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Published February 23, 2015 | Published + Supplemental Material
Journal Article Open

Thermal relaxation of lithium dendrites


The average lengths λ^- of lithium dendrites produced by charging symmetric Li^0 batteries at various temperatures are matched by Monte Carlo computations dealing both with Li^+ transport in the electrolyte and thermal relaxation of Li0 electrodeposits. We found that experimental λ^-(T) variations cannot be solely accounted by the temperature dependence of Li^+ mobility in the solvent but require the involvement of competitive Li-atom transport from metastable dendrite tips to smoother domains over ΔE^(‡)_R ~ 20 kJ mol^−1 barriers. A transition state theory analysis of Li-atom diffusion in solids yields a negative entropy of activation for the relaxation process: ΔS^(‡)_R ≈ −46 J mol^−1 K^−1 that is consistent with the transformation of amorphous into crystalline Li0 electrodeposits. Significantly, our ΔE^(‡)R ~ 20 kJ mol^−1 value compares favorably with the activation barriers recently derived from DFT calculations for self-diffusion on Li^0(001) and (111) crystal surfaces. Our findings suggest a key role for the mobility of interfacial Li-atoms in determining the morphology of dendrites at temperatures above the onset of surface reconstruction: TSR ≈ 0.65 T_MB (T_MB = 453 K: the melting point of bulk Li^0).

Additional Information

© 2015 Royal Society of Chemistry. Received 11 Dec 2014; Accepted 20 Feb 2015; First published online 23 Feb 2015. Authors gratefully acknowledge support from the Bill and Melinda Gates Foundation Grant No. OPP1069500 on environmental sustainability and, in part, from Bosch Energy Research Network Grant No. 13.01.CC11.

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