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      High rate and stable cycling of lithium metal anode

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          Abstract

          Lithium metal is an ideal battery anode. However, dendrite growth and limited Coulombic efficiency during cycling have prevented its practical application in rechargeable batteries. Herein, we report that the use of highly concentrated electrolytes composed of ether solvents and the lithium bis(fluorosulfonyl)imide salt enables the high-rate cycling of a lithium metal anode at high Coulombic efficiency (up to 99.1%) without dendrite growth. With 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane as the electrolyte, a lithium|lithium cell can be cycled at 10 mA cm −2 for more than 6,000 cycles, and a copper|lithium cell can be cycled at 4 mA cm −2 for more than 1,000 cycles with an average Coulombic efficiency of 98.4%. These excellent performances can be attributed to the increased solvent coordination and increased availability of lithium ion concentration in the electrolyte. Further development of this electrolyte may enable practical applications for lithium metal anode in rechargeable batteries.

          Abstract

          Lithium metal is an ideal anode material for rechargeable batteries, but lithium dendritic growth and limited Columbic efficiency prevent its applications. Here, the authors report the use of highly concentrated electrolytes composed of ether solvents and the salt lithium bis(fluorosulfonyl)imide to enable high-rate cycling of lithium anode.

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          Most cited references37

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          Dendrite-free lithium deposition via self-healing electrostatic shield mechanism.

          Rechargeable lithium metal batteries are considered the "Holy Grail" of energy storage systems. Unfortunately, uncontrollable dendritic lithium growth inherent in these batteries (upon repeated charge/discharge cycling) has prevented their practical application over the past 40 years. We show a novel mechanism that can fundamentally alter dendrite formation. At low concentrations, selected cations (such as cesium or rubidium ions) exhibit an effective reduction potential below the standard reduction potential of lithium ions. During lithium deposition, these additive cations form a positively charged electrostatic shield around the initial growth tip of the protuberances without reduction and deposition of the additives. This forces further deposition of lithium to adjacent regions of the anode and eliminates dendrite formation in lithium metal batteries. This strategy may also prevent dendrite growth in lithium-ion batteries as well as other metal batteries and transform the surface uniformity of coatings deposited in many general electrodeposition processes.
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            A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions

            D Aurbach (2002)
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              Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

              Rechargeable lithium, sodium and aluminium metal-based batteries are among the most versatile platforms for high-energy, cost-effective electrochemical energy storage. Non-uniform metal deposition and dendrite formation on the negative electrode during repeated cycles of charge and discharge are major hurdles to commercialization of energy-storage devices based on each of these chemistries. A long-held view is that unstable electrodeposition is a consequence of inherent characteristics of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid electrolytes reinforced with halogenated salt blends exhibit stable long-term cycling at room temperature, often with no signs of deposition instabilities over hundreds of cycles of charge and discharge and thousands of operating hours. We rationalize these observations with the help of surface energy data for the electrolyte/lithium interface and impedance analysis of the interface during different stages of cell operation. Our findings provide support for an important recent theoretical prediction that the surface mobility of lithium is significantly enhanced in the presence of lithium halide salts. Our results also show that a high electrolyte modulus is unnecessary for stable electrodeposition of lithium.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Pub. Group
                2041-1723
                20 February 2015
                : 6
                : 6362
                Affiliations
                [1 ]Joint Center for Energy Storage Research
                [2 ]Energy & Environment Directorate, Pacific Northwest National Laboratory , Richland, Washington 99352, USA
                [3 ]Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory , Richland, Washington 99352, USA
                [4 ]Electrochemistry Branch, Sensor & Electron Devices Directorate, U.S. Army Research Laboratory , Adelphi, Maryland 20783, USA
                Author notes
                Author information
                http://orcid.org/0000-0001-7343-4609
                Article
                ncomms7362
                10.1038/ncomms7362
                4346622
                25698340
                1ef1c704-b20c-4cbc-b654-66a0970a7414
                Copyright © 2015, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 10 November 2014
                : 23 January 2015
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