Abstract
Carbon-coated and titanium-substituted lithium vanadium phosphate composites have been successfully prepared through a sol-gel method followed by solid-state reaction under argon. Li3V1.9Ti0.1(PO4)3-C (LVT10PC) and Li3V1.85Ti0.15(PO4)3-C (LVT15PC) were investigated using X-ray powder diffraction, thermal analysis, transmission electron microscopy, cyclic voltammetry, and galvanostatic tests. Different models for the solid solution mechanism in this system are discussed. Electrochemical tests, at a charge-discharge rate of 0.2 C, in the range 2.8–4.4 V show that LVT10PC delivers the highest discharge capacity of 121 mA h g−1 and declines to 115.7 mA h g−1 up to the 60th cycle, corresponding to a 4.4 % loss. At low levels, titanium substitution is found to increase initial discharge capacity compared to the carbon-coated unsubstituted system (LVPC). Further substitution is found to have detrimental effects on initial discharge capacity and cycling behaviour.
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Mizushima K, Jones PC, Wiseman PJ, Goodenough JB (1980) LixCoO2 (0 < x ≤1): a new cathode material for batteries of high energy density. Mater Res Bull 15(6):783–789. doi:10.1016/0025-5408(80)90012-4
Padhi AK, Nanjundaswamy KS, Goodenough JB (1997) Phospho‐olivines as positive‐electrode materials for rechargeable lithium batteries. J Electrochem Soc 144(4):1188–1194. doi:10.1149/1.1837571
Barker J, Saidi Y (1999) Lithium-containing phosphates, method of preparation, and use thereof. US Patent 5:871,866
Rui X, Yan Q, Skyllas-Kazacos M, Lim TM (2014) Li3V2(PO4)3 cathode materials for lithium-ion batteries: a review. J Power Sources 258:19–38. doi:10.1016/j.jpowsour.2014.01.126
Bakenov Z, Taniguchi I (2010) Electrochemical performance of nanocomposite LiMnPO4/C cathode materials for lithium batteries. Electrochem Commun 12(1):75–78. doi:10.1016/j.elecom.2009.10.039
Amine K, Yasuda H, Yamachi M (2000) Olivine LiCoPO4 as 4.8 V electrode material for lithium batteries. Electrochem Solid-State Lett 3(4):178–179. doi:10.1149/1.1390994
Wolfenstine J, Allen J (2005) Ni3+/Ni2+ redox potential in LiNiPO4. J Power Sources 142(1–2):389–390. doi:10.1016/j.jpowsour.2004.11.024
Barker J, Gover RKB, Burns P, Bryan A, Saidi MY, Swoyer JL (2005) Structural and electrochemical properties of lithium vanadium fluorophosphate, LiVPO4F. J Power Sources 146(1–2):516–520. doi:10.1016/j.jpowsour.2005.03.126
Morgan D, Van der Ven A, Ceder G (2004) Li conductivity in LixMPO 4 (M = Mn, Fe, Co, Ni) olivine materials. Electrochem Solid-State Lett 7(2):A30–A32. doi:10.1149/1.1633511
Rissouli K, Benkhouja K, Ramos-Barrado JR, Julien C (2003) Electrical conductivity in lithium orthophosphates. Mater Sci Eng B 98(3):185–189. doi:10.1016/S0921-5107(02)00574-3
Wang L, Tang Z, Ma L, Zhang X (2011) High-rate cathode based on Li3V2(PO4)3/C composite material prepared via a glycine-assisted sol–gel method. Electrochem Commun 13(11):1233–1235. doi:10.1016/j.elecom.2011.08.036
Li Y, Hong L, Sun J, Wu F, Chen S (2012) Electrochemical performance of Li3V2(PO4)3/C prepared with a novel carbon source, EDTA. Electrochim Acta 85:110–115. doi:10.1016/j.electacta.2012.08.038
Lan Y, Wang X, Zhang J, Zhang J, Wu Z, Zhang Z (2011) Preparation and characterization of carbon-coated LiFePO4 cathode materials for lithium-ion batteries with resorcinol–formaldehyde polymer as carbon precursor. Powder Technol 212(2):327–331. doi:10.1016/j.powtec.2011.06.005
Saïdi MY, Barker J, Huang H, Swoyer JL, Adamson G (2003) Performance characteristics of lithium vanadium phosphate as a cathode material for lithium-ion batteries. J Power Sources 119–121:266–272. doi:10.1016/S0378-7753(03)00245-3
Tang A, Wang X, Liu Z (2008) Electrochemical behavior of Li3V2(PO4)3/C composite cathode material for lithium-ion batteries. Mater Lett 62(10–11):1646–1648. doi:10.1016/j.matlet.2007.09.064
Li Y-Z, Zhou Z, Ren M-M, Gao X-P, Yan J (2007) Improved electrochemical Li insertion performances of Li3V2(PO4)3/carbon composite materials prepared by a sol–gel route. Mater Lett 61(23–24):4562–4564. doi:10.1016/j.matlet.2007.02.057
Chen Y, Zhao Y, An X, Liu J, Dong Y, Chen L (2009) Preparation and electrochemical performance studies on Cr-doped Li3V2(PO4)3 as cathode materials for lithium-ion batteries. Electrochim Acta 54(24):5844–5850. doi:10.1016/j.electacta.2009.05.041
Yuan W, Yan J, Tang Z, Sha O, Wang J, Mao W, Ma L (2012) Mo-doped Li3V2(PO4)3/C cathode material with high rate capability and long term cyclic stability. Electrochim Acta 72:138–142. doi:10.1016/j.electacta.2012.04.030
Zhong S, Liu L, Jiang J, Li Y, Wang J, Liu J, Li Y (2009) Preparation and electrochemical properties of Y-doped Li3V2(PO4)3 cathode materials for lithium batteries. J Rare Earths 27(1):134–137. doi:10.1016/S1002-0721(08)60207-0
Son JN, Kim SH, Kim MC, Kim GJ, Aravindan V, Lee YG, Lee YS (2013) Superior charge-transfer kinetics of NASICON-type Li3V2(PO4)3 cathodes by multivalent Al3+ and Cl− substitutions. Electrochim Acta 97:210–215. doi:10.1016/j.electacta.2013.02.118
Mateyshina YG, Uvarov NF (2011) Electrochemical behavior of Li3−xM'xV2−yM''y(PO4)3 (M'=K, M'' = Sc, Mg+ Ti)/C composite cathode material for lithium-ion batteries. J Power Sources 196(3):1494–1497. doi:10.1016/j.jpowsour.2010.08.078
Liu S-Q, Li S-C, Huang K-L, Chen Z-H (2007) Effect of doping Ti4+ on the structure and performances of Li3V2(PO4)3. Acta Phys -Chim Sin 23(4):537–542
Larson AC, Von Dreele RB (1987) General structure analysis system (GSAS). Los Alamos National Laboratory
Yin SC, Grondey H, Strobel P, Anne M, Nazar LF (2003) Electrochemical property: structure relationships in monoclinic Li3-yV2(PO4)3. J Am Chem Soc 125(34):10402–10411. doi:10.1021/ja034565h
Loehman RE, Rao CNR, Honig JM (1969) Crystallography and defect chemistry of solid solutions of vanadium and titanium oxides. J Phys Chem 73(6):1781–1784. doi:10.1021/j100726a025
Huang C, Chen D, Huang Y, Guo Y (2013) Sol–gel synthesis of Li3V2(PO4)3 cathode materials with high electrical conductivity. Electrochim Acta 100:1–9. doi:10.1016/j.electacta.2013.03.073
Shannon R (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A 32(5):751–767. doi:10.1107/S0567739476001551
Stankov SM, Momchilov A, Abrahams I, Popov I, Stankulov T, Trifonova A (2014) Synthesis and characterisation of Si and Mg substituted lithium vanadium(III) phosphate. Bulgarian chemical communications
Acknowledgments
This study was supported by Project BG051PO001/3.3-05-0001 “Science and Business” and “Human Resources Development” Operational Programme co-financed by the European Social Fund of the EU and the Bulgarian national budget. We wish to thank Dr R.M. Wilson at Queen Mary University of London for his help in X-ray data collection.
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Stankov, S.M., Abrahams, I., Momchilov, A. et al. Effect of Ti-doping on the electrochemical performance of lithium vanadium(III) phosphate. Ionics 21, 1501–1508 (2015). https://doi.org/10.1007/s11581-014-1325-7
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DOI: https://doi.org/10.1007/s11581-014-1325-7