DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electrocatalysis paradigm for protection of cathode materials in high-voltage lithium-ion batteries

Journal Article · · Journal of Physical Chemistry. C
 [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)

A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives. Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1337951
Journal Information:
Journal of Physical Chemistry. C, Vol. 120, Issue 28; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

References (104)

The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model journal January 1979
Identification of Surface Films Formed on Lithium in Propylene Carbonate Solutions journal January 1987
Failure and Stabilization Mechanisms of Graphite Electrodes journal March 1997
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries journal August 2000
Review on electrode–electrolyte solution interactions, related to cathode materials for Li-ion batteries journal March 2007
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Electrolytes and Interphases in Li-Ion Batteries and Beyond journal October 2014
Prospects and Limits of Energy Storage in Batteries journal February 2015
A Review of Solid Electrolyte Interphases on Lithium Metal Anode journal November 2015
Materials Challenges and Opportunities of Lithium Ion Batteries journal January 2011
Issues and challenges facing rechargeable lithium batteries journal November 2001
Building better batteries journal February 2008
Recent progress in high-voltage lithium ion batteries journal September 2013
Electrochemical Behavior of Nonflammable Organo-Fluorine Compounds for Lithium Ion Batteries journal January 2009
Electrochemical investigation of carbonate-based electrolytes for high voltage lithium-ion cells journal August 2013
Fluorinated electrolytes for 5-V Li-ion chemistry: Dramatic enhancement of LiNi0.5Mn1.5O4/graphite cell performance by a lithium reservoir journal July 2014
Perfluoroalkyl-substituted ethylene carbonates: Novel electrolyte additives for high-voltage lithium-ion batteries journal January 2014
Sulfone-Based Electrolytes for Lithium-Ion Batteries journal January 2002
New sulfone electrolytes for rechargeable lithium batteries.: Part I. Oligoether-containing sulfones journal March 2005
Doped sulfone electrolytes for high voltage Li-ion cell applications journal July 2009
Sulfone-based electrolytes for high-voltage Li-ion batteries journal May 2009
Electrochemical Windows of Sulfone-Based Electrolytes for High-Voltage Li-Ion Batteries journal October 2011
Electrolyte Systems for High Withstand Voltage and Durability I. Linear Sulfones for Electric Double-Layer Capacitors journal January 2011
Electrode/Electrolyte Interface in Sulfolane-Based Electrolytes for Li Ion Batteries: A Molecular Dynamics Simulation Study journal November 2012
On the possibility of using ionic liquids as electrolyte solutions for rechargeable 5V Li ion batteries journal August 2006
On the application of ionic liquids for rechargeable Li batteries: High voltage systems journal April 2009
High-Voltage Electrolytes Based on Adiponitrile for Li-Ion Batteries journal January 2009
High Voltage Performances of Li[sub 2]NiPO[sub 4]F Cathode with Dinitrile-Based Electrolytes journal January 2010
Effects of Some Organic Additives on Lithium Deposition in Propylene Carbonate journal January 2002
Additives-containing functional electrolytes for suppressing electrolyte decomposition in lithium-ion batteries journal October 2004
Functional electrolytes: Novel type additives for cathode materials, providing high cycleability performance journal February 2006
A review on electrolyte additives for lithium-ion batteries journal November 2006
New boron compounds as additives for lithium polymer electrolytes journal December 2007
The Effect of Vinylene Carbonate Additive on Surface Film Formation on Both Electrodes in Li-Ion Batteries journal January 2009
Electrolyte Additive in Support of 5 V Li Ion Chemistry journal January 2011
Inorganic additives for passivation of high voltage cathode materials journal February 2011
Tris(trimethylsilyl)phosphite as electrolyte additive for high voltage layered lithium nickel cobalt manganese oxide cathode of lithium ion battery journal November 2014
Reduction mechanisms of additives on Si anodes of Li-ion batteries journal January 2014
Comparative Study of Tris(trimethylsilyl) Phosphate and Tris(trimethylsilyl) Phosphite as Electrolyte Additives for Li-Ion Cells journal January 2014
Improving the electrochemical performance of high voltage spinel cathode at elevated temperature by a novel electrolyte additive journal January 2016
An investigation of functionalized electrolyte using succinonitrile additive for high voltage lithium-ion batteries journal February 2016
Anodic Decomposition of Trimethylboroxine as Additive for High Voltage Li-Ion Batteries journal January 2014
Improving cyclic stability of lithium nickel manganese oxide cathode at elevated temperature by using dimethyl phenylphosphonite as electrolyte additive journal January 2015
Why is tris(trimethylsilyl) phosphite effective as an additive for high-voltage lithium-ion batteries? journal January 2015
Tris(2,2,2-trifluoroethyl) phosphite as an electrolyte additive for high-voltage lithium-ion batteries using lithium-rich layered oxide cathode journal November 2015
Mechanistic Insight in the Function of Phosphite Additives for Protection of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode in High Voltage Li-Ion Cells journal April 2016
Triethylborate as an electrolyte additive for high voltage layered lithium nickel cobalt manganese oxide cathode of lithium ion battery journal March 2016
Development of novel lithium borate additives for designed surface modification of high voltage LiNi 0.5 Mn 1.5 O 4 cathodes journal January 2016
Strategies for improving the cyclability and thermo-stability of LiMn 2 O 4 -based batteries at elevated temperatures journal January 2015
Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries journal January 2012
Microscopy and Spectroscopy of Lithium Nickel Oxide-Based Particles Used in High Power Lithium-Ion Cells journal January 2003
Manganese in Graphite Anode and Capacity Fade in Li Ion Batteries journal October 2014
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
On the Electrochemical Behavior of Aluminum Electrodes in Nonaqueous Electrolyte Solutions of Lithium Salts journal January 2010
Aluminum Corrosion in Lithium Batteries An Investigation Using the Electrochemical Quartz Crystal Microbalance journal January 2000
Aluminum corrosion in electrolyte of Li-ion battery journal July 2002
Current Collectors for Positive Electrodes of Lithium-Based Batteries journal January 2005
Corrosion of Aluminum Current Collectors in High-Power Lithium-Ion Batteries for Use in Hybrid Electric Vehicles journal January 2007
Allotropic Control: How Certain Fluorinated Carbonate Electrolytes Protect Aluminum Current Collectors by Promoting the Formation of Insoluble Coordination Polymers journal August 2016
Electrochemical behavior and passivation of current collectors in lithium-ion batteries journal January 2011
Mechanism of hydrofluoric acid formation in ethylene carbonate electrolytes with fluorine salt additives journal November 2015
Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries journal January 2005
Interfacial Origin of Performance Improvement and Fade for 4.6 V LiNi 0.5 Co 0.2 Mn 0.3 O 2 Battery Cathodes journal May 2014
Mitigating Performance Degradation of High-Capacity Lithium-Ion Cells with Boronate-Based Electrolyte Additives journal January 2014
Lifetime limit of tris(trimethylsilyl) phosphite as electrolyte additive for high voltage lithium ion batteries journal January 2016
Electrolyte solution for the improved cycling performance of LiCoPO4/C composite cathodes journal March 2013
Computation of Thermodynamic Oxidation Potentials of Organic Solvents Using Density Functional Theory journal January 2001
Theoretical Investigations on Oxidative Stability of Solvents and Oxidative Decomposition Mechanism of Ethylene Carbonate for Lithium Ion Battery Use journal December 2009
Density Functional Theory Study of the Role of Anions on the Oxidative Decomposition Reaction of Propylene Carbonate journal December 2011
Oxidation induced decomposition of ethylene carbonate from DFT calculations – importance of explicitly treating surrounding solvent journal January 2012
Why Do Sulfone-Based Electrolytes Show Stability at High Voltages? Insight from Density Functional Theory journal November 2013
Oxidative Decomposition of Propylene Carbonate in Lithium Ion Batteries: A DFT Study journal July 2013
Oxidative Stability and Initial Decomposition Reactions of Carbonate, Sulfone, and Alkyl Phosphate-Based Electrolytes journal April 2013
Quantum chemistry study of the oxidation-induced stability and decomposition of propylene carbonate-containing complexes journal January 2014
Molecular Modeling of Electrolytes book January 2014
Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights journal October 2015
Importance of Reduction and Oxidation Stability of High Voltage Electrolytes and Additives journal August 2016
Proton transfer rates in ionized water clusters (H 2 O) n (n = 2–4) journal January 2015
Chasing charge localization and chemical reactivity following photoionization in liquid water journal December 2011
First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li x Mn 2 O 4 (100) Surfaces journal April 2012
Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries journal December 2012
Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results journal May 1995
Understanding TiO 2 Photocatalysis: Mechanisms and Materials journal May 2014
Mechanistic Insight into the Protective Action of Bis(oxalato)borate and Difluoro(oxalate)borate Anions in Li-Ion Batteries. journal October 2013
Identifying Trapped Electronic Holes at the Aqueous TiO 2 Interface journal March 2014
Towards high throughput screening of electrochemical stability of battery electrolytes journal August 2015
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 2. Radiolytically Induced Polymerization of Ethylene Carbonate journal September 2013
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 1. Spectroscopic Observations of Radical Intermediates Generated in One-Electron Reduction of Carbonates journal September 2013
Ion-radical intermediates of the radiation-chemical transformations of organic carbonates journal July 2016
Second-order perturbation treatment of the general spin hamiltonian in an arbitrary coordinate system journal December 1974
Comments on second-order spin-hamiltonian energies journal April 1975
Electron spin resonance spectrum of trimethyl borate ([(MeO)3B.cntdot.B(OMe)3]-). A novel .sigma. radical with a one-electron bond journal November 1977
Radiation Stability of Organosilicon Compounds. journal April 1961
The radiation chemistry of some polysiloxanes: An electron spin resonance study journal January 1963
Radical formation in polydimethylsiloxanes and polydimethyldiphenylsiloxanes studied by the ESR spintrap technique journal January 1987
The radiation chemistry of poly(dimethyl-siloxane) journal July 2000
NMR study of the gamma radiolysis of poly(dimethyl siloxane) under vacuum at 303 K journal February 2002
Electron spin resonance studies. Part XLVII. Sulphinyl- and sulphonyl-substituted aliphatic radicals journal January 1975
Sulfinyl, α-Sulfinyl, Sulfonyl, and α-Sulfonyl Radicals journal October 1985
Electron spin resonance spectrum of radicals in γ-irradiated trimethyl phosphite: P(OMe) 4 , HP(OMe) 3 , P(OMe) 2 , (MeO) 3 P-P(OMe) 3 + and H 2 COP(OMe) 2 journal October 1972
Electron spin resonance identification of the dimer radical cation (CH 3 O) 3 P-P(OCH 3 )3/+ in γ-irradiated trimethyl phosphite from second-order hyperfine structure journal November 1974
Mechanism of oxygen evolution on perovskites journal July 1983
Electrocatalytic properties of transition metal oxides for oxygen evolution reaction journal May 1986
A Fundamental Relationship between Reaction Mechanism and Stability in Metal Oxide Catalysts for Oxygen Evolution journal January 2016

Cited By (5)

Enhancing the cycle stability of Li–O 2 batteries via functionalized carbon nanotube-based electrodes journal January 2020
Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds journal January 2019
Chemical Weathering of Layered Ni-Rich Oxide Electrode Materials: Evidence for Cation Exchange journal January 2017
Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells journal December 2016
Preformed Anodes for High-Voltage Lithium-Ion Battery Performance: Fluorinated Electrolytes, Crosstalk, and the Origins of Impedance Rise journal January 2018