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      High Power Energy Storage via Electrochemically Expanded and Hydrated Manganese-Rich Oxides

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          Abstract

          Understanding the materials design features that lead to high power electrochemical energy storage is important for applications from electric vehicles to smart grids. Electrochemical capacitors offer a highly attractive solution for these applications, with energy and power densities between those of batteries and dielectric capacitors. To date, the most common approach to increase the capacitance of electrochemical capacitor materials is to increase their surface area by nanostructuring. However, nanostructured materials have several drawbacks including lower volumetric capacitance. In this work, we present a scalable “top-down” strategy for the synthesis of EC electrode materials by electrochemically expanding micron-scale high temperature-derived layered sodium manganese-rich oxides. We hypothesize that the electrochemical expansion induces two changes to the oxide that result in a promising electrochemical capacitor material: (1) interlayer hydration, which improves the interlayer diffusion kinetics and buffers intercalation-induced structural changes, and (2) particle expansion, which significantly improves electrode integrity and volumetric capacitance. When compared with a commercially available activated carbon for electrochemical capacitors, the expanded materials have higher volumetric capacitance at charge/discharge timescales of up to 40 s. This shows that expanded and hydrated manganese-rich oxide powders are viable candidates for electrochemical capacitor electrodes.

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          Most cited references54

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          Relation between the ion size and pore size for an electric double-layer capacitor.

          The research on electrochemical double layer capacitors (EDLC), also known as supercapacitors or ultracapacitors, is quickly expanding because their power delivery performance fills the gap between dielectric capacitors and traditional batteries. However, many fundamental questions, such as the relations between the pore size of carbon electrodes, ion size of the electrolyte, and the capacitance have not yet been fully answered. We show that the pore size leading to the maximum double-layer capacitance of a TiC-derived carbon electrode in a solvent-free ethyl-methylimmidazolium-bis(trifluoro-methane-sulfonyl)imide (EMI-TFSI) ionic liquid is roughly equal to the ion size (approximately 0.7 nm). The capacitance values of TiC-CDC produced at 500 degrees C are more than 160 F/g and 85 F/cm(3) at 60 degrees C, while standard activated carbons with larger pores and a broader pore size distribution present capacitance values lower than 100 F/g and 50 F/cm(3) in ionic liquids. A significant drop in capacitance has been observed in pores that were larger or smaller than the ion size by just an angstrom, suggesting that the pore size must be tuned with sub-angstrom accuracy when selecting a carbon/ion couple. This work suggests a general approach to EDLC design leading to the maximum energy density, which has been now proved for both solvated organic salts and solvent-free liquid electrolytes.
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            Achieving high energy density and high power density with pseudocapacitive materials

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              Structural classification and properties of the layered oxides

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                Author and article information

                Contributors
                Journal
                Front Chem
                Front Chem
                Front. Chem.
                Frontiers in Chemistry
                Frontiers Media S.A.
                2296-2646
                18 August 2020
                2020
                : 8
                : 715
                Affiliations
                [1] 1Department of Materials Science and Engineering, North Carolina State University , Raleigh, NC, United States
                [2] 2Department of Chemistry, Stanford University , Stanford, CA, United States
                [3] 3Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory , Menlo Park, CA, United States
                Author notes

                Edited by: Jennifer L. Schaefer, University of Notre Dame, United States

                Reviewed by: Yanliang Liang, University of Houston, United States; Liqiang Mai, Wuhan University of Technology, China

                *Correspondence: Veronica Augustyn vaugust@ 123456ncsu.edu

                This article was submitted to Electrochemistry, a section of the journal Frontiers in Chemistry

                Article
                10.3389/fchem.2020.00715
                7461800
                32974280
                527bae12-4ab5-4033-b7aa-9c9faca6676e
                Copyright © 2020 Boyd, Geise, Toney and Augustyn.

                This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.

                History
                : 14 May 2020
                : 09 July 2020
                Page count
                Figures: 9, Tables: 0, Equations: 0, References: 55, Pages: 12, Words: 8792
                Categories
                Chemistry
                Original Research

                aqueous electrolyte,manganese oxide,interlayer,confined water,electrochemical capacitor

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