Skip to main content
SpringerLink
Log in

Electrochemical and structural study on LiMn0.8Fe0.2PO4 and Mn0.8Fe0.2PO4 battery cathodes: diffusion limited lithium transport

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

Abstract

Electrochemical reactions in the particulate crystal of olivine cathodes topotactically proceed in the lithiated and delithiated phases. Optimized-synthesis conditions for 4 V class LiMn0.8Fe0.2PO4 cathode materials permitted the surface modification and cation-mixing reduction for the resulting powder particles. The discharge capacities of a Li/LiMn0.8Fe0.2PO4 cell in the C–rate range of 0.1C (17.1 mA/g) and 5C (855 mA/g) were of practical values and compatible with those of a Li/LiFePO4 cell. However, since the crystallite size of LiMn0.8Fe0.2PO4 was about 80 nm and almost half as large as LiFePO4, the electrode density of LiMn0.8Fe0.2PO4 was 83 percentage of LiFePO4, meaning the reduction of the volumetric energy density. To examine the necessity of the reduced crystallite size to obtain the excellent gravimetric energy density, the charge–density distributions around the diffusion pathways of Li+ ions for the lithiated and delithiated materials have been investigated, which allows us to discuss the atomic scale diffusivities of Li+ ions.

ᅟ

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

Similar content being viewed by others

References

  1. Armand M, Tarascon JM (2008) Building better batteries. Nature 451:652–657

  2. Andre D, Kim SJ, Lamp P, Lux SF, Maglia F, Paschosa O, Stiaszny B (2015) Future generations of cathode materials: an automotive industry perspective. J Mater Chem A 3:6709–6732

  3. Goodenough JB, Manthiram A (2014) A perspective on electrical energy storage. MRS Communications 4:135–142

  4. Nazri GA, Pistoia G (2003) Lithium batteries: science and technology. Kluwer Academic Publishers, Massachusetts

    Book  Google Scholar 

  5. Scrosati B, Garche J (2010) Lithium batteries: Status, prospects and future. J Power Sources 195:2419–2430

  6. Fergus JW (2010) Recent developments in cathode materials for lithium ion batteries. J Power Sources 195:939–954

  7. Hausbrand R, Cherkashinin G, Ehrenberg H, Gröting M, Albe K, Hess C, Jaegermann W (2015) Fundamental degradation mechanisms of layered oxide Li–ion battery cathode materials: methodology, insights and novel approaches. Mater Sci Eng B 192:3–25

  8. Wang J, Sun X (2012) Understanding and recent development of carbon coating on LiFePO4 cathode materials for lithium–ion batteries. Energy Environ Sci 5:5163–5185

  9. Franco AA (2013) Multiscale modelling and numerical simulation of rechargeable lithium ion batteries: concepts, methods and challenges. RSC Adv 3:13027–13058

  10. Masquelier C, Croguennec L (2013) Polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable Li (or Na) batteries. Chem Rev 113:6552–6591

  11. Li D, Zhou H (2014) Two–phase transition of Li–intercalation compounds in Li–ion batteries. Mater Today 17:451–463

  12. Dominko R, Bele M, Gaberscek M, Remskar M, Hanzel D, Pejovnik S, Jamnik J (2005) Impact of the carbon coating thickness on the electrochemical performance of LiFePO4 / C composites. J Electrochem Soc 152:A607–A610

  13. Chang ZR, Lv HJ, Tang HW, Li HJ, Yuan XZ, Wang H (2009) Synthesis and characterization of high–density LiFePO4 /C composites as cathode materials for lithium–ion batteries. Electrochim Acta 54:4595–4599

  14. Kang B, Ceder G (2009) Battery materials for ultrafast charging and discharging. Nature 458:190–193

  15. Morgan D, Van der Ven A, Ceder G (2004) Li conductivity in LixMPO4 (M = Mn, Fe, Co, Ni ) olivine materials. Electrochem Solid-State Lett 7:A30–A32

  16. Islam MS, Driscoll DJ, Fisher CAJ, Slater PR (2005) Atomic–scale investigation of defects, dopants, and lithium transport in the LiFePO4 olivine–type battery material. Chem Mater 17:5085–5092

  17. Yang J, Tse JS (2011) Li ion diffusion mechanisms in LiFePO4: an ab initio molecular dynamics study. J Phys Chem A 115:13045–13049

  18. Nishimura S, Kobayashi G, Ohoyama K, Kanno R, Yashima M, Yamada A (2008) Experimental visualization of lithium diffusion in LixFePO4. Nat Mater 7:707–711

  19. Tealdi C, Spreafico C, Mustarelli P (2012) Lithium diffusion in Li1-xFePO4: the effect of cationic disorder. J Mater Chem A 22:24870–24876

  20. Adams S (2010) Lithium ion pathways in LiFePO4 and related olivines. J Solid State Electrochem 14:1787–1792

  21. Avdeev M, Sale M, Adams S, Rao RP (2012) Screening of the alkali–metal ion containing materials from the Inorganic Crystal Structure Database (ICSD) for high ionic conductivity pathways using the bond valence method. Solid State Ionics 225:43–46

  22. Malik R, Abdellahi A, Ceder G (2013) A critical review of the Li insertion mechanisms in LiFePO4 electrodes. J Electrochem Soc 160:A3179–A3197

  23. Delmas C, Maccario M, Croguennec L, Le Cras F, Weill F (2008) Lithium deintercalation in LiFePO4 nanoparticles via a domino–cascade model. Nat Mater 7:665–671

  24. Brunetti G, Robert D, Bayle-Guillemaud P, Rouvière JL, Rauch EF, Martin JF, Colin JF, Bertin F, Cayron C (2011) Confirmation of the domino–cascade model by LiFePO4/FePO4 precession electron diffraction. Chem Mater 23:4515–4524

  25. Dreyer W, Jamnik J, Guhlke C, Huth R, Moškon J, Gaberšček M (2010) The thermodynamic origin of hysteresis in insertion batteries. Nat Mater 9:448–453

  26. Malik R, Zhou F, Ceder G (2011) Kinetics of non–equilibrium lithium incorporation in LiFePO4. Nat Mater 10:587–590

  27. Bai P, Cogswell DA, Bazant MZ (2011) Suppression of phase separation in LiFePO4 nanoparticles during battery discharge. Nano Lett 11:4890–4896

  28. Orikasa Y, Maeda T, Koyama Y, Murayama H, Fukuda K, Tanida H, Arai H, Matsubara E, Uchimoto Y, Ogumi Z (2013) Direct observation of a metastable crystal phase of LixFePO4 under electrochemical phase transition. J Am Chem Soc 135:5497–5500

  29. Liu Q, He H, Li ZF, Liu Y, Ren Y, Lu W, Lu J, Stach EA, Xie J (2014) Rate–dependent, Li–ion insertion/deinsertion behavior of LiFePO4 cathodes in commercial 18650 LiFePO4 cells. Appl Mater Interfaces 6:3282–3289

  30. Suo L, Han W, Lu X, Gu L, Hu YS, Li H, Chen D, Chen L, Tsukimoto S, Ikuhara Y (2012) Highly ordered staging structural interface between LiFePO4 and FePO4. Phys Chem Chem Phys 14:5363–5367

  31. Bakenov Z, Taniguchi I (2010) Physical and electrochemical properties of LiMnPO4/C composite cathode prepared with different conductive carbons. J Power Sources 195:7445–7451

  32. Oh SM, Myung ST, Park JB, Scrosati B, Amine K, Sun YK (2012) Double–structured LiMn0.85Fe0.15PO4 coordinated with LiFePO4 for rechargeable lithium batteries. Angew Chem Int Ed 51:1853–1856

  33. Aravindan V, Gnanaraj J, Lee YS, Madhavi S (2013) LiMnPO4 – a next generation cathode material for lithium–ion batteries. J Mater Chem A 1:3518–3539

  34. Yamada A, Kudo Y, Liu KY (2001) Reaction mechanism of the olivine–type Lix ( Mn0.6Fe0.4) PO4 ( 0 ⩽ x ⩽ 1 ). J Electrochem Soc 148:A747–A754

  35. Meethong N, Huang HYS, Speakman SA, Carter WC, Chiang YM (2007) Strain accommodation during phase transformations in olivine–based cathodes as a materials selection criterion for high–power rechargeable batteries. Adv Funct Mater 17:1115–1123

  36. Yashima M (2008) Crystal structures, structural disorders and diffusion paths of ionic conductors from diffraction experiments. Solid State Ionics 179:797–803

  37. Brown ID (2009) Recent developments in the methods and applications of the bond valence model. Chem Rev 109:6858–6919

  38. Filsø MØ, Turner MJ, Gibbs GV, Adams S, Spackman MA, Iversen BB (2013) Visualizing lithium–ion migration pathways in battery materials. Chem Eur J 19:15535–15544

  39. Han J, Zhu J, Li Y, Yu X, Wang S, Wu G, Xie H, Vogel SC, Izumi F, Momma K, Kawamura Y, Huang Y, Goodenough JB, Zhao Y (2012) Experimental visualization of lithium conduction pathways in garnet–type Li7La3Zr2O12. Chem Commun 48:9840–9842

  40. Anurova NA, Blatov VA, Ilyushin GD, Blatova OA, Ivanov-Shits AK, Dem’yanets LN (2009) Analysis of Li+ cation migration paths in oxygen–containing compounds. Russian J Electrochem 45:417–428

  41. Kuroiwa Y, Aoyagi S, Sawada A, Harada J, Nishibori E, Takata M, Sakata M (2011) Evidence for Pb–O covalency in tetragonal PbTiO3. Phys Rev Lett 87:217601

  42. Tanaka H, Takata M, Nishibori E, Kato K, Iishi T, Sakata M (2002) ENIGMA: maximum–entropy method program package for huge systems. J Appl Crystallogr 35:282–286

  43. Nishibori E, Sunaoshi E, Yoshida A, Aoyagi S, Kato K, Takata M, Sakata M (2007) Accurate structure factors and experimental charge densities from synchrotron X–ray powder diffraction data at SPring–8. Acta Cryst A63:43–52

  44. Takata M (2008) The MEM/Rietveld method with nano–applications – accurate charge–density studies of nano–structured materials by synchrotron–radiation powder diffraction. Acta Cryst A64:232–245

  45. Nishibori E, Shibata T, Kobayashi W, Morimoto Y (2015) Bonding nature of LiCoO2 by topological analysis of electron density from X–ray diffraction. Electrochemistry 83:840–842

  46. Mishima Y, Hojo T, Nishio T, Sadamura H, Oyama N, Moriyoshi C, Kuroiwa Y (2013) MEM charge density study of olivine LiMPO4 and MPO4 (M = Mn, Fe) as cathode materials for lithium–ion batteries. J Phys Chem C 117:2608–2615

  47. Mishima Y, Hojo T, Nishio T, Kajiyama A, Moriyoshi C, Kuroiwa Y (2015) Structural and electrochemical properties of 20–micron Li(Co1-xLix)O2-δ (x > 0) agglomerates with layered structures: identification of tetravalent cobalt. J Phys Chem Solids 87:48–52

  48. Mishima Y, Honda S, Sadamura H, Nakayama N, Moriyoshi C, Kuroiwa Y (2011) Characterization of carbon composite LiMn1-xFexPO4 cathodes. IOP Conf Series: Materials Science and Engineering 18:122002

  49. Sakata M, Sato M (1990) Accurate structure analysis by the maximum–entropy method. Acta Cryst A46:263–270

  50. Momma K, Izumi F (2011) VESTA 3 for three–dimensional visualization of crystal, volumetric and morphology data. J Appl Crystallogr 44:1272–1276

  51. Chen J, Vacchio MJ, Wang S, Chernova N, Zavalij PY, Whittingham MS (2008) The hydrothermal synthesis and characterization of olivines and related compounds for electrochemical applications. Solid State Ionics 178:1676–1693

  52. Mishima Y, Nishio T, Hojo T, Sadamura H (2014) Method for producing carbon composite lithium manganese iron phosphate particle powder, carbon composite lithium manganese iron phosphate particle powder, and nonaqueous electrolyte secondary battery using carbon composite lithium manganese iron phosphate particle powder. WO2014034775 A1

  53. Malik R, Burch D, Bazant M, Ceder G (2010) Particle size dependence of the ionic diffusivity. Nano Lett 10:4123–4127

  54. Seo DH, Gwon H, Kim SW, Kim J, Kang K (2010) Multicomponent olivine cathode for lithium rechargeable batteries: a first–principles study. Chem Mater 22:518–523

Download references

Acknowledgments

The authors would like to thank Mr. Takuma Hojo, Mr. Taisei Inoue, and Mr. Takahisa Nishio for their help and support. The Synchrotron XRD experiments were performed at SPring–8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal nos. 2009B0084, 2010A0084, and 2010B0084).

Author information

Authors and Affiliations

  1. R & D Division, Todakogyo Corporation, 1-4 Meijishinkai, Otake, Hiroshima, 739-0652, Japan

    Yuji Mishima

  2. Department of Physical Science, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan

    Chikako Moriyoshi & Yoshihiro Kuroiwa

Authors
  1. Yuji Mishima
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chikako Moriyoshi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yoshihiro Kuroiwa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yuji Mishima.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mishima, Y., Moriyoshi, C. & Kuroiwa, Y. Electrochemical and structural study on LiMn0.8Fe0.2PO4 and Mn0.8Fe0.2PO4 battery cathodes: diffusion limited lithium transport. J Solid State Electrochem 21, 3221–3228 (2017). https://doi.org/10.1007/s10008-017-3636-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-017-3636-x

Keywords

Search

Navigation