Skip to main content
SpringerLink
Log in

Mo2C catalyzed low-voltage prelithiation using nano-Li2C2O4 for high-energy lithium-ion batteries

Mo2C催化的低压纳米Li2C2O4预锂化用于高能量锂离子电池

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Irreversible lithium loss in the initial cycles appreciably reduces the energy density of lithium-ion batteries. Prelithiation is an effective way to compensate for such lithium loss, but current methods suffer from either the instability or low capacity of prelithiation reagents. Lithium oxalate (Li2C2O4) has shown great potential as a lithium-compensation material because of its high theoretical capacity (equivalent to lithium metal), low cost, and air stability. However, the practical applications of Li2C2O4 are limited by its low electrochemical activity and high critical decomposition voltage. In this study, we performed the prelithiation of a low-voltage cathode by using Mo2C catalysis and nano-Li2C2O4. Results show that the Mo2C catalyst changes the electron cloud distribution around Li2C2O4 and greatly reduces the activation energy, thereby significantly accelerating the lithium release from Li2C2O4. The nano-Li2C2O4 prepared by freeze-drying shows accelerated ionic and electronic conduction as well as close contact with Mo2C. Benefiting from the synergistic effect, the decomposition potential of Li2C2O4 is decreased by 0.5 V with an efficiency close to 100%. The LiCoO2∥SiO full cell empowered with the nano-Li2C2O4/Mo2C prelithiation composite demonstrates 46.9% higher capacity than the control and thus has great potential for practical applications.

摘要

初始循环中不可逆的锂损失显著降低了锂离子电池的能量密度. 预锂化是补偿锂损失的有效方法之一, 但目前的方法存在预锂化试剂不稳定或容量低的问题. 草酸锂(Li2C2O4)作为一种高理论容量(相当于锂金属)、 低成本和空气稳定的锂补偿材料已显示出巨大的潜力. 然而, 低电化学活性和高分解电位严重阻碍了其实际应用. 本文中, 我们报道了一种低压预锂化技术. 通过配合使用Mo2C催化剂和纳米Li2C2O4, Mo2C催化剂改变了Li2C2O4周围的电子云分布, 大大降低了活化能, 从而显著加速了锂从Li2C2O4中的释放. 通过冷冻干燥制备的纳米Li2C2O4与Mo2C催化剂形成良好接触并展现出快速的离子和电子传导. 得益于这种协同效应, Li2C2O4的分解电位降低了0.5 V, 分解效率接近100%. 纳米Li2C2O4/Mo2C复合材料补偿的LiCoO2∥SiO全电池展现出可以高于对照组46.9%的比容量, 显示出巨大的实际应用潜力.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Stephan AK. The age of Li-ion batteries. Joule, 2019, 3: 2583–2584

    Article  Google Scholar 

  2. Masias A, Marcicki J, Paxton WA. Opportunities and challenges of lithium ion batteries in automotive applications. ACS Energy Lett, 2021, 6: 621–630

    Article  CAS  Google Scholar 

  3. Wang F, Wang B, Li J, et al. Prelithiation: A crucial strategy for boosting the practical application of next-generation lithium ion battery. ACS Nano, 2021, 15: 2197–2218

    Article  CAS  Google Scholar 

  4. Xin C, Gao J, Luo R, et al. Prelithiation reagents and strategies on high energy lithium-ion batteries. Chem Eur J, 2022, 28: e202104282

    CAS  Google Scholar 

  5. Min X, Xu G, Xie B, et al. Challenges of prelithiation strategies for next generation high energy lithium-ion batteries. Energy Storage Mater, 2022, 47: 297–318

    Article  Google Scholar 

  6. Jin L, Shen C, Wu Q, et al. Pre-lithiation strategies for next-generation practical lithium-ion batteries. Adv Sci, 2021, 8: 2005031

    Article  CAS  Google Scholar 

  7. Zhan R, Wang X, Chen Z, et al. Promises and challenges of the practical implementation of prelithiation in lithium-ion batteries. Adv Energy Mater, 2021, 11: 2101565

    Article  CAS  Google Scholar 

  8. Sun Y, Lee HW, Seh ZW, et al. High-capacity battery cathode prelithiation to offset initial lithium loss. Nat Energy, 2016, 1: 15008

    Article  CAS  Google Scholar 

  9. Liu X, Liu T, Wang R, et al. Prelithiated Li-enriched gradient interphase toward practical high-energy NMC-silicon full cell. ACS Energy Lett, 2021, 6: 320–328

    Article  CAS  Google Scholar 

  10. Park K, Yu BC, Goodenough JB. Li3N as a cathode additive for high-energy-density lithium-ion batteries. Adv Energy Mater, 2016, 6: 1502534

    Article  Google Scholar 

  11. Zhan Y, Yu H, Ben L, et al. Application of Li2S to compensate for loss of active lithium in a Si-C anode. J Mater Chem A, 2018, 6: 6206–6211

    Article  CAS  Google Scholar 

  12. Zhang L, Jeong S, Reinsma N, et al. Decomposition of Li2O2 as the cathode prelithiation additive for lithium-ion batteries without an additional catalyst and the initial performance investigation. J Electrochem Soc, 2021, 168: 120520

    Article  CAS  Google Scholar 

  13. Fan M, Meng Q, Chang X, et al. In situ electrochemical regeneration of degraded LiFePO4 electrode with functionalized prelithiation separator. Adv Energy Mater, 2022, 12: 2103630

    Article  CAS  Google Scholar 

  14. Ding R, Tian S, Zhang K, et al. Recent advances in cathode prelithiation additives and their use in lithium-ion batteries. J Electroanal Chem, 2021, 893: 115325

    Article  CAS  Google Scholar 

  15. Solchenbach S, Wetjen M, Pritzl D, et al. Lithium oxalate as capacity and cycle-life enhancer in LNMO/graphite and LNMO/SiG full cells. J Electrochem Soc, 2018, 165: A512–A524

    Article  CAS  Google Scholar 

  16. Zhang Z, Wang R, Zeng J, et al. Size effects in sodium ion batteries. Adv Funct Mater, 2021, 31: 2106047

    Article  CAS  Google Scholar 

  17. Zhou X, Yu Z, Yao Y, et al. A high-efficiency Mo2C electrocatalyst promoting the polysulfide redox kinetics for Na-S batteries. Adv Mater, 2022, 34: 2200479

    Article  CAS  Google Scholar 

  18. Hou Y, Wang J, Liu L, et al. Mo2C/CNT: An efficient catalyst for rechargeable Li-CO2 batteries. Adv Funct Mater, 2017, 27: 1700564

    Article  Google Scholar 

  19. Wang C, Yan J, Li T, et al. A coral-like FeP@NC anode with increasing cycle capacity for sodium-ion and lithium-ion batteries induced by particle refinement. Angew Chem Int Ed, 2021, 60: 25013–25019

    Article  CAS  Google Scholar 

  20. Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci, 1996, 6: 15–50

    Article  CAS  Google Scholar 

  21. Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865–3868

    Article  CAS  Google Scholar 

  22. Perdew JP, Ernzerhof M, Burke K. Rationale for mixing exact exchange with density functional approximations. J Chem Phys, 1996, 105: 9982–9985

    Article  CAS  Google Scholar 

  23. Grimme S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem, 2006, 27: 1787–1799

    Article  CAS  Google Scholar 

  24. Malik R, Burch D, Bazant M, et al. Particle size dependence of the ionic diffusivity. Nano Lett, 2010, 10: 4123–4127

    Article  CAS  Google Scholar 

  25. Jacob R, Nair HG, Isac J. Structural and morphological studies of nanocrystalline ceramic BaSr0.9Fe0.1TiO4. Inter Lett Chem, Phys Astron, 2014, 41: 100–117

    Article  Google Scholar 

  26. Huerta-Flores AM, Torres-Martínez LM, Sánchez-Martínez D, et al. SrZrO3 powders: Alternative synthesis, characterization and application as photocatalysts for hydrogen evolution from water splitting. Fuel, 2015, 158: 66–71

    Article  CAS  Google Scholar 

  27. Li W, Chen K, Xu Q, et al. Mo2C/C hierarchical double-shelled hollow spheres as sulfur host for advanced Li-S batteries. Angew Chem Int Ed, 2021, 60: 21512–21520

    Article  CAS  Google Scholar 

  28. Qi G, Zhang J, Chen L, et al. Binder-free MoN nanofibers catalysts for flexible 2-electron oxalate-based Li-CO2 batteries with high energy efficiency. Adv Funct Mater, 2022, 32: 2112501

    Article  CAS  Google Scholar 

  29. Su TT, Jiang H, Gong H, et al. Preparation of nanocrystalline lithium niobate powders at low temperature. Cryst Res Technol, 2010, 45: 977–982

    Article  CAS  Google Scholar 

  30. He M, Shi H, Wang P, et al. Porous molybdenum carbide nanostructures synthesized on carbon cloth by CVD for efficient hydrogen production. Chem Eur J, 2019, 25: 16106–16113

    Article  CAS  Google Scholar 

  31. Hind AR, Bhargava SK, van Bronswijk W, et al. On the aqueous vibrational spectra of alkali metal oxalates. Appl Spectrosc, 1998, 52: 683–691

    Article  CAS  Google Scholar 

  32. Liang Q, Jin H, Wang Z, et al. Metal-organic frameworks derived reverse-encapsulation Co-NC@Mo2C complex for efficient overall water splitting. Nano Energy, 2019, 57: 746–752

    Article  CAS  Google Scholar 

  33. Yang C, Guo K, Yuan D, et al. Unraveling reaction mechanisms of Mo2C as cathode catalyst in a Li-CO2 battery. J Am Chem Soc, 2020, 142: 6983–6990

    Article  CAS  Google Scholar 

  34. Zhong W, Tang W, Wu Y, et al. Heterogeneous interface designing of bimetallic selenides nanocubes for superior sodium storage. J Power Sources, 2021, 506: 230249

    Article  CAS  Google Scholar 

  35. Rao Z, Wu J, He B, et al. A prelithiation separator for compensating the initial capacity loss of lithium-ion batteries. ACS Appl Mater Interfaces, 2021, 13: 38194–38201

    Article  CAS  Google Scholar 

  36. Tang K, Du A, Dong S, et al. A stable solid electrolyte interphase for magnesium metal anode evolved from a bulky anion lithium salt. Adv Mater, 2020, 32: 1904987

    Article  CAS  Google Scholar 

  37. Shen B, Zhang H, Wu Y, et al. Co3O4 quantum dot-catalyzed lithium oxalate as a capacity and cycle-life enhancer in lithium-ion full cells. ACS Appl Energy Mater, 2022, 5: 2112–2120

    Article  CAS  Google Scholar 

  38. Li Y, Li W, Shimizu R, et al. Elucidating the effect of borate additive in high-voltage electrolyte for Li-rich layered oxide materials. Adv Energy Mater, 2022, 12: 2103033

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (U1966214 and 22008082). We gratefully acknowledge the Analytical and Testing Center of HUST for allowing us to use its facilities

Author information

Authors and Affiliations

  1. State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan, 430000, China

    Wei Zhong  (钟伟), Ce Zhang  (张策), Siwu Li  (李思吾), Wei Zhang  (张薇), Ziqi Zeng  (曾子琪), Shijie Cheng  (程时杰) & Jia Xie  (谢佳)

  2. State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China

    Wei Zhong  (钟伟) & Ce Zhang  (张策)

Authors
  1. Wei Zhong  (钟伟)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ce Zhang  (张策)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Siwu Li  (李思吾)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wei Zhang  (张薇)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ziqi Zeng  (曾子琪)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Shijie Cheng  (程时杰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jia Xie  (谢佳)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Author contributions Xie J and Cheng S conceived the idea and revised the manuscript; Zeng Z, Zhang W, and Li S guided the experiment and revised the manuscript; Zhang C participated in the investigation; Zhong W performed the experiments, processed and analyzed the data, and wrote the original manuscript. All authors contributed to the general discussion.

Corresponding author

Correspondence to Jia Xie  (谢佳).

Ethics declarations

Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Wei Zhong received his Master’s degree from Southwest University in 2021. He is currently a PhD candidate under the supervision of Prof. Jia Xie at Huazhong University of Science and Technology. His research interests focus on prelithiation technology.

Jia Xie received his PhD degree from the Department of Chemistry of Stanford University. He is now a professor at Huazhong University of Science and Technology. He was a Senior Researcher at Dow Chemical from 2008 to 2012 and the CTO of Hefei Guoxuan High-Tech Power Energy Co., Ltd. from 2012 to 2015. His research interests focus on advanced energy storage materials and devices.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhong, W., Zhang, C., Li, S. et al. Mo2C catalyzed low-voltage prelithiation using nano-Li2C2O4 for high-energy lithium-ion batteries. Sci. China Mater. 66, 903–912 (2023). https://doi.org/10.1007/s40843-022-2235-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-022-2235-4

Keywords

Search

Navigation