First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF
Abstract
The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively. The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0–4 V, corresponding to conditions relevant to both anode and cathode SEI’s. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. Thesemore »
- Authors:
-
- Purdue Univ., West Lafayette, IN (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1370674
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 34; Related Information: CEES partners with Argonne National Laboratory (lead); University of Illinois, Urbana-Champaign; Northwest University; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; energy storage (including batteries and capacitors); charge transport; materials and chemistry by design; synthesis (novel materials); solid electrolyte interface; LiF; NaF; DFT; defect thermodynamics; diffusion
Citation Formats
Yildirim, Handan, Kinaci, Alper, Chan, Maria K. Y., and Greeley, Jeffrey P. First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF. United States: N. p., 2015.
Web. doi:10.1021/acsami.5b02904.
Yildirim, Handan, Kinaci, Alper, Chan, Maria K. Y., & Greeley, Jeffrey P. First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF. United States. https://doi.org/10.1021/acsami.5b02904
Yildirim, Handan, Kinaci, Alper, Chan, Maria K. Y., and Greeley, Jeffrey P. Mon .
"First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF". United States. https://doi.org/10.1021/acsami.5b02904. https://www.osti.gov/servlets/purl/1370674.
@article{osti_1370674,
title = {First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF},
author = {Yildirim, Handan and Kinaci, Alper and Chan, Maria K. Y. and Greeley, Jeffrey P.},
abstractNote = {The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively. The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0–4 V, corresponding to conditions relevant to both anode and cathode SEI’s. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. These conductivities are more than ten orders of magnitude smaller in NaF than in LiF. As compared to the diffusivity of Li in other common inorganic SEI compounds, such as Li2CO3 and Li2O, the cation diffusivity in LiF and NaF is quite low, with at least three orders of magnitude lower ionic conductivities. Furthermore, the results quantify the extent to which fluorides pose rate limitations in Li and Na batteries.},
doi = {10.1021/acsami.5b02904},
journal = {ACS Applied Materials and Interfaces},
number = 34,
volume = 7,
place = {United States},
year = {Mon Aug 10 00:00:00 EDT 2015},
month = {Mon Aug 10 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Sodium-Ion Batteries
journal, May 2012
- Slater, Michael D.; Kim, Donghan; Lee, Eungje
- Advanced Functional Materials, Vol. 23, Issue 8, p. 947-958
Direct Calculation of Li-Ion Transport in the Solid Electrolyte Interphase
journal, September 2012
- Shi, Siqi; Lu, Peng; Liu, Zhongyi
- Journal of the American Chemical Society, Vol. 134, Issue 37
Solvent Oligomerization during SEI Formation on Model Systems for Li-Ion Battery Anodes
journal, January 2012
- Tavassol, Hadi; Buthker, Joseph W.; Ferguson, Glen A.
- Journal of The Electrochemical Society, Vol. 159, Issue 6
Computational Study on the Solubility of Lithium Salts Formed on Lithium Ion Battery Negative Electrode in Organic Solvents
journal, April 2010
- Tasaki, Ken; Harris, Stephen J.
- The Journal of Physical Chemistry C, Vol. 114, Issue 17
The Correlation Between the Surface Chemistry and the Performance of Li-Carbon Intercalation Anodes for Rechargeable ‘Rocking-Chair’ Type Batteries
journal, January 1994
- Aurbach, Doron
- Journal of The Electrochemical Society, Vol. 141, Issue 3
Capacity Fade Mechanisms and Side Reactions in Lithium-Ion Batteries
journal, January 1998
- Arora, Pankaj; White, Ralph E.; Doyle, Marc
- Journal of The Electrochemical Society, Vol. 145, Issue 10, p. 3647-3667
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries
journal, August 2000
- Aurbach, Doron
- Journal of Power Sources, Vol. 89, Issue 2
On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries
journal, September 1999
- Aurbach, D.; Markovsky, B.; Weissman, I.
- Electrochimica Acta, Vol. 45, Issue 1-2
Battery Cycle Life Prediction with Coupled Chemical Degradation and Fatigue Mechanics
journal, January 2012
- Deshpande, Rutooj; Verbrugge, Mark; Cheng, Yang-Tse
- Journal of The Electrochemical Society, Vol. 159, Issue 10
Ageing mechanisms in lithium-ion batteries
journal, September 2005
- Vetter, J.; Novák, P.; Wagner, M. R.
- Journal of Power Sources, Vol. 147, Issue 1-2
Surface Characterization of Electrodes from High Power Lithium-Ion Batteries
journal, January 2002
- Andersson, A. M.; Abraham, D. P.; Haasch, R.
- Journal of The Electrochemical Society, Vol. 149, Issue 10
Chemical Composition and Morphology of the Elevated Temperature SEI on Graphite
journal, January 2001
- Andersson, A. M.; Edström, K.
- Journal of The Electrochemical Society, Vol. 148, Issue 10
Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard-Carbon Electrodes and Application to Na-Ion Batteries
journal, August 2011
- Komaba, Shinichi; Murata, Wataru; Ishikawa, Toru
- Advanced Functional Materials, Vol. 21, Issue 20
Syntheses and Characterization of Lithium Alkyl Mono- and Dicarbonates as Components of Surface Films in Li-Ion Batteries
journal, March 2006
- Xu, Kang; Zhuang, Guorong V.; Allen, Jan L.
- The Journal of Physical Chemistry B, Vol. 110, Issue 15
Lithium Ion Battery Graphite Solid Electrolyte Interphase Revealed by Microscopy and Spectroscopy
journal, January 2013
- Nie, Mengyun; Chalasani, Dinesh; Abraham, Daniel P.
- The Journal of Physical Chemistry C, Vol. 117, Issue 3, p. 1257-1267
In situ investigation of electrochemical lithium intercalation into graphite powder
journal, July 2000
- Wang, Chunsheng; Kakwan, Imran; Appleby, A. John
- Journal of Electroanalytical Chemistry, Vol. 489, Issue 1-2
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010
- Verma, Pallavi; Maire, Pascal; Novák, Petr
- Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341
Progression of Solid Electrolyte Interphase Formation on Hydrogenated Amorphous Silicon Anodes for Lithium-Ion Batteries
journal, April 2012
- Arreaga-Salas, David E.; Sra, Amandeep K.; Roodenko, Katy
- The Journal of Physical Chemistry C, Vol. 116, Issue 16
The Study of Surface Phenomena Related to Electrochemical Lithium Intercalation into Li[sub x]MO[sub y] Host Materials (M = Ni, Mn)
journal, January 2000
- Aurbach, Doron; Gamolsky, Kira; Markovsky, Boris
- Journal of The Electrochemical Society, Vol. 147, Issue 4
Acetone as oxidative decomposition product in propylene carbonate containing battery electrolyte
journal, December 2005
- Ufheil, Joachim; Würsig, Andreas; Schneider, Oliver D.
- Electrochemistry Communications, Vol. 7, Issue 12
The study of the anodic stability of alkyl carbonate solutions by in situ FTIR spectroscopy, EQCM, NMR and MS
journal, February 2001
- Moshkovich, M.; Cojocaru, M.; Gottlieb, H. E.
- Journal of Electroanalytical Chemistry, Vol. 497, Issue 1-2
Electron-Spin-Resonance Study of the Reaction of Electrolytic Solutions on the Positive Electrode for Lithium-Ion Secondary Batteries
journal, January 2001
- Matsuta, Shigeki; Kato, Yoshio; Ota, Taeko
- Journal of The Electrochemical Society, Vol. 148, Issue 1
Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries
journal, January 2010
- Yang, Li; Ravdel, Boris; Lucht, Brett L.
- Electrochemical and Solid-State Letters, Vol. 13, Issue 8
Transfer mechanism in solid-electrolyte layers on lithium: influence of temperature and polarization
journal, April 2001
- Churikov, A. V.
- Electrochimica Acta, Vol. 46, Issue 15
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model
journal, January 1979
- Peled, E.
- Journal of The Electrochemical Society, Vol. 126, Issue 12
LiTFSI Structure and Transport in Ethylene Carbonate from Molecular Dynamics Simulations
journal, March 2006
- Borodin, Oleg; Smith, Grant D.
- The Journal of Physical Chemistry B, Vol. 110, Issue 10
Combined ab Initio Quantum Mechanics and Classical Molecular Dynamics Studies of Polyphosphazene Polymer Electrolytes: Competitive Solvation of Li + and LiCF 3 SO 3
journal, October 2004
- Wang, Yixuan; Balbuena, Perla B.
- The Journal of Physical Chemistry B, Vol. 108, Issue 40
Accurate Static and Dynamic Properties of Liquid Electrolytes for Li-Ion Batteries from ab initio Molecular Dynamics
journal, March 2011
- Ganesh, P.; Jiang, De-en; Kent, P. R. C.
- The Journal of Physical Chemistry B, Vol. 115, Issue 12
Li + −Diglyme Complexes: Barriers to Lithium Cation Migration
journal, February 1998
- Sutjianto, Amin; Curtiss, Larry A.
- The Journal of Physical Chemistry A, Vol. 102, Issue 6
Rational design of electrolyte components by ab initio calculations
journal, February 2006
- Johansson, Patrik; Jacobsson, Per
- Journal of Power Sources, Vol. 153, Issue 2
Lithium Diffusion in Layered Li[sub x]CoO[sub 2]
journal, January 1999
- Van der Ven, A.
- Electrochemical and Solid-State Letters, Vol. 3, Issue 7
Lithium Transport in Amorphous Al 2 O 3 and AlF 3 for Discovery of Battery Coatings
journal, April 2013
- Hao, Shiqiang; Wolverton, C.
- The Journal of Physical Chemistry C, Vol. 117, Issue 16
Li Ion Diffusion Mechanisms in Bulk Monoclinic Li 2 CO 3 Crystals from Density Functional Studies
journal, October 2010
- Iddir, H.; Curtiss, L. A.
- The Journal of Physical Chemistry C, Vol. 114, Issue 48
Defect Thermodynamics and Diffusion Mechanisms in Li 2 CO 3 and Implications for the Solid Electrolyte Interphase in Li-Ion Batteries
journal, March 2013
- Shi, Siqi; Qi, Yue; Li, Hong
- The Journal of Physical Chemistry C, Vol. 117, Issue 17
Anion receptor for enhanced thermal stability of the graphite anode interface in a Li-ion battery
journal, June 2003
- Herstedt, M.; Stjerndahl, M.; Gustafsson, T.
- Electrochemistry Communications, Vol. 5, Issue 6, p. 467-472
Evaluation of Migration Energy of Lithium Ions in Chalcogenides and Halides by First Principles Calculation
journal, January 2002
- Koyama, Yukinori; Yamada, Yasuhiro; Tanaka, Isao
- MATERIALS TRANSACTIONS, Vol. 43, Issue 7
Electrical and Lithium Ion Dynamics in Three Main Components of Solid Electrolyte Interphase from Density Functional Theory Study
journal, March 2011
- Chen, Y. C.; Ouyang, C. Y.; Song, L. J.
- The Journal of Physical Chemistry C, Vol. 115, Issue 14
Defect Chemistry: Composition, Transport, and Reactions in the Solid State; Part I: Thermodynamics
journal, March 1993
- Maier, Joachim
- Angewandte Chemie International Edition in English, Vol. 32, Issue 3
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
The energy and elastic dipole tensor of defects in ionic crystals calculated by the supercell method
journal, February 1985
- Leslie, M.; Gillan, N. J.
- Journal of Physics C: Solid State Physics, Vol. 18, Issue 5
Intrinsic stoichiometry and oxygen-induced -type conductivity of pyrite FeS
journal, July 2011
- Sun, Ruoshi; Chan, M. K. Y.; Kang, ShinYoung
- Physical Review B, Vol. 84, Issue 3
Periodic boundary conditions in ab initio calculations
journal, February 1995
- Makov, G.; Payne, M. C.
- Physical Review B, Vol. 51, Issue 7
First-principles calculations for defects and impurities: Applications to III-nitrides
journal, April 2004
- Van de Walle, Chris G.; Neugebauer, Jörg
- Journal of Applied Physics, Vol. 95, Issue 8
Ab initio energetics of charge compensating point defects: A case study on MgO
journal, June 2013
- Lin, Shih-kang; Yeh, Chao-kuei; Puchala, Brian
- Computational Materials Science, Vol. 73
Optimization methods for finding minimum energy paths
journal, April 2008
- Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme
- The Journal of Chemical Physics, Vol. 128, Issue 13
The electron energy loss spectra of some alkali halides in the band gap region
journal, April 1985
- Roy, G.; Singh, G.; Gallon, T. E.
- Surface Science, Vol. 152-153
Density-based mixing parameter for hybrid functionals
journal, January 2011
- Marques, Miguel A. L.; Vidal, Julien; Oliveira, Micael J. T.
- Physical Review B, Vol. 83, Issue 3
Low-Frequency Dielectric Constant of LiF, NaF, NaCl, NaBr, KCl, and KBr by the Method of Substitution
journal, December 1970
- Andeen, Carl; Fontanella, John; Schuele, Donald
- Physical Review B, Vol. 2, Issue 12
Mathematical modeling of high-power-density insertion electrodes for lithium ion batteries
journal, August 2002
- Verbrugge, Mark W.; Baker, Daniel R.; Koch, Brian J.
- Journal of Power Sources, Vol. 110, Issue 2
Calculations of intrinsic defect energies in the alkali halides
journal, July 1981
- Rowell, D. K.; Sangster, M. J. L.
- Journal of Physics C: Solid State Physics, Vol. 14, Issue 21
The contribution of vacancy defects to mass transport in alkali halides-an assessment using theoretical calculations of defect energies
journal, February 1979
- Catlow, C. R. A.; Corish, J.; Diller, K. M.
- Journal of Physics C: Solid State Physics, Vol. 12, Issue 3
General method to predict voltage-dependent ionic conduction in a solid electrolyte coating on electrodes
journal, April 2015
- Pan, Jie; Cheng, Yang-Tse; Qi, Yue
- Physical Review B, Vol. 91, Issue 13
Ionic conductivity in lithium compounds
journal, August 1971
- Pizzini, S.
- Journal of Applied Electrochemistry, Vol. 1, Issue 3
The ionic conductivity of Li-halide crystals
journal, January 1950
- Haven, Y.
- Recueil des Travaux Chimiques des Pays-Bas, Vol. 69, Issue 12
Measurement of ionic diffusion in lithium fluoride by nuclear magnetic resonance techniques
journal, May 1966
- Stoebe, T. G.; Huggins, R. A.
- Journal of Materials Science, Vol. 1, Issue 2
Ionic Conductivity of Sodium fluoride
journal, January 1970
- Bauer, C. F.; Whitmore, D. H.
- physica status solidi (b), Vol. 37, Issue 2
Formation Energy of Individual Cation Vacancies in LiF and NaCl
journal, January 1969
- Spencer, O. S.; Plint, C. A.
- Journal of Applied Physics, Vol. 40, Issue 1
Ionic Conductivity of Doped NaCl Crystals
journal, May 1962
- Dreyfus, R. W.; Nowick, A. S.
- Physical Review, Vol. 126, Issue 4
Intrinsic defects and conduction characteristics of Sc O in thermionic cathode systems
journal, August 2012
- Jacobs, Ryan M.; Booske, John H.; Morgan, Dane
- Physical Review B, Vol. 86, Issue 5
Advances in electronic structure methods for defects and impurities in solids
journal, November 2010
- Van de Walle, Chris G.; Janotti, Anderson
- physica status solidi (b), Vol. 248, Issue 1
First-principles theory of ionic diffusion with nondilute carriers
journal, October 2001
- Van der Ven, A.; Ceder, G.; Asta, M.
- Physical Review B, Vol. 64, Issue 18
Alkali Halides
book, January 2001
- Sirdeshmukh, D. B.; Sirdeshmukh, L.; Subhadra, K. G.
- Springer Series in Materials Science
Charge Carrier Accumulation in Lithium Fluoride Thin Films due to Li-Ion Absorption by Titania (100) Subsurface
journal, February 2012
- Li, Chilin; Gu, Lin; Guo, Xiangxin
- Nano Letters, Vol. 12, Issue 3
Ionic space charge effects in lithium fluoride thin films
journal, October 2012
- Li, Chilin; Maier, Joachim
- Solid State Ionics, Vol. 225
Works referencing / citing this record:
Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon
journal, March 2017
- Soto, Fernando A.; Yan, Pengfei; Engelhard, Mark H.
- Advanced Materials, Vol. 29, Issue 18
An Armored Mixed Conductor Interphase on a Dendrite-Free Lithium-Metal Anode
journal, September 2018
- Yan, Chong; Cheng, Xin-Bing; Yao, Yu-Xing
- Advanced Materials, Vol. 30, Issue 45
Electrolytes and Electrolyte/Electrode Interfaces in Sodium‐Ion Batteries: From Scientific Research to Practical Application
journal, March 2019
- Huang, Yongxin; Zhao, Luzi; Li, Li
- Advanced Materials, Vol. 31, Issue 21
Sodium-Ion Battery Electrolytes: Modeling and Simulations
journal, February 2018
- Åvall, Gustav; Mindemark, Jonas; Brandell, Daniel
- Advanced Energy Materials, Vol. 8, Issue 17
Rational Method for Improving the Performance of Lithium-Sulfur Batteries: Coating the Separator with Lithium Fluoride
journal, April 2017
- Li, Chao; Zhang, Peng; Dai, Jianhui
- ChemElectroChem, Vol. 4, Issue 6
Effect of Residual Lithium Rearrangement on Ni-rich Layered Oxide Cathodes for Lithium-Ion Batteries
journal, June 2018
- Park, Jun-Ho; Choi, Byungjin; Kang, Yoon-Sok
- Energy Technology, Vol. 6, Issue 7
Electrolytes, SEI Formation, and Binders: A Review of Nonelectrode Factors for Sodium-Ion Battery Anodes
journal, January 2018
- Bommier, Clement; Ji, Xiulei
- Small, Vol. 14, Issue 16
Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries
journal, March 2018
- Wang, Aiping; Kadam, Sanket; Li, Hong
- npj Computational Materials, Vol. 4, Issue 1
Advances in sodium secondary batteries utilizing ionic liquid electrolytes
journal, January 2019
- Matsumoto, Kazuhiko; Hwang, Jinkwang; Kaushik, Shubham
- Energy & Environmental Science, Vol. 12, Issue 11
The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium
journal, December 2019
- He, Mingfu; Guo, Rui; Hobold, Gustavo M.
- Proceedings of the National Academy of Sciences, Vol. 117, Issue 1
Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries
journal, January 2017
- Benitez, Laura; Seminario, Jorge M.
- Journal of The Electrochemical Society, Vol. 164, Issue 11
Simulations of a LiF Solid Electrolyte Interphase Cracking on Silicon Anodes Using Molecular Dynamics
journal, January 2018
- Galvez-Aranda, Diego E.; Seminario, Jorge M.
- Journal of The Electrochemical Society, Vol. 165, Issue 3
SEI Composition on Hard Carbon in Na-Ion Batteries After Long Cycling: Influence of Salts (NaPF 6 , NaTFSI) and Additives (FEC, DMCF)
journal, January 2020
- Fondard, J.; Irisarri, E.; Courrèges, C.
- Journal of The Electrochemical Society, Vol. 167, Issue 7