Sodium Rich Vanadium Oxy‐Fluorophosphate – Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O – as Advanced Cathode for Sodium Ion Batteries

Essehli, Rachid; Yahia, Hamdi Ben; Amin, Ruhul; Li, Mengya; Morales, Daniel; Greenbaum, Steven G.; Abouimrane, Ali; Parejiya, Anand; Mahmoud, Abdelfattah; Boulahya, Khalid; Dixit, Marm; Belharouak, Ilias

doi:10.1002/advs.202301091

Title: Sodium Rich Vanadium Oxy‐Fluorophosphate – Na _3.2 Ni _0.2 V _1.8 (PO ₄ ) ₂ F ₂ O – as Advanced Cathode for Sodium Ion Batteries

Journal Article · Thu May 18 00:00:00 EDT 2023 · Advanced Science

DOI:https://doi.org/10.1002/advs.202301091· OSTI ID:1974479

Essehli, Rachid ^[1]; Yahia, Hamdi Ben ^[2]; Amin, Ruhul ^[1]; Li, Mengya ^[1]; Morales, Daniel ^[3]; Greenbaum, Steven G. ^[4]; Abouimrane, Ali ^[1]; Parejiya, Anand ^[1]; Mahmoud, Abdelfattah ^[5]; Boulahya, Khalid ^[6]; Dixit, Marm ^[1];

^[1]

Electrification and Energy Infrastructures Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Qatar Environment and Energy Research Institute Hamad Bin Khalifa University Qatar Foundation Doha 34110 Qatar
Exponent, Inc. Natick MA 01760 USA
Department of Physics &, Astronomy Hunter College of the City University of New York New York NY 10065 USA
Electrification and Energy Infrastructures Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA, Exponent, Inc. Natick MA 01760 USA, Department of Physics &, Astronomy Hunter College of the City University of New York New York NY 10065 USA, Greenmat Cesam Research Unit University of Liège Department of Chemistry Liège 4000 Belgium, Departamento de Química Inorgánica Facultad de Químicas Universidad Complutense Madrid 28040 Spain
Departamento de Química Inorgánica Facultad de Químicas Universidad Complutense Madrid 28040 Spain

Abstract Conventional sodium‐based layered oxide cathodes are extremely air sensitive and possess poor electrochemical performance along with safety concerns when operating at high voltage. The polyanion phosphate, Na ₃ V ₂ (PO ₄ ) ₃ stands out as an excellent candidate due to its high nominal voltage, ambient air stability, and long cycle life. The caveat is that Na ₃ V ₂ (PO ₄ ) ₃ can only exhibit reversible capacities in the range of 100 mAh g ⁻¹ , 20% below its theoretical capacity. Here, the synthesis and characterizations are reported for the first time of the sodium‐rich vanadium oxyfluorophosphate, Na _3.2 Ni _0.2 V _1.8 (PO ₄ ) ₂ F ₂ O, a tailored derivative compound of Na ₃ V ₂ (PO ₄ ) ₃ , with extensive electrochemical and structural analyses. Na _3.2 Ni _0.2 V _1.8 (PO ₄ ) ₂ F ₂ O delivers an initial reversible capacity of 117 mAh g ⁻¹ between 2.5 and 4.5 V under the 1C rate at room temperature, with 85% capacity retention after 900 cycles. The cycling stability is further improved when the material is cycled at 50 °C within 2.8–4.3 V for 100 cycles. When paired with a presodiated hard carbon, Na _3.2 Ni _0.2 V _1.8 (PO ₄ ) ₂ F ₂ O cycled with a capacity retention of 85% after 500 cycles. Cosubstitution of the transition metal and fluorine in Na _3.2 Ni _0.2 V _1.8 (PO ₄ ) ₂ F ₂ O as well as the sodium‐rich structure are the major factors behind the improvement of specific capacity and cycling stability, which paves the way for this cathode in sodium‐ion batteries.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Electricity (OE); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

Grant/Contract Number:: DE‐AC05‐00OR22725; AC05-00OR22725

OSTI ID:: 1974479

Alternate ID(s):: OSTI ID: 1975348; OSTI ID: 1983413

Journal Information:: Advanced Science, Journal Name: Advanced Science Vol. 10 Journal Issue: 22; ISSN 2198-3844

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Title: Sodium Rich Vanadium Oxy‐Fluorophosphate – Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O – as Advanced Cathode for Sodium Ion Batteries

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Title: Sodium Rich Vanadium Oxy‐Fluorophosphate – Na _3.2 Ni _0.2 V _1.8 (PO ₄ ) ₂ F ₂ O – as Advanced Cathode for Sodium Ion Batteries