Issue

Vol. 15 (2023)

Regulating the Solvation Structure of Li+ Enables Chemical Prelithiation of Silicon-Based Anodes Toward High-Energy Lithium-Ion Batteries

https://doi.org/10.1007/s40820-023-01068-8
Wenjie He
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China
Hai Xu
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China
Zhijie Chen
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China
Jiang Long
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China
Jing Zhang
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China
Jiangmin Jiang
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China
Hui Dou
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China
Xiaogang Zhang
Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, People’s Republic of China

Corresponding Author: Xiaogang Zhang

azhangxg@163.com

Nano-Micro Letters, Vol. 15 (2023), Article Number: 107

Abstract

The solvation structure of Li+ in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency (ICE) and poor cycle performance of silicon-based materials. Nevertheless, the chemical prelithiation agent is difficult to dope active Li+ in silicon-based anodes because of their low working voltage and sluggish Li+ diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized SiO/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential (E1/2), and the prelithiation efficiency is determined by the specific influencing factors (E1/2, Li+ concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li+. Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.


Highlights:


1 By selecting 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized SiO/C anode can achieve an initial Coulombic efficiency of ~100%.
2 Molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li+.
3 The positive effect of pre-lithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film.

Keywords

Lithium-ion batteries Silicon-based anodes Prelithiation Molecular dynamics simulations Solvation structure
He, Wenjie, Hai Xu, Zhijie Chen, Jiang Long, Jing Zhang, Jiangmin Jiang, Hui Dou, and Xiaogang Zhang. 2023. “Regulating the Solvation Structure of Li+ Enables Chemical Prelithiation of Silicon-Based Anodes Toward High-Energy Lithium-Ion Batteries”. Nano-Micro Letters 15 (April):107. https://doi.org/10.1007/s40820-023-01068-8.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. M. Ge, C. Cao, G.M. Biesold, C.D. Sewell, S.M. Hao et al., Recent advances in silicon-based electrodes: from fundamental research toward practical applications. Adv. Mater. 33, 2004577 (2021). https://doi.org/10.1002/adma.202004577
  2. P. Li, H. Kim, S. Myung, Y. Sun, Diverting exploration of silicon anode into practical way: a review focused on silicon-graphite composite for lithium ion batteries. Energy Storage Mater. 35, 550–576 (2021). https://doi.org/10.1016/j.ensm.2020.11.028
  3. Z. Liu, Q. Yu, Y. Zhao, R. He, M. Xu et al., Silicon oxides: a promising family of anode materials for lithium-ion batteries. Chem. Soc. Rev. 48, 285–309 (2019). https://doi.org/10.1039/C8CS00441B
  4. C. Zhang, F. Wang, J. Han, S. Bai, J. Tan et al., Challenges and recent progress on silicon-based anode materials for next-generation lithium-ion batteries. Small Struct. 2, 2100009 (2021). https://doi.org/10.1002/sstr.202170015
  5. H. Zhang, L. Wang, H. Li, X. He, Criterion for identifying anodes for practically accessible high-energy-density lithium-ion batteries. ACS Energy Lett. 6, 3719–3724 (2021). https://doi.org/10.1021/acsenergylett.1c01713
  6. J. Wu, F. Ma, X. Liu, X. Fan, L. Shen et al., Recent progress in advanced characterization methods for silicon-based lithium-ion batteries. Small Methods 3, 1900158 (2019). https://doi.org/10.1002/smtd.201900158
  7. G. Yang, S. Frisco, R. Tao, N. Philip, T.H. Bennett et al., Robust solid/electrolyte interphase (SEI) formation on Si anodes using glyme-based electrolytes. ACS Energy Lett. 6, 1684–1693 (2021). https://doi.org/10.1021/acsenergylett.0c02629
  8. H. Jia, L. Zou, P. Gao, X. Cao, W. Zhao et al., High-performance silicon anodes enabled by nonflammable localized high-concentration electrolytes. Adv. Energy Mater. 9, 1900784 (2019). https://doi.org/10.1002/aenm.201900784
  9. Z. Hu, L. Zhao, T. Jiang, J. Liu, A. Rashid et al., Trifluoropropylene carbonate-driven interface regulation enabling greatly enhanced lithium storage durability of silicon-based anodes. Adv. Funct. Mater. 29, 1906548 (2019). https://doi.org/10.1002/adfm.201906548
  10. J. Chen, X. Fan, Q. Li, H. Yang, M.R. Khoshi et al., Electrolyte design for LiF-rich solid-electrolyte interfaces to enable high-performance microsized alloy anodes for batteries. Nat. Energy 5, 386–397 (2020). https://doi.org/10.1038/s41560-020-0601-1
  11. P. Li, G. Zhao, X. Zheng, X. Xu, C. Yao et al., Recent progress on silicon-based anode materials for practical lithium-ion battery applications. Energy Storage Mater. 15, 422–446 (2018). https://doi.org/10.1016/j.ensm.2018.07.014
  12. T. Chen, J. Wu, Q. Zhang, X. Su, Recent advancement of SiOx based anodes for lithium-ion batteries. J. Power Sources 363, 126–144 (2017). https://doi.org/10.1016/j.jpowsour.2017.07.073
  13. Y. Jin, B. Zhu, Z. Lu, N. Liu, J. Zhu, Challenges and recent progress in the development of Si anodes for lithium-ion battery. Adv. Energy Mater. 7, 1700715 (2017). https://doi.org/10.1002/aenm.201700715
  14. M. Jiang, P. Mu, H. Zhang, T. Dong, B. Tang et al., An endotenon sheath-inspired double-network binder enables superior cycling performance of silicon electrodes. Nano-Micro Lett. 14, 87 (2022). https://doi.org/10.1007/s40820-022-00833-5
  15. J. Wu, Y. Cao, H. Zhao, J. Mao, Z. Guo, The critical role of carbon in marrying silicon and graphite anodes for high-energy lithium-ion batteries. Carbon Energy 1, 57–76 (2019). https://doi.org/10.1002/cey2.2
  16. J. Zhong, T. Wang, L. Wang, L. Peng, S. Fu et al., A silicon monoxide lithium-ion battery anode with ultrahigh areal capacity. Nano-Micro Lett. 14, 50 (2022). https://doi.org/10.1007/s40820-022-00790-z
  17. X. Chen, H. Li, Z. Yan, F. Cheng, J. Chen, Structure design and mechanism analysis of silicon anode for lithium-ion batteries. Sci. China Mater. 62, 1515–1536 (2019). https://doi.org/10.1007/s40843-019-9464-0
  18. G. Zhu, D. Chao, W. Xu, M. Wu, H. Zhang, Microscale silicon-based anodes: fundamental understanding and industrial prospects for practical high-energy lithium-ion batteries. ACS Nano 15, 15567–15593 (2021). https://doi.org/10.1021/acsnano.1c05898
  19. D. Wang, C. Zhou, B. Cao, Y. Xu, D. Zhang et al., One-step synthesis of spherical Si/C composites with onion-like buffer structure as high-performance anodes for lithium-ion batteries. Energy Storage Mater. 24, 312–318 (2020). https://doi.org/10.1016/j.ensm.2019.07.045
  20. W. He, T. Zhang, J. Jiang, C. Chen, Y. Zhang et al., Efficient synthesis of N-doped SiOx/C composite based on the defect-enriched graphite flake for lithium-ion battery. ACS Appl. Energy Mater. 3, 4394–4402 (2020). https://doi.org/10.1021/acsaem.0c00090
  21. F. Wang, B. Wang, T. Ruan, T. Gao, R. Song et al., Construction of structure-tunable Si@void@C anode materials for lithium-ion batteries through controlling the growth kinetics of resin. ACS Nano 13, 12219–12229 (2019). https://doi.org/10.1021/acsnano.9b07241
  22. Y. Xiang, L. Xu, L. Yang, Y. Ye, Z. Ge et al., Natural stibnite for lithium-/sodium-ion batteries: carbon dots evoked high initial coulombic efficiency. Nano-Micro Lett. 14, 136 (2022). https://doi.org/10.1007/s40820-022-00873-x
  23. K. Zou, Z. Song, X. Gao, H. Liu, Z. Luo et al., Molecularly compensated pre-metallation strategy for metal-ion batteries and capacitors. Angew. Chem. Int. Ed. 60, 17070–17079 (2021). https://doi.org/10.1002/anie.202103569
  24. K. Zou, Z. Song, H. Liu, Y. Wang, A. Massoudi et al., Electronic effect and regiochemistry of substitution in pre-sodiation chemistry. J. Phys. Chem. Lett. 12, 11968–11979 (2021). https://doi.org/10.1021/acs.jpclett.1c03078
  25. J. Zhao, H. Lee, J. Sun, K. Yan, Y. Liu et al., Metallurgically lithiated SiOx anode with high capacity and ambient air compatibility. Proc. Natl. Acad. Sci. 113, 7408–7413 (2016). https://doi.org/10.1073/pnas.1603810113
  26. M. Xu, M. Liu, Z. Yang, C. Wu, J. Qian, Research progress on presodiation strategies for high energy sodium-ion batteries. Acta Phys. Chim. Sin. 39, 2210043 (2022). https://doi.org/10.3866/pku.whxb202210043
  27. K. Lin, X. Xu, X. Qin, M. Liu, L. Zhao et al., Commercially viable hybrid Li-ion/metal batteries with high energy density realized by symbiotic anode and prelithiated cathode. Nano-Micro Lett. 14, 149 (2022). https://doi.org/10.1007/s40820-022-00899-1
  28. F. Wang, B. Wang, J. Li, B. Wang, Y. Zhou et al., Prelithiation: a crucial strategy for boosting the practical application of next-generation lithium ion battery. ACS Nano 15, 2197–2218 (2021). https://doi.org/10.1021/acsnano.0c10664
  29. H.J. Kim, S. Choi, S.J. Lee, M.W. Seo, J.G. Lee et al., Controlled prelithiation of silicon monoxide for high performance lithium-ion rechargeable full cells. Nano Lett. 16, 282–288 (2015). https://doi.org/10.1021/acs.nanolett.5b03776
  30. Y. An, Y. Tian, H. Wei, B. Xi, S. Xiong et al., Porosity- and graphitization-controlled fabrication of nanoporous silicon@carbon for lithium storage and its conjugation with mxene for lithium-metal anode. Adv. Funct. Mater. 30, 1908721 (2019). https://doi.org/10.1002/adfm.201908721
  31. L. Jin, C. Shen, Q. Wu, A. Shellikeri, J. Zheng et al., Pre-lithiation strategies for next-generation practical lithium-ion batteries. Adv. Sci. 8, 2005031 (2021). https://doi.org/10.1002/advs.202005031
  32. Y. Li, Y. Qian, J. Zhou, N. Lin, Y. Qian, Molten-LiCl induced thermochemical prelithiation of SiOx: regulating the active Si/O ratio for high initial coulombic efficiency. Nano Res. 15, 230–237 (2022). https://doi.org/10.1007/s12274-021-3464-2
  33. Q. Wang, M. Zhu, G. Chen, N. Dudko, Y. Li et al., High-performance microsized Si anodes for lithium-ion batteries: insights into the polymer configuration conversion mechanism. Adv. Mater. 34, 2109658 (2022). https://doi.org/10.1002/adma.202109658
  34. H. Wang, M. Zhang, Q. Jia, D. Du, F. Liu et al., Exploiting the capacity merits of Si anodes in the energy-dense prototypes via a homogeneous prelithiation therapy. Nano Energy 95, 107026 (2022). https://doi.org/10.1016/j.nanoen.2022.107026
  35. X. Liu, T. Liu, R. Wang, Z. Cai, W. Wang et al., Prelithiated Li-enriched gradient interphase toward practical high-energy NMC–silicon full cell. ACS Energy Lett. 6, 320–328 (2021). https://doi.org/10.1021/acsenergylett.0c02487
  36. Y. Shen, X. Shen, M. Yang, J. Qian, Y. Cao et al., Achieving desirable initial coulombic efficiencies and full capacity utilization of Li-ion batteries by chemical prelithiation of graphite anode. Adv. Funct. Mater. 31, 2101181 (2021). https://doi.org/10.1002/adfm.202101181
  37. X. Liu, Y. Tan, T. Liu, W. Wang, C. Li et al., A simple electrode-level chemical presodiation route by solution spraying to improve the energy density of sodium-ion batteries. Adv. Funct. Mater. 29, 1903795 (2019). https://doi.org/10.1002/adfm.201903795
  38. Y. Shen, J. Zhang, Y. Pu, H. Wang, B. Wang et al., Effective chemical prelithiation strategy for building a silicon/sulfur Li-ion battery. ACS Energy Lett. 4, 1717–1724 (2019). https://doi.org/10.1021/acsenergylett.9b00889
  39. J. Jang, I. Kang, J. Choi, H. Jeong, K.W. Yi et al., Molecularly tailored lithium–arene complex enables chemical prelithiation of high-capacity lithium-ion battery anodes. Angew. Chem. Int. Ed. 59, 14473–14480 (2020). https://doi.org/10.1002/anie.202002411
  40. X. Zhang, H. Qu, W. Ji, D. Zheng, T. Ding et al., An electrode-level prelithiation of SiO anodes with organolithium compounds for lithium-ion batteries. J. Power Sources 478, 229067 (2020). https://doi.org/10.1016/j.jpowsour.2020.229067
  41. J. Choi, H. Jeong, J. Jang, A. Jeon, I. Kang et al., Weakly solvating solution enables chemical prelithiation of graphite–SiOx anodes for high-energy Li-ion batteries. J. Am. Chem. Soc. 143, 9169–9176 (2021). https://doi.org/10.1021/jacs.1c03648
  42. W. He, T. Zhang, Z. Li, J. Jiang, C. Chen et al., B-doped SiOx composite with three dimensional conductive network for high performance lithium-ion battery anode. J. Materiomic 7, 802–809 (2021). https://doi.org/10.1016/j.jmat.2020.12.016
  43. H. Deng, Z. Chang, F. Qiu, Y. Qiao, H. Yang et al., A safe organic oxygen battery built with Li-based liquid anode and MOFs separator. Adv. Energy Mater. 10, 1903953 (2020). https://doi.org/10.1002/aenm.201903953
  44. Y. Shen, J. Qian, H. Yang, F. Zhong, X. Ai, Chemically prelithiated hard-carbon anode for high power and high capacity Li-ion batteries. Small 16, 1907602 (2020). https://doi.org/10.1002/smll.201907602
  45. H.J. Reich, Role of organolithium aggregates and mixed aggregates in organolithium mechanisms. Chem. Rev. 113, 7130–7178 (2013). https://doi.org/10.1021/cr400187u
  46. Y. Huang, C. Liu, F. Wei, G. Wang, L. Xiao et al., Chemical prelithiation of Al for use as an ambient air compatible and polysulfide resistant anode for Li-ion/S batteries. J. Mater. Chem. A 8, 18715 (2020). https://doi.org/10.1039/d0ta06694j
  47. G. Wang, B. Huang, D. Liu, D. Zheng, J. Harris et al., Exploring polycyclic aromatic hydrocarbons as an anolyte for nonaqueous redox flow batteries. J. Mater. Chem A 6, 13286–13293 (2018). https://doi.org/10.1039/c8ta03221a
  48. P.G. Bruce, B. Scrosati, J. Tarascon, Nanomaterials for rechargeable lithium batteries. Angew. Chem. Int. Ed. 47, 2930–2946 (2008). https://doi.org/10.1002/anie.200702505
  49. S. Jung, I. Hwang, D. Chang, K. Park, S.J. Kim et al., Nanoscale phenomena in lithium-ion batteries. Chem. Rev. 120, 6684–6737 (2020). https://doi.org/10.1021/acs.chemrev.9b00405
  50. S. Fang, L. Shen, S. Li, G. Kim, D. Bresser et al., Alloying reaction confinement enables high-capacity and stable anodes for lithium-ion batteries. ACS Nano 13, 9511–9519 (2019). https://doi.org/10.1021/acsnano.9b04495
  51. D. Yoon, M. Marinaro, P. Axmann, M. Wohlfahrt-Mehrens, Study of the binder influence on expansion/contraction behavior of silicon alloy negative electrodes for lithium-ion batteries. J. Electrochem. Soc. 167, 160537 (2020). https://doi.org/10.1149/1945-7111/abcf4f
  52. C. Chen, T. Zhou, D.L. Danilov, L. Gao, S. Benning et al., Impact of dual-layer solid-electrolyte interphase inhomogeneities on early-stage defect formation in Si electrodes. Nat. Commun. 11, 3283 (2020). https://doi.org/10.1038/s41467-020-17104-9
  53. M. Yan, G. Li, J. Zhang, Y. Tian, Y. Yin et al., Enabling SiOx/C anode with high initial coulombic efficiency through a chemical pre-lithiation strategy for high-energy-density lithium-ion batteries. ACS Appl. Mater. Interfaces 12, 27202–27209 (2020). https://doi.org/10.1021/acsami.0c05153
  54. X. Zhang, H. Qu, W. Ji, D. Zheng, T. Ding et al., Fast and controllable prelithiation of hard carbon anodes for lithium-ion batteries. ACS Appl. Mater. Interfaces 12, 11589–11599 (2020). https://doi.org/10.1021/acsami.9b21417
  55. Z. Piao, P. Xiao, R. Luo, J. Ma, R. Gao et al., Constructing a stable interface layer by tailoring solvation chemistry in carbonate electrolytes for high performance lithium metal batteries. Adv. Mater. 34, 2108400 (2021). https://doi.org/10.1002/adma.202108400
  56. F. Aupperle, N. von Aspern, D. Berghus, F. Weber, G.G. Eshetu et al., The role of electrolyte additives on the interfacial chemistry and thermal reactivity of Si-anode-based Li-ion battery. ACS Appl. Energ. Mater. 2, 6513–6527 (2019). https://doi.org/10.1021/acsaem.9b01094
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 3053 Download : 2290

Most read articles by the same author(s)

1 2 > >>