Electrochemical and Diffusional Investigation of Na2FeIIPO4F Fluorophosphate Sodium Insertion Material Obtained from FeIII Precursor

Lalit Sharma; Prasant Kumar Nayak; Ezequiel De La Llave; Haomin Chen; Stefan Adams; Doron Aurbach; Prabeer Barpanda

doi:10.1021/acsami.7b10637

Electrochemical and Diffusional Investigation of Na₂Fe^IIPO₄F Fluorophosphate Sodium Insertion Material Obtained from Fe^III Precursor

Lalit Sharma, Prasant Kumar Nayak, Ezequiel De La Llave, Haomin Chen, Stefan Adams, Doron Aurbach, Prabeer Barpanda

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

Sodium iron fluorophosphate (Na₂Fe^IIPO₄F) was synthesized by economic solvothermal combustion technique using Fe^III precursors, developing one-step carbon-coated homogeneous product. Synchrotron diffraction and Mössbauer spectroscopy revealed the formation of single-phase product assuming an orthorhombic structure (s.g. Pbcn) with Fe^II species. This Fe^III precursor derived Na₂Fe^IIPO₄F exhibited reversible Na⁺ (de)intercalation with discharge capacity of 100 mAh/g at a rate of C/10 involving flat Fe^III/Fe^II redox plateaus located at 2.92 and 3.05 V (vs Na/Na⁺). It delivered good cycling stability and rate kinetics at room temperature. The stability of Na₂FePO₄F cathode was further verified by electrochemical impedance spectroscopy at different stages of galvanostatic analysis. Bond valence site energy (BVSE) calculations revealed the existence of 2-dimensional Na⁺ percolation pathways in the a-c plane with a moderate migration barrier of 0.6 eV. Combustion synthesized Na₂Fe^IIPO₄F forms an economically viable sodium battery material. Although the capacity of this cathode is relatively low, this study continues systematic work, which attempts to broaden the scope of reversible sodium insertion materials.

Original language	English
Pages (from-to)	34961-34969
Number of pages	9
Journal	ACS applied materials & interfaces
Volume	9
Issue number	40
DOIs	https://doi.org/10.1021/acsami.7b10637
State	Published - 11 Oct 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

Funding

The authors thank the Department of Science and Technology (DST), Government of India, for financial support under the aegis of Indo-Israel project (DST/INT/ISR/P-10/2014). L.S. is thankful to Ministry of Human Resource Development (MHRD) for financial support. PB thanks the Department of Atomic Energy (DAE) for a DAE-BRNS Young Scientists Research Award (YSRA). Rajeev Kumar and Prof. Balaram Sahoo are acknowledged for their help in Mössbauer spectroscopy. The authors acknowledge the Saha Institute of Nuclear Physics (SINP), India, for facilitating the synchrotron experiments at the Indian Beamline (BL-18B), KEK Photon Factory (KEK-PF), Japan. Crystalline structure was illustrated using the VESTA software.38 SA, HC and RPR are grateful to National Research Foundation, Prime Minister’s Office, Singapore for support under the Competitive Research Programme (CRP Award NRF-CRP 10-2012-6) and acknowledge support from the NUS “Centre for Energy Research” seed grant.

Funders	Funder number
DAE-BRNS
Department of Atomic Energy
National Research Foundation	NRF-CRP 10-2012-6
National University of Singapore
Ministry of Human Resource Development
Department of Science and Technology, Government of Kerala	DST/INT/ISR/P-10/2014

Keywords

Na-ion battery
NaFePOF
bond-valence site energy
combustion
fluorophosphate

Access to Document

10.1021/acsami.7b10637

Cite this

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title = "Electrochemical and Diffusional Investigation of Na2FeIIPO4F Fluorophosphate Sodium Insertion Material Obtained from FeIII Precursor",

abstract = "Sodium iron fluorophosphate (Na2FeIIPO4F) was synthesized by economic solvothermal combustion technique using FeIII precursors, developing one-step carbon-coated homogeneous product. Synchrotron diffraction and M{\"o}ssbauer spectroscopy revealed the formation of single-phase product assuming an orthorhombic structure (s.g. Pbcn) with FeII species. This FeIII precursor derived Na2FeIIPO4F exhibited reversible Na+ (de)intercalation with discharge capacity of 100 mAh/g at a rate of C/10 involving flat FeIII/FeII redox plateaus located at 2.92 and 3.05 V (vs Na/Na+). It delivered good cycling stability and rate kinetics at room temperature. The stability of Na2FePO4F cathode was further verified by electrochemical impedance spectroscopy at different stages of galvanostatic analysis. Bond valence site energy (BVSE) calculations revealed the existence of 2-dimensional Na+ percolation pathways in the a-c plane with a moderate migration barrier of 0.6 eV. Combustion synthesized Na2FeIIPO4F forms an economically viable sodium battery material. Although the capacity of this cathode is relatively low, this study continues systematic work, which attempts to broaden the scope of reversible sodium insertion materials.",

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author = "Lalit Sharma and Nayak, {Prasant Kumar} and {De La Llave}, Ezequiel and Haomin Chen and Stefan Adams and Doron Aurbach and Prabeer Barpanda",

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AU - Sharma, Lalit

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AU - De La Llave, Ezequiel

AU - Chen, Haomin

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