Designing a 3D framework NaVOPO4 as a high-power, low-strain and  long-life positive electrode material for Na-ion batteries

Shraer, S.; Dembitskiy, A.; Trussov, I.; Komayko, A.; Aksyonov, D.; Luchinin, N.; Morozov, A.; Pollastri, S.; Aquilanti, G.; Ryazantsev, S.; Nikitina, V.; Abakumov, A.; Antipov, E.; Fedotov, S.

Авторы: Shraer Semyon, Dembitskiy Artem, Trussov Ivan, Komayko Alena, Aksyonov Dmitry, Luchinin Nikita, Morozov Anatolii, Pollastri Simone, Aquilanti Giuliana, Ryazantsev Sergey, Nikitina Victoria, Abakumov Artem, Antipov Evgeny, Fedotov Stanislav
Журнал: Energy Storage Materials
Том: 68
Год издания: 2024
Номер статьи: 103358
DOI: 10.1016/j.ensm.2024.103358
Аннотация: Advances in sodium-ion batteries hugely rely on perfecting the performance of active electrode materials. In this paper, we offer a new NaVOPO4 polymorph adopting a KTiOPO4-type framework as a promising high-rate, low- strain and long-life positive electrode material for sodium-ion batteries. NaVOPO4 is prepared via a facile hydrothermally-assisted solid-state ion exchange. The crystal structure is reﬁned based on synchrotron X-ray powder diffraction (XRD) and validated by X-ray absorption spectroscopy (XAS), transmission electron micro-scopy analysis and density functional theory (DFT) calculations. The electrochemical performance of NaVOPO4 is evaluated through galvanostatic charge/discharge tests, cyclic voltammetry, potentiostatic intermittent titration and electrochemical impedance spectroscopy. A carbon-coated NaVOPO4 demonstrates a speciﬁc capacity of ~110 mAh g–1 at a C/10 rate at an average potential of ~3.93 V vs. Na+/Na. The material exhibits decent capacity retention and rate capability, maintaining over 74 % of the initial capacity after 1000 cycles at a C/2 rate and around 87% at a 2C charge/discharge rate. Diffusion coefﬁcients of 10–11 cm2 s–1 and DFT-calculated energy barriers of ~0.15–0.35 eV indicate fast Na+ ion diffusion within the NaVOPO4 framework. The vana-dium oxidation state and charge compensation mechanism in NaVOPO4 are studied by XAS and DFT. Moreover, the operando XRD analysis coupled with DFT elucidates several phase transitions occurring in NaVOPO4 with an exceptionally low volume variation of 2.4% in total, highlighting the reversibility and structural stability during Na+ de/insertion. Overall, NaVOPO4 exhibits attractive electrochemical performance and stability, making it a potential candidate for sodium-ion battery cathode materials.
Добавил в систему: Антипов Евгений Викторович

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