Skip to main content
SpringerLink
Log in

Highly [010]-oriented, gradient Co-doped LiMnPO4 with enhanced cycling stability as cathode for Li-ion batteries

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

Abstract

LiMnPO4 has been attracting attention for high energy density (701 Wh kg−1) and excellent safety. However, LiMnPO4 suffers from the cycling instability coming from the fragile solid electrolyte interface, besides the Jahn-Teller effect of Mn3+, the poor electrical conductivity and the sluggish ionic conductivity. The substitution of cation with less ionic radius for Mn2+ is conducive to stabilize the solid-electrolyte interface and retard the erosion from electrolyte; therefore, the gradient Co-doped LiMn0.98Co0.02PO4 was synthesized with 25.93 (mol) % Co on the surface by the secondary solvothermal method, and the permeated depth reaches more than 20 nm because of the coprecipitation and cation exchange of Co2+ and Mn2+. LiMn0.98Co0.02PO4/Li cell that demonstrates the cycling performance is remarkably enhanced with 87% capacity retention after 380 cycles at room temperature, even 87% after 100 cycles at 60 °C. Meanwhile, the preferential growth along the a–c plane results in the highly [010]-oriented LiMnPO4 by the solvothermal, which afford more channels for Li+ migration by exposing more reaction sites, and the infrared spectrum also reflects the less Mn2+-Li+ antisite defects in the crystal. So the samples show the superior rate performance as well.

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

Scheme 1
Fig. 1
Fig. 2
Fig.3

Similar content being viewed by others

References

  1. Liu D, Fan X, Li Z, Liu T, Sun M, Qian C, Ling M, Liu Y, Liang C (2019) A cation/anion co-doped Li1.12Na0.08Ni0.2Mn0.6O1.95F0.05 cathode for lithium ion batteries. Nano Energy 58:786–796

    CAS  Google Scholar 

  2. Gao Y, Zhao Y, Li YC, Huang Q, Mallouk TE, Wang D (2017) Interfacial chemistry regulation via a skin-grafting strategy enables high-performance lithium-metal batteries. J Am Chem Soc 139(43):15288–15291

    CAS  PubMed  Google Scholar 

  3. Hu L-H, Wu F-Y, Lin C-T, Khlobystov AN, Li L-J (2013) Graphene-modified LiFePO4 cathode for lithium ion battery beyond theoretical capacity. Nat Commun 4:1687

    Google Scholar 

  4. An W, Gao B, Mei S, Xiang B, Fu J, Wang L, Zhang Q, Chu PK, Huo K (2019) Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes. Nat Commun 10:1447

    PubMed  PubMed Central  Google Scholar 

  5. Ji L, Lin Z, Alcoutlabi M, Zhang X (2011) Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries. Energy Environ Sci 4(8):2682–2699

    CAS  Google Scholar 

  6. Takahashi Y, Kumatani A, Munakata H, Inomata H, Ito K, Ino K, Shiku H, Unwin PR, Korchev YE, Kanamura K, Matsue T (2014) Nanoscale visualization of redox activity at lithium-ion battery cathodes. Nat Commun 5:5450

    PubMed  Google Scholar 

  7. Zhou Y-N, Ma J, Hu E, Yu X, Gu L, Nam K-W, Chen L, Wang Z, Yang X-Q (2014) Tuning charge-discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries. Nat Commun 5:5381

    PubMed  Google Scholar 

  8. Devaraj A, Gu M, Colby R, Yan P, Wang CM, Zheng JM, Xiao J, Genc A, Zhang JG, Belharouak I, Wang D, Amine K, Thevuthasan S (2015) Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes. Nat Commun 6:8014

    CAS  PubMed  PubMed Central  Google Scholar 

  9. Lin R, Hu E, Liu M, Wang Y, Cheng H, Wu J, Zheng J-C, Wu Q, Bak S, Tong X, Zhang R, Yang W, Persson KA, Yu X, Yang X-Q, Xin HL (2019) Anomalous metal segregation in lithium-rich material provides design rules for stable cathode in lithium-ion battery. Nat Commun 10:1650

    PubMed  PubMed Central  Google Scholar 

  10. Sharifi-Asl S, Soto FA, Foroozan T, Asadi M, Yuan Y, Deivanayagam R, Rojaee R, Song B, Bi X, Amine K, Lu J, Salehi-khojin A, Balbuena PB, Shahbazian-Yassar R (2019) Anti-oxygen leaking LiCoO2. Adv Funct Mater 29(23):1901110

    Google Scholar 

  11. Nishijima M, Ootani T, Kamimura Y, Sueki T, Esaki S, Murai S, Fujita K, Tanaka K, Ohira K, Koyama Y, Tanaka I (2014) Accelerated discovery of cathode materials with prolonged cycle life for lithium-ion battery. Nat Commun 5:4553

    CAS  PubMed  Google Scholar 

  12. Zaghib K, Mauger A, Julien CM (2012) Overview of olivines in lithium batteries for green transportation and energy storage. J Solid State Electrochem 16(3):835–845

    CAS  Google Scholar 

  13. Gwon H, Seo D-H, Kim S-W, Kim J, Kang K (2009) Combined first-principle calculations and experimental study on multi-component olivine cathode for lithium rechargeable batteries. Adv Funct Mater 19(20):3285–3292

    CAS  Google Scholar 

  14. Manjunatha H, Venkatesha TV, Suresh GS (2011) Electrochemical studies of LiMnPO4 as aqueous rechargeable lithium–ion battery electrode. J Solid State Electrochem 16(5):1941–1952

    Google Scholar 

  15. Wang Y, Wu C-Y, Yang H, Duh J-G (2018) Rational design of a synthetic strategy, carburizing approach and pore-forming pattern to unlock the cycle reversibility and rate capability of micro-agglomerated LiMn0.8Fe0.2PO4 cathode materials. J Mater Chem A 6(22):10395–10403

    CAS  Google Scholar 

  16. Wang Y, Yang H, Wu C-Y, Duh J-G (2017) Facile and controllable one-pot synthesis of nickel-doped LiMn0.8Fe0.2PO4 nanosheets as high performance cathode materials for lithium-ion batteries. J Mater Chem A 5(35):18674–18683

    CAS  Google Scholar 

  17. Oh S-M, Oh S-W, Yoon C-S, Scrosati B, Amine K, Sun Y-K (2010) High-performance carbon-LiMnPO4 nanocomposite cathode for lithium batteries. Adv Funct Mater 20(19):3260–3265

    CAS  Google Scholar 

  18. Wang K, Wang Y, Wang C, Xia Y (2014) Graphene oxide assisted solvothermal synthesis of LiMnPO4 nanoplates cathode materials for lithium ion batteries. Electrochim Acta 146(10):8–14

    CAS  Google Scholar 

  19. Li J, Luo S-h, Ding X, Wang Q, He P (2018) NaCl-template assisted synthesis of 3D honeycomb-like LiMnPO4/C with high rate and stable performance as lithium-ion battery cathodes. ACS Sustain Chem Eng 6(12):16683–16691

    CAS  Google Scholar 

  20. Rajammal K, Sivakumar D, Duraisamy N, Ramesh K, Ramesh S (2016) Enhanced electrochemical properties of ZnO-coated LiMnPO4 cathode materials for lithium ion batteries. Ionics 22(9):1551–1556

    CAS  Google Scholar 

  21. Chen F-J, Tao F, Wang C-M, Zhang W-L, Chen L (2015) The influence of improved carbon coating layer with nanometer-sized CeO2 interconnector on the enhanced electrochemical performance of LiMnPO4. J Power Sources 285(1):367–373

    CAS  Google Scholar 

  22. Yang C-C, Hung Y-W, Lue SJ (2016) Improved electrochemical properties of LiFe0.5Mn0.5PO4/C composite materials via a surface coating process. J Power Sources 325(1):565–574

    CAS  Google Scholar 

  23. Huang W, Hu J, Yang L, Zhao W, Wang Z, Wang H, Guo Z, Li Y, Liu J, Yang K, Pan F (2019) Revealing the degradation mechanism of LiMnxFe1- xPO4 by the single-particle electrochemistry method. ACS Appl Mater Inter 11(1):957–962

    CAS  Google Scholar 

  24. Liang L, Sun X, Zhang J, Hou L, Sun J, Liu Y, Wang S, Yuan C (2019) In situ synthesis of hierarchical core double-shell Ti-doped LiMnPO4@NaTi2(PO4)3@C/3D graphene cathode with high-rate capability and long cycle life for lithium-ion batteries. Adv Energy Mater 9(11):1802847

    Google Scholar 

  25. Li J, Luo S, Ding X, Wang Q, He P (2018) Three-dimensional honeycomb-structural LiAlO2-modified LiMnPO4 composite with superior high rate capability as Li-ion battery cathodes. ACS Appl Mater Inter 10(13):10786–10795

    CAS  Google Scholar 

  26. Chen W, Li Y, Zhao J, Yang F, Zhang J, Shi Q, Mi L (2016) Controlled synthesis of concentration gradient LiNi0.84Co0.10Mn0.04Al0.02O1.90F0.10 with improved electrochemical properties in Li-ion batteries. RSC Adv 6(63):58173–58181

    CAS  Google Scholar 

  27. Yang L, Xia Y, Qin L, Yuan G, Qiu B, Shi J, Liu Z (2016) Concentration-gradient LiMn0.8Fe0.2PO4 cathode material for high performance lithium ion battery. J Power Sources 304(1):293–300

    CAS  Google Scholar 

  28. von Hagen R, Lorrmann H, Möller K-C, Mathur S (2012) Electrospun LiFe1−yMnyPO4/C nanofiber composites as self-supporting cathodes in Li-ion batteries. Adv Energy Mater 2(5):553–559

    Google Scholar 

  29. Fang H, Yi H, Hu C, Yang B, Yao Y, Ma W, Dai Y (2012) Effect of Zn doping on the performance of LiMnPO4 cathode for lithium ion batteries. Electrochim Acta 71(1):266–269

    CAS  Google Scholar 

  30. Yuan LF, Ge LL, Shen YH, Zhang H, Wang CP, Xie AJ (2013) Synthesis and electrochemical properties of cu-doped LiMnPO4/C nanorods as cathode materials of Lithium-ion batteries. J Nano Res 25:1–7

    CAS  Google Scholar 

  31. Lu Q, Hutchings GS, Zhou Y, Xin HL, Zheng H, Jiao F (2014) Nanostructured flexible mg-modified LiMnPO4 matrix as high-rate cathode materials for Li-ion batteries. J Mater Chem A 2(18):6368–6373

    CAS  Google Scholar 

  32. Lee KS, Lee KJ, Kang YS, Shin TJ, Sung YE, Ahn D (2015) Effects of Ag-embedment on electronic and ionic conductivities of LiMnPO4 and its performance as a cathode for lithium-ion batteries. Nanoscale 7(33):13860–13867

    CAS  PubMed  Google Scholar 

  33. Yang Z, Cao G-S, Xie J, Zhao X-B (2011) Oleic acid-assisted preparation of LiMnPO4 and its improved electrochemical performance by co doping. J Solid State Electrochem 16(3):1271–1277

    Google Scholar 

  34. Su L, Li X, Ming H, Adkins J, Liu M, Zhou Q, Zheng J (2013) Effect of vanadium doping on electrochemical performance of LiMnPO4 for lithium-ion batteries. J Solid State Electrochem 18(3):755–762

    Google Scholar 

  35. Zhang J, Luo S, Wang Q, Wang Z, Zhang Y, Hao A, Liu Y, Xu Q, Zhai Y (2017) Yttrium substituting in Mn site to improve electrochemical kinetics activity of sol-gel synthesized LiMnPO4/C as cathode for lithium ion battery. J Solid State Electrochem 21(11):3189–3194

    CAS  Google Scholar 

  36. Yang X, Mi Y, Zhang W, Wu B, Zhou H (2015) Enhanced electrochemical performance of LiFe0.6Mn0.4PO4/C cathode material prepared by ferrocene-assisted calcination process. J Power Sources 275(1):823–830

    CAS  Google Scholar 

  37. Chen Z, Qin Y, Amine K, Sun YK (2010) Role of surface coating on cathode materials for lithium-ion batteries. J Mater Chem 20(36):7606–7612

    CAS  Google Scholar 

  38. Yang G, Ni H, Liu H, Gao P, Ji H, Roy S, Pinto J, Jiang X (2011) The doping effect on the crystal structure and electrochemical properties of LiMnxM1−xPO4 (M=Mg, V, Fe, Co, Gd). J Power Sources 196(10):4747–4755

    CAS  Google Scholar 

  39. Ma F, Zhang X, He P, Zhang X, Wang P, Zhou H (2017) Synthesis of hierarchical and bridging carbon-coated LiMn0.9Fe0.1PO4 nanostructure as cathode material with improved performance for lithium ion battery. J Power Sources 359(15):408–414

    CAS  Google Scholar 

  40. Fang L, Zhang H, Zhang Y, Liu L, Wang Y (2016) Design and synthesis of two-dimensional porous Fe-doped LiCoPO4 nano-plates as improved cathode for lithium ion batteries. J Power Sources 312(30):101–108

    CAS  Google Scholar 

  41. Yan X, Sun D, Wang Y, Zhang Z, Yan W, Jiang J, Ma F, Liu J, Jin Y, Kanamura K (2017) Enhanced electrochemical performance of LiMn0.75Fe0.25PO4 nanoplates from multiple interface modification by using fluorine-doped carbon coating. ACS Sustain Chem Eng 5(6):4637–4644

    CAS  Google Scholar 

  42. Cheng G, Zuo P, Wang L, Shi W, Ma Y, Du C, Cheng X, Gao Y, Yin G (2014) High-performance carbon-coated LiMnPO4 nanocomposites by facile two-step solid-state synthesis for lithium-ion battery. J Solid State Electrochem 19(1):281–288

    Google Scholar 

  43. Yang W, Bi Y, Qin Y, Liu Y, Zhang X, Yang B, Wu Q, Wang D, Shi S (2015) LiMn0.8Fe0.2PO4/C cathode material synthesized via co-precipitation method with superior high-rate and low-temperature performances for lithium-ion batteries. J Power Sources 275(1):785–791

    CAS  Google Scholar 

  44. Minakshi M, Kandhasamy S (2012) Utilizing active multiple dopants (Co and Ni) in olivine LiMnPO4. Curr Opin Solid St M 16(4):163–167

    CAS  Google Scholar 

  45. Xie Z, Chang K, Li B, Tang H, Fu X, Chang Z, Yuan X-Z, Wang H (2016) Glucose-assisted synthesis of highly dispersed LiMnPO4 nanoparticles at a low temperature for lithium ion batteries. Electrochim Acta 189(20):205–214

    CAS  Google Scholar 

  46. Wang D, Buqa H, Crouzet M, Deghenghi G, Drezen T, Exnar I, Kwon N-H, Miners JH, Poletto L, Grätzel M (2009) High-performance, nano-structured LiMnPO4 synthesized via a polyol method. J Power Sources 189(1):624–628

    CAS  Google Scholar 

  47. Kobayashi S, Fisher CA, Kato T, Ukyo Y, Hirayama T, Ikuhara Y (2016) Atomic-scale observations of (010) LiFePO4 surfaces before and after chemical delithiation. Nano Lett 16(9):5409–5414

    CAS  PubMed  Google Scholar 

  48. Taniguchi I, Doan TNL, Shao B (2011) Synthesis and electrochemical characterization of LiCoxMn1−xPO4/C nanocomposites. Electrochim Acta 56(22):7680–7685

    CAS  Google Scholar 

  49. Shen CH, Liu RS, Gundakaram R, Chen JM, Huang SM, Chen JS, Wang CM (2001) Effect of Co doping in LiMn2O4. J Power Sources 102(1–2):21–28

    CAS  Google Scholar 

  50. Kim M-S, Jegal J-P, Roh KC, Kim K-B (2014) Synthesis of LiMn0.75Fe0.25PO4/C microspheres using a microwave-assisted process with a complexing agent for high-rate lithium ion batteries. J Mater Chem A 2(27):10607–10613

    CAS  Google Scholar 

  51. Qin X, Wang J, Xie J, Li F, Wen L, Wang X (2012) Hydrothermally synthesized LiFePO4 crystals with enhanced electrochemical properties: simultaneous suppression of crystal growth along [010] and antisite defect formation. Phys Chem Phys 14(8):2669–2677

    CAS  Google Scholar 

  52. Long Y, Zhang Z, Wu Z, Su J, Lv X, Wen Y (2017) Microwave-assisted polyol synthesis of LiMnPO4/C and its use as a cathode material in lithium-ion batteries. Particuology 33:42–49

    CAS  Google Scholar 

  53. Zheng J, Ni L, Lu Y, Qin C, Liu P, Wu T, Tang Y, Chen Y (2015) High-performance, nanostructure LiMnPO4/C composites synthesized via one-step solid state reaction. J Power Sources 282:444–451

    CAS  Google Scholar 

  54. Xu X, Wang T, Bi Y, Liu M, Yang W, Peng Z, Wang D (2017) Improvement of electrochemical activity of LiMnPO4-based cathode by surface iron enrichment. J Power Sources 341(15):175–182

    CAS  Google Scholar 

  55. Chen W, Li Y, Yang D, Feng X, Guan X, Mi L (2016) Controlled synthesis of spherical hierarchical LiNi1−x−yCoxAlyO2 (0<x, y<0.2) via a novel cation exchange process as cathode materials for high-performance lithium batteries. Electrochim Acta 190(1):932–938

    CAS  Google Scholar 

  56. Li B, Gu P, Feng Y, Zhang G, Huang K, Xue H, Pang H (2017) Ultrathin nickel-cobalt phosphate 2D nanosheets for electrochemical energy storage under aqueous/solid-state electrolyte. Adv Funct Mater 27(12):1605784

    Google Scholar 

  57. Wang D, Wang Z, Huang X, Chen L (2005) Continuous solid solutions LiFe1−xCoxPO4 and its electrochemical performance. J Power Sources 146(1–2):580–583

    CAS  Google Scholar 

  58. Xu H, Zong J, Ding F, Lu Z-w, Li W, X-j L (2016) Effects of Fe2+ ion doping on LiMnPO4 nanomaterial for lithium ion batteries. RSC Adv 6(32):27164–27169

    CAS  Google Scholar 

  59. Lu J, Zhan C, Wu T, Wen J, Lei Y, Kropf AJ, Wu H, Miller DJ, Elam JW, Sun YK, Qiu X, Amine K (2014) Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach. Nat Commun 5:5693

    CAS  PubMed  Google Scholar 

  60. He X, Li J, Cai Y, Wang Y, Ying J, Jiang C, Wan C (2005) Preparation of co-doped spherical spinel LiMn2O4 cathode materials for Li-ion batteries. J Power Sources 150(4):216–222

    CAS  Google Scholar 

  61. Li Z, Feng X, Mi L, Zheng J, Chen X, Chen W (2018) Hierarchical porous onion-shaped LiMn2O4 as ultrahigh-rate cathode material for lithium ion batteries. Nano Res 11(8):4038–4048

    CAS  Google Scholar 

  62. Chen W, Qi S, Yu M, Feng X, Cui S, Zhang J, Mi L (2017) Design of FeS2@rGO composite with enhanced rate and cyclic performances for sodium ion batteries. Electrochim Acta 230(10):1–9

    CAS  Google Scholar 

  63. Hong Y, Tang Z, Wang S, Quan W, Zhang Z (2015) High-performance LiMnPO4 nanorods synthesized via a facile EG-assisted solvothermal approach. J Mater Chem A 3(19):10267–10274

    CAS  Google Scholar 

  64. Liao L, Wang H, Guo H, Zhu P, Xie J, Jin C, Zhang S, Cao G, Zhu T, Zhao X (2015) Facile solvothermal synthesis of ultrathin LiFexMn1−xPO4 nanoplates as advanced cathodes with long cycle life and superior rate capability. J Mater Chem A 3(38):19368–19375

    CAS  Google Scholar 

Download references

Funding

This work was supported by the National Natural Science Foundation of China (No. 21771164) and (No. U1804129).

Author information

Authors and Affiliations

  1. College of Chemistry, Zhengzhou University, Zhengzhou, 450001, People’s Republic of China

    Ruijie Wang, Jinyun Zheng, Xiangming Feng, Ge Yao, Huiting Niu, Qingyi Liu & Weihua Chen

Authors
  1. Ruijie Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jinyun Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiangming Feng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ge Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Huiting Niu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Qingyi Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Weihua Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Xiangming Feng.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note

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

Electronic supplementary material

ESM 1

(DOC 5921 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, R., Zheng, J., Feng, X. et al. Highly [010]-oriented, gradient Co-doped LiMnPO4 with enhanced cycling stability as cathode for Li-ion batteries. J Solid State Electrochem 24, 511–519 (2020). https://doi.org/10.1007/s10008-019-04485-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-019-04485-1

Keywords

Search

Navigation