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• Self-discharge kinetics behavior of Li-Si anode is investigated by theoretical model and experiment. • Effective diffusion coefficients of soluble lithium in porous electrode are determined to verify the availability of model. • Effects of temperature, discharge current and electrode thickness on self-discharge kinetics behavior are discussed. • The three factors are coupled in the form of arrhenius equation by multivariate nonlinear regression. Self-discharge has significant influence on the service life of thermal batteries. The kinetics process of self-discharge depends on both the structure evolution and intrinsic property of electrodes. Herein, the kinetics model to quantify the self-discharge degree of the Li-Si anode is constructed according to the structure of thermal cells. Typical operation and preparation parameters, i.e. temperature, discharge current and electrode thickness, are evaluated based on the specially designed combined-discharge scheme. Then the effective diffusion coefficients (D eff) of soluble lithium (Li0) that are affected by the three variables are calculated and fitted. The calculation results consequently confirm self-discharge process of the Li-Si anode can be described by the derived equations exactly, and then the process is demonstrated to be diffusion-controlled. Further, D eff increase at the higher temperature and larger discharge current, while decrease with the increased electrode thickness, which is analyzed by scanning electron microscope and X-ray microcomputed tomography. The entire effects on D eff can be coupled in one fitting expression based on Arrhenius equation, and the apparent activation energies decrease under the larger discharge current and smaller electrode thickness. Finally, the additional experiments were conducted to verify the accuracy of the fitting expression. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • The combined electrochemical and transport kinetic parameters of CoS 2 /LiCl-LiBr-KBr system at the varied high temperature were systematically studied. • The effects of electrochemical and transport behavior on the impedance characteristic of CoS 2 /LiCl-LiBr-KBr were explored by proposing a equivalent-circuit model. • The results of this research is basis for the design and optimization of the new thermal battery cell. Systematic researches of ionic transport and electrochemical characteristics have been seldom implemented for the porous CoS 2 electrode in ternary LiCl-LiBr-KBr, which are ideal and main form for advanced thermal batteries. In the work, we systematically measured the combined electrochemical and transport kinetic parameters of CoS 2 /LiCl-LiBr-KBr system at the varied high temperature. Specifically, we firstly explored the discharge mechanism of CoS 2 /molten LiCl-LiBr-KBr using galvanostatic discharge experiment and X-ray diffraction (XRD). For the ionic transport performance, the diffusion coefficient of active Li ions was calculated from cyclic voltammograms (CV) data, and the ionic conductivity of LiCl-LiBr-KBr and electric conductivity of CoS 2 and generated Co 9 S 8 were also measured. Then, the interfacial electrochemical characteristics (exchange current density and transfer coefficients) were comparatively studied by the electrochemical impedance spectroscopy (EIS) and linear sweep voltammograms (LSV) method. Based on the above-mentioned results, we further investigated the comprehensive effects of these factors on the electrochemical and transport behavior by proposing a equivalent-circuit model of the porous CoS 2 electrode soaked in LiCl-LiBr-KBr molten salts. The results of this research is basis for the design and optimization of the new thermal battery cell, and will contribute to a knowledge-based development of the advanced TBs in the future. [ABSTRACT FROM AUTHOR]