Skip to main content
SpringerLink
Log in

High rate capability and thermal stability of monoclinic-Li2MnSiO4 – A promising high capacity cathode material for lithium batteries

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

Li2MnSiO4 has attracted significant attention as cathode material for lithium ion batteries due to its structural diversity, abundance, low cost, thermal stability, and high theoretical capacity (330 mAh g−1). However, it suffers from low electronic conductivity, poor cycling performance, and limited reversible capacity. To overcome these deficiencies, as well as to further enhance its thermal stability and rate capability, we discover that surface modification utilizes an ex-situ carbon coating method using sucrose as the carbon source. Our approach enabled a uniform coating of amorphous carbon on Li2MnSiO4 with a monoclinic crystalline structure, which was confirmed by X-ray diffraction, electron microscopy, and Raman studies. The influence of sucrose on the performance of carbon coating has been analyzed in the half-cell configuration employing 1.0 M LiPF6 in ethylene carbonate/diethyl carbonate (1:1 v/v) as an electrolyte. Hence, the impact on the controlled carbon coating significantly improves the cycle characteristics of redox peaks (Mn2+/Mn3+ and Mn3+/Mn4+) originally observed in the pristine monoclinic phase of Li2MnSiO4 within a potential range of 2.5–4.4 V vs. Li/Li+. A well-tuned carbon-coated product benefits from the optimum thickness results in achieving excellent thermal stability by protective action of carbon coating and rate capability retains ~ 92% of its initial capacity of 159 mAh g−1 after 200 cycles at a higher current rate 0.5 C.

Graphical abstract

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Chen S, Dai F, Cai M (2020) Opportunities and challenges of high-energy lithium metal batteries for electric vehicle applications. ACS Energy Lett 5:3140–3151

    Article  CAS  Google Scholar 

  2. Liu S, Xu J, Li D, Hu Y, Liu X, Xie K (2013) High capacity Li2MnSiO4/C nanocomposite prepared by sol-gel method for lithium-ion batteries. J Power Sources 15(232):258–263

    Article  Google Scholar 

  3. Huang Y, Lin YC, Jenkins DM, Chernova NA, Chung Y, Radhakrishnan B, Chu IH, Fang J, Wang Q, Omenya F, Ong SP (2016) Thermal stability and reactivity of cathode materials for Li-ion batteries. ACS Appl Mater Interfaces 8:7013–7021

    Article  CAS  PubMed  Google Scholar 

  4. Ding Y, Cano ZP, Yu A, Lu J, Chen Z (2019) Automotive Li-ion batteries: current status and future perspectives. Electrochemical Energy Reviews 2:1–28

    Article  CAS  Google Scholar 

  5. Pei Y, Chen Q, Xu CY, Wang HX, Fang HT, Zhou C, Zhen L, Cao G (2016) Chelate-induced formation of Li2MnSiO4 nanorods as a high capacity cathode material for Li-ion batteries. J Mater Chem A 4:9447–9454

    Article  CAS  Google Scholar 

  6. Li YX, Gong ZL, Yang Y (2007) Synthesis and characterization of Li2MnSiO4/C nanocomposite cathode material for lithium ion batteries. J Power Sources 174(2):528–532

    Article  CAS  Google Scholar 

  7. Cheng Q, He W, Zhang X, Li M, Wang L (2017) Modification of Li2MnSiO4 cathode materials for lithium-ion batteries: a review. J Mater Chem A 5:10772–10797

    Article  CAS  Google Scholar 

  8. Shree Kesavan K, Michael MS, Prabaharan SRS (2019) Facile electrochemical activity of monoclinic Li2MnSiO4 as potential cathode for Li-ion batteries. ACS Appl Mater Interfaces 11:28868–28877

    Article  CAS  PubMed  Google Scholar 

  9. Shree Kesavan K, Michael MS, Prabaharan SRS (2019) Battery-active monoclinic Li2MnSiO4 synthesized via temperature programmed reaction. J Taiwan Inst Chem Engrs 105:28–38

    Article  Google Scholar 

  10. Liu C, Li F, Ma LP, Cheng HM (2010) Advanced materials for energy storage. Adv Mater 22:E28–E62

    Article  CAS  PubMed  Google Scholar 

  11. Won S, Lee KK, Park G, Sun HJ, An JC, Shim J (2015) Physical and electrochemical characteristics of carbon content in carbon-coated Li2MnSiO4 for rechargeable lithium batteries. J Appl Electrochem 45:169–176

    Article  CAS  Google Scholar 

  12. Chen W, Zhu D, Li Y, Li C, Feng X, Guan X, Mi L (2015) How to synthesize pure Li2- xFeSi1-xPxO4/C (x=0.03–0.15) easily from low-cost Fe3+ as cathode materials for Li-ion batteries. Dalton Trans 44:14805–14812

  13. Babbar P, Tiwari B, Purohit B, Ivanishchev A, Churikov A, Dixit A (2017) Charge/discharge characteristics of Jahn-Teller distorted nanostructured orthorhombic and monoclinic Li2MnSiO4 cathode materials. RSC Adv 7:22990–22997

    Article  CAS  Google Scholar 

  14. Fantini C, Cruz E, Jorio A, Terrones M, Terrones H, Van Lier G, Charlier JC, Dresselhaus MS, Saito R, Kim YA, Hayashi T, Muramatsu H, Endo M, Pimenta MA (2006) Resonance Raman study of linear carbon chains formed by the heat treatment of double-wall carbon nanotubes. Phys Rev B 73:193408

    Article  Google Scholar 

  15. Wu H, Zhang Y, Zhang X, San Hui K, Zhu J, He W (2020) Low cost Na2FeSiO4/H-N-doped hard carbon nanosphere hybrid cathodes for high energy and power sodium-ion supercapacitors. J Alloys Compd 842:155797

    Article  CAS  Google Scholar 

  16. Bhaskar A, Deepa M, Rao TN, Varadaraju UV (2012) In situ carbon coated Li2MnSiO4/C composites as cathodes for enhanced performance Li-ion batteries. J Electrochem Soc 159:A1954

    Article  CAS  Google Scholar 

  17. Aravindan V, Karthikeyan K, Kang KS, Yoon WS, Kim WS, Lee YS (2011) Influence of carbon towards improved lithium storage properties of Li2MnSiO4 cathodes. J Mater Chem 21:2470–2475

    Article  CAS  Google Scholar 

  18. Jin YH, Park KS, Kang LS, Kim BS, Hong HS (2015) Electrochemical performances of Li2MnSiO4 cathodes synthesized by mechanical alloying process. J Nanosci Nanotechnol 15:2418–2421

    Article  CAS  PubMed  Google Scholar 

  19. Park KS, Jin YH, Kang LS, Lee GH, Lee NH, Kim DW, Hong HS (2014) Enhanced electrochemical performance of carbon-coated Li2MnSiO4 nanoparticles synthesized by tartaric acid-assisted sol-gel process. Ceram Int 40:9413–9418

    Article  CAS  Google Scholar 

  20. Jiang X, Xu H, Liu J, Qian Y (2013) Hydrothermal synthesis of the Li2MnSiO4/C nanocomposite as a cathode material for lithium-ion batteries. Mater Lett 113:9–12

    Article  CAS  Google Scholar 

  21. Park H, Song T, Tripathi R, Nazar LF, Paik U (2014) Li2MnSiO4/carbon nanofiber cathodes for Li-ion batteries. Ionics 20:1351–1359

    Article  CAS  Google Scholar 

  22. Wang F, Wang Y, Sun D, Wang L, Yang J, Jia H (2014) High performance Li2MnSiO4 prepared in molten KCl-NaCl for rechargeable lithium ion batteries. Electrochim Acta 119:131–137

    Article  CAS  Google Scholar 

  23. Li X, Liu Y, Xiao Z, Guo W, Zhang R (2014) Ionothermal synthesis and characterization of Li2MnSiO4/C composites as cathode materials for lithium-ion batteries. Ceram Int 40:289–296

    Article  CAS  Google Scholar 

  24. Shao B, Taniguchi I (2014) Synthesis of Li2MnSiO4/C nanocomposites for lithium battery cathode employing sucrose as carbon source. Electrochim Acta 128:156–162

    Article  CAS  Google Scholar 

  25. Kuezma M, Devaraj S, Balaya P (2012) Li2MnSiO4 obtained by microwave assisted solvothermal method: electrochemical and surface studies. J Mater Chem 22:21279–21284

    Article  CAS  Google Scholar 

  26. Muraliganth T, Stroukoff KR, Manthiram A (2010) On the energetic stability and electrochemistry of Li2MnSiO4 polymorphs. Chem Mater 22:5754–5761

    Article  CAS  Google Scholar 

  27. Gong H, Zhu Y, Wang L, Wei D, Liang J, Qian Y (2014) Solid-state synthesis of uniform Li2MnSiO4/C/graphene composites and their performance in lithium-ion batteries. J Power Sources 246:192–197

    Article  CAS  Google Scholar 

  28. Wang Z, He W, Zhang X, Yue Y, Liu J, Zhang C, Fang L (2017) Multilevel structures of Li3V2(PO4)3/phosphorus-doped carbon nanocomposites derived from hybrid V-MOFs for long-life and cheap lithium ion battery cathodes. J Power Sources 366:9–17

    Article  CAS  Google Scholar 

  29. Gummow RJ, He Y (2014) Recent progress in the development of Li2MnSiO4 cathode materials. J Power Sources 253:315–331

    Article  CAS  Google Scholar 

  30. Wang R, Xu G, He Y (2017) Structure and properties of polytetrafluoroethylene (PTFE) fibers. e-Polymers 17:215–220

  31. Mancini M, Fleischhammer M, Fleischmann S, Diemant T, Behm RJ, Axmann P, Wohlfahrt-Mehrens M (2017) Investigation on the thermal stability of Li2MnSiO4-based cathodes for Li-ion batteries: effect of electrolyte and state of charge. Energy Technol 5:1561–1570

    Article  CAS  Google Scholar 

  32. Odochian L, Moldoveanu C, Maftei D (2014) TG-FTIR study on thermal degradation mechanism of PTFE under nitrogen atmosphere and in air. Influence of the grain size. Thermochim Acta 598:28–35

    Article  CAS  Google Scholar 

Download references

Acknowledgements

One of the authors (M.S.M) is indebted to the Naval Research Board (NRB), DRDO, New Delhi for the financial support (NRB/4003/PG/343), to carry out this work. The authors (K.S.K and M.S.M) would like to acknowledge the SSN management for providing the necessary infrastructure facilities. K.S.K acknowledges the Central Scientific Industrial Research for providing CSIR-SRF fellowship (File. No. 08/542(0014)/2020 EMR-I).

Author information

Authors and Affiliations

  1. Chemical Science Research Centre, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam, Chennai, 603110, India

    K. Shree Kesavan & M. S. Michael

Authors
  1. K. Shree Kesavan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. S. Michael
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

This manuscript was written through the contributions of both authors. All authors have approved the final version of the manuscript.

Corresponding author

Correspondence to M. S. Michael.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 3322 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shree Kesavan, K., Michael, M.S. High rate capability and thermal stability of monoclinic-Li2MnSiO4 – A promising high capacity cathode material for lithium batteries. J Solid State Electrochem 26, 1431–1443 (2022). https://doi.org/10.1007/s10008-022-05180-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-022-05180-4

Keywords

Search

Navigation