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Thermal relaxation of lithium dendrites

Aryanfar, Asghar and Brooks, Daniel J. and Colussi, Agustín J. and Merinov, Boris V. and Goddard, William A., III and Hoffmann, Michael R. (2015) Thermal relaxation of lithium dendrites. Physical Chemistry Chemical Physics, 17 (12). pp. 8000-8005. ISSN 1463-9076. https://resolver.caltech.edu/CaltechAUTHORS:20150304-095911991

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Abstract

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).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c4cp05786dDOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2015/CP/C4CP05786DPublisherArticle
http://www.rsc.org/suppdata/cp/c4/c4cp05786d/c4cp05786d1.pdfPublisherSupplementary Information
ORCID:
AuthorORCID
Aryanfar, Asghar0000-0002-8890-077X
Colussi, Agustín J.0000-0002-3400-4101
Merinov, Boris V.0000-0002-2783-4262
Goddard, William A., III0000-0003-0097-5716
Hoffmann, Michael R.0000-0001-6495-1946
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.
Funders:
Funding AgencyGrant Number
Bill and Melinda Gates FoundationOPP1069500
Bosch Energy Research Network13.01.CC11
Issue or Number:12
Record Number:CaltechAUTHORS:20150304-095911991
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150304-095911991
Official Citation:Aryanfar, A., Brooks, D. J., Colussi, A. J., Merinov, B. V., Goddard Iii, W. A., & Hoffmann, M. R. (2015). Thermal relaxation of lithium dendrites. [10.1039/C4CP05786D]. Physical Chemistry Chemical Physics, 17(12), 8000-8005. doi: 10.1039/c4cp05786d
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55505
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:04 Mar 2015 20:45
Last Modified:03 Mar 2020 13:01

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