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
 

Revealing the Anion–Solvent Interaction for Ultralow Temperature Lithium Metal Batteries

Journal Article · · Advanced Materials
 [1];  [2];  [3];  [3];  [3];  [3];  [4];  [4];  [2];  [3]
  1. Univ. of Maryland, College Park, MD (United States); City Univ. of Hong Kong, Kowloon (Hong Kong)
  2. University of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
  3. Univ. of Maryland, College Park, MD (United States)
  4. Univ. of Rhode Island, Kingston, RI (United States)
+ Show Author Affiliations
Anion solvation in electrolytes can largely change the electrochemical performance of the electrolytes, yet has been rarely investigated. Herein, three anions of bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), and derived asymmetric (fluorosulfonyl)(trifluoro-methanesulfonyl)imide (FTFSI) are systematically examined in a weakly Li+ cation solvating solvent of bis(3-fluoropropyl)ether (BFPE). In-situ liquid secondary ion mass spectrometry demonstrates that FTFSI- and FSI- anions are associated with BFPE solvent, while weak TFSI-/BFPE cluster signals are detected. Molecular modeling further reveals that the anion–solvent interaction is accompanied by the formation of H-bonding-like interactions. Further, anion solvation enhances the Li+ cation transfer number and reduces the organic component in solid electrolyte interphase, which enhances the Li plating/stripping Coulombic efficiency at a low temperature of -30 °C from 42.4% in TFSI-based electrolytes to 98.7% in 1.5 m LiFTFSI and 97.9% in LiFSI-BFPE electrolytes. The anion–solvent interactions, especially asymmetric anion solvation also accelerate the Li+ desolvation kinetics. The 1.5 m LiFTFSI-BFPE electrolyte with strong anion–solvent interaction enables LiNi0.8Mn0.1Co0.1O2 (NMC811)||Li (20 µm) full cell with stable cyclability even under -40 °C, retaining over 92% of initial capacity (115 mAh g-1, after 100 cycles). The anion–solvent interactions insights allow to rational design the electrolyte for lithium metal batteries and beyond to achieve high performance.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE; USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)
Grant/Contract Number:
AC02-06CH11357; AC05-76RL01830; AR0000389
OSTI ID:
2345046
Alternate ID(s):
OSTI ID: 2229828
Journal Information:
Advanced Materials, Journal Name: Advanced Materials Journal Issue: 7 Vol. 36; ISSN 0935-9648
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (34)

High‐Safety and High‐Energy‐Density Lithium Metal Batteries in a Novel Ionic‐Liquid Electrolyte journal May 2020
Hitherto Unknown Solvent and Anion Pairs in Solvation Structures Reveal New Insights into High‐Performance Lithium‐Ion Batteries journal August 2022
Accurate Determination of Coulombic Efficiency for Lithium Metal Anodes and Lithium Metal Batteries journal October 2017
Stable Anion‐Derived Solid Electrolyte Interphase in Lithium Metal Batteries journal September 2021
Non‐Solvating and Low‐Dielectricity Cosolvent for Anion‐Derived Solid Electrolyte Interphases in Lithium Metal Batteries journal April 2021
Anion‐Regulated Weakly Solvating Electrolytes for High‐Voltage Lithium Metal Batteries journal November 2022
Critical Review on cathode–electrolyte Interphase Toward High-Voltage Cathodes for Li-Ion Batteries journal August 2022
Enabling High-Voltage Lithium-Metal Batteries under Practical Conditions journal July 2019
Electrochemical properties and lithium ion solvation behavior of sulfone–ester mixed electrolytes for high-voltage rechargeable lithium cells journal May 2008
Modeling Insight into Battery Electrolyte Electrochemical Stability and Interfacial Structure journal November 2017
Investigation of Ion–Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS journal February 2018
Before Li Ion Batteries journal November 2018
Role of Mixed Solvation and Ion Pairing in the Solution Structure of Lithium Ion Battery Electrolytes journal June 2015
Spectroscopic and Density Functional Theory Characterization of Common Lithium Salt Solvates in Carbonate Electrolytes for Lithium Batteries journal January 2017
In Situ Mass Spectrometric Determination of Molecular Structural Evolution at the Solid Electrolyte Interphase in Lithium-Ion Batteries journal August 2015
Operando Investigation into Dynamic Evolution of Cathode–Electrolyte Interfaces in a Li-Ion Battery journal February 2019
In-Depth Interfacial Chemistry and Reactivity Focused Investigation of Lithium–Imide- and Lithium–Imidazole-Based Electrolytes journal June 2016
Effect of Building Block Connectivity and Ion Solvation on Electrochemical Stability and Ionic Conductivity in Novel Fluoroether Electrolytes journal July 2021
An All-Fluorinated Ester Electrolyte for Stable High-Voltage Li Metal Batteries Capable of Ultra-Low-Temperature Operation journal April 2020
Emerging Era of Electrolyte Solvation Structure and Interfacial Model in Batteries journal January 2022
Oxidative Stabilization of Dilute Ether Electrolytes via Anion Modification journal January 2022
Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes journal October 2017
First-Principles Density Functional Theory Modeling of Li Binding: Thermodynamics and Redox Properties of Quinone Derivatives for Lithium-Ion Batteries journal February 2016
Ultrahigh Performance All Solid-State Lithium Sulfur Batteries: Salt Anion’s Chemistry-Induced Anomalous Synergistic Effect journal July 2018
A New Class of Ionically Conducting Fluorinated Ether Electrolytes with High Electrochemical Stability journal April 2020
Solvation Sheath of Li + in Nonaqueous Electrolytes and Its Implication of Graphite/Electrolyte Interface Chemistry journal May 2007
Spectroscopic Identification of the Lithium Ion Transporting Species in LiTFSI-Doped Ionic Liquids journal January 2009
A materials perspective on Li-ion batteries at extreme temperatures journal July 2017
Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature journal February 2021
Aqueous electrolyte design for super-stable 2.5 V LiMn2O4 || Li4Ti5O12 pouch cells journal February 2022
Electrochemical energy storage devices working in extreme conditions journal January 2021
Electrolyte design implications of ion-pairing in low-temperature Li metal batteries journal January 2022
Anion electric field is related to hydration energy journal May 2003
Identification of Surface Films Formed on Lithium in Dimethoxyethane and Tetrahydrofuran Solutions journal January 1988

Similar Records

Electrolyte Solvation and Ionic Association. V. Acetonitrile-Lithium Bis(fluorosulfonyl)imide (LiFSI) Mixtures
Journal Article · Tue Sep 30 00:00:00 EDT 2014 · Journal of the Electrochemical Society, 161(14):A2042-A2053 · OSTI ID:1167619
Electrolyte Solvation and Ionic Association: Part IX. Structures and Raman Spectroscopic Characterization of LiFSI Solvates
Journal Article · Sun Nov 27 19:00:00 EST 2022 · Journal of the Electrochemical Society · OSTI ID:2419630

Related Subjects

25 ENERGY STORAGE
Anion solvation
Li metal batteries
asymmetric
electrolyte design
low temperature