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      Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries

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          Abstract

          The demand of sustainable power supply requires high-performance cost-effective energy storage technologies. Here we report a high-rate long-life low-cost sodium-ion battery full-cell system by innovating both the anode and the electrolyte. The redox couple of manganese(I/II) in Prussian blue analogs enables a high-rate and stable anode. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering provide direct evidence suggesting the existence of monovalent manganese in the charged anode. There is a strong hybridization between cyano ligands and manganese- 3d states, which benefits the electronic property for improving rate performance. Additionally, we employ an organic–aqueous cosolvent electrolyte to solve the long-standing solubility issue of Prussian blue analogs. A full-cell sodium-ion battery with low-cost Prussian blue analogs in both electrodes and co-solvent electrolyte retains 95% of its initial discharge capacity after 1000 cycles at 1C and 95% depth of discharge. The revealed manganese(I/II) redox couple inspires conceptual innovations of batteries based on atypical oxidation states.

          Abstract

          Sodium ion batteries offer more cost-effective storage than lithium and could be used for grid-scale energy storage. Here, the authors demonstrate a full cell based on a MnHCMn anode and an organic-aqueous cosolvent electrolyte. X-ray spectroscopy evidence further suggests the presence of Mn(I).

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          Most cited references32

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          Prussian blue: a new framework of electrode materials for sodium batteries.

          Prussian blue and its analogues consisting of different transition-metal ions (Fe, Mn, Ni, Cu, Co and Zn) have been synthesized at room temperature. Insertion of Na into KFe(2)(CN)(6) in a carbonate electrolyte exhibited a reversible capacity near 100 mA h g(-1) with no capacity fade in 30 cycles. The data indicate that a Na-ion battery with a Prussian blue framework as a cathode will be feasible.
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            Copper hexacyanoferrate battery electrodes with long cycle life and high power.

            Short-term transients, including those related to wind and solar sources, present challenges to the electrical grid. Stationary energy storage systems that can operate for many cycles, at high power, with high round-trip energy efficiency, and at low cost are required. Existing energy storage technologies cannot satisfy these requirements. Here we show that crystalline nanoparticles of copper hexacyanoferrate, which has an ultra-low strain open framework structure, can be operated as a battery electrode in inexpensive aqueous electrolytes. After 40,000 deep discharge cycles at a 17 C rate, 83% of the original capacity of copper hexacyanoferrate is retained. Even at a very high cycling rate of 83 C, two thirds of its maximum discharge capacity is observed. At modest current densities, round-trip energy efficiencies of 99% can be achieved. The low-cost, scalable, room-temperature co-precipitation synthesis and excellent electrode performance of copper hexacyanoferrate make it attractive for large-scale energy storage systems.
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              2px-ray absorption of 3dtransition-metal compounds: An atomic multiplet description including the crystal field

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                Author and article information

                Contributors
                WLYang@lbl.gov
                colin@alveoenergy.com
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                28 February 2018
                28 February 2018
                2018
                : 9
                : 861
                Affiliations
                [1 ]Alveo Energy, Palo Alto, CA 94303 USA
                [2 ]ISNI 0000 0001 2231 4551, GRID grid.184769.5, Advanced Light Source, , Lawrence Berkeley National Laboratory, ; Berkeley, CA 94720 USA
                [3 ]ISNI 0000 0004 1936 8753, GRID grid.137628.9, Department of Physics, , New York University, ; New York,, NY 10003 USA
                Author information
                http://orcid.org/0000-0003-0666-8063
                Article
                3257
                10.1038/s41467-018-03257-1
                5830409
                29491414
                25806330-c05d-4280-a3d4-873278d88161
                © The Author(s) 2018

                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
                : 24 December 2015
                : 30 January 2018
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