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      Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes

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          Abstract

          Although silicon is a promising anode material for lithium-ion batteries, scalable synthesis of silicon anodes with good cyclability and low electrode swelling remains a significant challenge. Herein, we report a scalable top-down technique to produce ant-nest-like porous silicon from magnesium-silicon alloy. The ant-nest-like porous silicon comprising three-dimensional interconnected silicon nanoligaments and bicontinuous nanopores can prevent pulverization and accommodate volume expansion during cycling resulting in negligible particle-level outward expansion. The carbon-coated porous silicon anode delivers a high capacity of 1,271 mAh g −1 at 2,100 mA g −1 with 90% capacity retention after 1,000 cycles and has a low electrode swelling of 17.8% at a high areal capacity of 5.1 mAh cm −2. The full cell with the prelithiated silicon anode and Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode boasts a high energy density of 502 Wh Kg −1 and 84% capacity retention after 400 cycles. This work provides insights into the rational design of alloy anodes for high-energy batteries.

          Abstract

          Silicon is a promising anode material for lithium-ion batteries but experiences large volume changes during cycling. Here the authors report a scalable method to synthesize porous ant-nest-like silicons. The unique structure of this anode solves the swelling problem and enables impressive performance.

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          Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control.

          Although the performance of lithium ion-batteries continues to improve, their energy density and cycle life remain insufficient for applications in consumer electronics, transport and large-scale renewable energy storage. Silicon has a large charge storage capacity and this makes it an attractive anode material, but pulverization during cycling and an unstable solid-electrolyte interphase has limited the cycle life of silicon anodes to hundreds of cycles. Here, we show that anodes consisting of an active silicon nanotube surrounded by an ion-permeable silicon oxide shell can cycle over 6,000 times in half cells while retaining more than 85% of their initial capacity. The outer surface of the silicon nanotube is prevented from expansion by the oxide shell, and the expanding inner surface is not exposed to the electrolyte, resulting in a stable solid-electrolyte interphase. Batteries containing these double-walled silicon nanotube anodes exhibit charge capacities approximately eight times larger than conventional carbon anodes and charging rates of up to 20C (a rate of 1C corresponds to complete charge or discharge in one hour).
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            High-performance lithium-ion anodes using a hierarchical bottom-up approach.

            Si-based Li-ion battery anodes have recently received great attention, as they offer specific capacity an order of magnitude beyond that of conventional graphite. The applications of this transformative technology require synthesis routes capable of producing safe and easy-to-handle anode particles with low volume changes and stable performance during battery operation. Herein, we report a large-scale hierarchical bottom-up assembly route for the formation of Si on the nanoscale--containing rigid and robust spheres with irregular channels for rapid access of Li ions into the particle bulk. Large Si volume changes on Li insertion and extraction are accommodated by the particle's internal porosity. Reversible capacities over five times higher than that of the state-of-the-art anodes (1,950 mA h g(-1)) and stable performance are attained. The synthesis process is simple, low-cost, safe and broadly applicable, providing new avenues for the rational engineering of electrode materials with enhanced conductivity and power.
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              A major constituent of brown algae for use in high-capacity Li-ion batteries.

              The identification of similarities in the material requirements for applications of interest and those of living organisms provides opportunities to use renewable natural resources to develop better materials and design better devices. In our work, we harness this strategy to build high-capacity silicon (Si) nanopowder-based lithium (Li)-ion batteries with improved performance characteristics. Si offers more than one order of magnitude higher capacity than graphite, but it exhibits dramatic volume changes during electrochemical alloying and de-alloying with Li, which typically leads to rapid anode degradation. We show that mixing Si nanopowder with alginate, a natural polysaccharide extracted from brown algae, yields a stable battery anode possessing reversible capacity eight times higher than that of the state-of-the-art graphitic anodes.
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                Author and article information

                Contributors
                zhangqiaobao@xmu.edu.cn
                kfhuo@hust.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                29 March 2019
                29 March 2019
                2019
                : 10
                : 1447
                Affiliations
                [1 ]ISNI 0000 0000 9868 173X, GRID grid.412787.f, The State Key Laboratory of Refractories and Metallurgy and Institute of Advanced Materials and Nanotechnology, , Wuhan University of Science and Technology, ; 430081 Wuhan, China
                [2 ]ISNI 0000 0004 0368 7223, GRID grid.33199.31, Wuhan National Laboratory for Optoelectronics (WNLO), , Huazhong University of Science and Technology, ; 430074 Wuhan, China
                [3 ]ISNI 0000 0004 1792 6846, GRID grid.35030.35, Department of Physics and Department of Materials Science and Engineering, , City University of Hong Kong, ; Tat Chee Avenue, Kowloon, 999077 Hong Kong China
                [4 ]ISNI 0000 0001 2264 7233, GRID grid.12955.3a, Department of Materials Science and Engineering, College of Materials, , Xiamen University, ; 361005 Xiamen, Fujian China
                Author information
                http://orcid.org/0000-0001-9275-8457
                http://orcid.org/0000-0002-5581-4883
                http://orcid.org/0000-0001-5670-8233
                Article
                9510
                10.1038/s41467-019-09510-5
                6441089
                30926799
                bcf50486-66db-4568-b663-9520acf8fe89
                © The Author(s) 2019

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 27 September 2018
                : 15 March 2019
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