Progress in 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, the paper discusses the main challenges currently faced in this field, such as poor uniformity of composite materials, the 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 materials, mechanical ball milling, electrochemical performance

CLC Number:

TQ174

LI Hantao, SHEN Qiang, LUO Guoqiang, WANG Xuefei, GAO Ming, CHEN Chen. Progress in Structure and Performance Regulation of Silicon-based Anode Materials via Mechanical Ball Milling[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250304.

References

[1] BRANDT K.Historical development of secondary lithium batteries.Solid State Ionics, 1994, 69(3/4): 173.
[2] SELVARAJ V, VAIRAVASUNDARAM I.A comprehensive review of state of charge estimation in lithium-ion batteries used in electric vehicles.Journal of Energy Storage, 2023, 72: 108777.
[3] ZHANG Y, LIU H, XIE Z,et al. Progress and perspectives of lithium aluminum germanium phosphate-based solid electrolytes for lithium batteries. Advanced Functional Materials, 2023, 33(32): 2300973.
[4] LI P, KIM H, MYUNG S T,et al. Diverting exploration of silicon anode into practical way: a review focused on silicon-graphite composite for lithium ion batteries. Energy Storage Materials, 2021, 35: 550.
[5] ZHANG X, WANG D, QIU X, et al. Stable high-capacity and high-rate silicon-based lithium battery anodes upon two-dimensional covalent encapsulation. Nature Communications, 2020, 11(1): 3826.
[6] HE S, HUANG S, WANG S,et al. Considering critical factors of silicon/graphite anode materials for practical high-energy lithium-ion battery applications. Energy & Fuels, 2020, 35(2): 944.
[7] STODDART A.Lithium-ion batteries: Stress relief for silicon.Nature Reviews Materials, 2017, 2(8): 1.
[8] WU H, CUI Y.Designing nanostructured Si anodes for high energy lithium ion batteries.Nano Today, 2012, 7(5): 414.
[9] HAN M, LIN Z, JI X,et al. Growth of flexible and porous surface layers of vertical graphene sheets for accommodating huge volume change of silicon in lithium-ion battery anodes. Materials Today Energy, 2020, 17: 100445.
[10] KIM S Y, KIM C H, YANG C M.Binder-free silicon anodes wrapped in multiple graphene shells for high-performance lithium-ion batteries.Journal of Power Sources, 2021, 486: 229350.
[11] CHOU S L, WANG J Z, CHOUCAIR M,et al. Enhanced reversible lithium storage in a nanosize silicon/graphene composite. Electrochemistry Communications, 2010, 12(2): 303.
[12] DENG T, ZHOU H, LIU Y,et al. Research progress in the preparation of silicon-carbons anode by chemical vapor deposition. Energy Storage Science and Technology, 2025, 14(9): 3354.
[13] XIAO Z, H. WU H, QUAN L,et al. Micro-sized CVD-derived Si-C anodes: challenges, strategies, and prospects for next-generation high-energy lithium-ion batteries. Energy & Environmental Science, 2025, 18: 4037.
[14] JUNG D, HWANG T, PARK S, et al. Spray drying method for large-scale and high-performance silicon negative electrodes in Li-ion batteries. Nano Letters, 2013 ,13(5): 2092.
[15] SHIH J, CHEN Y, Y. JAMES Y, et al. Suppressed volume change of a spray-dried 3D spherical-like Si/graphite composite anode for high-rate and long-term lithium-ion batteries. ACS Sustainable Chemistry & Engineering, 2022, 10(38): 12706.
[16] HUANG B, TSUI L, RAMKI S,et al. Synthesizing Si/SiOC composites through different Sol-Gel reaction routes for lithium-ion battery anode materials. Heliyon, 2024, 10(13): e33612.
[17] HUANG H, HUANG B, HSU H, et al. Synthesis of silicon oxycarbide beads from alkoxysilane as anode materials for lithium-ion batteries. ACS Omega, 2023, 8(4): 4165.
[18] YAN M, MARTELL S, PATWARDHAN S V, et al. Key developments in magnesiothermic reduction of silica: insights into reactivity and future prospects. Chemical Science, 2024, 15(39): 15954.
[19] HOOVER H, BELL R, RIPPY K, et al. Emerging technologies for decarbonizing silicon production. Journal of Sustainable Metallurgy, 2024, 10: 1921.
[20] CETINKAYA T, CEVHER O, TOCOGLU U, et al. Electrochemical characterization of the powder silicon anodes reinforced with graphite using planetary ball milling. Acta Physica Polonica A, 2013, 123(2): 393.
[21] KORAAG P, FIRDAUS A, HAWARI N, et al. Covalently bonded ball-milled silicon/CNT nanocomposite as lithium-ion battery anode material. Batteries, 2022, 8(10): 165.
[22] SPEIGHT I R, ARDILA-FIERRO K J, HERNÁNDEZ J G,et al. Ball milling for mechanochemical reactions. Nature Reviews Methods Primers, 2025, 5(1): 1.
[23] GE M, CAO C, BIESOLD G M,et al. Recent advances in silicon-based electrodes: from fundamental research toward practical applications. Advanced Materials, 2021, 33(16): 2004577.
[24] ZHAO X, LEHTO V P.Challenges and prospects of nanosized silicon anodes in lithium-ion batteries.Nanotechnology, 2020, 32(4): 042002.
[25] ZHANG Q, YANG Y, WANG D,et al. A silicon/carbon/reduced-graphene composite of honeycomb structure for high-performance lithium-ion batteries. Journal of Alloys and Compounds, 2023, 944: 169185.
[26] ROBERTS G A, CAIRNS E J, REIMER J A.Magnesium silicide as a negative electrode material for lithium-ion batteries. Journal of Power Sources, 2002, 110(2): 424.
[27] B-science.net. Li-ion battery high-energy silicon anode innovation & patent review. (2025-02-03) [2025-11-3]. Li-Ion-Battery-High-Energy-Anode-Innovation-Patent-Review-b-science.net-Preview.
[28] BURMEISTER C F, KWADE A.Process engineering with planetary ball mills.Chemical Society Reviews, 2013, 42(18): 7660.
[29] GAUTHIER M, MAZOUZI D, REYTER D,et al. A low-cost and high performance ball-milled Si-based negative electrode for high-energy Li-ion batteries. Energy & Environmental Science, 2013, 6(7): 2145.
[30] PAN W, CAI X, YANG C,et al. Amorphous Si/TiC/Graphite composite fabricated by high-energy ball-milling as an anode for lithium-ion batteries. Journal of Electronic Materials, 2021, 50(5): 2584.
[31] ZHANG L, HUANG S, DING Y,et al. Research progress in the preparation of sodium-ion battery anode materials using ball milling. RSC Advances, 2025, 15(8): 6324.
[32] GOYAL A, DEMMENIE M, HUANG C C,et al. Photophysical properties of ball milled silicon nanostructures. Faraday Discussions, 2020, 222: 96.
[33] CAO Y, DUNLAP R A, OBROVAC M N.Electrochemistry and thermal behavior of SiO_x made by reactive gas milling. Journal of The Electrochemical Society, 2020, 167(11): 110501.
[34] CAO Y, BENNETT J C, DUNLAP R A,et al. Li insertion in ball milled Si-Mn alloys. Journal of The Electrochemical Society, 2018, 165(9): A1734.
[35] LIU B, LU H, CHU G,et al. Size effect of Si particles on the electrochemical performances of Si/C composite anodes. Chinese Physics B, 2018, 27(8): 088201.
[36] LIU X H, ZHONG L, HUANG S,et al. Size-dependent fracture of silicon nanoparticles during lithiation. ACS Nano, 2012, 6(2): 1522.
[37] ZHU B, JIN Y, TAN Y, et al. Scalable production of Si nanoparticles directly from low grade sources for lithium-ion battery anode. Nano Letters, 2015, 15(9): 5750.
[38] ZHANG Y, MA H, YU C,et al. Si nanoplates prepared by ball milling photovoltaic silicon sawdust waste as lithium-ion batteries anode material. Materials Letters, 2023, 331: 133469.
[39] XU B, CHEN Q, QIU B,et al. Effect of process control agents on preparation of nano-silicon powders by ball milling. Journal of Functional Materials, 2018, 49(12): 12205.
[40] HE S, SHUAI Y, WANG Z,et al. Surface modification and electrochemical performance of amorphous silicon matrix composites by wet ball milling. Shandong Chemical Industry, 2022, 51(08): 32.
[41] HU J, MENG Y S, HU Q R.Synthesis of nickel phosphide/nitrogen phosphorus co-doped carbon and its application in lithium ion batteries.Journal of Electrochemistry, 2021, 27(5): 540.
[42] MA C, WANG Z, ZHAO Y,et al. A novel raspberry-like yolk-shell structured Si/C micro/nano-spheres as high-performance anode materials for lithium-ion batteries. Journal of Alloys and Compounds, 2020, 844: 156201.
[43] WANG F, SONG C, ZHAO B,et al. One-pot solution synthesis of carbon-coated silicon nanoparticles as an anode material for lithium-ion batteries. Chemical Communications, 2020, 56(7): 1109.
[44] ZHANG Y, ZHOU Q, ZHU J,et al. Nanostructured metal chalcogenides for energy storage and electrocatalysis. Advanced Functional Materials, 2017, 27(35): 1702317.
[45] DOS REIS G S, MOLAIYAN P, SUBRAMANIYAM C M,et al. Biomass-derived carbon-silicon composites (C@Si) as anodes for lithium-ion and sodium-ion batteries: a promising strategy towards long-term cycling stability: a mini review. Electrochemistry Communications, 2023, 153: 107536.
[46] SUN J, LUO B, LI H.A review on the conventional capacitors, supercapacitors, and emerging hybrid ion capacitors: past, present, and future.Advanced Energy and Sustainability Research, 2022, 3(6): 2100191.
[47] DU Y, YANG Z, YANG Y,et al. Mussel-pearl-inspired design of Si/C composite for ultrastable lithium storage anodes. Journal of Alloys and Compounds, 2021, 872: 159717.
[48] HAN J, ZHAO C, WANG L,et al. Simple ball milling-assisted method enabling N-doped carbon embedded Si for high performance lithium-ion battery anode. Journal of Alloys and Compounds, 2023, 966: 171668.
[49] YANG D, LV T, SONG J,et al. Enabling stable high-performance CoO-assisted Si@C anode via ball milling strategy. Journal of Physics and Chemistry of Solids, 2024, 189: 111956.
[50] ZHANG Y, CHENG Y, SONG J,et al. Functionalization-assistant ball milling towards Si/graphene anodes in high performance Li-ion batteries. Carbon, 2021, 181: 300.
[51] DING B, CAI Z, AHSAN Z,et al. A review of metal silicides for lithium-ion battery anode application. Acta Metallurgica Sinica, 2021, 34: 291.
[52] ZHAO W, DU N, XIAO C,et al. Large-scale synthesis of Ag-Si core-shell nanowall arrays as high-performance anode materials of Li-ion batteries. Journal of Materials Chemistry A, 2014, 2(34): 13949.
[53] KIM H, SON Y, PARK C,et al. Germanium silicon alloy anode material capable of tunable overpotential by nanoscale Si segregation. Nano Letters, 2015, 15(6): 4135.
[54] LIU K, GUO D, LI Y,et al. Preparation of Si/Sn@C composite anodes through in-situ self-formed templating for enhanced lithium storage. Journal of Electroanalytical Chemistry, 2025, 978: 118879.
[55] MORIGA T, WATANABE K, TSUJI D,et al. Reaction mechanism of metal silicide Mg₂Si for Li insertion. Journal of Solid State Chemistry, 2000, 153(2): 386.
[56] CHEN Z, WANG X, JIAN T,et al. One-step mild fabrication of branch-like multimodal porous Si/Zn composites as high performance anodes for Li-ion batteries. Solid State Ionics, 2020, 354: 115406.
[57] LIU W R, WU N L, SHIEH D T,et al. Synthesis and characterization of nanoporous NiSi-Si composite anode for lithium-ion batteries. Journal of The Electrochemical Society, 2006, 154(2): A97.
[58] ZHANG K, MAO H, GU X,et al. ZIF-derived cobalt-containing N-doped carbon-coated SiO_x nanoparticles for superior lithium storage. ACS Applied Materials & Interfaces, 2020, 12(6): 7206.
[59] XI F, ZHANG Z, WAN X,et al. High-performance porous silicon/nanosilver anodes from industrial low-grade silicon for lithium-ion batteries. ACS Applied Materials & Interfaces, 2020, 12(43): 49080.
[60] KUMAR P, BERHAUT C L, ZAPATA DOMINGUEZ D,et al. Nano-architectured composite anode enabling long-term cycling stability for high-capacity lithium-ion batteries. Small, 2020, 16(11): 1906812.
[61] LIN L, MA Y, XIE Q,et al. Copper-nanoparticle-induced porous Si/Cu composite films as an anode for lithium ion batteries. ACS Nano, 2017, 11(7): 6893.
[62] 赵静. 高熵锂/钠离子电池负极材料的设计及性能研究. 长春: 吉林大学博士学位论文, 2022.
[63] ZHANG Y, CHEN M, CHEN Z,et al. Constructing cycle-stable Si/TiSi₂ composites as anode materials for lithium ion batteries through direct utilization of low-purity Si and Ti-bearing blast furnace slag. Journal of Alloys and Compounds, 2021, 876: 160125.
[64] RUTTERT M, SIOZIOS V, WINTER M, et al. Mechanochemical synthesis of iron silicon alloys and their electrochemical characterization as high energy anode materials. The Electrochemical Society, 2019(1): 19.
[65] 冯志远. 锂离子电池硅合金负极材料的制备及其储锂性能研究. 长沙: 中南大学硕士学位论文, 2022.
[66] LI W, LI X, LIAO J,et al. A new family of cation-disordered Zn(Cu)-Si-P compounds as high-performance anodes for next-generation Li-ion batteries. Energy & Environmental Science, 2019, 12(7): 2286.
[67] Zhao T, Zhu D, Li W,et al. Novel design and synthesis of carbon-coated porous silicon particles as high-performance lithium-ion battery anodes. Journal of Power Sources, 2019, 439: 227027.
[68] LI W, TANG Y, KANG W,et al. Core-shell Si/C nanospheres embedded in bubble sheet-like carbon film with enhanced performance as lithium ion battery anodes. Small, 2015, 11(11): 1345.
[69] SOURICE J, QUINSAC A, LECONTE Y, et al. One-step synthesis of Si@C nanoparticles by laser pyrolysis: High-capacity anode material for lithium-ion batteries. ACS Applied Materials & Interfaces, 2015, 7(12): 6637.
[70] SHI J, GAO H, HU G,et al. Core-shell structured Si@C nanocomposite for high-performance Li-ion batteries with a highly viscous gel as precursor. Journal of Power Sources, 2019, 438: 227001.
[71] SUNG J, KIM N, MA J,et al. Subnano-sized silicon anode via crystal growth inhibition mechanism and its application in a prototype battery pack. Nature Energy, 2021, 6(12): 1164.
[72] YU C, LIN X, CHEN X, et al. Suppressing the side reaction by a selective blocking layer to enhance the performance of Si-based anodes. Nano Letters, 2020, 20(7): 5176.
[73] AI Q, FANG Q, LIANG J,et al. Lithium-conducting covalent-organic-frameworks as artificial solid-electrolyte-interphase on silicon anode for high performance lithium ion batteries. Nano Energy, 2020, 72: 104657.
[74] LI L, FANG C, WEI W,et al. Nano-ordered structure regulation in delithiated Si anode triggered by homogeneous and stable Li-ion diffusion at the interface. Nano Energy, 2020, 72: 104651.
[75] SI Q, HANAI K, ICHIKAWA T,et al. Improvement of cyclic behavior of a ball-milled SiO and carbon nanofiber composite anode for lithium-ion batteries. Journal of Power Sources, 2011, 196(22): 9774.
[76] GUO B, SHU J, WANG Z,et al. Electrochemical reduction of nano-SiO₂ in hard carbon as anode material for lithium ion batteries. Electrochemistry Communications, 2008, 10(12): 1876.
[77] LIU Z, YU Q, ZHAO Y,et al. Silicon oxides: a promising family of anode materials for lithium-ion batteries. Chemical Society Reviews, 2019, 48(1): 285.
[78] TIE X, HAN Q, LIANG C,et al. Si@SiO_x/graphene nanosheets composite: ball milling synthesis and enhanced lithium storage performance. Frontiers in Materials, 2017, 4: 47.
[79] WANG D, GAO M, PAN H, et al. High performance amorphous-Si@SiO_x/C composite anode materials for Li-ion batteries derived from ball-milling and in situ carbonization. Journal of Power Sources, 2014, 256: 190.
[80] MARTIÍN-GIL M, RABANAL M E, VÁREZ A,et al. Mechanical grinding of Si₃N₄ to be used as an electrode in lithium batteries. Materials Letters, 2003, 57(20): 3063.
[81] YANG J, TAKEDA Y, IMANISHI N,et al. Novel composite anodes based on nano-oxides and Li_2.6Co_0.4N for lithium ion batteries. Electrochimica Acta, 2001, 46(17): 2659.
[82] SUZUKI N, CERVERA R B, OHNISHI T,et al. Silicon nitride thin film electrode for lithium-ion batteries. Journal of Power Sources, 2013, 231: 186.
[83] AHN D, KIM C, LEE J G,et al. The effect of nitrogen on the cycling performance in thin-film Si₁-_xN_x anode. Journal of Solid State Chemistry, 2008, 181(9): 2139.
[84] SHAW L L, YANG Z G, REN R M.Synthesis of nanostructured Si₃N₄/SiC composite powders through high energy reaction milling.Materials Science and Engineering: A, 1998, 244(1): 113.
[85] XIAO Z, LEI C, YU C,et al. Si@Si₃N₄@C composite with egg-like structure as high-performance anode material for lithium ion batteries. Energy Storage Materials, 2020, 24: 565.
[86] DE GUZMAN R C, YANG J, CHENG M M C,et al. High capacity silicon nitride-based composite anodes for lithium ion batteries. Journal of Materials Chemistry A, 2014, 2(35): 14577.
[87] MEI S, GUO S, XIANG B,et al. Enhanced ion conductivity and electrode-electrolyte interphase stability of porous Si anodes enabled by silicon nitride nanocoating for high-performance Li-ion batteries. Journal of Energy Chemistry, 2022, 69: 616.
[88] CALKA A, WILLIAMS J S.Synthesis of nitrides by mechanical alloying.Materials science forum, 1992, 88: 787.
[89] HERNANDHA R F H, UMESH B, RATH P C,et al. N-containing carbon-coated β-Si₃N₄ enhances Si anodes for high-performance Li-ion batteries. Advanced Science, 2023, 10(21): 2301218.