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Title: Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries

Abstract

In the quest for high energy density rechargeable batteries, conversion-type cathode materials stand out with their appealing multielectron transfer properties. However, they undergo a series of complex phase transitions upon initial cycling as opposed to conventional intercalation-type materials. Within this category, iron-based mixed-anion solid solutions (FeO xF 2-x) have captured the most attention of the battery community, owing to their high theoretical capacity and moderate cyclability. In the meantime, it was recently demonstrated, via a series of electrochemical cycling experiments, the in situ preparation of manganese-based mixed-anion cathode materials based on decomposition of electrolyte salt LiPF6 in the presence of MnO. To take a step forward, we herein report a routine protocol to prepare 220 mAh g -1-class composite cathodes. In addition, we provide a comprehensive understanding of the in situ fluorination and locally reversible phase transitions using complementary analytical techniques. The charged phase, with an average Mn oxidation state of ca. +2.8, consists of a highly disordered O-rich cubic-spinel-like core and an F-rich amorphous shell. Upon discharge, lithiation induces further phase transition, forming LiF, MnO, and a lithiated rocksalt-like phase. Furthermore this work, which we also extended to the iron-based system, offers insights into modification of chemical and electronicmore » properties of electrode materials by in situ fluorination.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5];  [5]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [8];  [9]
  1. College de France, Paris Cedex (France); The Hong Kong Univ. of Science and Technology, Hong Kong SAR (China); The Hong Kong Polytechnic Univ., Hong Kong SAR (China)
  2. Sorbonne Univ., Paris (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France)
  3. Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France)
  4. College de France, Paris Cedex (France); Univ. of Antwerp, Antwerp (Belgium)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
  6. Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France); Univ. d'Orleans, Orleans Cedex (France)
  7. The Hong Kong Univ. of Science and Technology, Hong Kong (China)
  8. The Hong Kong Polytechnic Univ., Hong Kong SAR (China)
  9. College de France, Paris Cedex (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amicens (France); Sorbonne Univ., Paris (France)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Agence Nationale de la recherche (ANR); USDOE
OSTI Identifier:
1480116
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 15; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; battery

Citation Formats

Zhang, Leiting, Dambournet, Damien, Iadecola, Antonella, Batuk, Dmitry, Borkiewicz, Olaf J., Wiaderek, Kamila M., Salager, Elodie, Shao, Minhua, Chen, Guohua, and Tarascon, Jean -Marie. Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b02182.
Zhang, Leiting, Dambournet, Damien, Iadecola, Antonella, Batuk, Dmitry, Borkiewicz, Olaf J., Wiaderek, Kamila M., Salager, Elodie, Shao, Minhua, Chen, Guohua, & Tarascon, Jean -Marie. Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries. United States. doi:10.1021/acs.chemmater.8b02182.
Zhang, Leiting, Dambournet, Damien, Iadecola, Antonella, Batuk, Dmitry, Borkiewicz, Olaf J., Wiaderek, Kamila M., Salager, Elodie, Shao, Minhua, Chen, Guohua, and Tarascon, Jean -Marie. Tue . "Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries". United States. doi:10.1021/acs.chemmater.8b02182. https://www.osti.gov/servlets/purl/1480116.
@article{osti_1480116,
title = {Origin of the High Capacity Manganese-Based Oxyfluoride Electrodes for Rechargeable Batteries},
author = {Zhang, Leiting and Dambournet, Damien and Iadecola, Antonella and Batuk, Dmitry and Borkiewicz, Olaf J. and Wiaderek, Kamila M. and Salager, Elodie and Shao, Minhua and Chen, Guohua and Tarascon, Jean -Marie},
abstractNote = {In the quest for high energy density rechargeable batteries, conversion-type cathode materials stand out with their appealing multielectron transfer properties. However, they undergo a series of complex phase transitions upon initial cycling as opposed to conventional intercalation-type materials. Within this category, iron-based mixed-anion solid solutions (FeOxF2-x) have captured the most attention of the battery community, owing to their high theoretical capacity and moderate cyclability. In the meantime, it was recently demonstrated, via a series of electrochemical cycling experiments, the in situ preparation of manganese-based mixed-anion cathode materials based on decomposition of electrolyte salt LiPF6 in the presence of MnO. To take a step forward, we herein report a routine protocol to prepare 220 mAh g-1-class composite cathodes. In addition, we provide a comprehensive understanding of the in situ fluorination and locally reversible phase transitions using complementary analytical techniques. The charged phase, with an average Mn oxidation state of ca. +2.8, consists of a highly disordered O-rich cubic-spinel-like core and an F-rich amorphous shell. Upon discharge, lithiation induces further phase transition, forming LiF, MnO, and a lithiated rocksalt-like phase. Furthermore this work, which we also extended to the iron-based system, offers insights into modification of chemical and electronic properties of electrode materials by in situ fluorination.},
doi = {10.1021/acs.chemmater.8b02182},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 15,
volume = 30,
place = {United States},
year = {2018},
month = {7}
}

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