Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes

Ong, Mitchell T.; Bhatia, Harsh; Gyulassy, Attila G.; Draeger, Erik W.; Pascucci, Valerio; Bremer, Peer -Timo; Lordi, Vincenzo; Pask, John E.

doi:10.1021/acs.jpcc.7b02006

Title: Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes

Journal Article · Mon Mar 06 00:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b02006· OSTI ID:1375301

Ong, Mitchell T. ^[1]; Bhatia, Harsh ^[1]; Gyulassy, Attila G. ^[2]; Draeger, Erik W. ^[1]; Pascucci, Valerio ^[2]; Bremer, Peer -Timo ^[1];

^[1]; Pask, John E. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Utah, Salt Lake City, UT (United States)

Li-ion battery performance is strongly influenced by ionic conductivity, which depends on the mobility of the Li ions in solution, and is related to their solvation structure. In this work, we have performed first-principles molecular dynamics (FPMD) simulations of a LiPF6 salt solvated in different Li-ion battery organic electrolytes. We employ an analytical method using relative angles from successive time intervals to characterize complex ionic motion in multiple dimensions from our FPMD simulations. We find different characteristics of ionic motion on different time scales. We find that the Li ion exhibits a strong caging effect due to its strong solvation structure, while the counterion, PF6– undergoes more Brownian-like motion. Lastly, our results show that ionic motion can be far from purely diffusive and provide a quantitative characterization of the microscopic motion of ions over different time scales.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1375301

Report Number(s):: LLNL-JRNL-674755

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 12; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 15 works

Citation information provided by
Web of Science

References (25)

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
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
Über die von der molekularkinetischen Theorie der Wärme geforderte Bewegung von in ruhenden Flüssigkeiten suspendierten Teilchen Einstein, A. Annalen der Physik, Vol. 322, Issue 8 https://doi.org/10.1002/andp.19053220806	journal	January 1905
LiTFSI Structure and Transport in Ethylene Carbonate from Molecular Dynamics Simulations Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 110, Issue 10 https://doi.org/10.1021/jp056249q	journal	March 2006
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
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
Density functional theory calculations and *ab initio* molecular dynamics simulations for diffusion of Li ⁺ within liquid ethylene carbonate Bhatt, Mahesh Datt; Cho, Maenghyo; Cho, Kyeongjae Modelling and Simulation in Materials Science and Engineering, Vol. 20, Issue 6 https://doi.org/10.1088/0965-0393/20/6/065004	journal	July 2012
Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W. The Journal of Physical Chemistry B, Vol. 119, Issue 4 https://doi.org/10.1021/jp508184f	journal	January 2015
Pulse-Gradient Spin-Echo ¹ H, ⁷ Li, and ¹⁹ F NMR Diffusion and Ionic Conductivity Measurements of 14 Organic Electrolytes Containing LiN(SO ₂ CF ₃ ) ₂ Hayamizu, Kikuko; Aihara, Yuichi; Arai, Shigemasa The Journal of Physical Chemistry B, Vol. 103, Issue 3 https://doi.org/10.1021/jp9825664	journal	January 1999
Distribution of directional change as a signature of complex dynamics Burov, S.; Tabei, S. M. A.; Huynh, T. Proceedings of the National Academy of Sciences, Vol. 110, Issue 49 https://doi.org/10.1073/pnas.1319473110	journal	November 2013
Persistent Subdiffusive Proton Transport in Perfluorosulfonic Acid Membranes Savage, John; Voth, Gregory A. The Journal of Physical Chemistry Letters, Vol. 5, Issue 17 https://doi.org/10.1021/jz5014467	journal	August 2014
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
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
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
ReaxFF: A Reactive Force Field for Hydrocarbons van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois The Journal of Physical Chemistry A, Vol. 105, Issue 41 https://doi.org/10.1021/jp004368u	journal	October 2001
ReaxFF Reactive Force Field Simulations on the Influence of Teflon on Electrolyte Decomposition during Li/SWCNT Anode Discharge in Lithium-Sulfur Batteries Islam, Md Mahbubul; Bryantsev, Vyacheslav S.; van Duin, Adri C. T. Journal of The Electrochemical Society, Vol. 161, Issue 8 https://doi.org/10.1149/2.005408jes	journal	January 2014
Reactions of Singly-Reduced Ethylene Carbonate in Lithium Battery Electrolytes: A Molecular Dynamics Simulation Study Using the ReaxFF Bedrov, Dmitry; Smith, Grant D.; van Duin, Adri C. T. The Journal of Physical Chemistry A, Vol. 116, Issue 11 https://doi.org/10.1021/jp210345b	journal	December 2011
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Parallel reactive molecular dynamics: Numerical methods and algorithmic techniques Aktulga, H. M.; Fogarty, J. C.; Pandit, S. A. Parallel Computing, Vol. 38, Issue 4-5 https://doi.org/10.1016/j.parco.2011.08.005	journal	April 2012
Competitive lithium solvation of linear and cyclic carbonates from quantum chemistry Borodin, Oleg; Olguin, Marco; Ganesh, P. Physical Chemistry Chemical Physics, Vol. 18, Issue 1 https://doi.org/10.1039/C5CP05121E	journal	January 2016

Cited By (3)

Structure and dynamics in the lithium solvation shell of nonaqueous electrolytes Han, Sungho Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-42050-y	journal	April 2019
An ab initio molecular dynamics study of the solvation structure and ultrafast dynamics of lithium salts in organic carbonates: A comparison between linear and cyclic carbonates Zhang, Xiaoliu; Kuroda, Daniel G. The Journal of Chemical Physics, Vol. 150, Issue 18 https://doi.org/10.1063/1.5088820	journal	May 2019
Boosting Rechargeable Batteries R&D by Multiscale Modeling: Myth or Reality? Franco, Alejandro A.; Rucci, Alexis; Brandell, Daniel Chemical Reviews, Vol. 119, Issue 7 https://doi.org/10.1021/acs.chemrev.8b00239	journal	March 2019

Similar Records

Operando FTIR Studies of Electrolyte Solution Structures and Dynamics at Electrode-Electrolyte Interfaces

Conference · Wed Aug 21 00:00:00 EDT 2019 · OSTI ID:1375301

Tremolet de Villers, Bertrand J; Pekarek, Ryan; Neale, Nathan R; +1 more

Investigation of Ion–Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

Journal Article · Tue Feb 06 00:00:00 EST 2018 · Analytical Chemistry · OSTI ID:1375301

Zhang, Yanyan; Su, Mao; Yu, Xiaofei; +13 more

Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

Journal Article · Tue Mar 06 00:00:00 EST 2018 · Analytical Chemistry · OSTI ID:1375301

Zhang, Yanyan; Su, Mao; Yu, Xiaofei; +13 more

Related Subjects

25 ENERGY STORAGE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY

Title: Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes

Citation Formats

References (25)

Cited By (3)

Similar Records

Related Subjects