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      Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

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          Abstract

          Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm −2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.

          Abstract

          Lithium metal is a promising anode for batteries, but problems such as volume change and dendrite growth currently prevent it from practical usage. Here, the authors overcome these problems by infusing molten lithium into a polymeric matrix via a lithiophilic coating to make a stable nanoporous lithium electrode.

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          Most cited references 17

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          High-performance lithium battery anodes using silicon nanowires.

          There is great interest in developing rechargeable lithium batteries with higher energy capacity and longer cycle life for applications in portable electronic devices, electric vehicles and implantable medical devices. Silicon is an attractive anode material for lithium batteries because it has a low discharge potential and the highest known theoretical charge capacity (4,200 mAh g(-1); ref. 2). Although this is more than ten times higher than existing graphite anodes and much larger than various nitride and oxide materials, silicon anodes have limited applications because silicon's volume changes by 400% upon insertion and extraction of lithium which results in pulverization and capacity fading. Here, we show that silicon nanowire battery electrodes circumvent these issues as they can accommodate large strain without pulverization, provide good electronic contact and conduction, and display short lithium insertion distances. We achieved the theoretical charge capacity for silicon anodes and maintained a discharge capacity close to 75% of this maximum, with little fading during cycling.
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            High rate capabilities Fe3O4-based Cu nano-architectured electrodes for lithium-ion battery applications.

            All battery technologies are known to suffer from kinetic problems linked to the solid-state diffusion of Li in intercalation electrodes, the conductivity of the electrolyte in some cases and the quality of interfaces. For Li-ion technology the latter effect is especially acute when conversion rather than intercalation electrodes are used. Nano-architectured electrodes are usually suggested to enhance kinetics, although their realization is cumbersome. To tackle this issue for the conversion electrode material Fe3O4, we have used a two-step electrode design consisting of the electrochemically assisted template growth of Cu nanorods onto a current collector followed by electrochemical plating of Fe3O4. Using such electrodes, we demonstrate a factor of six improvement in power density over planar electrodes while maintaining the same total discharge time. The capacity at the 8C rate was 80% of the total capacity and was sustained over 100 cycles. The origin of the large hysteresis between charge and discharge, intrinsic to conversion reactions, is discussed and approaches to reduce it are proposed. We hope that such findings will help pave the way for the use of conversion reaction electrodes in future-generation Li-ion batteries.
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              Electrolytes and interphases in Li-ion batteries and beyond.

               Kang Xu (2014)
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                18 March 2016
                2016
                : 7
                Affiliations
                [1 ]Department of Materials Science and Engineering, Stanford University , Stanford, California 94305, USA
                [2 ]Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory , 2575 Sand Hill Road, Menlo Park, California 94025, USA
                Author notes
                [*]

                These authors contributed equally to this work

                Article
                ncomms10992
                10.1038/ncomms10992
                4802050
                26987481
                Copyright © 2016, 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/

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