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Elucidation of the sodiation/desodiation mechanism in Ca_(0.5)Ti_(2)(PO_(4))_(3)/C as promising electrode for sodium batteries: New insights into the phase transitions

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Journal of Energy Chemistry 2022年第7期31卷 36-44,I0002页

作者： Abdelhaq Nassiri Noha Sabi Angelina Sarapulova Yingjin Wei Bouchaib Manoun Sylvio Indris Alexandr missyul Helmut Ehrenberg Ismael Saadoune IMED-Lab Faculty of Science and Technology-Cadi Ayyad University(UCA)Av.A.El KhattabiP.B.549MarrakeshMorocco Institute for Applied Materials(IAM) Karlsruhe Institute of Technology(KIT)P.O.Box 364076021 KarlsruheGermany Key Laboratory of Physics and Technology for Advanced Batteries(Ministry of Education) Jilin Engineering Laboratory of New Energy Materials and TechnologyCollege of PhysicsJilin UniversityChangchun 130012JilinChina MSN Mohamed VI Polytechnic UniversityLot 660Hay Moulay RachidBen Guerir 43150Morocco CELLS-ALBA Synchrotron E-08290 Cerdanyola del VallesBarcelonaSpain Technology Development Cell(Techcell) Technology Transfer Office(TTO)Mohamed VI Polytechnic UniversityLot 660Hay Moulay RachidBen Guerir 43150Morocco

The structure evolution and electrochemical performance of Na SICON-type Ca_(0.5)Ti_(2)(PO_(4))_(3) for sodium batteries are *** phosphate was synthesized by a solid-state method,and the obtained particles were coated with carbon using *** compound crystallizes in the rhombohedral system with space group *** presence of carbon in the Ca_(0.5)Ti_(2)(PO_(4))_(3)/C composite was confirmed by Raman and Thermogravimetric *** electrochemical performance of Ca_(0.5)Ti_(2)(PO_(4))_(3)/C was investigated in the potential window 1.5–3.0 V *** metal at different scan *** compound is able to initially intercalate/deintercalate 1.6/1.15 Na per formula unit,*** operando synchrotron diffraction was done in the potential window 0.02–3.0 V ***|Na+and revealed the occurrence of several reaction regions upon first *** to 4 Na+ion per formula unit can be inserted during the first *** intensive refinement of the synchrotron X-ray diffraction(SXRD)patterns of discharged Ca_(0.5)Ti_(2)(PO_(4))_(3) evidenced the existence of five regions depending on the sodium content while the crystal structures of new phases were elucidated for the first time where sodium insertion occurs in the unusual M3 and M’3 sites of the Na SICON structure.

关键词： Sodium-ion batteries Phosphates Synchrotron Mechanism Energy storage

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In operando study of orthorhombic V_(2)O_(5) as positive electrode materials for K-ion batteries

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Journal of Energy Chemistry 2021年第11期30卷 627-636,I0015页

作者： Qiang Fu Angelina Sarapulova Lihua Zhu Georgian Melinte a.exa.der missyul Edmund Welter Xianlin Luo Michael Knapp Helmut Ehrenberg Sonia Dsoke Institute for Applied Materials(IAM) Karlsruhe Institute of Technology(KIT)Hermann-von-Helmholtz-Platz 1D-76344 Eggenstein-LeopoldshafenGermany Helmholtz Institute Ulm for Electrochemical Energy Storage(HIU) Helmholtzstrasse 1189081 UlmGermany Institute of Nanotechnology(INT) Karlsruhe Institute of Technology(KIT)Hermann-von-Helmholtz-Platz 1D-76344 Eggenstein-LeopoldshafenGermany CELLS-ALBA Synchrotron E-08290 Cerdanyola del VallesBarcelonaSpain Deutsches Elektronen-Synchrotron DESY Notkestraße 85D-22607 HamburgGermany

Herein, the electrochemical performance and the mechanism of potassium insertion/deinsertion in orthorhombic V_(2)O_(5) nanoparticles are studied. The V2O5 electrode displays an initial potassiation/depotassiation capacity of 200 mAh g^(−1)/217 mAh g^(−1) in the voltage range 1.5–4.0 V vs. K^(+)/K at C/12 rate, suggesting fast kinetics for potassium insertion/deinsertion. However, the capacity quickly fades during cycling, reaching 54 mAh g^(−1) at the 31st cycle. Afterwards, the capacity slowly increases up to 80 mAh g^(−1) at the 200th cycle. The storage mechanism upon K ions insertion into V2O5 is elucidated. In operando synchrotron diffraction reveals that V_(2)O_(5) first undergoes a solid solution to form K_(0.6)V_(2)O_(5) phase and then, upon further K ions insertion, it reveals coexistence of a solid solution and a two-phase reaction. During K ions deinsertion, the coexistence of solid solution and the two-phase reaction is identified together with an irreversible process. In operando XAS confirms the reduction/oxidation of vanadium during the K insertion/extraction with some irreversible contributions. This is consistent with the results obtained from synchrotron diffraction, ex situ Raman, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Moreover, ex situ XPS confirms the “cathode electrolyte interphase” (CEI) formation on the electrode and the decomposition of CEI film during cycling.

关键词： Orthorhombic V_(2)O_(5) In operando synchrotron diffraction In operando X-ray absorption spectroscopy K-ion batteries

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