Doctoral candidate; E-mail: dujing@gig.ac.cn;

LI Xiangjun (1986-), male, Master. 823369523@qq.com

出版时间: 2024-10-20 doi: 10.14062/j.issn.0454-5648.20240122

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摘要

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纳米硅的储锂容量高，被认为是最有应用前景的新一代锂电负极材料。然而纳米硅的体积膨胀效应和低电导性不利于其实际应用。将天然蒙脱石酸活化和铁负载改性，再经过镁热还原反应，得到了原位复合的硅/硅化铁纳米复合材料。硅化铁具有良好的导电性和机械稳定性，可显著提升硅负极的循环稳定性和倍率性能。在1 A/g的电流密度下循环500圈后，硅/硅化铁纳米复合材料的比容量高达781 mA·h/g，容量保持率为77%。该方法为制备高性能硅基负极材料提供了新思路。

关键词

蒙脱石 / 镁热还原 / 硅化铁 / 硅纳米材料 / 锂离子电池负极

Abstract

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Introduction

Silicon is considered as one of the most promising lithium anode materials due to its high lithium storage capacity. However, the volume expansion effect and semiconductor properties of silicon hinder its practical application. Two effective strategies exist for mitigating this issue, i.e., reducing the size of silicon to nanoscale; and introducing non-active matrices to improve stability and conductivity. In recent decades, the incorporation of iron silicide (FeSi₂) with silicon (Si) has attracted much attention due to its high conductivity, mechanical hardness and environmental friendliness. Unfortunately, the Si/FeSi₂ nanocomposites are mainly prepared by high-energy ball milling, which has some drawbacks such as low purity, large particle size, and uncontrollable morphology, making it difficult to achieve the commercial application. Porous silica derived from clay minerals is extensively investigated for the preparation of silicon nanoparticles by magnesiothermic reduction. In addition, porous silica has a large specific surface area, which facilitates the effective dispersion and loading of iron oxides. The reduction of iron oxide and silica dioxide to Fe and Si can be achieved by magnesium. In this paper, a natural montmorillonite (Mnt) with a high content of silica (65%, in mass) was utilized as a raw material. Silicon/iron silicide (Si/FeSi₂) nanocomposites were synthesized via modification of Mnt (including acid etching and iron loading) and molten salt-assisted magnesiothermic reduction.

Methods

A porous silica (SiO₂) was prepared via leaching Mnt at a high concentration of HCl. Subsequently, a iron oxide was loaded on SiO₂ via precipitation in different Fe/Si mass ratios (i.e., 0, 10%, and 20%). Modified SiO₂ (Fe-SiO₂) was mixed with Mg and NaCl in a mass ratio of 1.00∶0.85∶3.00. Afterwards, the mixture was heated in an inert atmosphere at 650 ℃ for 5 h in a heating rate of 5 ℃/min. After cooling naturally, the product was washed with 1 mol/L HCl and 1% (in mass) HF in sequence to remove the by-product. Finally, it was rinsed with ultra-pure water until neutral and dried at 80 ℃. The sample were named as Si, Si/FeSi₂-1, and Si-FeSi₂-2, corresponding to the Fe/Si mass ratio of 0, 10%, and 20%, respectively.

Results and discussion

The XRD patterns show that Si/FeSi₂ nanocomposites are consisted of Si and ɑ-FeSi₂. An increase in Fe content in precursors leads to a higher α-FeSi₂ content in the product. Based on the results of RIR value method and elemental composition analysis, the mass ratio of FeSi₂ to Si in Si/FeSi₂-1 and Si/FeSi₂-2 is 5% and 10%, respectively. The average grain sizes of Si, Si/FeSi₂-1, and Si/FeSi₂-2 are 20, 40 nm, and 48 nm, respectively, according to Scherrer's equation,. The grain size of silicon increases with the augmentation of Fe content in the precursor. This phenomenon analyzed by both transmission electron microscopy and scanning electron microscopy images is since the melting temperature of silicon nanoparticle is lower than that of bulk silicon (~1 410 ℃), the addition of iron greatly increases the local temperature (ΔH_Fe₂O₃= -309 kJ/mol vs. ΔH_SiO₂= -130 kJ/mol), and the addition of Fe can effectively reduces the melting point of nanocrystalline grains in Fe/Si eutectic alloys. Moreover, the specific surface areas of Si, Si/FeSi₂-1, and Si/FeSi₂-2 are 89, 42 m²/g, and 33 m²/g, respectively. The gradual decrease in specific surface area coincides with the concurrent increase in grain size.

As anode electrodes, Si/FeSi₂ nanocomposites exhibit a higher initial coulombic efficiency, compared with Si due to the smaller specific surface area. The rate performance show that Si exhibits higher capacity than Si/FeSi₂-1 and Si/FeSi₂-2 at a low current density of 0.1 A/g. However, when the current density increases gradually, the capacity of Si is lower than that of Si/FeSi₂-1 and Si/FeSi₂-2. This phenomenon indicates that the incorporation of ɑ-FeSi₂ enhances both electron conduction and ion diffusion rates. After undergoing 500 cycles at a current of 1 A/g, the capacities of Si, Si/FeSi₂-1, and Si/FeSi₂-2 are 417, 781 mA·h/g, and 561 mA·h/g, respectively. The corresponding capacity retention rates are 35%, 77%, and 50%, respectively. The cycling performance demonstrates that Si/FeSi₂ nanocomposites have a more robust structure, compared to the Si electrode. In addition, the cyclic stability of Si/FeSi₂-1 is inferior to that of Si/FeSi₂-2, potentially due to the reduced structural stability resulting from a larger particle size.

Conclusions

The Si/FeSi₂ nanocomposites were prepared via modification of montmorillonite and molten salt-assisted magnesiothermic reduction. This method utilized magnesium powder to reduce Fe₂O₃ and SiO₂ for the in-situ formation of Si/FeSi₂ nanocomposites. The composition of Si and FeSi₂ nanocomposites could be adjusted via altering the ratio of Si/Fe in the precursor. Moreover, the reduction of Fe₂O₃ resulted in an increase in grain size and a decrease in specific surface area of silicon nanoparticles. As anode materials, Si/FeSi₂ composites demonstrated the superior rate performance and cycle stability, compared to Si. This phenomenon could be due to the incorporation of ɑ-FeSi₂, effectively enhancing the kinetics of lithium ions and electrons on the electrode. In addition, as an inert substance, FeSi₂ could reduce the volume expansion effect of silicon, thereby maintaining the stability of electrode structural. The structural stability of the Si/FeSi₂-2 electrode was relatively weaker than that of the Si/FeSi₂-1 electrode. Therefore, Fe content in the precursor could be of paramount importance for achieving high-performance silicon-based nanocomposite anodes.

Key words

montmorillonite / magnesiothermic reduction / iron silicide / silicon nanomaterials / lithium-ion battery anode

引用本文

杜静, 李向军, 谢捷洋, 韦寿淑, 熊涛, 何诗雅, 陈情泽, 朱润良. 铁负载酸活化蒙脱石制备硅/硅化铁纳米复合材料及其储锂性能. 硅酸盐学报, 2024 , 52 (10) : 3252 -3262 . DOI: 10.14062/j.issn.0454-5648.20240122

Jing DU, Xiangjun LI, Jieyang XIE, Shoushu WEI, Tao XIONG, Shiya HE, Qingze CHEN, Runliang ZHU. Iron Silicide/Silicon Nanomaterials Derived from Iron/Acid-Montmorillonite for High Performance Lithium-Ion Battery Anode[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (10) : 3252 -3262 . DOI: 10.14062/j.issn.0454-5648.20240122

基金

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广东省重点领域研发计划项目(2020B0101370003)
广东省自然科学基金杰出青年基金项目(2023B1515020006)
中国科学院青年创新促进会项目(2020347)
广东省科技计划项目(2023B1212060048)
惠州市重点领域科技攻关“揭榜挂帅”项目

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2024年第52卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240122

接收时间：2024-02-12
首发时间：2026-10-22
出版时间：2024-10-20

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收稿日期：2024-02-12
修回日期：2024-03-17

基金

广东省重点领域研发计划项目(2020B0101370003)

广东省自然科学基金杰出青年基金项目(2023B1515020006)

中国科学院青年创新促进会项目(2020347)

广东省科技计划项目(2023B1212060048)

惠州市重点领域科技攻关“揭榜挂帅”项目

作者信息

^1．中国科学院广州地球化学研究所中国科学院矿物学与成矿学重点实验室/广东省矿物物理与材料研究开发重点实验室，广州 510640

^2．中国科学院深地科学卓越创新中心，广州 510640

^3．中国科学院大学，北京 100049

^4．惠州市鼎元新能源科技有限公司，广东惠州 516227

通讯作者:

陈情泽（1991—），男，博士，副研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240122

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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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