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Synthesis and characterization of carbon-modified Li2MnP2O7/C composites prepared by spray pyrolysis

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Abstract

Pure crystalline Li2MnP2O7/C composite was prepared by spray pyrolysis (SP) followed by annealing (AN) process. Citric acid (CA) was added into the precursor solution as a carbon source to enhance the electrochemical property. The physical and electrochemical properties in conjunction with various synthesis conditions were evaluated. Variation of carbon content, specific surface area, lattice cell volume, and anti-site concentration was revealed along with different preparation conditions of the SP followed by AN process. Electrochemical properties were relevant to various physical properties of samples, and it provided a critical factor to find the most efficient synthesis condition in the SP method. Since incorporated carbon has a significant role in enhancing the electrical conductivity as well as inducing a delicate variation of physical properties, the limitation of incorporated carbon by CA was addressed with associated reaction mechanism. For the sake of exceeding these limitations, further carbon modification with acetylene black was carried out by ball milling (BM) process. The optimal condition of BM process was designated by the resulting of electrochemical property and observing the carbon distribution on the cross section of particles. Li2MnP2O7/C composite prepared under the whole optimal condition delivered the initial discharge capacity of 64 mAh g−1 at a current rate of C/10. The potential of Mn3+/Mn2+ redox couple revealed at 4.3 V versus Li/Li+ upon the discharge process.

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References

  1. Nagaura T, Tozawa K (1990) Lithium ion rechargeable battery. Prog Batter Sol Cells 9:209–217

    Google Scholar 

  2. Ozawa K (1994) Lithium-ion rechargeable batteries with LiCoO2 and carbon electrodes: the LiCoO2/C system. Solid State Ionics 69:212–221

    Article  Google Scholar 

  3. Padhi AK, Nanjundaswamy KS, Goodenough JB (1997) Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J Electrochem Soc 144:1188–1194

    Article  Google Scholar 

  4. Yamada A, Hosoya M, Chung S-C et al (2003) Olivine-type cathodes. J Power Sources 119–121:232–238

    Article  Google Scholar 

  5. Tang P, Holzwarth NAW (2003) Electronic structure of FePO4, LiFePO4, and related materials. Phys Rev B 68:165107. https://doi.org/10.1103/PhysRevB.68.165107

    Article  Google Scholar 

  6. Yamada A, Chung SC, Hinokuma K (2001) Optimized LiFePO4 for lithium battery cathodes. J Electrochem Soc 148:A224–A229

    Article  Google Scholar 

  7. Yamada A, Chung S-C (2001) Crystal chemistry of the olivine-type Li(MnyFe1−y)PO4 and (MnyFe1−y)PO4 as possible 4 V cathode materials for lithium batteries. J Electrochem Soc 148:A960–A967

    Article  Google Scholar 

  8. Adam L, Guesdon A, Raveau B (2008) A new lithium manganese phosphate with an original tunnel structure in the A2MP2O7 family. J Solid State Chem 181:3110–3115

    Article  Google Scholar 

  9. Zhou H, Upreti S, Chernova NA et al (2011) Iron and manganese pyrophosphates as cathodes for lithium-ion batteries. Chem Mater 23:293–300

    Article  Google Scholar 

  10. Rasiman MSA, Badrudin FW, Kudin TIT et al (2014) Determination of electronic structure and band gap of Li2MnP2O7 via first-principle study. Integr Ferroelectr 155:71–79

    Article  Google Scholar 

  11. Furuta N, Nishimura S, Barpanda P, Yamada A (2012) Fe3+/Fe2+ redox couple approaching 4 V in Li2–x(Fe1–yMny)P2O7 pyrophosphate cathodes. Chem Mater 24:1055–1061

    Article  Google Scholar 

  12. Tamaru M, Barpanda P, Yamada Y et al (2012) Observation of the highest Mn3+/Mn2+ redox potential of 4.45 V in a Li2MnP2O7 pyrophosphate cathode. J Mater Chem 22:24526–24529

    Article  Google Scholar 

  13. Nishimura S, Nakamura M, Natsui R, Yamada A (2010) New lithium iron pyrophosphate as 3.5 V class cathode material for lithium ion battery. J Am Chem Soc 132:13596–13597

    Article  Google Scholar 

  14. Clark JM, Nishimura S, Yamada A, Islam MS (2012) High-voltage pyrophosphate cathode: insights into local structure and lithium-diffusion pathways. Angew Chem Int Ed 51:13149–13153

    Article  Google Scholar 

  15. Dabas P, Hariharan K (2014) Lithium iron(ii) pyrophosphate as a cathode material: structure and transport studies. RSC Adv 4:14348–14351

    Article  Google Scholar 

  16. Kosova NV, Tsapina AM, Slobodyuk AB, Petrov SA (2015) Structure and electrochemical properties of mixed transition-metal pyrophosphates Li2Fe1−yMnyP2O7 (0 ≤ y≤1). Electrochim Acta 174:1278–1289

    Article  Google Scholar 

  17. Xu J, Chou S-L, Gu Q-F et al (2014) Study on vanadium substitution to iron in Li2FeP2O7 as cathode material for lithium-ion batteries. Electrochim Acta 141:195–202

    Article  Google Scholar 

  18. Mahesh MJ, Gopalakrishna GS, Ashamanjari KG (2007) Thermal, magnetic and impedance properties of Li2M2+P2O7 (M2+=Fe and Ni) single crystals. Mater Sci Semicond Process 10:117–123

    Article  Google Scholar 

  19. Barpanda P, Ye T, Chung S-C et al (2012) Eco-efficient splash combustion synthesis of nanoscale pyrophosphate (Li2FeP2O7) positive-electrode using Fe(iii) precursors. J Mater Chem 22:13455–13549

    Article  Google Scholar 

  20. Tan L, Zhang S, Deng C (2015) Fast lithium intercalation chemistry of the hierarchically porous Li2FeP2O7/C composite prepared by an iron-reduction method. J Power Sources 275:6–13

    Article  Google Scholar 

  21. Hasumi M, Taniguchi I (2014) Synthesis and characterization of Li2MnP2O7/C composite by a combination of spray pyrolsis and wet ball milling followed by annealing. Mater Lett 134:202–205

    Article  Google Scholar 

  22. Taniguchi I, Song D, Wakihara M (2002) Electrochemical properties of LiM1/6Mn11/6O4 (M = Mn Co, Al and Ni) as cathode materials for Li-ion batteries prepared by ultrasonic spray pyrolysis method. J Power Sources 109:333–339

    Article  Google Scholar 

  23. Lee S, Park S (2012) Structure, defect chemistry, and lithium transport pathway of lithium transition metal pyrophosphates (Li2MP2O7, M: Mn, Fe, and Co): atomistic simulation study. Chem Mater 24:3550–3557

    Article  Google Scholar 

  24. Kim J, Lee B, Kim H et al (2016) Redesign of Li2MP2O7 (M = Fe or Mn) by tuning the Li diffusion in rechargeable battery electrodes. Chem Mater 28:6894–6899

    Article  Google Scholar 

  25. Kim H, Lee S, Park Y-U et al (2011) Neutron and X-ray diffraction study of pyrophosphate-based Li2–xMP2O7 (M = Fe, Co) for lithium rechargeable battery electrodes. Chem Mater 23:3930–3937

    Article  Google Scholar 

  26. Molinari R, Poerio T, Argurio P (2005) Polymer assisted ultrafiltration for copper–citric acid chelate removal from wash solutions of contaminated soil. J Appl Electrochem 35:375–380

    Article  Google Scholar 

  27. Blyr A, Sigala C, Amatucci G et al (1998) Self-discharge of LiMn2O4/C li-ion cells in their discharged state. J Electrochem Soc 145:194–209

    Article  Google Scholar 

  28. Oh SM, Oh SW, Yoon CS et al (2010) High-performance carbon-LiMnPO4 nanocomposite cathode for lithium batteries. Adv Funct Mater 20:3260–3265

    Article  Google Scholar 

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Acknowledgements

The authors are grateful to Mr. Ryohei Kikuchi and Dr. Masaru Tada of the Center for Advanced Materials Analysis (Tokyo Institute of Technology, Japan) for the FESEM observation of the samples.

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Correspondence to Izumi Taniguchi.

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Jang, H., Miyasaka, K. & Taniguchi, I. Synthesis and characterization of carbon-modified Li2MnP2O7/C composites prepared by spray pyrolysis. J Mater Sci 53, 9138–9148 (2018). https://doi.org/10.1007/s10853-018-2219-2

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  • DOI: https://doi.org/10.1007/s10853-018-2219-2

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