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Title: High rate and stable cycling of lithium metal anode

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms7362· OSTI ID:1184948
 [1];  [1];  [1];  [2];  [3];  [4];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Joint Center for Energy Storage Research; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy & Environment Directorate
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy & Environment Directorate
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  4. U.S. Army Research Lab., Adelphi, MD (United States). Sensor & Electron Devices Directorate

Lithium (Li) metal is an ideal anode material for rechargeable batteries. However, dendritic Li growth and limited Coulombic efficiency (CE) during repeated Li deposition/stripping processes have prevented the application of this anode in rechargeable Li metal batteries, especially for use at high current densities. Here, we report that the use of highly concentrated electrolytes composed of ether solvents and the lithium bis(fluorosulfonyl)imide (LiFSI) salt enables the high rate cycling of a Li metal anode at high CE (up to 99.1 %) without dendrite growth. With 4 M LiFSI in 1,2-dimethoxyethane (DME) as the electrolyte, a Li|Li cell can be cycled at high rates (10 mA cm-2) for more than 6000 cycles with no increase in the cell impedance, and a Cu|Li cell can be cycled at 4 mA cm-2 for more than 1000 cycles with an average CE of 98.4%. These excellent high rate performances can be attributed to the increased solvent coordination and increased availability of Li+ concentration in the electrolyte. Lastly, further development of this electrolyte may lead to practical applications for Li metal anode in rechargeable batteries. The fundamental mechanisms behind the high rate ion exchange and stability of the electrolytes also shine light on the stability of other electrochemical systems.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1184948
Report Number(s):
PNNL-SA-107989; 48379; 48316; KC0208010
Journal Information:
Nature Communications, Vol. 6; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 1583 works
Citation information provided by
Web of Science

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Advances and issues in developing salt-concentrated battery electrolytes journal March 2019
Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization journal September 2019
2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li–S batteries journal February 2018
Suppressing the effect of lithium dendritic growth by the addition of magnesium bis(trifluoromethanesulfonyl)amide journal January 2018
“Solvent-in-salt” systems for design of new materials in chemistry, biology and energy research journal January 2018
A hybrid electrolyte for long-life semi-solid-state lithium sulfur batteries journal January 2017
A new ether-based electrolyte for lithium sulfur batteries using a S@pPAN cathode journal January 2018
Highly concentrated electrolyte solutions for 4 V class potassium-ion batteries journal January 2018
Applications of 2D MXenes in energy conversion and storage systems journal January 2019
Expanded-graphite embedded in lithium metal as dendrite-free anode of lithium metal batteries journal January 2019
Improving the Li–S battery performance by applying a combined interface engineering approach on the Li 2 S cathode journal January 2019
A new approach to very high lithium salt content quasi-solid state electrolytes for lithium metal batteries using plastic crystals journal January 2019
Composite lithium electrode with mesoscale skeleton via simple mechanical deformation journal March 2019
Graphitized Carbon Fibers as Multifunctional 3D Current Collectors for High Areal Capacity Li Anodes journal June 2017
High Areal Capacity and Lithium Utilization in Anodes Made of Covalently Connected Graphite Microtubes journal August 2017
High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes journal March 2018
Suppressing Li Metal Dendrites Through a Solid Li‐Ion Backup Layer journal August 2018
Passivation of Lithium Metal Anode via Hybrid Ionic Liquid Electrolyte toward Stable Li Plating/Stripping journal November 2016
A Concentrated Ternary‐Salts Electrolyte for High Reversible Li Metal Battery with Slight Excess Li journal December 2018
Efficient Li‐Ion‐Conductive Layer for the Realization of Highly Stable High‐Voltage and High‐Capacity Lithium Metal Batteries journal February 2019
3D Nanowire Arrayed Cu Current Collector toward Homogeneous Alloying Anode Deposition for Enhanced Sodium Storage journal June 2019
Eliminating Dendrites through Dynamically Engineering the Forces Applied during Li Deposition for Stable Lithium Metal Anodes journal December 2019
Fluorine and Lithium: Ideal Partners for High‐Performance Rechargeable Battery Electrolytes journal November 2019
Cation−Solvent, Cation−Anion, and Solvent−Solvent Interactions with Electrolyte Solvation in Lithium batteries journal January 2019
Atomic Layer Deposition of Li x Al y S Solid-State Electrolytes for Stabilizing Lithium-Metal Anodes journal April 2016
Electrolytes for Batteries with Earth-Abundant Metal Anodes journal November 2018
Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents journal July 2019
An Electrolyte for Reversible Cycling of Sodium Metal and Intercalation Compounds journal December 2016
Electrode Edge Effects and the Failure Mechanism of Lithium-Metal Batteries journal October 2018
Fast Charging Lithium Batteries: Recent Progress and Future Prospects journal March 2019
Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth journal February 2016
A facile surface chemistry route to a stabilized lithium metal anode journal July 2017
Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li-Na alloy–O2 batteries journal November 2018
A lithium-ion oxygen battery with a Si anode lithiated in situ by a Li 3 N-containing cathode journal January 2018
Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode journal January 2017
Monolayer InP 3 as a reversible anode material for ultrafast charging lithium- and sodium-ion batteries: a theoretical study journal January 2018
Water-tolerant lithium metal cycling in high lithium concentration phosphonium-based ionic liquid electrolytes journal January 2018
First principles studies of self-diffusion processes on metallic lithium surfaces journal January 2019
Liquid Structures and Transport Properties of Lithium Bis(fluorosulfonyl)amide/Glyme Solvate Ionic Liquids for Lithium Batteries journal January 2019
High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes journal May 2018
In operando plasmonic monitoring of electrochemical evolution of lithium metal journal October 2018
The energy-storage frontier: Lithium-ion batteries and beyond journal November 2015
Enhanced Cyclability of Lithium-Oxygen Batteries with Electrodes Protected by Surface Films Induced via In Situ Electrochemical Process journal January 2018
Magnetic Field–Suppressed Lithium Dendrite Growth for Stable Lithium‐Metal Batteries journal April 2019
Suppressing Lithium Dendrite Growth via Sinusoidal Ripple Current Produced by Triboelectric Nanogenerators journal April 2019
Cross Talk between Transition Metal Cathode and Li Metal Anode: Unraveling Its Influence on the Deposition/Dissolution Behavior and Morphology of Lithium journal April 2019
Ein Hybrid‐Anion für ionische Flüssigkeiten und Batterieelektrolytanwendungen: Halb Triflamid, halb Carbonat journal February 2019
High‐Energy Rechargeable Metallic Lithium Battery at −70 °C Enabled by a Cosolvent Electrolyte journal March 2019
Self‐Healable Solid Polymeric Electrolytes for Stable and Flexible Lithium Metal Batteries journal December 2019
Safe Lithium‐Metal Anodes for Li−O 2 Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection journal May 2019
Electrolytes for Dual‐Carbon Batteries journal March 2019
High-Performance Anode Materials for Rechargeable Lithium-Ion Batteries journal March 2018
Pathways for practical high-energy long-cycling lithium metal batteries journal February 2019
The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries journal October 2016
High-voltage positive electrode materials for lithium-ion batteries journal January 2017
Recent advances in inorganic 2D materials and their applications in lithium and sodium batteries journal January 2017
Suppression of dendritic lithium growth in lithium metal-based batteries journal January 2018
Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes journal January 2019
A graphite intercalation compound associated with liquid Na–K towards ultra-stable and high-capacity alkali metal anodes journal January 2019
Lithium-mediated ammonia synthesis from water and nitrogen: a membrane-free approach enabled by an immiscible aqueous/organic hybrid electrolyte system journal January 2019
Review—Li Metal Anode in Working Lithium-Sulfur Batteries journal June 2017
Solid Electrolyte Interphase Film on Lithium Metal Anode in Mixed-Salt System journal January 2019
Deterioration Analysis of Lithium Metal Anode in Full Cell during Long-Term Cycles journal January 2019
Rechargeable Mg–Li hybrid batteries: status and challenges journal September 2016
Nonflammable Lithium Metal Full Cells with Ultra-high Energy Density Based on Coordinated Carbonate Electrolytes journal February 2020
A Highly Reversible Room-Temperature Sodium Metal Anode journal November 2015
Dendrites and Pits: Untangling the Complex Behavior of Lithium Metal Anodes through Operando Video Microscopy journal October 2016
High-Purity Lithium Metal Films from Aqueous Mineral Solutions journal January 2018
Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes journal August 2015
Designing solid-liquid interphases for sodium batteries journal October 2017
Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries journal October 2017
High-energy-density dual-ion battery for stationary storage of electricity using concentrated potassium fluorosulfonylimide journal October 2018
Publisher Correction: Aligning academia and industry for unified battery performance metrics journal January 2019
Structural modulation of lithium metal-electrolyte interface with three-dimensional metallic interlayer for high-performance lithium metal batteries journal August 2016
Concentrated LiODFB Electrolyte for Lithium Metal Batteries journal July 2019
The Effect of Concentration of Lithium Salt on the Structural and Transport Properties of Ionic Liquid-Based Electrolytes journal February 2020
Lithiophilic Silver Coating on Lithium Metal Surface for Inhibiting Lithium Dendrites journal February 2020

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