Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Voltage and Temperature Limits of Advanced Electrolytes for Lithium-Metal Batteries

Journal Article · · ACS Energy Letters
 [1];  [1];  [1];  [2];  [3];  [4];  [4];  [2];  [2];  [3];  [5];  [4];  [1]
  1. State Univ. of New York (SUNY), Binghamton, NY (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Stanford Univ., CA (United States)
  4. Univ. of Maryland, College Park, MD (United States)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES)
+ Show Author Affiliations
Several advanced electrolytes (mainly ether-based) have recently demonstrated excellent electrochemical performance in high energy density lithium (Li)-metal batteries. However, the safety of these ether-based electrolytes is still unknown. This work evaluates the thermal stability of these new formulations to understand their safety limits of operation in comparison to carbonate electrolytes typically used in Li-ion batteries. Electrolyte stability is assessed in conjunction with LiNi0.8Mn0.1Co0.1O2 cathode and Li-metal anode at ultra-high voltages (≤ 4.8 V) and temperatures (≤ 300°C) to trigger thermal runaway, where onset and extent of heat release are monitored via isothermal microcalorimetry and differential scanning calorimetry Most ether-based electrolytes show improved thermal resilience over commercial carbonate formulations when heated up to 300°C. The thermal behavior in presence of charged cathode and Li-metal suggests that the new electrolytes may be better at stabilizing active material surfaces than carbonate electrolytes. Although extreme voltages severely destabilize the ether-based formulations, prompting thermal runaway, a phosphate based localized high concentration electrolyte exhibits superior stability over commercial carbonate electrolytes at all tested temperatures (32°C, 45°C, and 60°C). Although thermal analysis during the first charge process (as adopted in this preliminary study) may be insufficient to conclude the long-term advantages of these electrolytes, a more stable electrolyte identified under extreme voltage and temperature conditions will provide valuable guidance for the safety of future electrolyte designs.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)
Grant/Contract Number:
AC05-76RL01830; EE0007765
OSTI ID:
1962005
Report Number(s):
PNNL-SA-181739
Journal Information:
ACS Energy Letters, Journal Name: ACS Energy Letters Vol. 8; ISSN 2380-8195
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (28)

Electrolyte Design for Lithium Metal Anode‐Based Batteries Toward Extreme Temperature Application journal July 2021
High‐Fluorinated Electrolytes for Li–S Batteries journal February 2019
Formulation of Blended‐Lithium‐Salt Electrolytes for Lithium Batteries journal December 2019
An Inorganic‐Rich Solid Electrolyte Interphase for Advanced Lithium‐Metal Batteries in Carbonate Electrolytes journal December 2020
Salt‐in‐Salt Reinforced Carbonate Electrolyte for Li Metal Batteries journal September 2022
Thermally Stable and Nonflammable Electrolytes for Lithium Metal Batteries: Progress and Perspectives journal August 2021
Practical rechargeable lithium batteries journal May 1989
Performance of Li/TiS2 solid state batteries using phosphorous chalcogenide network former glasses as solid electrolyte journal September 1988
Enabling High-Voltage Lithium-Metal Batteries under Practical Conditions journal July 2019
Novel dual-salts electrolyte solution for dendrite-free lithium-metal based rechargeable batteries with high cycle reversibility journal December 2014
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review journal July 2017
Lithiation of Magnetite (Fe 3 O 4 ): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy journal April 2018
Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi 0.8 Co 0.15 Al 0.05 O 2 journal June 2017
Thermal Stability and Reactivity of Cathode Materials for Li-Ion Batteries journal March 2016
What is the Role of Nb in Nickel-Rich Layered Oxide Cathodes for Lithium-Ion Batteries? journal March 2021
The Potential of the Lithium Electrode. journal April 1913
Reviving the lithium metal anode for high-energy batteries journal March 2017
Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization journal September 2019
Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries journal June 2020
Rational solvent molecule tuning for high-performance lithium metal battery electrolytes journal January 2022
Determining the limiting factor of the electrochemical stability window for PEO-based solid polymer electrolytes: main chain or terminal –OH group? journal January 2020
Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries journal November 2020
Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries journal February 2021
Electrical Energy Storage and Intercalation Chemistry journal June 1976
Review—Localized High-Concentration Electrolytes for Lithium Batteries journal January 2021
Effects of Carbonate Solvents and Lithium Salts in High-Concentration Electrolytes on Lithium Anode journal June 2022
An Analysis of Artificial and Natural Graphite in Lithium Ion Pouch Cells Using Ultra-High Precision Coulometry, Isothermal Microcalorimetry, Gas Evolution, Long Term Cycling and Pressure Measurements journal January 2017
Stability and Rate Capability of Al Substituted Lithium-Rich High-Manganese Content Oxide Materials for Li-Ion Batteries journal January 2011

Similar Records

A Green, Fire–Retarding Ether Solvent for Sustainable High–Voltage Li–Ion Batteries at Standard Salt Concentration
Journal Article · Wed Jul 10 20:00:00 EDT 2024 · Advanced Energy Materials · OSTI ID:2432557

Related Subjects

25 ENERGY STORAGE
electrochemical cells
electrodes
electrolytes
ethers
inorganic carbon compounds