Abstract
Single particle microelectrode enables to evaluate the electrochemical responses for single particle of active material without binder and conductive agent. Thus, the influences of additive and electrode structure on the electrochemical performance of active materials can be ignored. Furthermore, this technology can be used to evaluate active materials fast. Therefore, single particle microelectrode allows fast and accurate determination of the intrinsic performance of active material. Cyclic voltammogram (CV), cycle performance, and kinetic behavior of LiFePO4 cathode materials were evaluated by the single particle microelectrode. CV curve of LiFePO4 particle with a pair of oxidation and reduction peaks was obtained with scan rates of 20 mV?s-1, which is 400 times larger than that of composite electrode. Besides, it is found that Li+ diffusion in LiFePO4 particle is the bottleneck of electrochemical process, and the Li+ diffusion coefficient in LiFePO4 particle is about 2.4 ~ 3.2 ? 10-11 cm2?s-1. Excellent cycle performance was also proved to be the intrinsic properties of LiFePO4 cathode materials by single particle microelectrode. Therefore, single particle microelectrode is an effective method for evaluation of active materials for lithium ion batteries.
Graphical Abstract
Keywords
LiFePO4, single particle microelectrode, cyclic voltammograms, Li+ diffusion coefficient
Publication Date
2015-12-23
Online Available Date
2015-08-18
Revised Date
2015-08-04
Received Date
2015-07-14
Recommended Citation
Fu-qing WANG, Yi-min WEI, Yu-zhuan SU, Bing-wei MAO, Kai WU, Feng-gang ZHAO, Chun-lei CHEN, Xing-lu LI, Jin CHONG.
Fast and Accurate Evaluation of LiFePO4 Cathode Materials by Single Particle Microelectrode[J]. Journal of Electrochemistry,
2015
,
21(6): 150714.
DOI: 10.13208/j.electrochem.150714
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol21/iss6/10
References
[1] Xiao L, Lu J T, Liu P F, et al. Proton diffusion determination and dual structure model for nickel hydroxide based on potential step measurements on single spherical beads[J]. The Journal of Physical Chemistry B, 2005, 109(9): 3860-3867.
[2] Liu J(刘军), Yang Y F(杨毅夫), Shao H X(邵慧霞), et al. Studies on electrochemical behavior of LaNi0.7Al0.3 single micro-particle electrode[J]. Chemical Journal of Chinese Universities(高等学校化学学报), 2006, 27(10): 1962-1964.
[3] Uchida I, Fujiyoshi H, Waki S, et al. Microvoltammetric studies on single particles of battery active materials[J]. Journal of Power Sources, 1997, 68(1): 139-144.
[4] Dokko K, Nishizawa M, Horikoshi S, et al. In situ observation of LiNiO2 single-particle fracture during Li-ion extraction and insertion[J]. Electrochemical and Solid-State Letters, 2000, 3(3): 125-127.
[5] Dokko K, Nakata N, Suzuki Y, et al. High-rate lithium deintercalation from lithiated graphite single-particle electrode[J]. The Journal of Physical Chemistry C, 2010, 114(18): 8646-8650.
[6] Zuleta M, Björnbom P, Lundblad P, et al. Effects of pore surface oxidation on electrochemical and mass-transport properties of nanoporous carbon[J]. Journal of The Electrochemical Society, 2005, 152(2): A270-A276.
[7] Nishikawa K, Munakata H, Kanamura K, et al. In-situ observation of one silicon particle during the first charging[J]. Journal of Power Sources, 2013, 243: 630-634.
[8] Churikov A V, Ivanishchev A V, Ivanishcheva I A, et al. Determination of lithium diffusion coefficient in LiFePO4 electrode by galvanostatic and potentiostatic intermittent titration techniques[J]. Electrochimica Acta, 2010, 55(8): 2939-2950.
[9] Zhu Y J, Wang C S. Galvanostatic intermittent titration technique for phase-transformation electrodes[J]. Journal of Physical Chemistry C, 2010, 114(6): 2830-2841.
[10] Wang F Q, Chen J, Tan Z C, et al. Low-temperature electrochemical performances of LiFePO4 cathode materials for lithium ion batteries[J]. Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(4): 1321-1330.
[11] Munakata H, Takemura B, Saito T, et al. Evaluation of real performance of LiFePO4 by using single particle technique[J]. Journal of Power Sources, 2012, 217: 444-448.
[12] Zhao X F, Zhang D, Ren X M, et al. Quasi-random assembled single particle electrode and instinct electrochemical performance of LiFePO4 in wide temperature scope[J]. Journal of Electroanalytical Chemistry, 2014, 712: 113-118.
[13] Huang Y H, Wang F M, Huang T Z, et al. Micro-electrode linked cyclic voltammetry study reveals ultra-fast discharge and high ionic transfer behavior of LiFePO4[J]. International Journal of Electrochemical Science, 2012, 7(2): 1205-1213.
[14] Come J, Tabema P L, Hamelet S, et al. Electrochemical kinetic study of LiFePO4 using cavity microelectrode[J]. Journal of The Electrochemical Society, 2011, 158(10): A1090-A1093.
[15] Nishizawa M, Koshika H, Hashitani R, et al. Ion- and electron-transport properties of a single particle of disordered carbon during the lithium insertion reaction[J]. The Journal of Physical Chemistry B, 1999, 103(24): 4933-4936.
[16] Morgan D, Van der Ven A, Ceder G, et al. Li Conductivity in LixMPO4 (M = Mn, Fe, Co, Ni) olivine materials[J]. Electrochemical and Solid-State Letters, 2004, 7(2): A30-A32.
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