基于富硅农作物的可规模化合成Si/SiOx@C纳米复合材料及其锂离子电池负极性能的研究

doi:10.15541/jim20260182

摘要/Abstract

摘要： 生物质衍生硅资源为开发高性能锂离子电池(LIBs)负极提供了一条可持续途径,但往往受限于复杂的合成工艺及结构不稳定性。本研究报道了一种可规模化的制备策略,通过熔盐辅助铝热还原法结合球磨技术,将稻壳转化为Si/SiO_x@C纳米复合材料。该工艺在导电碳基体中均匀嵌入~50 nm的Si/SiO_x (BH-12),有效缓解了硅在充放电过程中的巨大体积变化,并加速了电子和离子的传输。得益于这种协同结构,BH-12在0.1 A·g^-1电流密度下实现了437.1 mAh·g^-1的高可逆容量,且在160次循环后仍保持369.8 mAh·g^-1,其性能显著优于原始碳化稻壳及未还原样品。此外,BH-12||LiFePO₄ (LFP)全电池表现出优异的倍率性能和增强的锂离子扩散动力学(10^-10.5~10^-9 cm²·s^-1),这归因于颗粒尺寸的减小和界面稳定性的增强。本工作展示了一种环保且成本低廉的高性能硅基负极量产方法,为下一代锂离子电池提供了新的设计思路。

关键词: 稻壳衍生硅, 锂离子电池, 球磨工程, 铝热还原, Si/SiO_x@C纳米复合材料

Abstract: Biomass-derived silicon resources offer a sustainable pathway for high-performance lithium-ion battery (LIB) anodes but are often limited by complex synthesis routes and unstable structures. Herein, we report a scalable strategy that couples molten-salt-assisted aluminothermic reduction with ball milling to convert rice husks into a Si/SiO_x@C nanocomposite. The process enables the formation of uniformly dispersed ~50 nm Si/SiO_x domains embedded within a conductive carbon matrix (BH-12), which effectively mitigates the large volume variation of Si and accelerates electron/ion transport. Benefiting from the synergistic structure, BH-12 achieves a high reversible capacity of 437.1 mAh·g^-1 at 0.1 A·g^-1 and retains 369.8 mAh·g^-1 after 160 cycles, markedly outperforming pristine carbonized husks and unreduced samples. Furthermore, coupling with LiFePO₄ (LFP), the BH-12||LFP full cell exhibits superior rate capability and enhanced Li⁺ diffusion kinetics (10^-10.5-10^-9 cm²·s^-1), attributed to reduced particle size and strengthened interfacial stability. This work demonstrates an environmentally friendly and cost-effective approach for mass production of high-performance Si-based anodes, providing practical insights for next-generation LIBs.

Key words: rice husk-derived silicon, lithium-ion batteries, ball milling engineering, aluminothermic reduction, Si/SiO_x@C nanocomposite

中图分类号:

TM912

仵洁, 李妍, 顾宇辰, 张浩, 宋盈盈, YASSER A Attia, 马汝广. 基于富硅农作物的可规模化合成Si/SiO_x@C纳米复合材料及其锂离子电池负极性能的研究[J]. 无机材料学报, DOI: 10.15541/jim20260182.

WU Jie, LI Yan, GU Yuchen, ZHANG Hao, SONG Yingying, YASSER A Attia, MA Ruguang. Scalable Synthesis of Si/SiO_x@C Nanocomposite from Naturally Silicon-rich Crop as Anode for Lithium-ion Batteries[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260182.

参考文献

[1] ZHENG Y, SHEN Y, GUO J, et al. Recent advances in solid-state lithium batteries based on anode engineering. Nano Research Energy, 2024, 3(3): e9120118.
[2] SCHMUCH R, WAGNER R, HÖRPEL G, et al. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nature Energy, 2018, 3(4): 267.
[3] LIU G X, LI Y, TIAN J X, et al. Elucidating dynamic evolution of the sulfur cathode in sulfide-based all-solid-state lithium-sulfur batteries. Nano Letters, 2026, 26(10): 3542.
[4] SUN L, LIU Y, SHAO R, et al. Recent progress and future perspective on practical silicon anode-based lithium ion batteries. Energy Storage Materials, 2022, 46: 482.
[5] ESHETU G G, ZHANG H, JUDEZ X, et al. Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes. Nature Communications, 2021, 12(1): 5459.
[6] HU T, ZHOU H, ZHOU X, et al. Silicon cutting waste derived silicon nanosheets with adjustable native SiO₂ shell for highly‐stable lithiation/delithiation. Small, 2023, 19(7): 2204690.
[7] ZHANG Y-C, YOU Y, XIN S, et al. Rice husk-derived hierarchical silicon/nitrogen-doped carbon/carbon nanotube spheres as low-cost and high-capacity anodes for lithium-ion batteries. Nano Energy, 2016, 25: 120.
[8] SUN L, LIU Y, WANG L, et al. Advances and future prospects of micro‐silicon anodes for high‐energy‐density lithium‐ion batteries: a comprehensive review. Advanced Functional Materials, 2024, 34(39): 2403032.
[9] LIU L, XIE F, LYU J, et al. Tin-based anode materials with well-designed architectures for next-generation lithium-ion batteries. Journal of Power Sources, 2016, 321: 11.
[10] DONG H, WANG J, DING H, et al. Exploring the practical applications of silicon anodes: a review of silicon-based composites for lithium-ion batteries. Ionics, 2022, 28(7): 3057.
[11] YU Y, LIU G, CHEN R, et al. Constructing robust solid electrolyte interphase by coating Li_6.4La₃Zr_1.4Ta_0.6O₁₂ on silicon anodes for high-performance lithium-ion batteries. Science China Technological Sciences, 2025, 68(11): 1.
[12] KATSUYAMA Y, YANG Z, THIEL M, et al. A rapid, scalable laser‐scribing process to prepare Si/graphene composites for lithium‐ion batteries. Small, 2024, 20(28): 2305921.
[13] WANG L, ZHENG X, YU Y, et al. Scalable synthesis of high-performance Si/CNTs/C anodes for lithium-ion batteries based on recycling of silicon cutting waste. Journal of Electroanalytical Chemistry, 2024, 952: 117942.
[14] ZHANG R, DU Y, LI D, et al. Highly reversible and large lithium storage in mesoporous Si/C nanocomposite anodes with silicon nanoparticles embedded in a carbon framework. Advanced Materials, 2014, 26(39): 6749.
[15] WANG H M, ZHOU Y, LUO B R, et al. Improving electrochemical performance of silicon-carbon anode for lithium-ion batteries via one-step etching. Chemical Engineering Journal, 2025: 164382.
[16] OU S, MENG T, XIE Z, et al. Rational design of silicon nanodots/carbon anodes by partial oxidization strategy with high-performance lithium-ion storage. ACS Applied Materials & Interfaces, 2022, 14(43): 48801.
[17] LEE S H, CHO Y, JEON Y P, et al. Sustainable eco‐friendly sub‐micron NaCl crystal powder‐assisted method to synthesize SiO_x/C as anode materials originated from rice husk for lithium‐ion batteries. Ecomat, 2023, 5(11): e12401.
[18] TAO W, XU C, GAO P, et al. Synthesis of core-shell silicon-carbon nanocomposites via in-situ molten salt-based reduction of rice husks: a promising approach for the manufacture of lithium-ion battery anodes. Journal of Colloid and Interface Science, 2024, 669: 902.
[19] PRANEETHA S, MURUGAN A V.Development of sustainable rapid microwave assisted process for extracting nanoporous Si from earth abundant agricultural residues and their carbon-based nanohybrids for lithium energy storage.ACS Sustainable Chemistry & Engineering, 2015, 3(2): 224.
[20] LIN N, HAN Y, ZHOU J, et al. A low temperature molten salt process for aluminothermic reduction of silicon oxides to crystalline Si for Li-ion batteries. Energy & Environmental Science, 2015, 8(11): 3187.
[21] CHEN L, ZHENG J, LIN S, et al. Synthesis of SiO_x/C composite nanosheets as high-rate and stable anode materials for lithium-ion batteries. ACS Applied Energy Materials, 2020, 3(4): 3562.
[22] GUO Y, LIU K, LI X, et al. N/P co-doping regulates the local microcrystalline structure of hard carbon to facilitate sodium-ion storage. Journal of Materials Chemistry A, 2025, 13(27): 21808.
[23] SON I H, HWAN PARK J, KWON S, et al. Silicon carbide-free graphene growth on silicon for lithium-ion battery with high volumetric energy density. Nature Communications, 2015, 6(1): 7393.
[24] SUN M, XU Z, LIU K, et al. Construction of rice husk-derived SiO_x nanoparticles encapsulated with graphene aerogel hybrid for high-performance lithium ion batteries. Electrochimica Acta, 2022, 422: 140572.
[25] GUO Z, ZHAO Y, CAI Y, et al. A low-cost and energy-saving preparation method for silicon derived from rice husks and lithium ion battery applications. Materials Research Express, 2019, 6(4): 045505.
[26] WANG Y, GUO X, WANG Z, et al. Controlled pyrolysis of MIL-88A to Fe₂O₃@C nanocomposites with varied morphologies and phases for advanced lithium storage. Journal of Materials Chemistry A, 2017, 5(48): 25562.
[27] YANG S, LIU X, WANG X, et al. High-entropy type Fe-Ni-POC amorphous nanospheres: remarkable Fe-ion migration induced efficient surface reconstruction for oxygen evolution reaction. Advanced Powder Materials, 2025: 100329.
[28] ZHANG H, CHENG J, LIU H, et al. Prelithiation: a critical strategy towards practical application of high‐energy‐density batteries. Advanced Energy Materials, 2023, 13(27): 2300466.
[29] SHEN L, SUN K, XI F, et al. Conversion of photovoltaic waste silicon into amorphous silicon nanowire anodes. Energy & Environmental Science, 2025, 18(9): 4348.
[30] SU A, LI J, DONG J, et al. An amorphous/crystalline incorporated Si/SiO_x anode material derived from biomass corn leaves for lithium‐ion batteries. Small, 2020, 16(24): 2001714.
[31] ZHAO S F, LI C, CUI Z, et al. Biomass‐derived micro‐mesoporous carbon with oxygen functional groups for high‐rate Na-S batteries at room temperature. Advanced Energy Materials, 2023, 13(45): 2302490.
[32] WU J, DONG Q, ZHANG Q, et al. Fundamental Understanding of the low initial Coulombic efficiency in SiO_x anode for lithium‐ion batteries: mechanisms and solutions. Advanced Materials, 2024, 36(33): 2405751.
[33] MA L, CHEN Z, WANG Q, et al. “Gradient armor” design of the Si-C anode using biomass-derived porous carbon for high-stability pouch cells. Green Chemistry, 2025, 27(36): 11179.
[34] LI X, WANG L, GU Z, et al. In-situ formed LiAlO₂ coating enabling the prelithiated SiO_x@C anode with enhanced initial Coulombic efficiency and electrochemistry-active solid-state interfaces. Journal of Energy Chemistry, 2025, 106: 173.
[35] RUAN D, WU L, WANG F, et al. A low-cost silicon-graphite anode made from recycled graphite of spent lithium-ion batteries. Journal of Electroanalytical Chemistry, 2021, 884: 115073.
[36] ZHANG Z, XI F, MA Q, et al. A nanosilver-actuated high-performance porous silicon anode from recycling of silicon waste. Materials Today Nano, 2022, 17: 100162.
[37] LI M, QIU J, ZHANG S, et al. Micrometer-sized ferrosilicon composites wrapped with multi-layered carbon nanosheets as industrialized anodes for high energy lithium-ion batteries. Journal of Energy Chemistry, 2020, 50: 286.
[38] MA Q, ZHAO Y, HU Z, et al. Electrochemically converting micro-sized industrial Si/FeSi₂ to nano Si/FeSi for the high-performance lithium-ion battery anode. Materials Today Energy, 2021, 21: 100817.
[39] CHEN H X, XU D X, LI G, et al. Phase engineering of lithium silicate in SiO_x anodes for fast-charging lithium-ion batteries. ACS Applied Materials & Interfaces, 2026, 18(1): 1854.
[40] GUO C, WANG D, LIU T, et al. A three dimensional SiO_x/C@RGO nanocomposite as a high energy anode material for lithium-ion batteries. Journal of Materials Chemistry A, 2014, 2(10): 3521.
[41] WANG X, WEN Z, LIU Y, et al. Preparation and characterization of a new nanosized silicon-nickel-graphite composite as anode material for lithium ion batteries. Journal of Power Sources, 2009, 189(1): 121.
[42] KIM H, HAN B, CHOO J, et al. Three‐dimensional porous silicon particles for use in high‐performance lithium secondary batteries. Angewandte Chemie International Edition, 2008, 47(52): 10151.
[43] KASUKABE T, NISHIHARA H, IWAMURA S, et al. Remarkable performance improvement of inexpensive ball-milled Si nanoparticles by carbon-coating for Li-ion batteries. Journal of Power Sources, 2016, 319: 99.
[44] CHAE S, PARK S, AHN K, et al. Gas phase synthesis of amorphous silicon nitride nanoparticles for high-energy LIBs. Energy & Environmental Science, 2020, 13(4): 1212.
[45] ZHAO M, ZHANG J, ZHANG X, et al. Application of high-strength, high-density, isotropic Si/C composites in commercial lithium-ion batteries. Energy Storage Materials, 2023, 61: 102857.
[46] 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.
[47] LI P, HWANG J Y, SUN Y K.Nano/microstructured silicon-graphite composite anode for high-energy-density Li-ion battery.ACS Nano, 2019, 13(2): 2624.
[48] ZHANG J, LIU G, ZHAI P, et al. Stabilizing the interface of Li_1.3Al_0.3Ti_1.7(PO₄)₃ and lithium electrodes via an interlayer strategy in solid-state batteries. Chemical Communications, 2025, 61(14): 2949.