Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

doi:10.1021/acs.chemmater.6b04181

Title: Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

Abstract

Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A _xK _1–xFeF ₃ (A = Li, Na). By starting with KFeF ₃, approximately 75% of K+ ions were subsequently replaced by Li ⁺ and Na ⁺ through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe ^2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.

Authors:

Yi, Tanghong ^[1]; Chen, Wei ^[2]; Cheng, Lei ^[3]; Bayliss, Ryan D. ^[4];

^[5]; Plews, Michael R. ^[4]; Nordlund, Dennis ^[6]; Doeff, Marca M. ^[5]; Persson, Kristin A. ^[5];

^[4]

Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division; Illinois Inst. of Technology, Chicago, IL (United States). Dept. of Mechanical Materials and Aerospace Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: 2017-01-20

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)

OSTI Identifier:: 1353190

Alternate Identifier(s):: OSTI ID: 1459386

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 29; Journal Issue: 4; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    Yi, Tanghong, Chen, Wei, Cheng, Lei, Bayliss, Ryan D., Lin, Feng, Plews, Michael R., Nordlund, Dennis, Doeff, Marca M., Persson, Kristin A., and Cabana, Jordi. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites.  United States: N. p., 2017. 
        Web.  doi:10.1021/acs.chemmater.6b04181.

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                    Yi, Tanghong, Chen, Wei, Cheng, Lei, Bayliss, Ryan D., Lin, Feng, Plews, Michael R., Nordlund, Dennis, Doeff, Marca M., Persson, Kristin A., & Cabana, Jordi. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites.  United States.  doi:10.1021/acs.chemmater.6b04181.

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                    Yi, Tanghong, Chen, Wei, Cheng, Lei, Bayliss, Ryan D., Lin, Feng, Plews, Michael R., Nordlund, Dennis, Doeff, Marca M., Persson, Kristin A., and Cabana, Jordi. Fri .  
        "Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites".  United States.  doi:10.1021/acs.chemmater.6b04181.  https://www.osti.gov/servlets/purl/1353190.

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@article{osti_1353190,

  title        = {Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites},

  author       = {Yi, Tanghong and Chen, Wei and Cheng, Lei and Bayliss, Ryan D. and Lin, Feng and Plews, Michael R. and Nordlund, Dennis and Doeff, Marca M. and Persson, Kristin A. and Cabana, Jordi},

  abstractNote = {Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials AxK1–xFeF3 (A = Li, Na). By starting with KFeF3, approximately 75% of K+ ions were subsequently replaced by Li+ and Na+ through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.},

  doi          = {10.1021/acs.chemmater.6b04181},

  journal      = {Chemistry of Materials},

  number       = 4,

  volume       = 29,

  place        = {United States},

  year         = {2017},

  month        = {1}

}

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DOI: 10.1021/acs.chemmater.6b04181

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