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Nano-silicon/graphite composites caged by mesophase pitch-derived carbon as anode materials for stable lithium storage

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Abstract

The development of silicon/graphite composites is a feasible solution for improving the short cycling life of Si-based anodes. However, unsatisfactory solid interfaces and structural integrity impede the achievement of the anticipated electrochemical performance. Herein, naphthalene-based mesophase pitch is used as the carbon precursor to wrap nano-Si/artificial graphite (AG) composites through an impregnation-carbonization route. Structural characterization revealed that the pyrolyzed carbon formed graphitic and porous carbon cages, which not only promoted the transport of charge carriers but also mitigated the expansion of Si particles. After 500 charge–discharge cycles at a high current density of 1000 mA g−1, the anode material with a Si/graphite/pitch mass ratio of 2:5:10 achieved a specific capacity of 432 mAh g−1 and a coulombic efficiency of 99.5%. Considering the facile manufacturing technique, good cycling stability, and rate capability, Si/graphite/C anode materials possess promising industrialization prospects for next-generation lithium-ion batteries.

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References

  1. Yang R, Yin XC, **ao R, Mu TS, Huo H, Zuo PJ, Ma YL, Cheng XQ, Gao YZ, Yin GP, Li Y, Du CY (2022) Layered porous silicon encapsulated in carbon nanotube cage as ultra-stable anode for lithium-ion batteries. Chem Eng J 431:133982

    Article  Google Scholar 

  2. Lu XQ, Xu P, Song WJ, Zhou P, Liao MD, Zeng G, Hu XB, Li JX, Zhang MY, Huang QZ, Su Z (2023) Dual Carbon boosts silicon-based anodes for excellent initial coulombic efficiency and cycling stability of lithium-ion batteries. J Alloy Compd 938:168646

    Article  CAS  Google Scholar 

  3. Chaudhari KN, Rajeev KK, Kim SK, Nersisyan HK, Kirakosyan A, Jang WS, Choi JH, Lee JH, Kim TH, Kim YH (2022) Performance enhancement of carbon-coated Si nanoparticles for lithium-ion batteries through the generation of lithophilic sites by a simple oxidation process. Appl Surf Sci 602:154361

    Article  CAS  Google Scholar 

  4. Smrekar S, Bracamonte MV, Primo EN, Luque GL, Thomas J, Barraco DE, Leiva E (2020) A map** of the physical and electrochemical properties of composite lithium-ion batteries anodes made from graphite, Sn and Si. Batteries Supercaps 3:1248–1256

    Article  CAS  Google Scholar 

  5. Guo JG, Zhai W, Sun Q, Ai Q, Li J, Cheng J, Dai LN, Ci LJ (2020) Facilely tunable core-shell Si@SiOx nanostructures prepared in aqueous solution for lithium ion battery anode. Electrochim Acta 342:136068

    Article  CAS  Google Scholar 

  6. ** CX, Lai Q, Dan JL, Xu GJ, Yue ZH, Li XM, Sun FG, Huang HB, Zhou L, Wang L (2021) A novel scalable synthesis of high-rate performance silicon anode materials by liquid-phase coating do** method. Appl Surf Sci 540:148326

    Article  CAS  Google Scholar 

  7. He Q, Wu QY, Wang XX, Fu ST, Huang SC, Tong SF, Cao YF, Liu Z, Wu MM (2021) An anode material for lithium storage: Si@N、S-Doped carbon synthesized via in situ self-polymerization. ACS Applied Energy Materials 4:3555–3562

    Article  CAS  Google Scholar 

  8. Li Q, Liu XS, Han X, **ang YX, Zhong GM, Wang J, Zheng BZ, Zhou JG, Yang Y (2019) Identification of the solid electrolyte interface on the Si/C composite anode with FEC as the additive. ACS Appl Mater Interfaces 11:14066–14075

    Article  CAS  PubMed  Google Scholar 

  9. Yang Y, Lu ZJ, **a J, Liu Y, Wang K, Wang X (2021) Crystalline and amorphous carbon double-modified silicon anode: towards large-scale production and superior lithium storage performance. Chem Eng Sci 229:116054

    Article  CAS  Google Scholar 

  10. Shao R, Zhu F, Cao ZJ, Zhang ZP, Dou ML, Niu J, Zhu BN, Wang F (2020) Heteroatom-doped carbon networks enabling robust and flexible silicon anodes for high energy Li-ion batteries. Mater Chem A8:18338–18347

    Article  Google Scholar 

  11. Fan Z, Liu WR, Sun L, Nishio A, Szczęsny R, Lin YG, Okada S, Gregory DH (2023) Carbon-free conversion of SiO2 to Si via ultra-rapid alloy formation: toward the sustainable fabrication of nanoporous Si for lithium-ion batteries. ACS Appl Mater Interfaces 15:36076–36085

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. Shan JN, Yang XF, Yan C, Chen L, Zhao F, Ju YG (2019) Promoting Si-graphite composite anodes with SWCNT additives for half and NCM811 full lithium-ion batteries and assessment criteria from an industrial perspective. Frontiers in Energy 13(4):626–635

    Article  Google Scholar 

  13. Zhang Y, Cheng YQ, Song JH, Zhang YJ, Shi Q, Wang JX, Tian FH, Yuan S, Su Z, Zhou C, Wang Y, Yang S (2021) Functionalization-assistant ball milling towards Si/graphene anodes in high performance Li-ion batteries. Carbon 181:300–309

    Article  CAS  Google Scholar 

  14. Yi Z, Wang WW, Qian Y, Liu XY, Lin N, Qian YT (2018) Mechanical pressing route for scalable preparation of microstructured/nanostructured Si/graphite composite for lithium ion battery anodes. ACS Sustainable Chem Eng 6(11):14230–14238

    Article  CAS  Google Scholar 

  15. Lai J, Guo HJ, Wang ZX, Li XH, Zhang XP, Wu FX, Yue P (2012) Preparation and characterization of flake graphite/silicon/carbon spherical composite as anode materials for lithium-ion batteries. J Alloy Compd 530:30–35

    Article  CAS  Google Scholar 

  16. Lee D, Kondo A, Lee S, Myeong S, Sun S, Hwang I, Song T, Naito M, Paik U (2020) Controlled swelling behavior and stable cycling of silicon/graphite granular composite for high energy density in lithium-ion batteries. J Power Sources 457:228021

    Article  CAS  Google Scholar 

  17. Xu CJ, Shen L, Zhang WJ, Huang YL, Sun ZF, Zhao GY, Lin YB, Zhang QB, Huang ZG, Li JX (2023) Efficient implementation of kilogram-scale, high-capacity and long-life Si-C/TiO2 anodes. Energy Storage Mater 56:319–330

    Article  CAS  Google Scholar 

  18. Choi SH, Nam G, Chae S, Kim D, Kim N, Kim WS, Ma J, Sung J, Han SM, Ko M, Lee HW, Cho J (2019) Robust pitch on silicon nanolayer–embedded graphite for suppressing undesirable volume expansion. Adv Energy Mater 9:1803121

    Article  Google Scholar 

  19. Hsu YC, Hsieh CC, Liu WR (2020) Synthesis of double core-shell carbon/silicon/graphite composite anode materials for lithium-ion batteries. Surf Coat Technol 387:125528

    Article  CAS  Google Scholar 

  20. Liu WP, Xu HR, Qin HQ, Lv YL, Zhu GS, Lei XX, Lin F, Zhang ZJ, Wang LH (2020) Rapid coating of pitch to prepare carbon-encapsulated composites of nano-silicon and graphite for lithium battery anodes. J Mater Sci 55:4382–4394

    Article  CAS  Google Scholar 

  21. Phadatare M, Patil R, Blomquist N, Forsberg S, Örtegren J, Hummelgård M, Meshram J, Hernández G, Brandell D, Leifer K, Sathyanath SKM, Olin H (2019) Silicon-nanographite aerogel-based anodes for high performance lithium-ion batteries. Sci Rep 9:14621

    Article  PubMed  PubMed Central  Google Scholar 

  22. Liu P, Kong JR, Liu YR, Liu QC, Zhu HZ (2015) Graphitic mesoporous carbon based on aromatic polycondensation as catalyst support for oxygen reduction reaction. J Power Sources 278:522–526

    Article  CAS  Google Scholar 

  23. Xu Z, Du J, Feng C, He J, Li T, Jia H, Song K (2024) Constructing a buffer macroporous architecture on silicon/carbon anode for high-performance lithium-ion battery. J Mater Sci: Mater Electron 35(7):531

    CAS  Google Scholar 

  24. **e X, **ao P, Pang L, Zhou P, Li Y, Luo J, **ong J, Li Y (2023) Facile synthesis of yolk-shell Si/void/C nanoparticles with 3D conducting networks as free-standing anodes in lithium-ion batteries. J Alloy Compd 931:167473

    Article  CAS  Google Scholar 

  25. Huang XH, Guo RQ, Lin Y, Cao YQ, Wu JB (2022) Si/SiC/C in-situ composite microspindles as anode materials for lithium-ion batteries. Electrochemical Acta 422:140546

    Article  CAS  Google Scholar 

  26. Li H, Chen ZD, Kang ZR, Liu W, Chen YG (2023) High-density crack-resistant Si-C microparticles for lithium-ion batteries. Energy Storage Materials 56:40–49

    Article  Google Scholar 

  27. He YW, Ye ZB, Chamas M, Sougrati MT, Lippens PE (2021) Si/Cu-Zn(ox)/C composite as anode material for Li-ion batteries. Solid State Ionics 372:115774

    Article  CAS  Google Scholar 

  28. Hu XQ, Huang S, Hou XH, Chen HD, Qin HQ, Ru Q, Chu BL (2017) A Double Core-shell structure silicon carbon composite anode material for a lithium-ion battery. SILICON 10(4):1443–1450

    Article  Google Scholar 

  29. Batool S, Idrees M, Kong J, Zhang J, Kong S, Dong M, Hou H, Fan J, Wei H, Guo Z (2020) Assessment of the electrochemical behaviour of silicon/carbon nanocomposite anode for lithium-ion batteries. J Alloy Compd 832:154644

    Article  CAS  Google Scholar 

  30. Yang Z, Yang Y, Guo H, Wang Z, Li X, Zhou Y, Wang J (2018) Compact structured silicon/carbon composites as high-performance anodes for lithium-ion batteries. Ionics 24(11):3405–3411

    Article  CAS  Google Scholar 

  31. Huang Y, Li W, Peng J, Wu Z, Li X, Wang X (2021) Structure design and performance of the graphite/silicon/carbon nanotubes/carbon (GSCC) composite as the anode of a li-ion battery. Energy Fuels 35(16):13491–13498

    Article  CAS  Google Scholar 

  32. Chae S, Xu Y, Yi R, Lim HS, Velickovic D, Li X, Li Q, Wang C, Zhang JG (2021) A micrometer-sized silicon/carbon composite anode synthesized by impregnation of petroleum pitch in nanoporous silicon. Adv Mater 33(40):2103095

    Article  CAS  Google Scholar 

  33. Liu W, Xu H, Qin H, Lv Y, Zhu G, Lei X, Lin F, Zhang Z, Wang L (2019) Rapid coating of asphalt to prepare carbon-encapsulated composites of nano-silicon and graphite for lithium battery anodes. J Mater Sci 55(10):4382–4394

    Article  Google Scholar 

  34. Yang J, Wang Y, Li W, Wang L, Fan Y, Jiang W, Luo W, Wang Y, Kong B, Selomulya C (2017) Amorphous TiO2 shells: a vital elastic buffering layer on silicon nanoparticles for high-performance and safe lithium storage. Adv Mater 29(48):1700523

    Article  Google Scholar 

  35. Shi H, Zhang W, Wang D, Wang J, Wang C, **ong Z, Chen F-R, Dong H, Xu B, Yan X (2023) Facile preparation of silicon/carbon composite with porous architecture for advanced lithium-ion battery anode. Journal Electroanal Chem 937:117427

    Article  CAS  Google Scholar 

  36. Duan J, Kang K, Li P, Zhang W, Li X, Wang J, Liu Y (2024) The design and regulation of porous silicon-carbon composites for enhanced electrochemical lithium storage performance. J Ind Eng Chem 131:410–421

    Article  CAS  Google Scholar 

  37. Hsieh CC, Lin YG, Chiang CL, Liu WR (2020) Carbon-coated porous Si/C composite anode materials via two-step etching/coating processes for lithium-ion batteries. Ceram Int 46:26598–26607

    Article  CAS  Google Scholar 

  38. Hsieh CC, Liu WR (2020) Carbon-coated Si particles binding with few-layered graphene via a liquid exfoliation process as potential anode materials for lithium-ion batteries. Surf Coat Technol 387:125553

    Article  CAS  Google Scholar 

  39. Chen WT, Muruganantham R, Liu WR (2022) Construction of 3D porous graphene aerogel wrapped silicon composite as anode materials for high-efficient lithium-ion storage. Surf Coat Technol 434:128147

    Article  CAS  Google Scholar 

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Funding

The authors gratefully appreciate the financial support of the National Natural Science Foundation of China (No. 52172063), the Natural Science Foundation of Hunan Province (No. 2023JJ30017, 2023JJ30030), the Natural Science Foundation of Changsha (No. kq2208223), the National Undergraduate Innovation Training Program of China (No. 202110536005), and assistance of Dr. Lingjun Li and Dr. Kangyu Zou in completing the full cell test.

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Author notes

  1. Zhongtao Zhao and Liang Ye have contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha, 410114, People’s Republic of China

    Zhongtao Zhao, Liang Ye, **aolu Li, **anfeng Yang, Shuguang Chen, Peng Liu & Jiangrong Kong

  2. Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, People’s Republic of China

    Zhongtao Zhao, Liang Ye, **aolu Li, **anfeng Yang, Shuguang Chen, Peng Liu & Jiangrong Kong

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  1. Zhongtao Zhao
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Correspondence to Peng Liu or Jiangrong Kong.

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Zhao, Z., Ye, L., Li, X. et al. Nano-silicon/graphite composites caged by mesophase pitch-derived carbon as anode materials for stable lithium storage. J Solid State Electrochem (2024). https://doi.org/10.1007/s10008-024-05967-7

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