Probing Electric Double-Layer Composition via in Situ Vibrational Spectroscopy and Molecular Simulations.

Raberg, Jonathan H.; Vatamanu, Jenel; Harris, Stephen J.; van Oversteeg, Christina M.; Ramos, Axel; Borodin, Oleg; Cuk, Tanja

doi:10.1021/acs.jpclett.9b00879

Title: Probing Electric Double-Layer Composition via in Situ Vibrational Spectroscopy and Molecular Simulations.

Journal Article · 29 May 2019 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.9b00879 · OSTI ID:1650061

Raberg, Jonathan H. ^[1];

^[2]; Harris, Stephen J. ^[3];

^[4]; Ramos, Axel ^[1];

^[2];

^[5]

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

At an electrode, ions and solvent accumulate to screen charge, leading to a nanometer-scale electric double layer (EDL). The EDL guides electrode passivation in batteries, while in (super)capacitors, it determines charge storage capacity. Despite its importance, quantification of the nanometer-scale and potential-dependent EDL remains a challenging problem. Here, we directly probe changes in the EDL composition with potential using in situ vibrational spectroscopy and molecular dynamics simulations for a Li-ion battery electrolyte (LiClO₄ in dimethyl carbonate). The accumulation rate of Li⁺ ions at the negative surface and ClO₄^- ions at the positive surface from vibrational spectroscopy compares well to that predicted by simulations using a polarizable APPLE&P force field. The ion solvation shell structure and ion-pairing within the EDL differs significantly from the bulk, especially at the negative electrode, suggesting that the common rationalization of interfacial electrochemical processes in terms of bulk ion solvation should be applied with caution.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1650061

Journal Information:: Journal of Physical Chemistry Letters, Vol. 10, Issue 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Issues and challenges facing rechargeable lithium batteries Tarascon, J. -M.; Armand, M. Materials for Sustainable Energy https://doi.org/10.1142/9789814317665_0024	book	October 2010
Lithium batteries: Status, prospects and future Scrosati, Bruno; Garche, Jürgen Journal of Power Sources, Vol. 195, Issue 9 https://doi.org/10.1016/j.jpowsour.2009.11.048	journal	May 2010
The Development and Future of Lithium Ion Batteries Blomgren, George E. Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0251701jes	journal	December 2016
Efficient storage mechanisms for building better supercapacitors Salanne, M.; Rotenberg, B.; Naoi, K. Nature Energy, Vol. 1, Issue 6 https://doi.org/10.1038/nenergy.2016.70	journal	May 2016
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Energy management of fuel cell/battery/supercapacitor hybrid power source for vehicle applications Thounthong, Phatiphat; Raël, Stephane; Davat, Bernard Journal of Power Sources, Vol. 193, Issue 1 https://doi.org/10.1016/j.jpowsour.2008.12.120	journal	August 2009
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model Peled, E. Journal of The Electrochemical Society, Vol. 126, Issue 12 https://doi.org/10.1149/1.2128859	journal	January 1979
Chemical Composition and Morphology of the Elevated Temperature SEI on Graphite Andersson, A. M.; Edström, K. Journal of The Electrochemical Society, Vol. 148, Issue 10 https://doi.org/10.1149/1.1397771	journal	January 2001
Characterization of the Cathode Electrolyte Interface in Lithium Ion Batteries by Desorption Electrospray Ionization Mass Spectrometry Liu, Yao-Min; G. Nicolau, Bruno; Esbenshade, Jennifer L. Analytical Chemistry, Vol. 88, Issue 14 https://doi.org/10.1021/acs.analchem.6b01292	journal	July 2016
In Situ Visualized Cathode Electrolyte Interphase on LiCoO ₂ in High Voltage Cycling Lu, Wei; Zhang, Jiansheng; Xu, Jingjing ACS Applied Materials & Interfaces, Vol. 9, Issue 22 https://doi.org/10.1021/acsami.7b03024	journal	May 2017
In Situ Determination of the Liquid/Solid Interface Thickness and Composition for the Li Ion Cathode LiMn _1.5 Ni _0.5 O ₄ Browning, James F.; Baggetto, Loïc; Jungjohann, Katherine L. ACS Applied Materials & Interfaces, Vol. 6, Issue 21 https://doi.org/10.1021/am5032055	journal	October 2014
Evaluating the solid electrolyte interphase formed on silicon electrodes: a comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry Fears, T. M.; Doucet, M.; Browning, J. F. Physical Chemistry Chemical Physics, Vol. 18, Issue 20 https://doi.org/10.1039/C6CP00978F	journal	January 2016
Determination of the Solid Electrolyte Interphase Structure Grown on a Silicon Electrode Using a Fluoroethylene Carbonate Additive Veith, Gabriel M.; Doucet, Mathieu; Sacci, Robert L. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-06555-8	journal	July 2017
Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured In situ by Neutron Reflectometry Owejan, Jeanette E.; Owejan, Jon P.; DeCaluwe, Steven C. Chemistry of Materials, Vol. 24, Issue 11 https://doi.org/10.1021/cm3006887	journal	May 2012
Ramifications of Water-in-Salt Interfacial Structure at Charged Electrodes for Electrolyte Electrochemical Stability Vatamanu, Jenel; Borodin, Oleg The Journal of Physical Chemistry Letters, Vol. 8, Issue 18 https://doi.org/10.1021/acs.jpclett.7b01879	journal	August 2017
Molecular Dynamics Simulation Studies of the Structure of a Mixed Carbonate/LiPF ₆ Electrolyte near Graphite Surface as a Function of Electrode Potential Vatamanu, Jenel; Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry C, Vol. 116, Issue 1 https://doi.org/10.1021/jp2101539	journal	December 2011
Structure and dynamics of electrical double layers in organic electrolytes Feng, Guang; Huang, Jingsong; Sumpter, Bobby G. Physical Chemistry Chemical Physics, Vol. 12, Issue 20 https://doi.org/10.1039/c000451k	journal	January 2010
The nanoscale structure of the electrolyte–metal oxide interface Steinrück, Hans-Georg; Cao, Chuntian; Tsao, Yuchi Energy & Environmental Science, Vol. 11, Issue 3 https://doi.org/10.1039/C7EE02724A	journal	January 2018
External electric field dependence of the structure of the electric double layer at an ionic liquid/Au interface Yamamoto, Ryosuke; Morisaki, Hazuki; Sakata, Osami Applied Physics Letters, Vol. 101, Issue 5 https://doi.org/10.1063/1.4742920	journal	July 2012
Probing double layer structures of Au (111)–BMIPF ₆ ionic liquid interfaces from potential-dependent AFM force curves Zhang, Xiao; Zhong, Yun-Xin; Yan, Jia-Wei Chem. Commun., Vol. 48, Issue 4 https://doi.org/10.1039/C1CC15463J	journal	January 2012
Surface layering and melting in an ionic liquid studied by resonant soft X-ray reflectivity Mezger, M.; Ocko, B. M.; Reichert, H. Proceedings of the National Academy of Sciences, Vol. 110, Issue 10 https://doi.org/10.1073/pnas.1211749110	journal	February 2013
Temperature Dependence of Multilayering at the Free Surface of Ionic Liquids Probed by X-ray Reflectivity Measurements Nishi, Naoya; Uruga, Tomoya; Tanida, Hajime Langmuir, Vol. 27, Issue 12 https://doi.org/10.1021/la200252z	journal	June 2011
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
Modeling Insight into Battery Electrolyte Electrochemical Stability and Interfacial Structure Borodin, Oleg; Ren, Xiaoming; Vatamanu, Jenel Accounts of Chemical Research, Vol. 50, Issue 12 https://doi.org/10.1021/acs.accounts.7b00486	journal	November 2017
Concentrated electrolytes: decrypting electrolyte properties and reassessing Al corrosion mechanisms McOwen, Dennis W.; Seo, Daniel M.; Borodin, Oleg Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE42351D	journal	January 2014
Resolving Fine Structures of the Electric Double Layer of Electrochemical Interfaces in Ionic Liquids with an AFM Tip Modification Strategy Zhong, Yun-Xin; Yan, Jia-Wei; Li, Mian-Gang Journal of the American Chemical Society, Vol. 136, Issue 42 https://doi.org/10.1021/ja508222m	journal	October 2014
Surface Structure at the Ionic Liquid−Electrified Metal Interface Baldelli, Steven Accounts of Chemical Research, Vol. 41, Issue 3 https://doi.org/10.1021/ar700185h	journal	March 2008
Molecular Response of 1-Butyl-3-Methylimidazolium Dicyanamide Ionic Liquid at the Graphene Electrode Interface Investigated by Sum Frequency Generation Spectroscopy and Molecular Dynamics Simulations Xu, Siyun; Xing, Sirui; Pei, Shin-Shem The Journal of Physical Chemistry C, Vol. 119, Issue 46 https://doi.org/10.1021/acs.jpcc.5b08736	journal	November 2015
Preferential Adsorption of Solvents on the Cathode Surface of Lithium Ion Batteries Yu, Le; Liu, Huijin; Wang, Yan Angewandte Chemie, Vol. 125, Issue 22 https://doi.org/10.1002/ange.201209976	journal	April 2013
Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma Nature Materials, Vol. 16, Issue 12 https://doi.org/10.1038/nmat4974	journal	September 2017
In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors Griffin, John M.; Forse, Alexander C.; Tsai, Wan-Yu Nature Materials, Vol. 14, Issue 8 https://doi.org/10.1038/nmat4318	journal	June 2015
Electrochemical Quartz Crystal Microbalance (EQCM) Study of Ion Dynamics in Nanoporous Carbons Tsai, Wan-Yu; Taberna, Pierre-Louis; Simon, Patrice Journal of the American Chemical Society, Vol. 136, Issue 24 https://doi.org/10.1021/ja503449w	journal	June 2014
The use of fourier transform infrared spectroscopy for in situ recording of species in the electrode-electrolyte solution interphase Pons, Stanley Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, Issue 1-2 https://doi.org/10.1016/S0022-0728(83)80229-0	journal	July 1983
Spectroscopic and Density Functional Theory Characterization of Common Lithium Salt Solvates in Carbonate Electrolytes for Lithium Batteries Chapman, Navid; Borodin, Oleg; Yoon, Taeho The Journal of Physical Chemistry C, Vol. 121, Issue 4 https://doi.org/10.1021/acs.jpcc.6b12234	journal	January 2017
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
Vibrational Stark Effect Spectroscopy Chattopadhyay, Arun; Boxer, Steven G. Journal of the American Chemical Society, Vol. 117, Issue 4 https://doi.org/10.1021/ja00109a038	journal	February 1995
Influence of surface topology and electrostatic potential on water/electrode systems Siepmann, J. Ilja; Sprik, Michiel The Journal of Chemical Physics, Vol. 102, Issue 1 https://doi.org/10.1063/1.469429	journal	January 1995
Electrochemical interface between an ionic liquid and a model metallic electrode Reed, Stewart K.; Lanning, Oliver J.; Madden, Paul A. The Journal of Chemical Physics, Vol. 126, Issue 8 https://doi.org/10.1063/1.2464084	journal	February 2007
Efficient Handling of Gaussian Charge Distributions: An Application to Polarizable Molecular Models Kiss, Péter T.; Sega, Marcello; Baranyai, András Journal of Chemical Theory and Computation, Vol. 10, Issue 12 https://doi.org/10.1021/ct5009069	journal	November 2014
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
Molecular polarizabilities calculated with a modified dipole interaction Thole, B. T. Chemical Physics, Vol. 59, Issue 3 https://doi.org/10.1016/0301-0104(81)85176-2	journal	August 1981
Development of Many−Body Polarizable Force Fields for Li-Battery Applications: 2. LiTFSI-Doped Oligoether, Polyether, and Carbonate-Based Electrolytes Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 110, Issue 12 https://doi.org/10.1021/jp055080d	journal	March 2006
Electrode/Electrolyte Interface in Sulfolane-Based Electrolytes for Li Ion Batteries: A Molecular Dynamics Simulation Study Xing, Lidan; Vatamanu, Jenel; Borodin, Oleg The Journal of Physical Chemistry C, Vol. 116, Issue 45 https://doi.org/10.1021/jp3054179	journal	November 2012
Double Layer in Ionic Liquids: Overscreening versus Crowding Bazant, Martin Z.; Storey, Brian D.; Kornyshev, Alexei A. Physical Review Letters, Vol. 106, Issue 4 https://doi.org/10.1103/PhysRevLett.106.046102	journal	January 2011
A “counter-charge layer in generalized solvents” framework for electrical double layers in neat and hybrid ionic liquid electrolytes Feng, Guang; Huang, Jingsong; Sumpter, Bobby G. Physical Chemistry Chemical Physics, Vol. 13, Issue 32 https://doi.org/10.1039/c1cp21428d	journal	January 2011
Molecular Insights into the Electric Double Layers of Ionic Liquids on Au(100) Electrodes Sha, Maolin; Dou, Qiang; Luo, Fabao ACS Applied Materials & Interfaces, Vol. 6, Issue 15 https://doi.org/10.1021/am502413m	journal	July 2014
A comparative study of alkylimidazolium room temperature ionic liquids with FSI and TFSI anions near charged electrodes Hu, Zongzhi; Vatamanu, Jenel; Borodin, Oleg Electrochimica Acta, Vol. 145 https://doi.org/10.1016/j.electacta.2014.08.072	journal	November 2014
The importance of ion size and electrode curvature on electrical double layers in ionic liquids Feng, Guang; Qiao, Rui; Huang, Jingsong Phys. Chem. Chem. Phys., Vol. 13, Issue 3 https://doi.org/10.1039/C0CP02077J	journal	January 2011
Computational and Experimental Study of Li-Doped Ionic Liquids at Electrified Interfaces Haskins, Justin B.; Wu, James J.; Lawson, John W. The Journal of Physical Chemistry C, Vol. 120, Issue 22 https://doi.org/10.1021/acs.jpcc.6b02449	journal	May 2016
Evaluation of molecular dynamics simulation methods for ionic liquid electric double layers Haskins, Justin B.; Lawson, John W. The Journal of Chemical Physics, Vol. 144, Issue 18 https://doi.org/10.1063/1.4948938	journal	May 2016
Theory of the Double Layer in Water-in-Salt Electrolytes McEldrew, Michael; Goodwin, Zachary A. H.; Kornyshev, Alexei A. The Journal of Physical Chemistry Letters, Vol. 9, Issue 19 https://doi.org/10.1021/acs.jpclett.8b02543	journal	September 2018
Kinetic-Dominated Charging Mechanism within Representative Aqueous Electrolyte-based Electric Double-Layer Capacitors Yang, Huachao; Yang, Jinyuan; Bo, Zheng The Journal of Physical Chemistry Letters, Vol. 8, Issue 15 https://doi.org/10.1021/acs.jpclett.7b01525	journal	July 2017
Capacitive Performance of Water-in-Salt Electrolytes in Supercapacitors: A Simulation Study Li, Zhujie; Jeanmairet, Guillaume; Méndez-Morales, Trinidad The Journal of Physical Chemistry C, Vol. 122, Issue 42 https://doi.org/10.1021/acs.jpcc.8b07557	journal	September 2018
Molecular Insights into Carbon Nanotube Supercapacitors: Capacitance Independent of Voltage and Temperature Feng, Guang; Li, Song; Atchison, Jennifer S. The Journal of Physical Chemistry C, Vol. 117, Issue 18 https://doi.org/10.1021/jp403547k	journal	April 2013
Effects of Specific Adsorption on the Differential Capacitance of Imidazolium-Based Ionic Liquid Electrolytes Si, Xiujuan; Li, Shu; Wang, Yonglong ChemPhysChem, Vol. 13, Issue 7 https://doi.org/10.1002/cphc.201200013	journal	March 2012
Electric double-layer capacitance between an ionic liquid and few-layer graphene Uesugi, Eri; Goto, Hidenori; Eguchi, Ritsuko Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep01595	journal	April 2013
New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics Drüschler, Marcel; Borisenko, Natalia; Wallauer, Jens Physical Chemistry Chemical Physics, Vol. 14, Issue 15 https://doi.org/10.1039/c2cp40288b	journal	January 2012
Influence of temperature on the electrochemical characteristics of Bi(111)\|ionic liquid interface Siinor, Liis; Arendi, Rauno; Lust, Karmen Journal of Electroanalytical Chemistry, Vol. 689 https://doi.org/10.1016/j.jelechem.2012.11.018	journal	January 2013
Surface enhanced spectroscopy Metiu, H. Progress in Surface Science, Vol. 17, Issue 3-4 https://doi.org/10.1016/0079-6816(84)90017-0	journal	January 1984
Observation of the enhanced infrared absorption of p-nitrobenzoate on Ag island films with an ATR technique Hatta, A.; Ohshima, T.; Su�taka, W. Applied Physics A Solids and Surfaces, Vol. 29, Issue 2 https://doi.org/10.1007/BF00632429	journal	October 1982
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
Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries Fan, Xiulin; Chen, Long; Ji, Xiao Chem, Vol. 4, Issue 1 https://doi.org/10.1016/j.chempr.2017.10.017	journal	January 2018

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