Operando Synchrotron X-ray Diffraction in Calcium Batteries: Insights into the Redox Activity of 1D Ca3CoMO6 (M = Co and Mn)
| Autor: | Damien Monti, Deyana S. Tchitchekova, F. Fauth, Carlos Frontera, Maria Rosa Palacín, R. G. Houdeville, Ashley P. Black |
|---|---|
| Přispěvatelé: | Agencia Estatal de Investigación (España), European Commission |
| Rok vydání: | 2021 |
| Předmět: |
Materials science
General Chemical Engineering Synchrotron X-Ray Diffraction Energy Engineering and Power Technology 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 7. Clean energy Synchrotron Article 0104 chemical sciences law.invention Redox Activity Crystallography Fuel Technology law Powder diffraction Crystal structures 0210 nano-technology Hexagonal perovskite |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname Energy & Fuels Digital.CSIC: Repositorio Institucional del CSIC Consejo Superior de Investigaciones Científicas (CSIC) |
| Popis: | 1D Ca3Co2–zMzO6 (M = Co z = 0, M = Mn z = 1, and M = Fe z = 0.4) were prepared and tested electrochemically. While the iron-containing phase was not found to be active, the iron- and manganese-containing phases were found to be potentially interesting as positive electrode materials for calcium metal-based high-energy battery technologies and were investigated by operando synchrotron X-ray diffraction. Results indicate that electrochemically driven calcium deintercalation from the crystal structure (ca. 0.7 mol per formula unit) takes place upon oxidation in both cases. The oxidized phases have incommensurate modulated crystal structures with the space group R 3m(00γ)0s and a = 9.127(1) Å, c1 = 2.4226(3) Å and c2 = 4.1857(3) Å, and γ = 0.579 (M = Co) and a = 9.217(1) Å, c1 = 4.9076(4) Å and c2 = 4.3387(4) Å, and γ = 1.139 (M = Mn), which exhibit differences due to the presence of manganese and Mn/Co ordering. The degree of calcium re-intercalation within the structure was found to be extremely limited, if any. Complementary experiments carried out in lithium cells did not show any reversibility either, thus pointing at intrinsic structural/migration constraints in the oxidized phase rather than slow kinetics of high desolvation energies associated with divalent ion charge carriers. The authors are grateful to Alexandre Ponrouch and ALISTORE-ERI members for helpful discussions and to ALBA synchrotron for beamtime (proposal 2019073634). ICMAB-CSIC members thank the Spanish Agencia Estatal de Investigación Severo Ochoa Programme for Centres of Excellence in R&D (CEX2019-000917-S). D.M. acknowledges the EC for a H2020 MSCA-IF grant (contract number 743439). R.G.H. acknowledges the EC for a H2020 MSCADOC-FAM grant (contract number 754397). |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|