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Evaluation of apparent lithium-ion diffusion coefficients in FePO4/LiFePO4 cathode material particles from linear non-equilibrium thermodynamics and principle of electroneutrality

Lookup NU author(s): Emeritus Professor Keith Scott


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A generalized mathematical model, which describes the process of lithium extraction/insertion in active material particles of insertion cathodes, is developed from linear non-equilibrium thermodynamics and the principle of electroneutrality. The model reveals theoretical relations between the intrinsic and apparent transport parameters of lithium-ions and electrons. Calculation formulas for apparent lithium-ion diffusion coefficient D-1* are deduced from the model. A simple trial calculation is introduced to evaluate the cross-phenomenological coefficient of the Onsager reciprocal relationship.By means of referenced intrinsic diffusion coefficients, calculated by ab initio methods, calculations of D-1* upon charge/discharge for the lithium iron phosphate cathode material (FePO4/LiFePO4) are presented. The calculated values of D-1* are within those previously measured experimentally. In the range of lithium ion contents 0.02 <= x <= 1.0, the values of D-1* during charge/discharge vary in the range 10(-12)-10(-14) cm(2) s(-1) and decrease with increasing x. The mean value of D-1* is about 10(-13) cm(2) s(-1), which is five to six orders of magnitude lower than the intrinsic diffusion coefficients.The calculation results indicate that lithium ion diffusion in the active material particles is coupled with electron conduction, and the co-diffusion of lithium ions and electrons is limited by the electron conduction due to the low intrinsic conductivity of FePO4/LiFePO4. (C) 2016 Elsevier B.V. All rights reserved.

Publication metadata

Author(s): Mao ZY, Sun YP, Scott K

Publication type: Article

Publication status: Published

Journal: Journal of Electroanalytical Chemistry

Year: 2016

Volume: 766

Pages: 107-119

Print publication date: 01/04/2016

Online publication date: 26/01/2016

Acceptance date: 14/01/2016

ISSN (print): 1572-6657

ISSN (electronic): 1873-2569

Publisher: Elsevier BV


DOI: 10.1016/j.jelechem.2016.01.018


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Funder referenceFunder name
20776091NSFC by the China National Natural Science Foundation