Title: X-ray absorption spectroscopy of LiBF ₄ in propylene carbonate. A model lithium ion battery electrolyte

Abstract

Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF₄ in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li⁺ ion in this model electrolyte. By generating linear combinations of the computed spectra of Li⁺-associating and free PC molecules and comparing to the experimental spectrum, we find a Li⁺–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.

Authors:

Smith, Jacob W. ^[1]; Lam, Royce K. ^[1]; Sheardy, Alex T. ^[1]; Shih, Orion ^[2]; Rizzuto, Anthony M. ^[2]; Borodin, Oleg ^[3]; Harris, Stephen J. ^[4]; Prendergast, David ^[4]; Saykally, Richard J. ^[1]

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+ Show Author Affiliations

1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
2. Univ. of California, Berkeley, CA (United States)
3. U.S. Army Research Lab., Adelphi, MD (United States)
4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:

Wed Aug 20 00:00:00 EDT 2014

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1214423

Grant/Contract Number:  

AC02-05CH11231

Resource Type:

Journal Article: Accepted Manuscript

Journal Name:

Physical Chemistry Chemical Physics. PCCP

Additional Journal Information:

Journal Volume: 16; Journal Issue: 43; Journal ID: ISSN 1463-9076

Publisher:

Royal Society of Chemistry

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY