Title: Interfacial Electrochemical Lithiation and Dissolution Mechanisms at a Sulfurized Polyacrylonitrile Cathode Surface

Abstract

Advances in sulfurized-polyacrylonitrile (SPAN)- based cathode materials promise safer and more efficient lithium–sulfur (Li-S) battery performance. To elucidate electrolyte–cathode interfacial electrochemistry and polysulfide (PS) dissolution, we emulate discharge SPAN reactions via ab initio molecular dynamics (AIMD) simulations. Plausible structures and their lithiation profiles are cross-validated via Raman/IR spectroscopy and density functional theory (DFT). Lithium bis(fluorosulfonyl)imide (LiFSI) plays versatile roles in the Li-SPAN cell electrochemistry, primarily as the major source in forming the cathode–electrolyte interphase (CEI), further verified via X-ray photoelectron spectroscopy and AIMD. Besides being a charge carrier and CEI composer, LiFSI mediates the PS generation processes in SPAN electrochemical lithiation. Analysis of AIMD trajectories during progressive lithiation reveals that, compared to carbonates, ether solvents enable stronger solvation and chemical stabilization for both salt and SPAN structures. Differentiated CEI formation and electrochemical lithiation decomposition pathways and products are profoundly associated with the intrinsic nature of lithium bonding with oxygen and sulfur.

Authors:

Kuai, Dacheng ^[1]; Wang, Shen ^[2]; Perez-Beltran, Saul ^[3]; Yu, Sicen ^[2]; Real, Gerard A. ^[3]; Liu, Ping ^[4]; Balbuena, Perla B.  ^[5]

• Search DOE PAGES for author "Balbuena, Perla B."
• Search DOE PAGES for ORCID "0000-0002-2358-3910"

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+ Show Author Affiliations

1. Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States, Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States
2. Department of Nanoengineering, University of California, San Diego, La Jolla, California 92093, United States
3. Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States
4. Department of Nanoengineering, University of California, San Diego, La Jolla, California 92093, United States, Materials Science and Engineering Program, University of California, San Diego, La Jolla, California 92093, United States
5. Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States, Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States, Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843, United States

Publication Date:

Mon Feb 05 00:00:00 EST 2024

Research Org.:

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

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); National Science Foundation (NSF)

OSTI Identifier:

2284025

Alternate Identifier(s):

OSTI ID: 2322413

Grant/Contract Number:  

AC05-76RL01830; EE0007764; PNNL-595241; CHE-1338173

Resource Type:

Published Article

Journal Name:

ACS Energy Letters

Additional Journal Information:

Journal Name: ACS Energy Letters Journal Volume: 9 Journal Issue: 3; Journal ID: ISSN 2380-8195

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrolytes; Lithiation; Solvation; Solvents; Sulfur