Influence of Mn2+ and Fe2+ doping in LiNi0.8M0.2PO4·3H2O on H-bond strength in crystalline hydrates and thermal transformation mechanism

  • Saifon Kullyakool
  • Pittayagorn NoisongEmail author
  • Sira Sansuk
  • Chittima Laohpongspaisan
  • Chomsri Siriwong


The LiNi0.8M0.2PO4·3H2O (M = Mn2+, Fe2+) were successfully synthesized with a simple co-precipitation route to obtain the lithium binary transition metal phosphate hydrates, in which the corresponding calcined products can be used as cathode materials in Li-ion batteries. The hydrates and their calcined products were characterized using FTIR/FT Raman spectrophotometer, atomic absorption/atomic emission spectrophotometer, X-ray powder diffraction and TG/DTG/DTA. The morphologies of the synthesized compounds were investigated by using scanning electron microscope technique and found to be the thick-plate particles, which were changed to small-bead particles after the thermal treatment. The influence of the transition metal doping on the strength of hydrogen bonding in the structure of the studied compounds was investigated by using the FTIR and TG/DTG/DTA techniques. Moreover, the decomposition mechanism and vibrational properties of the products were studied and it was found that the H-bond strength and transformation mechanisms of three studied hydrates, namely LiNiPO4·3H2O, LiNi0.8Mn0.2PO4·3H2O and LiNi0.8Fe0.2PO4·3H2O, were significantly different. In addition, based on the results from both vibrational and kinetic properties, the strength of H-bonding of the title compounds was obtained in order of magnitude as LiNiPO4·3H2O > LiNi0.8Fe0.2PO4·3H2O > LiNi0.8Mn0.2PO4·3H2O.


Hydrogen bond Kinetic study Ni0.8M0.2PO4·3H2Transformation mechanism Vibrational spectroscopy 



We thank the Department of Chemistry, Faculty of Science, Khon Kaen University, for providing research facilities. The financial support from the Center of Excellence for Innovation in Chemistry (PERCH-CIC) and Materials Chemistry Research Center, Department of Chemistry, Faculty of Science, Khon Kaen University, is gratefully acknowledged.

Supplementary material

10973_2019_8665_MOESM1_ESM.docx (1.6 mb)
Supplementary material 1 (DOCX 1598 kb)


  1. 1.
    Szafran ZD, Komasa A, Olejniczak A, Katrusiak A, Szafran M. Spectroscopic and theoretical studies of the H-bonded complex of quinuclidine with 2,6-dichloro-4-nitrophenol. Vib Spectrosc. 2017;93:29–35.CrossRefGoogle Scholar
  2. 2.
    Furer VL, Vandyukov AE, Zaripov SR, Solovieva SE, Antipin IS, Kovalenko VI. FT-IR and FT-Raman study of hydrogen bonding in p-alkylcalix[8] arenes. Vib Spectrosc. 2018;95:38–43.CrossRefGoogle Scholar
  3. 3.
    Bogdanovic DB, Popa A, Markovic SU, Antunovic IH. Vibrational study of interaction between 12-tungstophosphoric acid and microporous/mesoporous supports. Vib Spectrosc. 2017;92:151–61.CrossRefGoogle Scholar
  4. 4.
    Rathod V, Anupama AV, Kumar RV, Jali VM, Sahoo B. Correlated vibrations of the tetrahedral and octahedral complexes and splitting of the absorption bands in FTIR spectra of Li–Zn ferrites. Vib Spectrosc. 2017;92:267–72.CrossRefGoogle Scholar
  5. 5.
    Osorio-Gullén JM, Hilm B, Ahuja R, Johnansson B. A theoretical study of olivine LiMPO4 cathodes. Solid State Ion. 2004;167:221–7.CrossRefGoogle Scholar
  6. 6.
    Bezza I, Kaus M, Heinzmann R, Yavuz M, Knapp M, Mangold S, Doyle S, Grey CP, Ehrenberg H, Indris S, Saadoune I. Mechanism of the delithiation/lithiation process in LiFe0.4Mn0.6PO4: in situ and ex situ investigations on long-range and local structures. Phys Chem C. 2015;119:9016–24.CrossRefGoogle Scholar
  7. 7.
    Perea A, Castro L, Aldon L, Stievano L, Dedryvère R, Gonbeau D, Tran N, Nuspl G, Bréger J, Tessier C. Study of C-coated LiFe0.33Mn0.67PO4 as positive electrode material for Li-ion batteries. J Solid State Chem. 2012;192:201–9.CrossRefGoogle Scholar
  8. 8.
    Manthiram A, Goodenough JB. Lithium insertion into Fe2(MO4)3 frameworks: comparison of M = W with M = Mo. J Solid State Chem. 1987;71(2):349–60.CrossRefGoogle Scholar
  9. 9.
    Ma F, Shang X, He P, Zhang X, Wang P, Zhou H. Synthesis of hierarchical and bridging carbon-coated LiMn0.9Fe0.1PO4 nanostructure as cathode material with improved performance for lithium ion battery. J Power Sources. 2017;359:408–14.CrossRefGoogle Scholar
  10. 10.
    Fisher CAJ, Prieto VMH, Islam MS. Lithium battery materials LiMPO4 (M = Mn, Fe, Co, and Ni): insights into defect association, transport mechanisms, and doping behavior. Chem Mater. 2008;20:5907–15.CrossRefGoogle Scholar
  11. 11.
    Prabu M, Selvasekarapandian S, Kulkkarni AR, Karthikeyan S, Sanjeeviraja C. Influence of europium doping on conductivity of LiNiPO4. Trans Nonferrous Metals Soc China. 2012;22:342–7.CrossRefGoogle Scholar
  12. 12.
    Zhou F, Cococcioni M, Kang K, Ceder G. The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M = Fe, Mn, Co, Ni. Electrochem Commun. 2004;6:1144–8.CrossRefGoogle Scholar
  13. 13.
    Wolfenstine J, Allen J. Ni3+/Ni2+ redox potential in LiNiPO4. J Power Sources. 2005;142:389–90.CrossRefGoogle Scholar
  14. 14.
    Yang L, Jiao LF, Miao YL, Yuan HT. Synthesis and characterization of LiFe0.99Mn0.01(PO4)2.99/3F0.01/C as a cathode material for lithium-ion battery. J Solid State Electrochem. 2009;14(6):1432–48.Google Scholar
  15. 15.
    Pouretedal HR, Damiri S, Nosrati P, Ghaemi EF. The kinetic of mass loss of grades A and B of melted TNT by isothermal and non-isothermal gravimetric methods. Defin Technol. 2018;14:126–31.CrossRefGoogle Scholar
  16. 16.
    Zhou T, Liu T, Zhang Z, Zhang G, Wang F, Wang X, Liu S, Zhang H, Wang S, Ma J. Investigation on catalytic properties of Au nanorods with different aspect ratios by kinetic and thermodynamic analysis. J Solid State Chem. 2018;263:11–7.CrossRefGoogle Scholar
  17. 17.
    Milicevic B, Marinovic-Cincovic M, Dramicanin MD. Non-isothermal crystallization kinetics of Y2Ti2O7. Powder Technol. 2017;310:67–73.CrossRefGoogle Scholar
  18. 18.
    Zdravkovic JD, Radovanovic L, Poleti D, Rogan JR, Volic PJ, Radovanovic Z, Minic DM. Mechanism and degradation kinetics of zinc complex containing isophthalato and 2,2′-dipyridylamine ligands under different atmospheres. Solid State Sci. 2018;80:123–31.CrossRefGoogle Scholar
  19. 19.
    Kullyakool S, Siriwong K, Noisong P, Danvirutai C. Studies of thermal decomposition kinetics and temperature dependence of thermodynamic functions of the new precursor LiNiPO4·3H2O for the synthesis of olivine LiNiPO4. J Therm Anal Calorim. 2015;122:665–77.CrossRefGoogle Scholar
  20. 20.
    Kullyakool S, Siriwong K, Noisong P, Danvirutai C. Kinetic triplet evaluation of a complicated dehydration of Co3(PO4)2·8H2O using the deconvolution and the simplified master plots combined with nonlinear regression. J Therm Anal Calorim. 2017;127:1963–74.CrossRefGoogle Scholar
  21. 21.
    Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.CrossRefGoogle Scholar
  22. 22.
    Flynn JH, Wall LA. General treatment of the thermogravimetry of polymers. J Res Natl Bur Stand Sect A. 1966;70A(6):487–523.CrossRefGoogle Scholar
  23. 23.
    Kullyakool S, Siriwong K, Noisong P, Danvirutai C. Determination of kinetic triplet of the synthesized Ni3(PO4)2·8H2O by non-isothermal and isothermal kinetic methods. J Therm Anal Calorim. 2014;115:1497–507.CrossRefGoogle Scholar
  24. 24.
    Noisong P, Danvirutai C. Kinetics and mechanism of thermal dehydration of KMnPO4·H2O in a nitrogen atmosphere. Ind Eng Chem Res. 2010;49:3146–51.CrossRefGoogle Scholar
  25. 25.
    Vlaev L, Nedelchev N, Gyurova K, Zagorcheva M. A comparative study of non-isothermal kinetics of decomposition of calcium oxalate monohydrate. J Anal Appl Pyrol. 2008;81(2):253–62.CrossRefGoogle Scholar
  26. 26.
    Vyazovkin S, Burnham AK, José MC, Pérez-Maqueda LA, Popescu C, Sbirrazzuoli N. ICTAC Kinetics committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520:1–19.CrossRefGoogle Scholar
  27. 27.
    Senum GI, Yang RT. Rational approximations of the integral of the Arrhenius function. J Therm Anal Calorim. 1977;11:445–7.CrossRefGoogle Scholar
  28. 28.
    Gotor FJ, Criado MJ, Malek J, Koga N. Kinetic analysis of solid-state reactions: the universality of master plots for analyzing isothermal and nonisothermal experiments. J Phys Chem A. 2000;104:10777–82.CrossRefGoogle Scholar
  29. 29.
    Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A. 1976;32:751–67.CrossRefGoogle Scholar
  30. 30.
    Suekkhayad A, Noisong P, Danvirutai C. Synthesis and isoconversional kinetic study of the formation of LiNiPO4 from Ni3(PO4)2·8H2O as a new precursor. J Therm Anal Calorim. 2018;134:1545–56.CrossRefGoogle Scholar
  31. 31.
    Khawam A, Flanagan D. Solid-state kinetic models: basics and mathematical fundamentals. J Phys Chem. 2006;110:17315–28.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  • Saifon Kullyakool
    • 1
  • Pittayagorn Noisong
    • 1
    • 2
    Email author
  • Sira Sansuk
    • 1
  • Chittima Laohpongspaisan
    • 1
  • Chomsri Siriwong
    • 1
    • 2
  1. 1.Department of Chemistry, Material Chemistry Research Center, Faculty of ScienceKhon Kaen UniversityKhon KaenThailand
  2. 2.Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of ScienceKhon Kaen UniversityKhon KaenThailand

Personalised recommendations