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Title: Facile in Situ Syntheses of Cathode Protective Electrolyte Additives for High Energy Density Li-Ion Cells

Journal Article · · Chemistry of Materials

Increasing the energy densities of Li-ion batteries necessitates operation of layered lithiated oxide cathodes at potentials exceeding 4 V vs Li/Li+. When continually exposed to such high potentials, these materials gradually deteriorate unless protected by sacrificial agents called electrolyte additives. During the formation cycles, these electrolyte additives decompose on the electrodes forming thin protective layers of insoluble products impeding further deleterious reactions. Some of these electrolyte additives spontaneously react when introduced into the electrolyte to yield specific surface-modifying products that alone protect the cathode; in other words, the nominal additive is the precursor and the secondary product is the protective agent. Guided by this insight, we used molecular engineering to obtain such surface-active secondary products in situ with 100% yield. Two of these electrolyte additives proved exceptional in that they delay both the impedance rise and capacity fade in the Li-ion cells. We demonstrate this protective action and scrutinize the activation of these additives in the electrolyte. As a result, by “taming” spontaneous reactions and regaining full control over the chemical structure, new avenues open to targeted synthesis of electrolyte additives extending the operation of high voltage Li-ion batteries.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1531165
Alternate ID(s):
OSTI ID: 1558998
Journal Information:
Chemistry of Materials, Vol. 31, Issue 7; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

References (28)

The cathode–electrolyte interface in the Li-ion battery journal November 2004
Electrolyte additive combinations that enhance performance of high-capacity Li1.2Ni0.15Mn0.55Co0.1O2–graphite cells journal November 2013
Challenges for Rechargeable Li Batteries journal February 2010
Synthesis and Characterization of Lithium Bis(fluoromalonato)borate for Lithium-Ion Battery Applications journal November 2013
Electrolyte additives for lithium ion battery electrodes: progress and perspectives journal January 2016
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Thermal Reactions of LiPF[sub 6] with Added LiBOB journal January 2007
A stable fluorinated and alkylated lithium malonatoborate salt for lithium ion battery application journal January 2015
Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells journal December 2016
Evaluation of Electrolyte Oxidation Stability on Charged LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Surface through Potentiostatic Holds journal January 2016
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
An accelerated calendar and cycle life study of Li-ion cells journal October 2001
Self-Terminated Artificial SEI Layer for Nickel-Rich Layered Cathode Material via Mixed Gas Chemical Vapor Deposition journal October 2015
Recent developments in cathode materials for lithium ion batteries journal February 2010
Investigating the influence of high temperatures on the cycling stability of a LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode using an innovative electrolyte additive journal May 2017
Investigation of Lithium Tetrafluorooxalatophosphate [LiPF[sub 4](C[sub 2]O[sub 4])] as a Lithium-Ion Battery Electrolyte for Elevated Temperature Performance journal January 2010
A Convenient Synthesis of Trimethylsilyl Carboxylates using N -Trimethylsilyl-2-oxazolidinone in the Absence of Catalysts journal January 1981
Tris(trimethylsilyl) Phosphite (TMSPi) and Triethyl Phosphite (TEPi) as Electrolyte Additives for Lithium Ion Batteries: Mechanistic Insights into Differences during LiNi 0.5 Mn 0.3 Co 0.2 O 2 -Graphite Full Cell Cycling journal January 2017
Positive Electrode Passivation by LiDFOB Electrolyte Additive in High-Capacity Lithium-Ion Cells journal January 2012
Understanding Long-Term Cycling Performance of Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 –Graphite Lithium-Ion Cells journal January 2013
Lifetime limit of tris(trimethylsilyl) phosphite as electrolyte additive for high voltage lithium ion batteries journal January 2016
Electrolytes and Interphases in Li-Ion Batteries and Beyond journal October 2014
The Impact of Electrolyte Additives and Upper Cut-off Voltage on the Formation of a Rocksalt Surface Layer in LiNi 0.8 Mn 0.1 Co 0.1 O 2 Electrodes journal January 2017
Enabling High-Energy, High-Voltage Lithium-Ion Cells: Standardization of Coin-Cell Assembly, Electrochemical Testing, and Evaluation of Full Cells journal January 2016
Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach journal October 2017
Investigation of Glutaric Anhydride as an Electrolyte Additive for Graphite/LiNi 0.5 Mn 0.3 Co 0.2 O 2 Full Cells journal December 2016
Structural Changes and Thermal Stability of Charged LiNi x Mn y Co z O 2 Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy journal December 2014
Chemical “Pickling” of Phosphite Additives Mitigates Impedance Rise in Li Ion Batteries journal April 2018

Cited By (2)

Simultaneously Boosting the Ionic Conductivity and Mechanical Strength of Polymer Gel Electrolyte Membranes by Confining Ionic Liquids into Hollow Silica Nanocavities journal September 2019
A Joint DFT and Experimental Study of an Imidazolidinone Additive in Lithium-Ion Cells journal January 2019