Research Progress on Structure and Performance Regulation of Silicon-based Anode Materials via Mechanical Ball Milling

doi:10.15541/jim20250304

Abstract

Abstract:

Silicon, due to its exceptionally high theoretical capacity, is widely regarded as an ideal candidate for the anode material in next-generation high-energy-density lithium-ion batteries. However, its practical application is limited by several critical issues, including significant volume expansion during repeated cycling, poor intrinsic conductivity, and instability at the electrode-electrolyte interface. Mechanical ball milling, a solid-state processing technique, offers significant advantages in the performance enhancement of silicon-based anode materials due to its adjustable structure, simplicity in operation, and scalability. This method enables precise control over particle size, morphology, and structural characteristics, providing an efficient and flexible strategy for improving material performance without the need for overly complex or stringent processing conditions. This review summarizes the recent progress in the application of mechanical ball milling for the performance optimization of silicon-based anode materials. Representative advancements include the controlled preparation of nanosilicon, rational design of silicon- carbon composite materials, construction of silicon-metal and metal silicide composite systems, and the implementation of in situ coating strategies. Overall, these studies clearly demonstrate that mechanical ball milling plays a key role in enhancing the structural stability and electrochemical performance of silicon-based anodes. Furthermore, this paper discusses the main challenges currently faced in this field, such as poor uniformity of composite materials, complexity of controlling energy input during milling, and limited understanding of the interface reaction mechanisms. Finally, emerging directions in the field are highlighted, including smart ball milling, interface engineering, and data-driven optimization, which are expected to provide valuable insights for the practical application and commercial promotion of high-performance silicon-based anode materials in high-energy-density lithium-ion batteries.

Key words: silicon, anode material, mechanical ball milling, electrochemical performance, review

CLC Number:

TQ174

LI Hantao, SHEN Qiang, LUO Guoqiang, WANG Xuefei, GAO Ming, CHEN Chen. Research Progress on Structure and Performance Regulation of Silicon-based Anode Materials via Mechanical Ball Milling[J]. Journal of Inorganic Materials, 2026, 41(5): 561-572.

Figures/Tables 8

Fig. 1 Si electrode failure mechanisms[8] (a) Material pulverization; (b) Continuous SEI growth; (c) Morphology and volume change of the entire Si electrode

Table 1 Comparison of common preparation methods for silicon-based anode materials[12-21]

Method	Representative feature and advantage	Issue and limitation	Applicability/industrialization potential	Ref.
Chemical vapor deposition	Constructing high-quality core- shell structures; ensuring good film uniformity	Expensive equipment; complex process; low yield; high energy consumption	Commonly used in laboratory research; limited industrialization	[12-13]
Spray drying	Enabling batch synthesis of spherical particles; suitable for composite material fabrication	High raw material requirements; uneven particle size distribution; complex structural control	Having pilot-scale potential, but precision is limited	[14-15]
Sol-Gel method	Allowing fine control of material structure and composition; suitable for porous or composite materials	Organic precursors are complex, highly sensitive to environment; heat treatment may cause composition changes	Suitable for laboratory use; difficult to scale up	[16-17]
High-temperature carbothermal reduction	Relatively low cost; suitable for synthesizing metal silicides	High processing temperature; poor structural control; limited product purity	Having limited application scope	[18-19]
Mechanical milling	Simple equipment; low cost; enabling nanosizing; in situ compositing; easy mass production	Slightly inferior control over particle morphology; requiring prevention of agglomeration and over-grinding; some contamination must be controlled	Highest industrialization potential and broad process applicability	[20-21]

Fig. 2 Electrochemical performance of silicon anodes prepared with silicon powders of various particle sizes[35] (a) Electrochemical performance of silicon powders with different particle sizes; (b) Scanning electron microscope (SEM) images of the fabricated anode electrode after different cycles

Fig. 3 Preparation of nanosilicon powders from silicon wafers by wet ball milling[38] (a) Schematic of the wet ball milling process; (b) Electrochemical performance of the resulting nanosilicon powders

Fig. 4 Two important failure mechanisms of Si electrode and positive effect of compositing Si with carbon materials (C@Si)[45] (a) Pulverization of silicon particles; (b) Collapse of the entire sole silicon electrode; (c) Reduction of pulverization and increasing of cycling life in C@Si; (d) Possible healing mechanism in C@Si and a more stable contact with current collector

Fig. 5 Preparation processes of various silicon-carbon composites by mechanical ball milling[47,49 -50] (a) Schematic representation of the preparation process of Si/C composite[47]; (b) Constructing schematic diagram of the Si@Co@C[49]; (c) Schematic of the fabrication process of the present Si@APTES/f-Gr composite[50]

Fig. 6 Schematic illustration of lithiation-active elements and process flow diagrams of various silicon-metal composites prepared by mechanical milling[62-64] (a) Schematic diagram of elements with lithium intercalation activity[62]; (b) Schematic of fabrication process of the Si/TiSi2 composite[63]; (c) Preparation process of Si/FeₓSiᵧ composite powder by mechanical ball milling[64]

Fig. 7 Schematic illustration of the construction of inorganic coatings on silicon surfaces via mechanical milling and the structural evolution of two coating materials (Si3N4 and carbon) after lithiation-delithiation cycles[78,80,89] (a) Flowchart for preparing Si@SiOx/GNS anode materials by ball milling[78]; (b) Schematic diagram of the structural evolution of Si3N4 and carbon-coated materials after lithiation-delithiation cycles[80]; (c) Flowchart for preparing silicon nitride compounds by ball milling[89]

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