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Self-discharge mechanism of high-voltage KVPO4F for K-ion batteries

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  • معلومة اضافية
    • Contributors:
      Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB); Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS); Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM); Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM); Université de Montpellier (UM); Réseau sur le stockage électrochimique de l'énergie (RS2E); Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP); Université Paris Sciences et Lettres (PSL)-Université Paris Sciences et Lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP); Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM); Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI); Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS); CELLS ALBA synchroton = ALBA Synchrotron (CELLS ALBA); This work was part of the TROPIC project supported by the Agence Nationale de la Recherche (ANR) under the grant ANR-19-CE05-0026. ANR is also acknowledged for funding the RS2E network through the STORE-EX Labex Project ANR-10-LABX-76-01. Synchrotron Soleil (France) is acknowledged for providing in-house beamtime at the beamline ROCK, which also benefits from an ANR grant as part of the “Investissements d’Avenir” program ANR-10-EQPX-45.; ANR-19-CE05-0026,TROPIC,Vers des batteries innovantes K-ion(2019); ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010)
    • بيانات النشر:
      CCSD
      ACS
    • الموضوع:
      2022
    • Collection:
      Université de Montpellier: HAL
    • نبذة مختصرة :
      International audience ; Current performances of Li-, Na-, or K-ion batteries are mainly limited by the specific capacity of the positive electrode. Therefore, it is important to reach the highest capacity possible for a given electrode material. Here, we investigate the performance limitation of KVPO4F, a prospective material for K-ion batteries, which can deliver only 80% of its theoretical capacity. We discover that the capacity limitation of KVPO4F is related to a kinetic competition between K+ deinsertion and side reactions ascribed to the electrolyte degradation at high potentials. Homeotypic VPO4F can be obtained from KVPO4F through a chemical deintercalation process, which disproves a possible structural limitation or instability. The deintercalated compound was characterized by electron and X-ray diffraction, X-ray absorption spectroscopy, and nuclear magnetic resonance spectroscopy. Despite the structural stability, a spontaneous reaction occurs between the deintercalated KxVPO4F (x < 0.5) and the electrolyte (0.8 M KPF6 in ethylene carbonate/diethylene carbonate), with an electron transfer to vanadium compensated by K+ intercalation. This reaction leads to self-discharge until the open circuit potential is lower than 4.7 V versus K+/K, corresponding to the K0.5VPO4F composition.
    • الرقم المعرف:
      10.1021/acsaem.2c02379
    • الدخول الالكتروني :
      https://hal.science/hal-03857373
      https://hal.science/hal-03857373v1/document
      https://hal.science/hal-03857373v1/file/WernerR_ACSAppliedEnergyMaterials_2022.pdf
      https://doi.org/10.1021/acsaem.2c02379
    • Rights:
      info:eu-repo/semantics/OpenAccess
    • الرقم المعرف:
      edsbas.984E98E8