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

Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; Shih, Orion; Rizzuto, Anthony M.; Borodin, Oleg; Harris, Stephen J.; Prendergast, David; Saykally, Richard J.

doi:10.1039/C4CP03240C

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

Journal Article · Wed Aug 20 00:00:00 EDT 2014 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C4CP03240C· OSTI ID:1214423

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]

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

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1214423

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 16, Issue 43; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 43 works

Citation information provided by
Web of Science

References (50)

The Li-Ion Rechargeable Battery: A Perspective Goodenough, John B.; Park, Kyu-Sung Journal of the American Chemical Society, Vol. 135, Issue 4 https://doi.org/10.1021/ja3091438	journal	January 2013
Challenges for Rechargeable Li Batteries Goodenough, John B.; Kim, Youngsik Chemistry of Materials, Vol. 22, Issue 3, p. 587-603 https://doi.org/10.1021/cm901452z	journal	February 2010
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries Aurbach, Doron Journal of Power Sources, Vol. 89, Issue 2 https://doi.org/10.1016/S0378-7753(00)00431-6	journal	August 2000
Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes Peled, E. Journal of The Electrochemical Society, Vol. 144, Issue 8 https://doi.org/10.1149/1.1837858	journal	January 1997
Solid–Electrolyte Interphase Formation and Electrolyte Reduction at Li-Ion Battery Graphite Anodes: Insights from First-Principles Molecular Dynamics Ganesh, P.; Kent, P. R. C.; Jiang, De-en The Journal of Physical Chemistry C, Vol. 116, Issue 46 https://doi.org/10.1021/jp3086304	journal	November 2012
Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes Leung, Kevin; Budzien, Joanne L. Physical Chemistry Chemical Physics, Vol. 12, Issue 25 https://doi.org/10.1039/b925853a	journal	January 2010
Theoretical Investigations on Oxidative Stability of Solvents and Oxidative Decomposition Mechanism of Ethylene Carbonate for Lithium Ion Battery Use Xing, Lidan; Li, Weishan; Wang, Chaoyang The Journal of Physical Chemistry B, Vol. 113, Issue 52 https://doi.org/10.1021/jp9074064	journal	December 2009
Evolution of Strategies for Modern Rechargeable Batteries Goodenough, John B. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar2002705	journal	June 2012
Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz Hung, Ivan; Zhou, Lina; Pourpoint, Frédérique Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja209600m	journal	January 2012
Direct in situ measurements of Li transport in Li-ion battery negative electrodes Harris, Stephen J.; Timmons, Adam; Baker, Daniel R. Chemical Physics Letters, Vol. 485, Issue 4-6 https://doi.org/10.1016/j.cplett.2009.12.033	journal	January 2010
Molecular Dynamics Simulations and Experimental Study of Lithium Ion Transport in Dilithium Ethylene Dicarbonate Borodin, Oleg; Zhuang, Guorong V.; Ross, Philip N. The Journal of Physical Chemistry C, Vol. 117, Issue 15 https://doi.org/10.1021/jp4000494	journal	April 2013
Interfacial Structure and Dynamics of the Lithium Alkyl Dicarbonate SEI Components in Contact with the Lithium Battery Electrolyte Borodin, Oleg; Bedrov, Dmitry The Journal of Physical Chemistry C, Vol. 118, Issue 32 https://doi.org/10.1021/jp504598n	journal	July 2014
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Role of Solution Structure in Solid Electrolyte Interphase Formation on Graphite with LiPF ₆ in Propylene Carbonate Nie, Mengyun; Abraham, Daniel P.; Seo, Daniel M. The Journal of Physical Chemistry C, Vol. 117, Issue 48 https://doi.org/10.1021/jp409765w	journal	November 2013
Preferential Solvation of Li+ Directs Formation of Interphase on Graphitic Anode von Cresce, Arthur; Xu, Kang Electrochemical and Solid-State Letters, Vol. 14, Issue 10 https://doi.org/10.1149/1.3615828	journal	January 2011
Solvation Sheath of Li ⁺ in Nonaqueous Electrolytes and Its Implication of Graphite/Electrolyte Interface Chemistry Xu, Kang; Lam, Yiufai; Zhang, Sheng S. The Journal of Physical Chemistry C, Vol. 111, Issue 20 https://doi.org/10.1021/jp068691u	journal	May 2007
Effects of Inhomogeneities—Nanoscale to Mesoscale—on the Durability of Li-Ion Batteries Harris, Stephen J.; Lu, Peng The Journal of Physical Chemistry C, Vol. 117, Issue 13 https://doi.org/10.1021/jp311431z	journal	February 2013
Differentiating Contributions to “Ion Transfer” Barrier from Interphasial Resistance and Li ⁺ Desolvation at Electrolyte/Graphite Interface Xu, Kang; von Cresce, Arthur; Lee, Unchul Langmuir, Vol. 26, Issue 13 https://doi.org/10.1021/la1009994	journal	July 2010
Li ⁺ -solvation/desolvation dictates interphasial processes on graphitic anode in Li ion cells Xu, Kang; von Wald Cresce, Arthur Journal of Materials Research, Vol. 27, Issue 18 https://doi.org/10.1557/jmr.2012.104	journal	August 2012
Conductivity and Viscosity of PC-DEC and PC-EC Solutions of LiBF[sub 4] Ding, Michael S. Journal of The Electrochemical Society, Vol. 151, Issue 1 https://doi.org/10.1149/1.1630593	journal	January 2004
Investigation of solvation in lithium ion battery electrolytes by NMR spectroscopy Yang, Li; Xiao, Ang; Lucht, Brett L. Journal of Molecular Liquids, Vol. 154, Issue 2-3 https://doi.org/10.1016/j.molliq.2010.04.025	journal	July 2010
[sup 13]C NMR Spectroscopic, CV, and Conductivity Studies of Propylene Carbonate-Based Electrolytes Containing Various Lithium Salts Reddy, V. Prakash; Smart, Marshall C.; Chin, Keith B. Electrochemical and Solid-State Letters, Vol. 8, Issue 6 https://doi.org/10.1149/1.1904466	journal	January 2005
Ion–ion interactions of LiPF6 and LiBF4 in propylene carbonate solutions Takeuchi, Munetaka; Kameda, Yasuo; Umebayashi, Yasuhiro Journal of Molecular Liquids, Vol. 148, Issue 2-3 https://doi.org/10.1016/j.molliq.2009.07.003	journal	September 2009
Spectroscopic Measurements of Ionic Association in Solutions of LiPF ₆ Burba, Christopher M.; Frech, Roger The Journal of Physical Chemistry B, Vol. 109, Issue 31 https://doi.org/10.1021/jp058045f	journal	August 2005
Conductivity and Solvation of Li ⁺ Ions of LiPF ₆ in Propylene Carbonate Solutions Kondo, Kazutaka; Sano, Mitsuru; Hiwara, Akio The Journal of Physical Chemistry B, Vol. 104, Issue 20 https://doi.org/10.1021/jp000142f	journal	May 2000
A Raman spectroscopic study of organic electrolyte solutions based on binary solvent systems of ethylene carbonate with low viscosity solvents which dissolve different lithium salts Morita, Masayuki; Asai, Yoshiko; Yoshimoto, Nobuko Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 23 https://doi.org/10.1039/a806278a	journal	January 1998
Accurate Static and Dynamic Properties of Liquid Electrolytes for Li-Ion Batteries from ab initio Molecular Dynamics Ganesh, P.; Jiang, De-en; Kent, P. R. C. The Journal of Physical Chemistry B, Vol. 115, Issue 12 https://doi.org/10.1021/jp2003529	journal	March 2011
Raman intensity study of local structure in non-aqueous electrolyte solutions—I. Cation-solvent interaction in LiClO4/ethylene carbonate Hyodo, Shi-Aki; Okabayashi, Katsuaki Electrochimica Acta, Vol. 34, Issue 11 https://doi.org/10.1016/0013-4686(89)87040-9	journal	November 1989
Combined quantum chemical/Raman spectroscopic analyses of Li+ cation solvation: Cyclic carbonate solvents—Ethylene carbonate and propylene carbonate Allen, Joshua L.; Borodin, Oleg; Seo, Daniel M. Journal of Power Sources, Vol. 267 https://doi.org/10.1016/j.jpowsour.2014.05.107	journal	December 2014
Solvation Structure of Li ⁺ in Concentrated LiPF ₆ −Propylene Carbonate Solutions Kameda, Yasuo; Umebayashi, Yasuhiro; Takeuchi, Munetaka The Journal of Physical Chemistry B, Vol. 111, Issue 22 https://doi.org/10.1021/jp072597b	journal	June 2007
Understanding Li ⁺ –Solvent Interaction in Nonaqueous Carbonate Electrolytes with ¹⁷ O NMR Bogle, Xavier; Vazquez, Rafael; Greenbaum, Steven The Journal of Physical Chemistry Letters, Vol. 4, Issue 10 https://doi.org/10.1021/jz400661k	journal	May 2013
Temperature dependence of lithium ion solvation in ethylene carbonate–LiClO4 solutions Castriota, Marco; Cazzanelli, Enzo; Nicotera, Isabella The Journal of Chemical Physics, Vol. 118, Issue 12 https://doi.org/10.1063/1.1528190	journal	March 2003
Investigation of volatile liquid surfaces by synchrotron x-ray spectroscopy of liquid microjets Wilson, Kevin R.; Rude, Bruce S.; Smith, Jared Review of Scientific Instruments, Vol. 75, Issue 3 https://doi.org/10.1063/1.1645656	journal	March 2004
X-Ray Absorption Spectra of Water from First Principles Calculations Prendergast, David; Galli, Giulia Physical Review Letters, Vol. 96, Issue 21 https://doi.org/10.1103/PhysRevLett.96.215502	journal	May 2006
Electronic structure of aqueous borohydride: a potential hydrogen storage medium Duffin, Andrew M.; England, Alice H.; Schwartz, Craig P. Physical Chemistry Chemical Physics, Vol. 13, Issue 38 https://doi.org/10.1039/c1cp21788g	journal	January 2011
p H-dependent x-ray absorption spectra of aqueous boron oxides Duffin, Andrew M.; Schwartz, Craig P.; England, Alice H. The Journal of Chemical Physics, Vol. 134, Issue 15 https://doi.org/10.1063/1.3574838	journal	April 2011
On the hydration and hydrolysis of carbon dioxide England, Alice H.; Duffin, Andrew M.; Schwartz, Craig P. Chemical Physics Letters, Vol. 514, Issue 4-6 https://doi.org/10.1016/j.cplett.2011.08.063	journal	October 2011
Cation-cation contact pairing in water: Guanidinium Shih, Orion; England, Alice H.; Dallinger, Gregory C. The Journal of Chemical Physics, Vol. 139, Issue 3 https://doi.org/10.1063/1.4813281	journal	July 2013
X-ray Spectroscopy of Liquid Water Microjets Wilson, Kevin R.; Rude, Bruce S.; Catalano, Tony The Journal of Physical Chemistry B, Vol. 105, Issue 17 https://doi.org/10.1021/jp010132u	journal	May 2001
Polarizable Force Field Development and Molecular Dynamics Simulations of Ionic Liquids Borodin, Oleg The Journal of Physical Chemistry B, Vol. 113, Issue 33 https://doi.org/10.1021/jp905220k	journal	August 2009
Correlating Li ⁺ Solvation Sheath Structure with Interphasial Chemistry on Graphite von Wald Cresce, Arthur; Borodin, Oleg; Xu, Kang The Journal of Physical Chemistry C, Vol. 116, Issue 50 https://doi.org/10.1021/jp303610t	journal	December 2012
Quantum Chemistry and Molecular Dynamics Simulation Study of Dimethyl Carbonate: Ethylene Carbonate Electrolytes Doped with LiPF ₆ Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 113, Issue 6 https://doi.org/10.1021/jp809614h	journal	February 2009
Electrolyte Solvation and Ionic Association II. Acetonitrile-Lithium Salt Mixtures: Highly Dissociated Salts Seo, Daniel M.; Borodin, Oleg; Han, Sang-Don Journal of The Electrochemical Society, Vol. 159, Issue 9 https://doi.org/10.1149/2.035209jes	journal	January 2012
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
NEXAFS Spectroscopy Stöhr, Joachim Springer Series in Surface Sciences https://doi.org/10.1007/978-3-662-02853-7	book	January 1992
On the importance of nuclear quantum motions in near edge x-ray absorption fine structure spectroscopy of molecules Schwartz, Craig P.; Uejio, Janel S.; Saykally, Richard J. The Journal of Chemical Physics, Vol. 130, Issue 18 https://doi.org/10.1063/1.3125509	journal	January 2009
VESTA : a three-dimensional visualization system for electronic and structural analysis Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 41, Issue 3 https://doi.org/10.1107/S0021889808012016	journal	May 2008
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang ChemInform, Vol. 35, Issue 50 https://doi.org/10.1002/chin.200450271	journal	December 2004
Ab initio Molecular Dynamics Simulations of the Initial Stages of Solid-electrolyte Interphase Formation on Lithium Ion Battery Graphitic Anodes Leung, Kevin; Budzien, Joanne arXiv https://doi.org/10.48550/arxiv.1009.4154	text	January 2010

Cited By (3)

Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions Chaudhari, Mangesh I.; Muralidharan, Ajay; Pratt, Lawrence R. Topics in Current Chemistry, Vol. 376, Issue 2 https://doi.org/10.1007/s41061-018-0187-2	journal	February 2018
Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14658	journal	March 2017
Structure and polarization near the Li ⁺ ion in ethylene and propylene carbonates Pollard, Travis P.; Beck, Thomas L. The Journal of Chemical Physics, Vol. 147, Issue 16 https://doi.org/10.1063/1.4992788	journal	October 2017

Similar Records

Highly Concentrated Electrolytes: Electrochemical and Physicochemical Characteristics of LiPF ₆ in Propylene Carbonate Solutions

Journal Article · Thu May 13 00:00:00 EDT 2021 · Journal of the Electrochemical Society · OSTI ID:1214423

Åvall, Gustav; Wallenstein, Joachim; Cheng, Gang; +3 more

NMR T{sub 1} relaxation time measurements and calculations with translational and rotational components for liquid electrolytes containing LiBF{sub 4} and propylene carbonate

Journal Article · Sat Dec 07 00:00:00 EST 2013 · Journal of Chemical Physics · OSTI ID:1214423

Infrared Spectroscopy of Li⁺ Solvation in EmimBF₄ and in Propylene Carbonate: Ab Initio Molecular Dynamics and Experiment

Journal Article · Thu Nov 03 00:00:00 EDT 2022 · Journal of Physical Chemistry. B · OSTI ID:1214423

Yan, Fangyong; Mukherjee, Kallol; Maroncelli, Mark; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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

Citation Formats

References (50)

Cited By (3)

Similar Records

Related Subjects

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