Skip to main content
SpringerLink
Log in

Remarkable electrochemical performance of 0.5Li2MnO3·0.5LiNi0.5Mn0.3Co0.2O2 synthesized by means of a citric acid–aided route

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

Abstract

Lithium-manganese-rich–lithiated nickel-manganese-cobalt oxides are advantageous for using in lithium-ion batteries due to low toxicity and high specific capacity but suffer from low high-rate capability. In this paper, characterization and electrochemical testing of 0.5Li2MnO3·0.5LiNi0.5Mn0.3Co0.2O2 (Li1.2Ni0.2Mn0.52Co0.08O2) obtained by means of a citric acid–aided route is described. It demonstrates excellent electrochemical performance possessing specific capacity equal to the theoretical value (280 mAh g−1), being able to be discharged with currents of 2240 mA g−1 (8 C), having high coulombic efficiency (~ 99%) even after high-rate tests, and manifesting low capacity fade after high current loads and upon further cycling by 0.1 C currents (0.144 mAh g−1 per cycle).

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

Similar content being viewed by others

References

  1. Blomgren GE (2017) The development and future of lithium ion batteries. J Electrochem Soc 164:A5019–A5025

    CAS  Google Scholar 

  2. Nayak PK, Erickson EM, Schipper F, Penki TR, Munichandraiah N, Adelhelm P, Sclar H, Amalraj F, Markovsky B, Aurbach D (2017) Review on challenges and recent advances in the electrochemical performance of high capacity Li- and Mn-rich cathode materials for Li-ion batteries. Adv Energy Mater 8:1702397

    Google Scholar 

  3. Thackeray MM, Croy JR, Lee E, Gutierrez A, He M, Park JS, Yonemoto BT, Long BR, Blauwkamp JD, Johnson CS, Shin Y, David WIF (2018) The quest for manganese-rich electrodes for lithium batteries: strategic design and electrochemical behavior. Sustain Energy Fuels 2:1375–1397

    CAS  Google Scholar 

  4. Hu S, Pillai AS, Liang G, Pang WK, Wang H, Li Q, Guo Z (2019) Li-rich layered oxides and their practical challenges: recent progress and perspectives. Electrochem Energy Rev 2:277–311

    CAS  Google Scholar 

  5. Yabuuchi N, Yoshida H, Komaba S (2012) Crystal structures and electrode performance of alpha-NaFeO2 for rechargeable sodium batteries. Electrochemistry 80:716–719

    CAS  Google Scholar 

  6. Ammundsen B, Desilvestro J, Groutso T, Hassell D, Metson JB, Regan E, Steiner R, Pickering PJ (2000) Formation and structural properties of layered LiMnO2 cathode materials. J Electrochem Soc 147:4078–4082

    CAS  Google Scholar 

  7. Ohzuku T, Makimura Y (2001) Layered lithium insertion material of LiNi1/2Mn1/2O2: a possible alternative to LiCoO2 for advanced lithium-ion batteries. Chem Lett 30:744–745

    Google Scholar 

  8. Yabuuchi N, Koyama Y, Nakayama N, Ohzuku T (2005) Solid-state chemistry and electrochemistry of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries. II Preparation and characterization. J Electrochem Soc 152:A1434–A1440

    CAS  Google Scholar 

  9. Strobel P, Lambert-Andron B (1988) Crystallographic and magnetic structure of Li2MnO3. J Solid State Chem 75:90–98

    CAS  Google Scholar 

  10. Lim J-H, Bang H, Lee K-S, Amine K, Sun Y-K (2009) Electrochemical characterization of Li2MnO3-Li[Ni1/3Co1/3Mn1/3]O2-LiNiO2 cathode synthesized via co-precipitation for lithium secondary batteries. J Power Sources 189:571–575

    CAS  Google Scholar 

  11. Assat G, Tarascon J-M (2018) Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat Energy 3:373–386

    CAS  Google Scholar 

  12. Xu G, Li J, Xue Q, Ren X, Yan G, Wang X, Kang F (2014) Enhanced oxygen reducibility of 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2 cathode material with mild acid treatment. J Power Sources 248:894–899

    CAS  Google Scholar 

  13. Prakasha KR, Sathish M, Bera P, Prakash AS (2017) Mitigating the surface degradation and voltage decay of Li1.2Ni0.13Mn0.54Co0.13O2 cathode material through surface modification using Li2ZrO3. ACS Omega 2:2308–2316

    CAS  PubMed  PubMed Central  Google Scholar 

  14. Doan TNL, Yoo K, Hoang TKA, Chen P (2014) Recent developments in synthesis of xLi2MnO3·(1-x)LiMO2 (M=Ni, Co, Mn) cathode powders for high-energy lithium rechargeable batteries. Front Energy Res 2:36

    Google Scholar 

  15. Zheng JM, Wu XB, Yang Y (2011) A comparison of preparation method on the electrochemical performance of cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 for lithium ion battery. Electrochim Acta 56:3071–3078

    CAS  Google Scholar 

  16. Li L, Xu M, Chen Z, Zhou X, Zhang Q, Zhu H, Wu C, Zhang K (2015) High-performance lithium-rich layered oxide materials: effects of chelating agents on microstructure and electrochemical properties. Electrochim Acta 174:446–455

    CAS  Google Scholar 

  17. Qiu B, Yin C, Xia Y, Liu Z (2017) Synthesis of three-dimensional nanoporous Li-rich layered cathode oxides for high volumetric and power energy density lithium-ion batteries. ACS Appl Mater Interfaces 9:3661–3666

    CAS  PubMed  Google Scholar 

  18. Chen Z, Yan X, Xu M, Cao K, Zhu H, Li L, Duan J (2017) Building honeycomb-like hollow microsphere architecture in a bubble template reaction for high-performance lithium-rich layered oxide cathode materials. ACS Appl Mater Interfaces 9(36):30617–30625

    CAS  PubMed  Google Scholar 

  19. Xu M, Chen Z, Zhu H, Yan X, Li L, Zhao Q (2015) Mitigating capacity fade by constructing highly-ordered mesoporous Al2O3/polyacene double-shelled architecture in Li-rich cathode materials. J Mater Chem A 3:13933–13945

    CAS  Google Scholar 

  20. Potapenko AV, Chernukhin SI, Kirillov SA (2014) A new method of pretreatment of lithium manganese spinels and high-rate electrochemical performance of Li[Li0.033Mn1.967]O4. Mater Renew Sustain Energy 3:40–48

    Google Scholar 

  21. Potapenko AV, Chernukhin SI, Romanova IV, Rabadanov KS, Gafurov MM, Kirillov SA (2014) Citric acid aided synthesis, characterization, and high-rate electrochemical performance of LiNi0.5Mn1.5O4. Electrochim Acta 134:442–449

    CAS  Google Scholar 

  22. Potapenko AV, Kirillov SA (2014) Lithium manganese spinel materials for high-rate electrochemical applications. J Energy Chem 23:543–558

    Google Scholar 

  23. Kosilov VV, Potapenko AV, Kirillov SA (2017) Effect of overdischarge (overlithiation) on electrochemical properties of LiMn2O4 samples of different origin. J Solid State Electrochem 21:3269–3279

    CAS  Google Scholar 

  24. Potapenko AV, Kirillov SA (2017) Enhancing high-rate electrochemical properties of LiMn2O4 in a LiMn2O4/LiNi0.5Mn1.5O4 core/shell composite. Electrochim Acta 258:9–16

    CAS  Google Scholar 

  25. Kirillov SА, Romanova IV, Lisnycha TV, Potapenko AV (2018) High-rate electrochemical performance of Li4Ti5O12 obtained from TiCl4 by means of a citric acid aided route. Electrochim Acta 286:163–171

    CAS  Google Scholar 

  26. Romanova I, Kirillov S (2018) (2018) preparation of Cu, Ni and Co oxides by a citric acid-aided route. Effect of metal ions on thermal decomposition and morphology. J Therm Anal Calorim 132:503–512

    CAS  Google Scholar 

  27. Kirillov SA (2019) Electrode materials and electrolytes for high-rate electrochemical energy systems: a review. Theor Exp Chem 55:73–95

    CAS  Google Scholar 

  28. Nayak PK, Grinblat J, Levi E, Penki TR, Levi M, Sun Y-K, Markovsky B, Aurbach D (2017) Remarkably improved electrochemical performance of Li- and Mn- rich cathodes upon substitution of Mn with Ni. ASC Appl Mater Interfaces 9:4309–4319

    Google Scholar 

  29. Wang G, Yi L, Yu R, Wang X, Wang Y, Liu Z, Wu B, Liu M, Zhang X, Yang X, Xiong X, Liu M (2017) Li1.2Ni0.13Co0.13Mn0.54O2 with controllable morphology and size for high performance lithium-ion batteries. ASC Appl Mater Interfaces 9:25358–25368

    CAS  Google Scholar 

  30. Zhao C, Shen Q (2014) Organic acid assisted solid-state synthesis of Li1.2Mn0.54Ni0.13Co0.13O2 nanoparticles as lithium ion battery cathodes. Current Appl Phys 14:1849–1853

    Google Scholar 

  31. Kim J-H, Park M-S, Song J-H, Byun D-J, Kim Y-J, Kim J-S (2012) Effect of aluminum fluoride coating on the electrochemical and thermal properties of 0.5Li2MnO3·0.5LiNi0.5Mn0.3Co0.2O2 composite material. J Alloys Compounds 517:20–25

    CAS  Google Scholar 

  32. Holland TJB, Redfern SAT (1997) Unit cell refinement from powder diffraction data: the use of regression diagnostics. Miner Mag 61:65–77

    CAS  Google Scholar 

  33. Holland TJB, Redfern SAT (1997) UNITCELL: a nonlinear least-squares program for cell-parameter refinement and implementing regression and deletion diagnostics. J Appl Crystallogr 30:81–84

    Google Scholar 

  34. Patterson AL (1939) The Scherrer formula for X-ray particle size determination. Phys Rev 56:978–982

    CAS  Google Scholar 

  35. Kirillov SA (2009) Surface area and pore volume of a system of particles as a function of their size and packing. Microporous Mesoporous Mater 122:234–239

    CAS  Google Scholar 

  36. Kosova NV, Devyatkina ET, Kaichev VV (2007) Optimization of Ni2+/Ni3+ ratio in layered Li(Ni,Mn,Co)O2 cathodes for better electrochemistry. J Power Sources 174:965–969

    CAS  Google Scholar 

  37. Wang P-B, Luo M-Z, Zheng J-C, He Z-J, Tong H, Yu W-j (2018) Comparative investigation of 0.5Li2MnO3·0.5LiNi0.5Mn0.3Co0.2O2 cathode materials synthesized by using different lithium sources. Frontiers Chem 6:159

    Google Scholar 

  38. Nesbitt HW, Banerjee D (1998) Interpretation of XPS Mn(2p) spectra of Mn oxyhydroxides and constraints on the mechanism of MnO2 precipitation. Am Mineral 83:305–315

    CAS  Google Scholar 

  39. Gupta RP, Sen SK (1974) Calculation of multiplet structure of core p-vacancy levels. Phys Rev B 10:71–77

    CAS  Google Scholar 

  40. Gupta RP, Sen SK (1975) Calculation of multiplet structure of core p-vacancy levels. II. Phys Rev B 12:15–19

    CAS  Google Scholar 

  41. Broussely M, Perton F, Biensan P, Bodet JM, Labat J, Lecerf A, Delmas C, Rougier A, Pérès JP (1995) LixNiO2, a promising cathode for rechargeable lithium batteries. J Power Sources 54:109–114

    CAS  Google Scholar 

  42. Chen Z, Dahn JR (2004) Improving the capacity retention of LiCoO2 cycled to 4.5 V by heat-treatment. Electrochem Solid-State Lett 7:A11–A14

    CAS  Google Scholar 

  43. Vitins G, West K (1997) Lithium intercalation into layered LiMnO2. J Electrochem Soc 144:2587–2592

    CAS  Google Scholar 

  44. Yabuuchi N, Makimura Y, Ohzuku T (2007) Solid-state chemistry and electrochemistry of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries. III Rechargeable capacity and cycleability. J Electrochem Soc 154:A314–A321

    CAS  Google Scholar 

  45. Pang S, Zhu M, Xu K, Shen X, Wen H, Su Y, Yang G, Wu X, Li S, Wang W, Xi X, Wang H (2018) Enhanced electrochemical performance of Li1.2Mn0.54Ni0.13Co0.13O2 via L-ascorbic acid-based treatment as cathode material for Li-ion batteries. J Electrochem Soc165:A1897–A1902

    Google Scholar 

  46. Pang S, Xu K, Wang Y, Shen X, Wang W, Su Y, Zhu M, Xi X (2017) Enhanced electrochemical performance of Li-rich layered cathode materials via chemical activation of Li2MnO3 component and formation of spinel/carbon coating layer. J Power Sources 365:68–75

    CAS  Google Scholar 

  47. Song B, Liu H, Liu Z, Xiao P, Lai MO, Lu L (2013) High rate capability caused by surface cubic spinels in Li-rich layer-structured cathodes for Li-ion batteries. Sci Rep 3:3094

    PubMed  PubMed Central  Google Scholar 

Download references

Funding

Financial support to A.V.P. from School of Materials and Energy, University of Electronic Science and Technology of China is gratefully acknowledged.

Author information

Authors and Affiliations

  1. School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu, 611731, People’s Republic of China

    Anna V. Potapenko & Mengqiang Wu

  2. Joint Department of Electrochemical Energy Systems, 38A Vernadsky Ave., Kyiv, 03142, Ukraine

    Anna V. Potapenko & Sviatoslav A. Kirillov

Authors
  1. Anna V. Potapenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mengqiang Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sviatoslav A. Kirillov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sviatoslav A. Kirillov.

Additional information

Publisher’s note

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Potapenko, A.V., Wu, M. & Kirillov, S.A. Remarkable electrochemical performance of 0.5Li2MnO3·0.5LiNi0.5Mn0.3Co0.2O2 synthesized by means of a citric acid–aided route. J Solid State Electrochem 23, 3383–3389 (2019). https://doi.org/10.1007/s10008-019-04442-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-019-04442-y

Keywords

Search

Navigation