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Direct relations between ion diffusion constants and ionic conductivity for lithium electrolyte solutions

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Abstract Lithium cation and anion diffusion constants ( D Li and D Anion ) are plotted versus ionic conductivity (σ) (σ– D relation) for lithium organic electrolyte solutions which are… Click to show full abstract

Abstract Lithium cation and anion diffusion constants ( D Li and D Anion ) are plotted versus ionic conductivity (σ) (σ– D relation) for lithium organic electrolyte solutions which are important to investigate Li secondary batteries. Lithium salts studied are LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 (LiTFSA), LiN(SO 2 C 2 F 5 ) 2 (LiBETI) , LiC 4 BO 8 (LiBOB), LiSO 3 CF 3 and Li 2 B 12 F 12 . Main organic solvents are propylene carbonate (PC), ethylene carbonate (EC), γ-butyrolactone (GBL), diethyl carbonate (DEC), four glymes and polyethylene glycol (PEG) dimethyl ethers of average molecular weights of 400 and 1,000. Mixing effects of two solvents are shown for EC-DEC-LiPF 6 systems. In total, about 20 organic electrolyte solutions were studied. In addition, for six binary ionic liquid systems, σ– D relations are plotted. Values for the degree of apparent ion dissociation (α) were calculated from the D Li , D Anion and σ using the Nernst-Einstein (NE) relation and are plotted against σ (σ–α relation). The number of charge-carrying ions ( N carrier ) was estimated from the α and salt concentration, and plotted versus σ (σ- N carrier relation). To estimate the velocity of ions, the σ– D solvent relations are plotted. Also, the apparent lithium transference number ( t Li ) obtained simply from the D Li and D anion values are plotted versus σ (σ − t Li relation). While we have already reported all the data in our previous papers, we did not plot directly the ion diffusion constants and other parameters versus ionic conductivity. In this paper, the importance of the direct relations of σ– D , σ–α, and σ- N carrier is demonstrated to understand functions of lithium electrolyte solutions. The numerical data are freely available in Supplementary Information (SI), covering broad aspects of the fundamental and practical lithium electrolyte solution systems. We believe that they will contribute to the research and development for next generation Li battery systems.

Keywords: ionic conductivity; lithium electrolyte; electrolyte solutions; lithium; diffusion constants

Journal Title: Electrochimica Acta
Year Published: 2017

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