Mechanism of ion conduction and dynamics in tris(N,N-dimethylformamide) perchloratosodium solid electrolytes

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dc.contributor.author Prakash, Prabhat
dc.contributor.author Shylendran, Ardhra
dc.contributor.author Fall, Birane
dc.contributor.author Zdilla, Michael J.
dc.contributor.author Wunder, Stephanie L.
dc.contributor.author Venkatnathan, Arun
dc.coverage.spatial United States of America
dc.date.accessioned 2012-09-20T03:32:51Z
dc.date.available 2012-09-20T03:32:51Z
dc.date.issued 2022-03
dc.identifier.citation Prakash, Prabhat; Shylendran, Ardhra; Fall, Birane; Zdilla, Michael J.; Wunder, Stephanie L. and Venkatnathan, Arun, “Mechanism of ion conduction and dynamics in tris(N,N-dimethylformamide) perchloratosodium solid electrolytes”, The Journal of Physical Chemistry C, DOI: 10.1021/acs.jpcc.1c09005, vol. 126, no. 10, pp. 4744-4750, Mar. 2022. en_US
dc.identifier.issn 1932-7447
dc.identifier.issn 1932-7455
dc.identifier.uri http://dx.doi.org/10.1021/acs.jpcc.1c09005
dc.identifier.uri https://repository.iitgn.ac.in/handle/123456789/7585
dc.description.abstract (DMF)3NaClO4 is a soft-solid cocrystalline electrolyte with channels of Na+ ions, which can be reversibly converted to a less conductive form (DMF)2NaClO4 by the application of pressure or heat, leading to a melt- or press-castable electrolyte. Molecular dynamics simulations performed on the 3:1 stoichiometry suggest that Na+ ions conduct via a one-dimensional channel, which is supported by van-Hove autocorrelation function analysis. The simulations show that the transference number for Na+ ions is 0.43 at room temperature and exceeds 0.5 at higher temperatures in the molten mixture. The calculated activation energy for the diffusion of Na+ ions from MD simulations is 45 kJ mol-1. The minimum-energy path of Na+ ion migration in a 3:1 crystal is assessed using periodic density functional theory calculations, which provides a barrier of 33 kJ mol-1 for Na+ ion conduction, in reasonable agreement with the experimental value of 25 kJ mol-1. The motion of Na+ ions during conduction is vacancy-driven because the presence of a vacancy site enables jump events for Na+ ions. The activation energy is the penalty for a sodium ion to leave the octahedrally coordinated DMF ligand field via a transition state where only three molecules of DMF form a 3-O-Na trigonal planar geometry, with no involvement of ClO4- in the coordination sphere of the transition state. In contrast, the calculated activation energy barrier for the 2:1 stoichiometry is higher (Ea,DFT = 43 kJ mol-1, Ea,exp = 49 kJ mol-1) due at least in part to the partial coordination of strongly binding perchlorate anions with Na+ ions in the transition state.
dc.description.statementofresponsibility by Prabhat Prakash, Ardhra Shylendran, Birane Fall, Michael J. Zdilla, Stephanie L. Wunder and Arun Venkatnathan
dc.format.extent vol. 126, no. 10, pp. 4744-4750
dc.language.iso en_US en_US
dc.publisher American Chemical Society en_US
dc.subject Cocrystalline electrolyte en_US
dc.subject Ion conduction en_US
dc.subject Perchloratosodium solid electrolytes en_US
dc.subject DMF ligand en_US
dc.subject Van-Hove autocorrelation en_US
dc.title Mechanism of ion conduction and dynamics in tris(N,N-dimethylformamide) perchloratosodium solid electrolytes en_US
dc.type Article en_US
dc.relation.journal Journal of Physical Chemistry C


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