Combustion synthesis and electrochemical evaluation of Cr-substituted lithium vanadium (III) phosphate

Abstract

In this work, the effect of Cr³⁺ partial substitution on vanadium site in monoclinic lithium vanadium(III) phosphate (LVP) structure resulting in compounds with general formula: Li₃V₂- _x Cr _x (PO₄)₃-C (x = 0, 0.05, 0.1, 0.15) was studied. A two-step sol-gel combustion method was employed in syntheses. The samples were characterized by X-ray powder diffraction, scanning electron microscopy, coupled plasma optical emission spectroscopy, and flash combustion. The electrochemical performance of the active materials was examined through rate capability tests and cyclic voltammetry. The unsubstituted compound LVPC delivers higher capacity compared to the Cr-containing samples due to chromium inactivity in the potential range 3.0–4.4 V vs. Li/Li⁺. However, the Cr-substituted materials show better overall capacity retention (97–97.6%) in contrast to Li₃V₂(PO₄)₃-C (96%) in long cycling.

Keywords

Li-ion battery lithium vanadium phosphate positive active material electrochemical performance substitution

Get full access to this article

View all access options for this article.

References

Yin

Grondey

Strobel

et al.

Electrochemical property: Structure relationships in monoclinic Li3-y V2(PO4)3. J Am Chem Soc 2003; 125: 10402–10411.

Huang

Faulkner

Barker

et al.

Lithium metal phosphates, power and automotive applications. J Power Sources 2009; 189: 748–751.

Jiang

Pan

Wang

et al.

Carbon coated Li3V2(PO4)3 cathode material prepared by a PVA assisted sol-gel method. Electrochim Acta 2010; 55: 3864–3869.

Chen

Zhao

et al.

Preparation and electrochemical performance studies on Cr-doped Li3V2(PO4)3 as cathode materials for lithium-ion batteries. Electrochim Acta 2009; 54: 5844–5850.

Yang

Zhang

et al.

Effects of Cr doping on the electrochemical performance of Li3V2(PO4)3 cathode material for lithium ion batteries. Electrochim Acta 2010; 55: 8482–8489.

Kim

Zhang

Wang

et al.

Electrochemical and structural investigation of the mechanism of irreversibility in Li3V2(PO4)3 cathodes. J Phys Chem C 2016; 120: 7005–7012.

Teng

et al.

Hydrothermal synthesis of plate-like carbon-coated Li3V 2(PO4)3 and its low temperature performance for high power lithium ion batteries. Electrochim Acta 2013; 91: 43–49.

Kee

Dimov

Kobayashi

et al.

Structural and electrochemical properties of Fe- and Al-doped Li3V2(PO4)3 for all-solid-state symmetric lithium ion batteries prepared by spray-drying-assisted carbothermal method. Solid State Ionics 2015; 272: 138–143.

Huang

Yang

Liu

et al.

Synthesis and characterization of Li3V(2−2x/3)Mgx(PO4)3/C cathode material for lithium-ion batteries. J Power Sources 2010; 195: 5013–5018.

10.

Deng

Zhang

Yang

et al.

Effect of Ti and Mg codoping on the electrochemical performance of Li3V2(PO4)3 cathode material for lithium ion batteries. Mater Chem Phys 2011; 128: 470–474.

11.

Jiang

et al.

Y-doped Li3V2(PO4)3/C as cathode material for lithium-ion batteries. J Appl Electrochem 2016; 46: 279–287.

12.

Yang

Zhang

et al.

Effects of Cr doping on the electrochemical properties of Li3V2(PO4)3 cathode material for lithium-ion batteries. Electrochim Acta 2010; 55: 8482–8489.

13.

Zhu X, Yan Z, Wu W, et al. Manipulating size of Li3V2(PO4)3 with reduced graphene oxide: Towards high-performance composite cathode for lithium ion batteries. In: APEnergy2014, 2014, pp.1–7.

14.

Genkina

Maksimov

Sigarev

et al.

X-ray structural investigation of the orthorhombic modification of Li3Cr2(PO4)3 at 293, 473, 573 K. Sov Phys Crystallogr 1991; 36: 352–354.

15.

Zhang

Xiang

et al.

Porous Li3V2(PO4)3/C cathode with extremely high-rate capacity prepared by a sol-gel-combustion method for fast charging and discharging. J Power Sources 2012; 203: 121–125.

16.

Patoux

Wurm

Morcrette

et al.

A comparative structural and electrochemical study of monoclinic Li3Fe2(PO4)3 and Li3V2(PO4)3. J Power Sources 2003; 119–121: 278–284.

17.

Shannon

. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A 1976; 32: 751–767.

18.

Kang

Mathew

Gim

et al.

Pyro-synthesis of a high rate nano-Li3V2(PO4)3/C cathode with mixed morphology for advanced Li-ion batteries. Sci Rep 2015; 4: 4047–4047.

19.

Sun

H-B

Zhang

L-L

Yang

X-L

et al.

Investigation of Co-incorporated pristine and Fe-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries. Dalt Trans 2016; 45: 15317–15325.

20.

Qiao

Wang

et al.

Synthesis and improved electrochemical performances of porous Li3V2(PO4)3/C spheres as cathode material for lithium-ion batteries. 2011. 196: 7715–7720.

21.

Wang

Liu

Yang

. An integrated core-shell structured Li3V2(PO4)3@C cathode material of LIBs prepared by a momentary freeze-drying method. J Mater Chem 2012; 22: 5281–5285.

22.

Herklotz

Scheiba

Glaum

et al.

Electrochemical oxidation of trivalent chromium in a phosphate matrix: Li3Cr2(PO4)3 as cathode material for lithium ion batteries. Electrochim Acta 2014; 139: 356–364.