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

Abstract

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.

Authors:

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

Publication Date:: Mon Apr 09 00:00:00 EDT 2018

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

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

OSTI Identifier:: 1433882

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Nature Catalysis

Additional Journal Information:: Journal Volume: 1; Journal Issue: 4; Journal ID: ISSN 2520-1158

Publisher:: Springer Nature

Country of Publication:: United States

Language:: English

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

Citation Formats


                    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, and Markovic, Nenad M. Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries.  United States: N. p., 2018. 
Web.  doi:10.1038/s41929-018-0047-z.

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                    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. Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries.  United States.  https://doi.org/10.1038/s41929-018-0047-z

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                    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, and Markovic, Nenad M. Mon .  
"Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries".  United States.  https://doi.org/10.1038/s41929-018-0047-z.  https://www.osti.gov/servlets/purl/1433882.

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@article{osti_1433882,

  title        = {Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries},

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

  abstractNote = {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.},

  doi          = {10.1038/s41929-018-0047-z},

  journal      = {Nature Catalysis},

  number       = 4,

  volume       = 1,

  place        = {United States},

  year         = {Mon Apr 09 00:00:00 EDT 2018},

  month        = {Mon Apr 09 00:00:00 EDT 2018}

}

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Phosphorus pentoxide (P₂O₅) is investigated as an acid scavenger to remove the acidic impurities in a commercial lithium hexafluorophosphate (LiPF₆) carbonate electrolyte to improve the electrochemical properties of Li metal batteries. Nuclear magnetic resonance (NMR) measurements reveal the detailed reaction mechanisms of P₂O₅ with the LiPF₆ electrolyte and its impurities, which removes hydrogen fluoride (HF) and difluor-ophosphoric acid (HPO₂F₂) and produces phosphorus oxyfluoride (POF₃), OF₂P-O-PF₅^- anions, and ethyl difluorophosphate (C₂H₅OPOF₂) as new electrolyte species. The P₂O₅-modified LiPF₆ electrolyte is chemically compatible with a Li metal anode and LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) cathode, generating a PO_xF_y-rich solid electrolyte interphase (SEI) that leads tomore »« less
https://doi.org/10.1021/acsami.2c09267

Full Text Available
First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF

Journal Article Yildirim, Handan ; Kinaci, Alper ; Chan, Maria K. Y. ; ... - ACS Applied Materials and Interfaces

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.more »« less
Cited by 165
https://doi.org/10.1021/acsami.5b02904

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

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Citation Formats

The interaction of water with solid surfaces: Fundamental aspects journal, October 1987

Origin of Anomalous Activities for Electrocatalysts in Alkaline Electrolytes journal, October 2012

Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction journal, November 2008

Decomposition reaction of LiPF6-based electrolytes for lithium ion cells journal, June 2006

Computational high-throughput screening of electrocatalytic materials for hydrogen evolution journal, October 2006

pH in Grand Canonical Statistics of an Electrochemical Interface 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 journal, September 1997

In Situ AFM Study of Surface Film Formation on the Edge Plane of HOPG for Lithium-Ion Batteries journal, December 2011

Surface Film Formation on Graphite Negative Electrode in Lithium-Ion Batteries: AFM Study in an Ethylene Carbonate-Based Solution journal, January 2001

Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy journal, June 2013

Origin of H 2 Evolution in LIBs: H 2 O Reduction vs. Electrolyte Oxidation journal, January 2016

Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method journal, June 2010

Surface film formation on a graphite electrode in Li-ion batteries: AFM and XPS study journal, January 2005

The interaction of water with solid surfaces: fundamental aspects revisited journal, May 2002

Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured In situ by Neutron Reflectometry 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 journal, March 2007

Energy and fuels from electrochemical interfaces journal, December 2016

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal, October 2004

Role of 1,3-Propane Sultone and Vinylene Carbonate in Solid Electrolyte Interface Formation and Gas Generation journal, May 2015

The mechanism of HF formation in LiPF6 based organic carbonate electrolytes journal, January 2012

Electric Potential Gradient at the Buried Interface between Lithium-Ion Battery Electrodes and the SEI Observed Using Photoelectron Spectroscopy journal, April 2016

Investigation of thermal aging and hydrolysis mechanisms in commercial lithium ion battery electrolyte journal, November 2013

Electrochemical SPM investigation of the solid electrolyte interphase film formed on HOPG electrodes journal, June 2000

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries journal, September 2010

Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries journal, November 2015

A new look at the solid electrolyte interphase on graphite anodes in Li-ion batteries journal, February 2006

Ultra-thin passivating film induced by vinylene carbonate on highly oriented pyrolytic graphite negative electrode in lithium-ion cell journal, June 2002

Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O journal, January 2005

Electrochemical AFM Observation of the HOPG Edge Plane in Ethylene Carbonate-Based Electrolytes Containing Film-Forming Additives journal, January 2012

Composition, depth profiles and lateral distribution of materials in the SEI built on HOPG-TOF SIMS and XPS studies journal, July 2001

When Small is Big: The Role of Impurities in Electrocatalysis journal, September 2015

Design principles for hydrogen evolution reaction catalyst materials journal, November 2016

Work function, electronegativity, and electrochemical behaviour of metals journal, September 1972

Surface science studies of model fuel cell electrocatalysts journal, April 2002

The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling journal, August 2016

Oxygen reduction reaction on Pt(111): effects of bromide journal, June 1999

Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media journal, October 2015

Effects of electrolyte-volume-to-electrode-area ratio on redox behaviors of graphite anodes for lithium-ion batteries journal, September 2014

A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures journal, January 1996

Electrode–solution interactions in Li-ion batteries: a short summary and new insights journal, June 2003

Manganese dissolution from LiMn2O4 cathodes at elevated temperature: methylene methanedisulfonate as electrolyte additive journal, August 2015

Towards the computational design of solid catalysts journal, April 2009

Understanding Transition-Metal Dissolution Behavior in LiNi 0.5 Mn 1.5 O 4 High-Voltage Spinel for Lithium Ion Batteries journal, July 2013

Comparison of Voltammetric Responses over the Cathodic Region in LiPF[sub 6] and LiBETI with and without HF journal, January 2005

Review—SEI: Past, Present and Future journal, January 2017

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal, December 2004

Work function, electronegativity, and electrochemical behaviour of metals journal, December 1971

Tuning the activities of cuprous oxide nanostructures via the oxide-metal interaction journal, May 2020

Deactivating Defects in Graphenes with Al 2 O 3 Nanoclusters to Produce Long-Life and High-Rate Sodium-Ion Batteries journal, November 2018

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite journal, July 2018

A Comparison of Formation Methods for Graphite//LiFePO 4 Cells journal, January 2019

High energy density of multivalent glass‐ceramic cathodes for Li‐ion rechargeable cells and as an efficient photocatalyst for organic degradation journal, January 2020

Fading Mechanisms and Voltage Hysteresis in FeF 2 -NiF 2 Solid Solution Cathodes for Lithium and Lithium-Ion Batteries journal, January 2019

Anion–π interactions in lithium–organic redox flow batteries journal, January 2019

The hydrogen evolution reaction: from material to interfacial descriptors journal, January 2019

Li-diffusion at the interface between Li-metal and [Pyr 14 ][TFSI]-ionic liquid: Ab initio molecular dynamics simulations journal, January 2020

Identifying Contact Resistances in High-Voltage Cathodes by Impedance Spectroscopy journal, January 2019

Quantification of PF 5 and POF 3 from Side Reactions of LiPF 6 in Li-Ion Batteries journal, January 2018

Electrolyte and SEI Decomposition Reactions of Transition Metal Ions Investigated by On-Line Electrochemical Mass Spectrometry journal, January 2018

The Impact of CO 2 Evolved from VC and FEC during Formation of Graphite Anodes in Lithium-Ion Batteries journal, January 2019

Editors' Choice—Capacity Fading Mechanisms of NCM-811 Cathodes in Lithium-Ion Batteries Studied by X-ray Diffraction and Other Diagnostics journal, January 2019

Sodium Borosilicate Glass Separators as an Electrolyte Additive Donor for Improving the Electrochemical Performance of Lithium-Ion Batteries 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 journal, January 2018

Formation of the Solid Electrolyte Interphase at Constant Potentials: a Model Study on Highly Oriented Pyrolytic Graphite journal, July 2018

Tuning the Selectivity and Activity of Electrochemical Interfaces with Defective Graphene Oxide and Reduced Graphene Oxide journal, August 2019

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

The interaction of water with solid surfaces: Fundamental aspects
journal, October 1987

Origin of Anomalous Activities for Electrocatalysts in Alkaline Electrolytes
journal, October 2012

Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction
journal, November 2008

Decomposition reaction of LiPF6-based electrolytes for lithium ion cells
journal, June 2006

Computational high-throughput screening of electrocatalytic materials for hydrogen evolution
journal, October 2006

pH in Grand Canonical Statistics of an Electrochemical Interface
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
journal, September 1997

In Situ AFM Study of Surface Film Formation on the Edge Plane of HOPG for Lithium-Ion Batteries
journal, December 2011

Surface Film Formation on Graphite Negative Electrode in Lithium-Ion Batteries: AFM Study in an Ethylene Carbonate-Based Solution
journal, January 2001

Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy
journal, June 2013

Origin of H ₂ Evolution in LIBs: H ₂ O Reduction vs. Electrolyte Oxidation
journal, January 2016

Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method
journal, June 2010

Surface film formation on a graphite electrode in Li-ion batteries: AFM and XPS study
journal, January 2005

The interaction of water with solid surfaces: fundamental aspects revisited
journal, May 2002

Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured In situ by Neutron Reflectometry
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
journal, March 2007

Energy and fuels from electrochemical interfaces
journal, December 2016

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004

Role of 1,3-Propane Sultone and Vinylene Carbonate in Solid Electrolyte Interface Formation and Gas Generation
journal, May 2015

The mechanism of HF formation in LiPF6 based organic carbonate electrolytes
journal, January 2012

Electric Potential Gradient at the Buried Interface between Lithium-Ion Battery Electrodes and the SEI Observed Using Photoelectron Spectroscopy
journal, April 2016

Investigation of thermal aging and hydrolysis mechanisms in commercial lithium ion battery electrolyte
journal, November 2013

Electrochemical SPM investigation of the solid electrolyte interphase film formed on HOPG electrodes
journal, June 2000

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010

Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries
journal, November 2015

A new look at the solid electrolyte interphase on graphite anodes in Li-ion batteries
journal, February 2006

Ultra-thin passivating film induced by vinylene carbonate on highly oriented pyrolytic graphite negative electrode in lithium-ion cell
journal, June 2002

Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O
journal, January 2005

Electrochemical AFM Observation of the HOPG Edge Plane in Ethylene Carbonate-Based Electrolytes Containing Film-Forming Additives
journal, January 2012

Composition, depth profiles and lateral distribution of materials in the SEI built on HOPG-TOF SIMS and XPS studies
journal, July 2001

When Small is Big: The Role of Impurities in Electrocatalysis
journal, September 2015

Design principles for hydrogen evolution reaction catalyst materials
journal, November 2016

Work function, electronegativity, and electrochemical behaviour of metals
journal, September 1972

Surface science studies of model fuel cell electrocatalysts
journal, April 2002

The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling
journal, August 2016

Oxygen reduction reaction on Pt(111): effects of bromide
journal, June 1999

Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media
journal, October 2015

Effects of electrolyte-volume-to-electrode-area ratio on redox behaviors of graphite anodes for lithium-ion batteries
journal, September 2014

A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures
journal, January 1996

Electrode–solution interactions in Li-ion batteries: a short summary and new insights
journal, June 2003

Manganese dissolution from LiMn2O4 cathodes at elevated temperature: methylene methanedisulfonate as electrolyte additive
journal, August 2015

Towards the computational design of solid catalysts
journal, April 2009

Understanding Transition-Metal Dissolution Behavior in LiNi _0.5 Mn _1.5 O ₄ High-Voltage Spinel for Lithium Ion Batteries
journal, July 2013

Comparison of Voltammetric Responses over the Cathodic Region in LiPF[sub 6] and LiBETI with and without HF
journal, January 2005

Review—SEI: Past, Present and Future
journal, January 2017

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, December 2004

Work function, electronegativity, and electrochemical behaviour of metals
journal, December 1971

Tuning the activities of cuprous oxide nanostructures via the oxide-metal interaction
journal, May 2020

Deactivating Defects in Graphenes with Al ₂ O ₃ Nanoclusters to Produce Long-Life and High-Rate Sodium-Ion Batteries
journal, November 2018

Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite
journal, July 2018

A Comparison of Formation Methods for Graphite//LiFePO ₄ Cells
journal, January 2019

High energy density of multivalent glass‐ceramic cathodes for Li‐ion rechargeable cells and as an efficient photocatalyst for organic degradation
journal, January 2020

Fading Mechanisms and Voltage Hysteresis in FeF ₂ -NiF ₂ Solid Solution Cathodes for Lithium and Lithium-Ion Batteries
journal, January 2019

Anion–π interactions in lithium–organic redox flow batteries
journal, January 2019

The hydrogen evolution reaction: from material to interfacial descriptors
journal, January 2019

Li-diffusion at the interface between Li-metal and [Pyr ₁₄ ][TFSI]-ionic liquid: Ab initio molecular dynamics simulations
journal, January 2020

Identifying Contact Resistances in High-Voltage Cathodes by Impedance Spectroscopy
journal, January 2019

Quantification of PF ₅ and POF ₃ from Side Reactions of LiPF ₆ in Li-Ion Batteries
journal, January 2018

Electrolyte and SEI Decomposition Reactions of Transition Metal Ions Investigated by On-Line Electrochemical Mass Spectrometry
journal, January 2018

The Impact of CO ₂ Evolved from VC and FEC during Formation of Graphite Anodes in Lithium-Ion Batteries
journal, January 2019

Editors' Choice—Capacity Fading Mechanisms of NCM-811 Cathodes in Lithium-Ion Batteries Studied by X-ray Diffraction and Other Diagnostics
journal, January 2019

Sodium Borosilicate Glass Separators as an Electrolyte Additive Donor for Improving the Electrochemical Performance of Lithium-Ion Batteries
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
journal, January 2018

Formation of the Solid Electrolyte Interphase at Constant Potentials: a Model Study on Highly Oriented Pyrolytic Graphite
journal, July 2018

Tuning the Selectivity and Activity of Electrochemical Interfaces with Defective Graphene Oxide and Reduced Graphene Oxide
journal, August 2019