硅酸盐学报

通过温和碱性蚀刻法制备蛋黄-壳/多孔硅氧碳负极材料

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陈垒 ¹ , 叶巧巧 ² , 韩成轩 ³ , 蒲敏捷 ³ , 冯怡雯 ¹ , 郑甜甜 ¹ , 杨建平 ²

硅酸盐学报 | 研究论文 2026,54(7): 2470-2480

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硅酸盐学报 |研究论文 2026 , 54 (7) : 2470 -2480

通过温和碱性蚀刻法制备蛋黄-壳/多孔硅氧碳负极材料

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陈垒¹, 叶巧巧², 韩成轩³, 蒲敏捷³, 冯怡雯¹, 郑甜甜¹, 杨建平²

作者信息

^1．河南工程学院材料工程学院，河南省电子陶瓷材料与应用重点实验室，郑州 450007

^2．东华大学材料科学与工程学院，上海 201620

^3．河南卓谷科技有限公司，郑州 450007

作者简介:

陈垒（1984—），男，博士，副教授。

Preparation of Egg Yolk-Shell/Porous Silicon Oxycarbide Anode Materials via Mild Alkaline Etching

Lei CHEN¹, Qiaoqiao YE², Chengxuan HAN³, Minjie PU³, Yiwen FENG¹, Tiantian ZHENG¹, Jianping YANG²

Affiliations

^1.Henan Key Laboratory of Electronic Ceramic Materials and Applications, College of Materials Engineering, Henan University of Engineering, Zhengzhou 450007, China

^2.College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

^3.Henan Zhuogu Technology Co., Ltd., Zhengzhou 450007, China

CHEN Lei (1984-), male, Ph.D., Associate Professor. E-mail: chenlei904@126.com

出版时间: 2026-04-28 doi: 10.14062/j.issn.0454-5648.20250561

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摘要

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硅氧碳（SiOC）负极材料具有理论比容量高、机械柔性好、结构稳定和价格低等一系列优良性能，被认为是极具潜力的锂离子电池负极材料之一。本工作通过溶胶-凝胶法，精确控制前驱体添加的顺序和时间，合成了一种具有独特蛋黄-壳结构且内核多孔的SiOC材料，在低能耗且温和的反应条件下使硅和碳在微观上均匀有效结合分布，该结构促进电极高倍率与长寿命的统一。所用原料为1，4-双（三乙氧基硅基）苯和四乙氧基硅烷的混合物，并在温和碱性条件下进行蚀刻处理。采用扫描电子显微镜、透射电子显微镜和X射线衍射等多种表征技术，细致地表征了材料的微观结构，阐明了温和碱性蚀刻如何影响材料形貌和孔结构的机理。蛋黄-壳（YS@C）和多孔（P@C）SiOC负极材料的比表面积分别为17.041 m²·g^-1和27.458 m²·g^-1。在0.5 A·g^-1的电流密度下，YS@C和P@C可稳定循环550次，比容量分别为453 mA·h·g^-1和384 mA·h·g^-1。即使在1 A·g^-1的高电流密度下，YS@C仍能稳定循环1000次，比容量达354 mA·h·g^-1。总体而言，本工作提供了一种高效温和的新方法来制备高性能蛋黄-壳/多孔结构材料，为解决硅基负极膨胀核心痛点，有效抑制电极粉化与固体电解质界面膜破裂提供了新思路新方法，并有利于商业化生产。

关键词

温和蚀刻法 / 硅氧碳基负极 / 高能量密度电池 / 碳包覆 / 溶胶-凝胶法

Abstract

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Introduction

Lithium-ion batteries (LIBs) with a high energy density are critical for advancing electric vehicles and renewable energy storage systems. Silicon oxycarbide (SiOC) anode materials emerge as promising candidates due to their high cycling stability, suitable operating potential, low cost, and environmental compatibility. Unlike conventional silicon anodes that suffer from severe volume expansion (i.e., >300%), SiOC materials benefit from the uniform distribution of silicon and carbon in an atomic scale, forming protective Li₂O and lithium silicate layers during initial lithiation that mitigate volume changes. However, a practical implementation of SiOC anodes remains challenging due to their intrinsically low electronic/ionic conductivity and significant volumetric changes during cycling, leading to electrode pulverization, loss of electrical contact, and excessive solid-electrolyte interphase (SEI) growth. In this study, a novel synthesis strategy was proposed to create SiOC anodes with engineered yolk-shell and porous architectures that could simultaneously optimize structural stability, ionic/electronic transport, and interfacial properties.

Methods

This work employed a meticulously controlled sol-gel process followed by selective etching under mild alkaline conditions to fabricate SiOC anode materials with distinctive architectures. A yolk-shell structured material (YS@C) was prepared by a sequential addition approach via incorporating 1,4-bis(triethoxysilyl)benzene (BTEB) to form the core, and then adding tetraethoxysilane (TEOS) to create the shell. For the porous material (P@C), BTEB and TEOS were introduced simultaneously. The structures both underwent selective etching with a 2.4 mol/L Na₂CO₃ solution, removing portions of the inorganic silica, while preserving the organic-inorganic hybrid framework. Subsequently, resorcinol-formaldehyde resin was coated onto the etched structures and carbonized in 10% H₂/Ar atmosphere at 800 ℃ to form conductive carbon layers. The structural and chemical properties were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and BET surface area analysis. The electrochemical performance was evaluated through cyclic voltammetry, galvanostatic charge-discharge testing, rate capability analysis, long-term cycling, and impedance spectroscopy, respectively.

Results and discussion

The mild alkaline etching strategy produces monodisperse YS@C particles (with the sizes of 250-270 nm) featuring a distinctive yolk-shell structure with an intermediate void space, and P@C particles (with the sizes of 320-350 nm) with uniformly distribute internal pores. The structural analyses reveals amorphous characteristics with carbon contents of 75.51% for YS@C and 68.2% for P@C. The specific surface areas measured are 17.041 m²/g for YS@C and 27.458 m²/g for P@C, with the average pore sizes of 2.371 nm and 2.561 nm, respectively. The XPS analysis demonstrates different silicon valence states, with the average values of 2.796 9 for YS@C and 2.999 2 for P@C, indicating varying degrees of silicon oxidation that affect the electrochemical behavior.

In electrochemical testing, YS@C delivers the superior performance with an initial Coulombic efficiency of 55%, compared to 49% for P@C. Most significantly, YS@C maintains an exceptional cycling stability with specific capacities of 453 mA·h·g^-1 after 550 cycles at 0.5 A/g and 361 mA·h·g^-1 after 1000 cycles at 1 A/g, with the Coulombic efficiency consistently of > 99% after the sixth cycle. The kinetic analyses reveals the superior Li⁺ diffusion coefficient and remarkable pseudocapacitive contribution of YS@C (i.e., 82.2% at 2.0 mV/s) due to its shortened ion diffusion pathways. The post-cycling SEM examination confirms the structural integrity after 300 cycles of YS@C, while P@C exhibits significant cracking and degradation.

Conclusions

This research demonstrated that the gradient composition and hierarchical architecture of YS@C, featuring a high-capacity siloxane-rich core, intermediate void space, and protective carbon/SiOx shell, could collectively address the fundamental limitations of SiOC anode materials. The internal void space effectively accommodated volume expansion during lithiation/delithiation, while the carbon-rich shell enhanced conductivity and minimized detrimental side reactions with the electrolyte. The mild alkaline etching approach presented could offer a gentle yet effective method for engineering complex architectures without damaging the organic components critical for performance. The exceptional electrochemical performance of YS@C, particularly its unprecedented cycling stability at high current densities, could establishe a benchmark for SiOC-based anodes. This work could advance the development of high-performance lithium-ion battery anodes and provide valuable design principles for engineering gradient-structured materials for various energy storage applications. Future research could focus on scaling this synthesis approach and exploring its applicability to other conversion/alloying-type electrode materials requiring volume change accommodation.

Key words

selective etching method / silicon-oxygen-carbon-based anode / high energy density battery / carbon coating / sol-gel method

引用本文

陈垒, 叶巧巧, 韩成轩, 蒲敏捷, 冯怡雯, 郑甜甜, 杨建平. 通过温和碱性蚀刻法制备蛋黄-壳/多孔硅氧碳负极材料. 硅酸盐学报, 2026 , 54 (7) : 2470 -2480 . DOI: 10.14062/j.issn.0454-5648.20250561

Lei CHEN, Qiaoqiao YE, Chengxuan HAN, Minjie PU, Yiwen FENG, Tiantian ZHENG, Jianping YANG. Preparation of Egg Yolk-Shell/Porous Silicon Oxycarbide Anode Materials via Mild Alkaline Etching[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (7) : 2470 -2480 . DOI: 10.14062/j.issn.0454-5648.20250561

基金

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国家自然科学基金(92163121)

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2026年第54卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250561

接收时间：2025-07-18
首发时间：2026-10-22
出版时间：2026-04-28

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收稿日期：2025-07-18
修回日期：2026-03-28

基金

国家自然科学基金(92163121)

作者信息

^1．河南工程学院材料工程学院，河南省电子陶瓷材料与应用重点实验室，郑州 450007

^2．东华大学材料科学与工程学院，上海 201620

^3．河南卓谷科技有限公司，郑州 450007

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250561

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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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