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Research Papers

Effect of Niobium Doping on Electrochemical Properties of Microwave Synthesized Carbon Coated Nanolithium Iron Phosphate for High Rate Underwater Applications

[+] Author and Article Information
A. Srinivas Kumar

Naval Science and Technological Laboratory,
Vigyan Nagar,
Visakhapatnam 530027, India
e-mail: adapakaeskay@yahoo.com

T. V. S. L. Satyavani, M. Senthilkumar

Naval Science and Technological Laboratory,
Vigyan Nagar,
Visakhapatnam 530027, India

P. S. V. Subba Rao

Department of Physics,
Andhra University,
Visakhapatnam 530003, India

1Corresponding author.

Manuscript received June 19, 2018; final manuscript received September 4, 2018; published online October 19, 2018. Assoc. Editor: Kevin Huang.

J. Electrochem. En. Conv. Stor. 16(2), 021002 (Oct 19, 2018) (8 pages) Paper No: JEECS-18-1063; doi: 10.1115/1.4041454 History: Received June 19, 2018; Revised September 04, 2018

Lithium iron phosphate (LiFePO4) for lithium-ion batteries is considered as perfect cathode material for various military applications, especially underwater combat vehicles. For deployment at high rate applications, the low conductivity of LiFePO4 needs to be improved. Cationic substitution of niobium in the native carbon coated LiFePO4 is one of the methods to enhance the conductivity. In the present work, how the niobium doped solid solution could be formed is studied. Nanopowders of LiFePO4/C and Li1−xNbxFePO4/C (x = 0.05, 0.1, 0.15, 0.16) are synthesized from precursors using microwave synthesis. The solid solution formation up to (x = 0.15) Li1−xNbxFePO4/C without impurity phases is confirmed by X-ray diffraction (XRD) pattern and Fourier transform infrared spectroscopic (FTIR) results. Particle distribution is obtained by scanning electron microscope from the synthesized powders. Energy dispersive X-ray spectrometer (EDS) results qualitatively confirmed the presence of niobium. Also, direct current (dc) conductivities are measured using sintered pellets and activation energies are calculated using Arrhenius equation. The dependence of conductivity and activation energy of LiFePO4/C on variation of niobium doping is investigated in this study. CR2032 type coin cells are fabricated with the synthesized materials and subjected to cyclic voltammetry studies, rate capability and cycle life studies. Diffusion coefficients are obtained from electrochemical impedance spectroscopy studies. It is observed that room temperature dc conductivity improved by niobium doping when compared to LiFePO4/C (0.379 × 10−2 S/cm) and is maximum for Li0.9Nb0.1FePO4/C (40.58 × 10−2 S/cm). It is also observed that diffusion coefficient of Li+ in Li0.9Nb0.1FePO4/C (13.306 × 10−9 cm2 s−1) improved by two orders of magnitude in comparison with the pure LiFePO4 (10 − 12 cm2 s−1) and carbon-coated nano LiFePO4/C (0.632 × 10−11 cm2 s−1). Cells with Li0.9Nb0.1FePO4/C are able to deliver useful capacity of around 104 mAh/g at 10 C rate. More than 500 cycles are achieved with Li0.9Nb0.1FePO4/C at 20 C rate.

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Figures

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Fig. 1

XRD pattern of Li 1−xNbxFePO4 (x = 0–0.16)

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Fig. 2

Room temperature FTIR spectra of Li1−xNbxFePO4 (x = 0, 0.05, 0.1, 0.15, 0.16)

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Fig. 3

(a) Scanning electron micrograph of LiFePO4/C powder with average particle size 33 nm, (b) scanning electron micrograph of Li0.95Nb0.05FePO4 powder with average particle size 36 nm, (c) scanning electron micrograph of Li0.9Nb 0.1FePO4 powder with average particle size 47 nm, and (d) scanning electron micrograph of Li0.85Nb0.15FePO4 powder with ave. particle size 62 nm

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Fig. 4

(a) Energy dispersive X-ray spectrometer spectrum ofLi0.95Nb0.05FePO4/C (x = 0.05), (b) EDS spectrum of Li0.9Nb0.1FePO4/C (x = 0.1), and (c) EDS spectrum of Li0.85Nb0.15FePO4/C (x = 0.15)

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Fig. 5

Selected area diffraction pattern of transmission electron micrograph for Li0.9Nb0.1FePO4/C

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Fig. 6

Comparison of cyclic voltammograms of Li1−xNbxFePO4

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Fig. 7

EIS plots of the cells containing (a) LiFePO4/C and(b)Li0.95Nb0.05FePO4/C, (c) Li0.9Nb0.1FePO4/C, and (d) Li0.85Nb0.15FePO4/C

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Fig. 8

Equivalent circuit to fit impedance data

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Fig. 9

(a) C/10 to 20 C rate discharge characteristics of LiFePO4/C half cell, (b) C/10 to 20 C rate discharge characteristics of Li0.95Nb0.05FePO4/C half cell, (c) C/10 to 20 C rate discharge characteristics of Li0.9Nb0.1FePO4/C half cell, (d) C/10 to 20 C rate discharge characteristics of Li0.85Nb0.15FePO4/C half cell, and (e) C/10 to 2 C rate discharge characteristics of commercial LiFePO4 half cell

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Fig. 10

Charge-discharge characteristics of Li0.9Nb0.1FePO4/C half cell in 20 C rate for 1–500 number of cycles

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