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Corresponding Author

Ding-guo XIA(dgxia@pku.edu.cn);
Zi-yu WU

Abstract

Despite there are many successful reports about the preparation of electrode materials with surface coating for lithium ion batteries, the study in surface self-coating of cathode materials using segregation of doping elements and their electrochemical properties is still very rare. The LiFePO4 particles with rich-Al on the surface were synthesized by one step solvothermal route. TEM results demonstrated that the surface of the obtained LiFePO4 particles was well-covered by the amorphous coating. The soft X-ray absorption spectroscopy (XAS) and Auger electron spectroscopy (AES) component analyses revealed that the amorphous coating was composed of LiFe1-xAlxPO4 by part of Al substitution to Fe. The LiFePO4 material with surface rich-Al showed good electrochemical rate capacity and low temperature performance. This could be attributed to the changes of the bulk and surface electron structures which promote the bulk electron and surface ionic conductivities.

Graphical Abstract

Keywords

LiFePO4, surface coating, electrochemical performances

Publication Date

2013-12-28

Online Available Date

2013-12-23

Revised Date

2013-05-24

Received Date

2013-05-06

References

[1] Weinstock I B. Recent advances in the US Department of Energy's energy storage technology research and development programs for hybrid electric and electric vehicles[J]. Journal of Power Sources, 2002, 110(2): 471-474.

[2] Vincent C A. Lithium batteries: A 50-year perspective, 1959-2009[J]. Solid State Ionics, 2000, 134(1/2): 159-167.

[3] Nishi Y. Lithium ion secondary batteries; past 10 years and the future[J]. Journal of Power Sources, 2001, 100(1/2): 101-106.

[4] Zhang Y, Wu X B, Feng H, et al. Effect of nanosized Mg0.8Cu0.20O on electrochemical properties of Li/S rechargeable batteries[J]. International Journal of Hydrogen Energy, 2009, 34(3): 1556-1559.

[5] Padhi A K, Nanjundaswamy K S, Goodenough J B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J]. Journal of the Electrochemical Society, 1997, 144(4): 1188-1194.

[6] Striebel K, Shim J, Srinivasan V, et al. Comparison of LiFePO4 from different sources[J]. Journal of the Electrochemical Society, 2005, 152(4): A664-A670.

[7] Prosini P P, Lisi M, Zane D, et al. Determination of the chemical diffusion coefficient of lithium in LiFePO4[J]. Solid State Ionics, 2002, 148(1/2): 45-51.

[8] Dell’Era A, Pasquali M. Comparison between different ways to determine diffusion coefficient and by solving Fick's equation for spherical coordinates[J]. Journal of Solid State Electrochemistry, 2009, 13(6): 849-859.

[9] Yin Y H, Gao M X. High-rate capability of LiFePO4 cathode materials containing Fe2P and trace carbon[J]. Journal of Power Sources, 2012, 199: 256-262.

[10] Doherty C M, Caryso R A. Colloidal crystal templating to produce hierarchically porous LiFePO4 electrode materials for high power lithium ion batteries[J]. Chemistry Materials, 2009, 21(13): 2895-2903.

[11] Zou H L, Zhang G H, Shen P K. Intermittent microwave heating synthesized high performance spherical LiFePO4/C for Li-ion batteries[J]. Materials Research Bulletin, 2010, 45(2): 149-152.

[12] Kim D H, Kim J. Synthesis of LiFePO4 nanoparticles in polyol medium and their electrochemical properties[J]. Electrochemical and Solid-State Letters, 2006, 9(9): A439-A442.

[13] Meethong N. Size-dependent lithium miscibility gap in nanoscale Li1-xFePO4[J]. Electrochemical and Solid-State Letters, 2001, 10(5): A174-A178.

[14] Chen Z H, Dahn J R. Reducing carbon in LiFePO4/C composite electrodes to maximize specific energy, volumetric energy, and tap density[J]. Journal of the Electrochemical Society, 2002, 149(9): A1184-A1189.

[15] Yamada A, Chung S C, Hinokurna K. Optimized LiFePO4 for lithium battery cathodes[J]. Journal of the Electrochemical Society, 2001, 148(3): A224-A229.

[16] Ni J F, Morishita M, Kawabe Y, et al. Hydrothermal preparation of LiFePO4 nanocrystals mediated by organic acid[J]. Journal of Power Sources, 2010, 195(9): 2877-2882.

[17] Choi D, Kumta P N. Surfactant based sol-gel approach to nanostructured LiFePO4 for high rate Li-ion batteries[J]. Journal of Power Sources, 2007, 163(2): 1064-1069.

[18] Konarova M, Taniguchi I. Synthesis of carbon-coated LiFePO4 nanoparticles with high rate performance in lithium secondary batteries[J]. Journal of Power Sources, 2010, 195(11): 3661-3667.

[19] Zhou W J, He W, Li Z M, et al. Biosynthesis and electrochemical characteristics of LiFePO4/C by microwave processing[J]. Journal of Solid State Electrochemistry, 2009, 13(12): 1819-1823.

[20] Chevrier F, Brochier R, Richter C. Reactivity and magnetism of Fe/In As(100) interfaces[J]. The European Physical Journal B, 2002, 28(3): 305-313.

[21] Zheng S, Hayakawa S, Gohshi Y. An experimental comparison of the total-electron-yield and conversion-electron-yield modes for near-surface characterization using X-ray excitation[J]. Journal of electron spectroscopy and related phenomena, 1997, 87(1): 81-89.

[22] Ankudinov A L, Ravel B, Rehr J J, et al. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure[J]. Physical Review B, 1998, 58(12): 7565-757.

[23] Lee P A, Pendry J B. Theory of extended X-ray absorption fine-structure[J]. Physical Review B, 1975, 11(8): 2795-2811.

[24] Natoli C R, Benfatto M, Brouder C, et al. Multichannel multiple-scattering theory with general potentials[J]. Physical Review B, 1990, 42(4): 1944-1968.

[25] Ou X Q, Pan L, Gu H C, et al. Temperature-dependent crystallinity and morphology of LiFePO4 prepared by hydrothermal synthesis[J]. Journal of Materials Chemistry, 2012, 22(18): 9064-9068.

[26] Azib T, Ammar S, Nowak S. Crystallinity of nano C-LiFePO4 prepared by the polyol process[J]. Journal of Power Sources, 2012, 217: 220-228.

[27] Sun C, Rajasekhara S, Goodenough J B, et al. Monodisperse porous LiFePO4 microspheres for a high power Li-ion battery cathode[J]. Journal of the American Chemical Society, 2011, 133(7): 2132-2135.

[28] Laffont L, Delacourt C, Gibot P, et al. Study of the LiFePO4/FePO4 two-phase system by high-resolution electron energy loss spectroscopy[J]. Chemistry of Materials, 2006, 18(23): 5520-5529.

[29] Kang B, Ceder G. Battery materials for ultrafast charging and discharging[J]. Nature, 2009, 458(7235): 190-193.

[30] Shang H F, Chu W S, Cheng J, et al. Surface phase composition of nanosized LiFePO4 and their enhanced electrochemical properties[J]. Journal of Materials Chemistry A, 2013, 1(22): 6635-6641.

[31] Abbate M, Pen H, Czyzyk M T, et al. Soft-X-ray absorption-spectroscopy of vanadium-oxides[J]. Journal of Electron Spectroscopy and Related Phenomena, 1993, 62(1/2): 185-195.

[32] Khang H, Michelle D J. First-principles studies of the effects of impurities on the ionic and electronic conduction in LiFePO4[J]. Journal of Power Sources, 2012, 206: 274-281.

[33] Chen H, Wang S Z. Preparation and electrochemical performance of LiFePO4/C composite with carbon core structure[J]. Materials Letters, 2009, 63(20): 1668-1670.

[34] Muxina K, Izumi T. Preparation of carbon coated LiFePO4 by a combination of spray pyrolysis with planetary ball-milling followed by heat treatment and their electrochemical properties[J]. Powder Technology, 2009, 191(1/2): 111-116.

[35] Liao L X, Zuo P J, Ma Y L, et al. Effects of temperature on charge/discharge behaviors of LiFePO4 cathode for Li-ion batteries[J]. Electrochemical Acta, 2012, 60: 269-273.

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