Hole Polaron Diffusion in the Final Discharge Product of Lithium–Sulfur Batteries

Liu, Zhixiao; Balbuena, Perla B.; Mukherjee, Partha P.

doi:10.1021/acs.jpcc.7b06869

Hole Polaron Diffusion in the Final Discharge Product of Lithium–Sulfur Batteries

Journal Article · Mon Jul 24 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b06869· OSTI ID:1430595

Liu, Zhixiao ^[1]; ^[2]; ^[3]

Texas A & M Univ., College Station, TX (United States). Dept. of Mechanical Engineering; Texas A&M University
Texas A & M Univ., College Station, TX (United States). Dept. of Chemical Engineering
Texas A & M Univ., College Station, TX (United States). Dept. of Mechanical Engineering

Poor electronic conductivity of bulk lithium sulfide (Li₂S) is a critical challenge for the debilitating performance of the lithium–sulfur battery. In this study we focus on investigating the thermodynamic and kinetic properties of native defects in Li₂S based on a first-principles approach. It is found that the hole polaron p⁺ can form in Li₂S by removing a 3p electron from an S²– anion. The p⁺ diffusion barrier is only 90 meV, which is much lower than the Li vacancy (V_Li^–) diffusion barrier. Hence p⁺ has the potential to serve as a charge carrier in the discharge product. Once the vacancy–polaron complex (V_Li^-––2p⁺) forms, the charge transport will be hindered due to the relatively higher diffusion barrier of the complex. Heteroatom dopants, which can decrease the p⁺ formation energy and increase V_Li^– formation energy, are expected to be introduced to the discharge product to improve the electronic conductivity.

View Accepted Manuscript (DOE)

Research Organization:: Texas A & M Univ., College Station, TX (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0006832

OSTI ID:: 1430595

Alternate ID(s):: OSTI ID: 1430631

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 32 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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