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Title: Li 2S Film Formation on Lithium Anode Surface of Li–S batteries

The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms and Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strongmore » chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less
 [1] ;  [2] ;  [3] ;  [1]
  1. Texas A & M Univ., College Station, TX (United States). Department of Mechanical Engineering
  2. Texas A & M Univ., College Station, TX (United States). Department of Materials Science and Engineering
  3. Texas A & M Univ., College Station, TX (United States). Department of Chemical Engineering and Department of Materials Science and Engineering
Publication Date:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 8; Journal Issue: 7; Journal ID: ISSN 1944-8244
American Chemical Society (ACS)
Research Org:
Texas A & M Univ., College Station, TX (United States). Perla B. Balbuena
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Contributing Orgs:
Texas A&M High Performance Computer Facilities, and Texas Advanced Computing Center
Country of Publication:
United States
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; lithium-sulfur battery; Li metal anode; Li2S precipitation; first-principles approach; density functional theory; ab initio molecular dynamics; polysulfide decomposition
OSTI Identifier: