Non-solvent and Low-temperature Preparation of Porous Silicon-carbon Anodes for Enhanced Lithium Storage

doi:10.15541/jim20250080

Abstract

Abstract: To solve the problems of large volume expansion, poor cycling stability, poor electrical conductivity and high energy consumption of silicon-anode materials, a porous silicon-carbon anode material (P-Si@G@C) was prepared by non-solvent low-temperature method with nano-silicon as active substance, graphite as conductive carrier, asphalt as carbon precursor and potassium chloride as pore-forming agent. The structure and performance of P-Si@G@C anode were systematically studied by comparing with a series of silicon-carbon anodes. The results showed that the insertion of silica nanoparticles in graphite matrix (Si@G) can improve the electrical conductivity of the whole material which is beneficial for electron transport, and the graphite matrix can alleviate the volume expansion of silica nanoparticles. Then the porous carbon shell coated on the surface of Si@G greatly reduced the volume expansion of nano-silicon, and improved the diffusion rate of lithium ion and electron transport rate. Compared with Si@G and unperforated Si@G@C anodes, the P-Si@G@C anode presented the best electrical performance with initial Coulombic efficiency of 85.8%. At the current density of 0.1, 0.2, 1.0, 2.0, 5.0 A·g^-1, the specific capacities of P-Si@G@C anode were 1403.6, 1291.7, 1206.1, 1093.6, 868.4 and 609.5 mAh·g^-1, respectively. And its recovery rate of specific capacity reached 98.3%, displaying excellent rate performance. The specific capacity is still above 770.7 mAh·g^-1 after 200 cycles at 1.0 A·g^-1, showing good long-cycle stability.

Key words: lithium-ion battery, silicon-carbon anode, dual-carbon coating, porous shell, lithium storage mechanism

CLC Number:

O646

YI Guogang, WU Yaoying, ZU Xihong. Non-solvent and Low-temperature Preparation of Porous Silicon-carbon Anodes for Enhanced Lithium Storage[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250080.

References

[1] DING J W, JI D F, YUE Y Z,et al. Amorphous materials for lithium-ion and post-lithium-ion batteries. Small, 2024, 20(5): 2304270.
[2] JELLA G, PANDA D K, SAPKOTA N,et al. Electrochemical performance of polymer-derived silicon-oxycarbide/graphene nanoplatelet composites for high-performance Li-ion batteries. ACS Appl. Mater. Interf., 2023, 15(25): 30039.
[3] KIM M J, LEE I, LEE J W,et al. A novel structured Si-based composite with 2D structured graphite for high-performance lithium-ion batteries. Small, 2024, 20: 2405005.
[4] SUN L, LIU Y X, SHAO R,et al. Recent progress and future perspective on practical silicon anode-based lithium ion batteries. Energy Storage Mater., 2022, 46: 482.
[5] LI P, ZHAO G, ZHENG X, et al. Recent progress on silicon-based anode materials for practical lithium-ion battery applications. Energy Storage Mater., 2018, 15: 422.
[6] LIU W J, SU S X, WANG Y,et al. Constructing a stable conductive network for high-performance silicon-based anode in lithium-ion batteries. ACS Appl. Mater. Interf., 2024, 16: 10703.
[7] SHI H F, ZHANG W Y, WANG D H,et al. Facile preparation of silicon/carbon composite with porous architecture for advanced lithium-ion battery anode. J. Electroanal. Chem., 2023, 937: 117427.
[8] LI H, YAO B H, LI M, et al. Three-dimensional carbon nanotubes buffering interfacial stress of the silicon/carbon anodes for long-cycle lithium storage. ACS Appl. Mater. Interf., 2024, 16: 53665.
[9] GAO J F, LIU Y, CHEN J Q, et al. Fabrication of honeycomb-like amorphous carbon-encapsulated Si nanoparticles/graphene composite for superior lithium storage. J. Energy Storage, 2023, 74: 109351.
[10] GAO Y J, SONG S S, HE F,et al. Controllable synthesis of hollow dodecahedral Si@C core-shell structures for ultrastable lithium-ion batteries. Small, 2024, 20: 2406489.
[11] LI X Z, ZHANG M, YUAN S X, et al. Research progress of silicon/carbon anode materials for lithium-ion batteries: structure design and synthesis method. ChemElectroChem, 2020, 7: 4289.
[12] LUO W, CHEN X Q, XIA Y,et al. Surface and interface engineering of silicon-based anode materials for lithium-ion batteries. Adv. Energy Mater., 2017, 7: 1701083.
[13] SU N, QIU J S, WANG ZY.F-doped carbon coated nano-Si anode with high capacity: preparation by gaseous fluorination and performance for lithium storage. J. Inorg. Mater., 2023, 38(8): 947.
[14] HU M F, HUANG L P, LI H,et al. Research progress on hard carbon anode for Li/Na-ion batteries. J. Inorg. Mater., 2024, 39(1): 32.
[15] MA Q, ZHAO Z, ZHAO Y,et al. A self-driven alloying/dealloying approach to nanostructuring micro-silicon for high-performance lithium-ion battery anodes. Energy Storage Mater., 2021, 34: 768.
[16] ZHANG L, HUANG Q, LIAO X,et al. Scalable and controllable fabrication of CNTs improved yolk-shelled Si anodes with advanced in operando mechanical quantification. Energ. Environ. Sci., 2021, 14(6): 3502.
[17] TAO H, FAN L Z, SONG W L,et al. Hollow core-shell structured Si/C nanocomposites as high-performance anode materials for lithium-ion batteries. Nanoscale, 2014, 6(6): 3138.
[18] LIU N, LIU J, JIA D,et al. Multi-core yolk-shell like mesoporous double carbon-coated silicon nanoparticles as anode materials for lithium-ion batteries. Energy Storage Mater., 2019, 18: 165.
[19] SU H, LI X, LIU C,et al. Scalable synthesis of micrometer-sized porous silicon/carbon composites for high-stability lithium-ion battery anodes. Chem. Eng. J., 2023, 451: 138394.
[20] SUN Y Q, ZU X H, LIU B W,et al. Low-cost integrated silicon-carbon anode based on Si-Cu bonds and asphalt-derived carbon towards high-performance lithium-ion battery. ACS Appl. Energy Mater., 2023, 6: 11376.
[21] KONG X, XI Z, JIANG Y,et al. Fe-NC decorated fibrous network-wrapped biomass SiO_x/C with gradient conductive structure for high performance Li-ion battery anodes. Chem. Eng. J., 2023, 477: 147178.
[22] PEI Y, WANG Y, CHANG A Y,et al. Nanofiber-in-microfiber carbon/silicon composite anode with high silicon content for lithium-ion batteries. Carbon, 2023, 203: 436.
[23] HU L, LUO B, WU C,et al. Yolk-shell Si/C composites with multiple Si nanoparticles encapsulated into double carbon shells as lithium-ion battery anodes. J. Energy Chem., 2019, 32: 124.
[24] ZHANG L, HU X, CHEN C, et al. In operando mechanism analysis on nanocrystalline silicon anode material for reversible and ultrafast sodium storage. Adv. Mater., 2017, 29: 1604708.
[25] ZHAO M, MCCORMACK A, KESWANI M.The formation mechanism of gradient porous Si in a contactless electrochemical process.J Mater. Chem. C, 2016, 4(19): 4204.
[26] DONG H, FU X, WANG J,et al. In-situ construction of porous Si@C composites with LiCl template to provide silicon anode expansion buffer. Carbon, 2021, 173: 687.
[27] CHAE S, XU Y, YI R,et al. A micrometer-sized silicon/carbon composite anode synthesized by impregnation of petroleum pitch in nanoporous silicon. Adv. Mater., 2021, 33(40): 2103095.
[28] MU T, ZUO P, LOU S,et al. A two-dimensional nitrogen-rich carbon/silicon composite as high performance anode material for lithium ion batteries. Chem. Eng. J., 2018, 341: 37.
[29] LI X, YANG D, HOU X,et al. Scalable preparation of mesoporous silicon@C/graphite hybrid as stable anodes for lithium-ion batteries. J. Alloys Compd., 2017, 728: 1.
[30] SHIN H J, HWANG J Y, KWON H J,et al. Sustainable encapsulation strategy of silicon nanoparticles in microcarbon sphere for high-performance lithium-ion battery anode. ACS Sustain. Chem. Eng., 2020, 8(37): 14150.
[31] 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): 2624-2633.
[32] ZHANG H, ZHANG X, JIN H,et al. A robust hierarchical 3D Si/CNTs composite with void and carbon shell as Li-ion battery anodes. Chem. Eng. J., 2019, 360: 974.
[33] WEI Q, CHEN Y M, HONG X J,et al. Novel bread-like nitrogen-doped carbon anchored nano-silicon as high-stable anode for lithium-ion batteries. Appl. Surf. Sci., 2020, 511: 145609.
[34] XIN X, ZHOU X, WANG F, et al. A 3D porous architecture of Si/graphene nanocomposite as high-performance anode materials for Li-ion batteries. J. Mater. Chem. A, 2012, 22(16): 7724.
[35] PAN Q, ZUO P, LOU S,et al. Micro-sized spherical silicon@carbon@graphene prepared by spray drying as anode material for lithium-ion batteries. J. Alloys Compd., 2017, 723: 434.
[36] FU L, XU A, SONG Y,et al. Pinecone-like silicon@carbon microspheres covered by Al₂O₃ nano-petals for lithium-ion battery anode under high temperature. Electrochim. Acta, 2021, 387: 138461.
[37] GAO R, TANG J, YU X,et al. In situ synthesis of MOF-derived carbon shells for silicon anode with improved lithium-ion storage. Nano Energy, 2020, 70: 104444.
[38] LU J, LIU S, LIU J,et al. Millisecond conversion of photovoltaic silicon waste to binder‐free high silicon content nanowires electrodes. Adv. Energy Mater., 2021, 11(40): 2102103.
[39] LIU G X, TIAN J X, WAN J,et al. Revealing the high salt concentration manipulated evolution mechanism on the lithium anode in quasi-solid-state lithium sulfur batteries. Angew. Chem. Int. Ed. 2022, 61(12): e202212744.
[40] ZHANG J H, LIU G X, ZHAI P B,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. Chem. Comm., 2025, 61(14): 2949.