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      Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

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          Abstract

          Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li 1.17– x Ni 0.21Co 0.08Mn 0.54O 2, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.

          Abstract

          Lithium ion battery electrodes employing anion redox exhibit high energy densities but suffer from poor cyclability. Here the authors reveal that the voltage of anion redox is strongly affected by structural changes that occur during battery cycling, explaining its unique electrochemical properties.

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          Generalized Gradient Approximation Made Simple

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            Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study

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              Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials

              Quantum ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). Quantum ESPRESSO stands for "opEn Source Package for Research in Electronic Structure, Simulation, and Optimization". It is freely available to researchers around the world under the terms of the GNU General Public License. Quantum ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively-parallel architectures, and a great effort being devoted to user friendliness. Quantum ESPRESSO is evolving towards a distribution of independent and inter-operable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.
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                Author and article information

                Contributors
                mftoney@slac.stanford.edu
                WLYang@lbl.gov
                dgprendergast@lbl.gov
                wchueh@stanford.edu
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                12 December 2017
                12 December 2017
                2017
                : 8
                : 2091
                Affiliations
                [1 ]ISNI 0000000419368956, GRID grid.168010.e, Department of Chemistry, , Stanford University, ; 333 Campus Drive, Stanford, CA 94305 USA
                [2 ]ISNI 0000 0001 2231 4551, GRID grid.184769.5, The Advanced Light Source, , Lawrence Berkeley National Laboratory, ; 1 Cyclotron Road, Berkeley, CA 94720 USA
                [3 ]ISNI 0000000419368956, GRID grid.168010.e, Department of Materials Science and Engineering, , Stanford University, ; 496 Lomita Mall, Stanford, CA 94305 USA
                [4 ]ISNI 0000 0001 0725 7771, GRID grid.445003.6, Stanford Synchrotron Radiation Lightsource, , SLAC National Accelerator Laboratory, ; 2575 Sand Hill Road, Menlo Park, CA 94025 USA
                [5 ]ISNI 0000 0001 2231 4551, GRID grid.184769.5, The Molecular Foundry, , Lawrence Berkeley National Laboratory, ; 1 Cyclotron Road, Berkeley, CA 94720 USA
                [6 ]ISNI 0000 0004 1761 1174, GRID grid.27255.37, School of Physics, , National Key Laboratory of Crystal Materials, Shandong University, ; 27 Shanda South road, Jinan, 250100 China
                [7 ]ISNI 0000 0001 1945 5898, GRID grid.419666.a, Energy Lab, , Samsung Advanced Institute of Technology, 130, Samsung-ro, ; Yeongtong-gu Suwon-si, Gyeonggi-do 16678 South Korea
                [8 ]ISNI 0000000419368956, GRID grid.168010.e, Department of Computer Science, , Stanford University, ; 353 Serra Mall, Stanford, CA 94305 USA
                [9 ]ISNI 0000 0001 1945 5898, GRID grid.419666.a, Energy1lab, , Samsung SDI, 130, Samsung-ro, ; Yeongtong-gu Suwon-si, Gyeonggi-do 16678 South Korea
                [10 ]ISNI 0000 0001 0725 7771, GRID grid.445003.6, Stanford Institute for Materials & Energy Sciences, , SLAC National Accelerator Laboratory, ; 2575 Sand Hill Road, Menlo Park, CA 94025 USA
                Author information
                http://orcid.org/0000-0001-7663-3988
                http://orcid.org/0000-0003-1387-1510
                http://orcid.org/0000-0002-8805-8690
                http://orcid.org/0000-0002-7513-1166
                http://orcid.org/0000-0003-0666-8063
                http://orcid.org/0000-0003-0598-1453
                Article
                2041
                10.1038/s41467-017-02041-x
                5727078
                29233965
                99f21646-92cd-486b-8b7a-8829e1909db5
                © The Author(s) 2017

                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
                : 7 September 2017
                : 2 November 2017
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