Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries

Strmcnik, Dusan; Castelli, Ivano E.; Connell, Justin G.; Haering, Dominik; Zorko, Milena; Martins, Pedro; Lopes, Pietro P.; Genorio, Bostjan; Ostergaard, Thomas; Gasteiger, Hubert A.; Maglia, Filippo; Antonopoulos, Byron K.; Stamenkovic, Vojislav R.; Rossmeisl, Jan; Markovic, Nenad M.

doi:10.1038/s41929-018-0047-z

Title: Electrocatalytic transformation of HF impurity to H₂ and LiF in lithium-ion batteries

Journal Article · Mon Apr 09 00:00:00 EDT 2018 · Nature Catalysis

DOI:https://doi.org/10.1038/s41929-018-0047-z· OSTI ID:1433882

Strmcnik, Dusan ^[1];

^[2];

^[1]; Haering, Dominik ^[3]; Zorko, Milena ^[1];

^[1];

^[1]; Genorio, Bostjan ^[1]; Ostergaard, Thomas ^[2]; Gasteiger, Hubert A. ^[3]; Maglia, Filippo ^[4];

^[4]; Stamenkovic, Vojislav R. ^[1]; Rossmeisl, Jan ^[2]; Markovic, Nenad M. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Univ. of Copenhagen (Denmark). Nano-Science Center. Dept. of Chemistry
Technical Univ. of Munich (Germany). Chair of Technical Electrochemistry. Dept. of Chemistry. Catalysis Research Center
BMW Group, Munich (Germany). Battery Cell Technology

The formation of solid electrolyte interphase on graphite anodes plays a key role in the efficiency of Li-ion batteries. However, to date, fundamental understanding of the formation of LiF as one of the main solid electrolyte interphase components in hexafluorophosphate-based electrolytes remains elusive. In this paper, we present experimental and theoretical evidence that LiF formation is an electrocatalytic process that is controlled by the electrochemical transformation of HF impurity to LiF and H₂. Although the kinetics of HF dissociation and the concomitant production of LiF and H₂ is dependent on the structure and nature of surface atoms, the underlying electrochemistry is the same. The morphology, and thus the role, of the LiF formed is strongly dependent on the nature of the substrate and HF inventory, leading to either complete or partial passivation of the interface. Finally, our finding is of general importance and may lead to new opportunities for the improvement of existing, and design of new, Li-ion technologies.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); BMW Group, Munich (Germany)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); BMW Technology Corporation (Germany)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1433882

Journal Information:: Nature Catalysis, Vol. 1, Issue 4; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 100 works

Citation information provided by
Web of Science

References (48)

The interaction of water with solid surfaces: Fundamental aspects Thiel, Patricia A.; Madey, Theodore E. Surface Science Reports, Vol. 7, Issue 6-8, p. 211-385 https://doi.org/10.1016/0167-5729(87)90001-X	journal	October 1987
Origin of Anomalous Activities for Electrocatalysts in Alkaline Electrolytes Subbaraman, Ram; Danilovic, N.; Lopes, P. P. The Journal of Physical Chemistry C, Vol. 116, Issue 42 https://doi.org/10.1021/jp3075783	journal	October 2012
Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction Strmcnik, Dusan S.; Tripkovic, Dusan V.; van der Vliet, Dennis Journal of the American Chemical Society, Vol. 130, Issue 46 https://doi.org/10.1021/ja8032185	journal	November 2008
Decomposition reaction of LiPF6-based electrolytes for lithium ion cells Kawamura, Tetsuya; Okada, Shigeto; Yamaki, Jun-ichi Journal of Power Sources, Vol. 156, Issue 2 https://doi.org/10.1016/j.jpowsour.2005.05.084	journal	June 2006
Computational high-throughput screening of electrocatalytic materials for hydrogen evolution Greeley, Jeff; Jaramillo, Thomas F.; Bonde, Jacob Nature Materials, Vol. 5, Issue 11, p. 909-913 https://doi.org/10.1038/nmat1752	journal	October 2006
pH in Grand Canonical Statistics of an Electrochemical Interface Hansen, Martin Hangaard; Rossmeisl, Jan The Journal of Physical Chemistry C, Vol. 120, Issue 51 https://doi.org/10.1021/acs.jpcc.6b09019	journal	December 2016
Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems Aurbach, D.; Zaban, A.; Ein-Eli, Y. Journal of Power Sources, Vol. 68, Issue 1 https://doi.org/10.1016/S0378-7753(97)02575-5	journal	September 1997
In Situ AFM Study of Surface Film Formation on the Edge Plane of HOPG for Lithium-Ion Batteries Domi, Yasuhiro; Ochida, Manabu; Tsubouchi, Sigetaka The Journal of Physical Chemistry C, Vol. 115, Issue 51 https://doi.org/10.1021/jp2064672	journal	December 2011
Surface Film Formation on Graphite Negative Electrode in Lithium-Ion Batteries: AFM Study in an Ethylene Carbonate-Based Solution Jeong, Soon-Ki; Inaba, Minoru; Abe, Takeshi Journal of The Electrochemical Society, Vol. 148, Issue 9 https://doi.org/10.1149/1.1387981	journal	January 2001
Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy Nie, Mengyun; Abraham, Daniel P.; Chen, Yanjing The Journal of Physical Chemistry C, Vol. 117, Issue 26 https://doi.org/10.1021/jp404155y	journal	June 2013
Origin of H ₂ Evolution in LIBs: H ₂ O Reduction vs. Electrolyte Oxidation Metzger, Michael; Strehle, Benjamin; Solchenbach, Sophie Journal of The Electrochemical Society, Vol. 163, Issue 5 https://doi.org/10.1149/2.1151605jes	journal	January 2016
Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method Enkovaara, J.; Rostgaard, C.; Mortensen, J. J. Journal of Physics: Condensed Matter, Vol. 22, Issue 25 https://doi.org/10.1088/0953-8984/22/25/253202	journal	June 2010
Surface film formation on a graphite electrode in Li-ion batteries: AFM and XPS study Leroy, S.; Blanchard, F.; Dedryvère, R. Surface and Interface Analysis, Vol. 37, Issue 10 https://doi.org/10.1002/sia.2072	journal	January 2005
The interaction of water with solid surfaces: fundamental aspects revisited Henderson, M. Surface Science Reports, Vol. 46, Issue 1-8 https://doi.org/10.1016/S0167-5729(01)00020-6	journal	May 2002
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
Influence of the lithium salt nature over the surface film formation on a graphite electrode in Li-ion batteries: An XPS study Leroy, S.; Martinez, H.; Dedryvère, R. Applied Surface Science, Vol. 253, Issue 11 https://doi.org/10.1016/j.apsusc.2006.10.071	journal	March 2007
Energy and fuels from electrochemical interfaces Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4738	journal	December 2016
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 1,3-Propane Sultone and Vinylene Carbonate in Solid Electrolyte Interface Formation and Gas Generation Zhang, Bo; Metzger, Michael; Solchenbach, Sophie The Journal of Physical Chemistry C, Vol. 119, Issue 21 https://doi.org/10.1021/acs.jpcc.5b00072	journal	May 2015
The mechanism of HF formation in LiPF6 based organic carbonate electrolytes Lux, S. F.; Lucas, I. T.; Pollak, E. Electrochemistry Communications, Vol. 14, Issue 1 https://doi.org/10.1016/j.elecom.2011.10.026	journal	January 2012
Electric Potential Gradient at the Buried Interface between Lithium-Ion Battery Electrodes and the SEI Observed Using Photoelectron Spectroscopy Maibach, Julia; Lindgren, Fredrik; Eriksson, Henrik The Journal of Physical Chemistry Letters, Vol. 7, Issue 10 https://doi.org/10.1021/acs.jpclett.6b00391	journal	April 2016
Investigation of thermal aging and hydrolysis mechanisms in commercial lithium ion battery electrolyte Terborg, Lydia; Weber, Sascha; Blaske, Franziska Journal of Power Sources, Vol. 242 https://doi.org/10.1016/j.jpowsour.2013.05.125	journal	November 2013
Electrochemical SPM investigation of the solid electrolyte interphase film formed on HOPG electrodes Alliata, D. Electrochemistry Communications, Vol. 2, Issue 6 https://doi.org/10.1016/S1388-2481(00)00056-4	journal	June 2000
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries Soto, Fernando A.; Ma, Yuguang; Martinez de la Hoz, Julibeth M. Chemistry of Materials, Vol. 27, Issue 23 https://doi.org/10.1021/acs.chemmater.5b03358	journal	November 2015
A new look at the solid electrolyte interphase on graphite anodes in Li-ion batteries Edström, Kristina; Herstedt, Marie; Abraham, Daniel P. Journal of Power Sources, Vol. 153, Issue 2 https://doi.org/10.1016/j.jpowsour.2005.05.062	journal	February 2006
Ultra-thin passivating film induced by vinylene carbonate on highly oriented pyrolytic graphite negative electrode in lithium-ion cell Matsuoka, O.; Hiwara, A.; Omi, T. Journal of Power Sources, Vol. 108, Issue 1-2 https://doi.org/10.1016/S0378-7753(02)00012-5	journal	June 2002
Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O Plakhotnyk, Andriy V.; Ernst, Ludger; Schmutzler, Reinhard Journal of Fluorine Chemistry, Vol. 126, Issue 1 https://doi.org/10.1016/j.jfluchem.2004.09.027	journal	January 2005
Electrochemical AFM Observation of the HOPG Edge Plane in Ethylene Carbonate-Based Electrolytes Containing Film-Forming Additives Domi, Yasuhiro; Ochida, Manabu; Tsubouchi, Shigetaka Journal of The Electrochemical Society, Vol. 159, Issue 8 https://doi.org/10.1149/2.059208jes	journal	January 2012
Composition, depth profiles and lateral distribution of materials in the SEI built on HOPG-TOF SIMS and XPS studies Peled, E.; Bar Tow, D.; Merson, A. Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00505-5	journal	July 2001
When Small is Big: The Role of Impurities in Electrocatalysis Strmcnik, Dusan; Li, Dongguo; Lopes, Pietro P. Topics in Catalysis, Vol. 58, Issue 18-20 https://doi.org/10.1007/s11244-015-0492-8	journal	September 2015
Design principles for hydrogen evolution reaction catalyst materials Strmcnik, Dusan; Lopes, Pietro Papa; Genorio, Bostjan Nano Energy, Vol. 29 https://doi.org/10.1016/j.nanoen.2016.04.017	journal	November 2016
Work function, electronegativity, and electrochemical behaviour of metals Trasatti, Sergio Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 39, Issue 1 https://doi.org/10.1016/S0022-0728(72)80485-6	journal	September 1972
Surface science studies of model fuel cell electrocatalysts Markovic, N. Surface Science Reports, Vol. 45, Issue 4-6 https://doi.org/10.1016/S0167-5729(01)00022-X	journal	April 2002
The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling An, Seong Jin; Li, Jianlin; Daniel, Claus Carbon, Vol. 105 https://doi.org/10.1016/j.carbon.2016.04.008	journal	August 2016
Oxygen reduction reaction on Pt(111): effects of bromide Marković, N. M.; Gasteiger, H. A.; Grgur, B. N. Journal of Electroanalytical Chemistry, Vol. 467, Issue 1-2 https://doi.org/10.1016/S0022-0728(99)00020-0	journal	June 1999
Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media Staszak-Jirkovský, Jakub; Subbaraman, Ram; Strmcnik, Dusan ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01779	journal	October 2015
Effects of electrolyte-volume-to-electrode-area ratio on redox behaviors of graphite anodes for lithium-ion batteries Kang, Sung-Jin; Yu, Sunghun; Lee, Chulhaeng Electrochimica Acta, Vol. 141 https://doi.org/10.1016/j.electacta.2014.07.090	journal	September 2014
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures Aurbach, D. Journal of The Electrochemical Society, Vol. 143, Issue 12 https://doi.org/10.1149/1.1837300	journal	January 1996
Electrode–solution interactions in Li-ion batteries: a short summary and new insights Aurbach, D. Journal of Power Sources, Vol. 119-121 https://doi.org/10.1016/S0378-7753(03)00273-8	journal	June 2003
Manganese dissolution from LiMn2O4 cathodes at elevated temperature: methylene methanedisulfonate as electrolyte additive Wang, Renheng; Li, Xinhai; Wang, Zhixing Journal of Solid State Electrochemistry, Vol. 20, Issue 1 https://doi.org/10.1007/s10008-015-2998-1	journal	August 2015
Towards the computational design of solid catalysts Nørskov, J.; Bligaard, T.; Rossmeisl, J. Nature Chemistry, Vol. 1, Issue 1, p. 37-46 https://doi.org/10.1038/nchem.121	journal	April 2009
Understanding Transition-Metal Dissolution Behavior in LiNi _0.5 Mn _1.5 O ₄ High-Voltage Spinel for Lithium Ion Batteries Pieczonka, Nicholas P. W.; Liu, Zhongyi; Lu, Peng The Journal of Physical Chemistry C, Vol. 117, Issue 31 https://doi.org/10.1021/jp405158m	journal	July 2013
Comparison of Voltammetric Responses over the Cathodic Region in LiPF[sub 6] and LiBETI with and without HF Lee, Hochun; Cho, Jeong-Ju; Kim, Jonggeol Journal of The Electrochemical Society, Vol. 152, Issue 6 https://doi.org/10.1149/1.1914748	journal	January 2005
Review—SEI: Past, Present and Future Peled, E.; Menkin, S. Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.1441707jes	journal	January 2017
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
Work function, electronegativity, and electrochemical behaviour of metals Trasatti, Sergio Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 33, Issue 2 https://doi.org/10.1016/s0022-0728(71)80123-7	journal	December 1971
Tuning the activities of cuprous oxide nanostructures via the oxide-metal interaction Huang, Wugen; Liu, Qingfei; Zhou, Zhiwen Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15965-8	journal	May 2020

Cited By (17)

Deactivating Defects in Graphenes with Al ₂ O ₃ Nanoclusters to Produce Long-Life and High-Rate Sodium-Ion Batteries Lin, Qiaowei; Zhang, Jun; Kong, Debin Advanced Energy Materials, Vol. 9, Issue 1 https://doi.org/10.1002/aenm.201803078	journal	November 2018
Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite Antonopoulos, Byron K.; Maglia, Filippo; Schmidt-Stein, Felix Batteries & Supercaps, Vol. 1, Issue 3 https://doi.org/10.1002/batt.201800029	journal	July 2018
A Comparison of Formation Methods for Graphite//LiFePO ₄ Cells Moretti, Arianna; Sharova, Varvara; Carvalho, Diogo V. Batteries & Supercaps, Vol. 2, Issue 3 https://doi.org/10.1002/batt.201800109	journal	January 2019
High energy density of multivalent glass‐ceramic cathodes for Li‐ion rechargeable cells and as an efficient photocatalyst for organic degradation Kirubakaran, Kiran Preethi; Senthil, Chenrayan; Priyadarshini, Marimuthu Energy Storage, Vol. 2, Issue 2 https://doi.org/10.1002/est2.133	journal	January 2020
Fading Mechanisms and Voltage Hysteresis in FeF ₂ -NiF ₂ Solid Solution Cathodes for Lithium and Lithium-Ion Batteries Huang, Qiao; Pollard, Travis P.; Ren, Xiaolei Small, Vol. 15, Issue 6 https://doi.org/10.1002/smll.201804670	journal	January 2019
Anion–π interactions in lithium–organic redox flow batteries Li, Lei; Hong, Yu-Jian; Chen, Dong-Yang Chemical Communications, Vol. 55, Issue 16 https://doi.org/10.1039/c8cc09834d	journal	January 2019
The hydrogen evolution reaction: from material to interfacial descriptors Dubouis, Nicolas; Grimaud, Alexis Chemical Science, Vol. 10, Issue 40 https://doi.org/10.1039/c9sc03831k	journal	January 2019
Li-diffusion at the interface between Li-metal and [Pyr ₁₄ ][TFSI]-ionic liquid: Ab initio molecular dynamics simulations Merinov, Boris V.; Naserifar, Saber; Zybin, Sergey V. The Journal of Chemical Physics, Vol. 152, Issue 3 https://doi.org/10.1063/1.5132566	journal	January 2020
Identifying Contact Resistances in High-Voltage Cathodes by Impedance Spectroscopy Pritzl, Daniel; Bumberger, Andreas E.; Wetjen, Morten Journal of The Electrochemical Society, Vol. 166, Issue 4 https://doi.org/10.1149/2.0451904jes	journal	January 2019
Quantification of PF ₅ and POF ₃ from Side Reactions of LiPF ₆ in Li-Ion Batteries Solchenbach, Sophie; Metzger, Michael; Egawa, Masamitsu Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0481813jes	journal	January 2018
Electrolyte and SEI Decomposition Reactions of Transition Metal Ions Investigated by On-Line Electrochemical Mass Spectrometry Solchenbach, Sophie; Hong, Gloria; Freiberg, Anna Teresa Sophie Journal of The Electrochemical Society, Vol. 165, Issue 14 https://doi.org/10.1149/2.0511814jes	journal	January 2018
The Impact of CO ₂ Evolved from VC and FEC during Formation of Graphite Anodes in Lithium-Ion Batteries Schwenke, K. Uta; Solchenbach, Sophie; Demeaux, Julien Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.0821910jes	journal	January 2019
Editors' Choice—Capacity Fading Mechanisms of NCM-811 Cathodes in Lithium-Ion Batteries Studied by X-ray Diffraction and Other Diagnostics Friedrich, Franziska; Strehle, Benjamin; Freiberg, Anna T. S. Journal of The Electrochemical Society, Vol. 166, Issue 15 https://doi.org/10.1149/2.0821915jes	journal	January 2019
Sodium Borosilicate Glass Separators as an Electrolyte Additive Donor for Improving the Electrochemical Performance of Lithium-Ion Batteries Schadeck, Ulrich; Hahn, Markus; Gerdes, Thorsten Journal of The Electrochemical Society, Vol. 166, Issue 14 https://doi.org/10.1149/2.1011914jes	journal	January 2019
Temperature Dependence of Oxygen Release from LiNi _0.6 Mn _0.2 Co _0.2 O ₂ (NMC622) Cathode Materials for Li-Ion Batteries Jung, Roland; Strobl, Philipp; Maglia, Filippo Journal of The Electrochemical Society, Vol. 165, Issue 11 https://doi.org/10.1149/2.1261811jes	journal	January 2018
Formation of the Solid Electrolyte Interphase at Constant Potentials: a Model Study on Highly Oriented Pyrolytic Graphite Antonopoulos, Byron K.; Maglia, Filippo; Schmidt-Stein, Felix Batteries & Supercaps, Vol. 1, Issue 3 https://doi.org/10.1002/batt.201800064	journal	July 2018
Tuning the Selectivity and Activity of Electrochemical Interfaces with Defective Graphene Oxide and Reduced Graphene Oxide Genorio, Bostjan; Harrison, Katharine L.; Connell, Justin G. ACS Applied Materials & Interfaces, Vol. 11, Issue 37 https://doi.org/10.1021/acsami.9b13391	journal	August 2019

Similar Records

Al₂O₃ Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

Journal Article · Thu Feb 25 00:00:00 EST 2021 · Frontiers in Energy Research · OSTI ID:1433882

Sahadeo, Emily; Rubloff, Gary; Lee, Sang Bok; +1 more

Role of Catalytic Conversions of Ethylene Carbonate, Water, and HF in Forming the Solid-Electrolyte Interphase of Li-Ion Batteries

Journal Article · Tue Jun 27 00:00:00 EDT 2023 · ACS Catalysis · OSTI ID:1433882

Martins, Milena; Haering, Dominik; Connell, Justin G.; +13 more

Direct Evidence of a Chemical Conversion Mechanism of Atomic-Layer-Deposited TiO₂ Anodes During Lithiation Using LiPF₆ Salt

Journal Article · Mon Nov 30 00:00:00 EST 2015 · Journal of Physical Chemistry. C · OSTI ID:1433882

Charlton, Matthew R.; Dylla, Anthony G.; Stevenson, Keith J.

Related Subjects

25 ENERGY STORAGE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
batteries
electrocatalysis
electrochemistry

Title: Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries

Citation Formats

References (48)

Cited By (17)

Similar Records

Related Subjects

Title: Electrocatalytic transformation of HF impurity to H₂ and LiF in lithium-ion batteries