Characterizing multiple continuous phase transitions at an alloying anode with voltammetric measurements and first-principles calculations

Yong Seok Choi, Jae Chul Lee

Research output: Contribution to journalArticle

Abstract

Electrochemical properties of batteries are closely related to phase transition behaviors at alloying anodes. This transition process in many cases occurs in a continuous and reversible manner with the formation of multiple phases with similar compositions and structures, making it difficult to identify the transition behaviors using conventional techniques. In this study, a combination of first-principles calculations and voltammetric measurements is used to identify multiple and continuous phase transition behaviors at an Sb anode during Na-Sb battery cycles. Calculations reveal that inflowing Na ions transform the fundamental structural motifs of NaxSb and generate various stable and metastable NaxSb phases. Plausible phases are selected by comparing the calculated formation energies with those determined from experimentally obtained polarization curves. The identities of the phases are verified by reproducing the experimental polarization curves by thermodynamic modeling. The formation of metastable phases during charging and discharging of the Sb anode is responsible for the hysteresis loss indicated in the polarization curve. The present model provides a simple yet effective means of identifying both stable and metastable phases formed during successive phase transition processes, which are difficult to analyze using traditional diffractometry and analytical techniques.

Original languageEnglish
Pages (from-to)23121-23129
Number of pages9
JournalJournal of Materials Chemistry A
Volume7
Issue number40
DOIs
Publication statusPublished - 2019 Jan 1

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Metastable phases
Alloying
Anodes
Phase transitions
Polarization
Electrochemical properties
Hysteresis
Thermodynamics
Ions
Chemical analysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

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abstract = "Electrochemical properties of batteries are closely related to phase transition behaviors at alloying anodes. This transition process in many cases occurs in a continuous and reversible manner with the formation of multiple phases with similar compositions and structures, making it difficult to identify the transition behaviors using conventional techniques. In this study, a combination of first-principles calculations and voltammetric measurements is used to identify multiple and continuous phase transition behaviors at an Sb anode during Na-Sb battery cycles. Calculations reveal that inflowing Na ions transform the fundamental structural motifs of NaxSb and generate various stable and metastable NaxSb phases. Plausible phases are selected by comparing the calculated formation energies with those determined from experimentally obtained polarization curves. The identities of the phases are verified by reproducing the experimental polarization curves by thermodynamic modeling. The formation of metastable phases during charging and discharging of the Sb anode is responsible for the hysteresis loss indicated in the polarization curve. The present model provides a simple yet effective means of identifying both stable and metastable phases formed during successive phase transition processes, which are difficult to analyze using traditional diffractometry and analytical techniques.",
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N2 - Electrochemical properties of batteries are closely related to phase transition behaviors at alloying anodes. This transition process in many cases occurs in a continuous and reversible manner with the formation of multiple phases with similar compositions and structures, making it difficult to identify the transition behaviors using conventional techniques. In this study, a combination of first-principles calculations and voltammetric measurements is used to identify multiple and continuous phase transition behaviors at an Sb anode during Na-Sb battery cycles. Calculations reveal that inflowing Na ions transform the fundamental structural motifs of NaxSb and generate various stable and metastable NaxSb phases. Plausible phases are selected by comparing the calculated formation energies with those determined from experimentally obtained polarization curves. The identities of the phases are verified by reproducing the experimental polarization curves by thermodynamic modeling. The formation of metastable phases during charging and discharging of the Sb anode is responsible for the hysteresis loss indicated in the polarization curve. The present model provides a simple yet effective means of identifying both stable and metastable phases formed during successive phase transition processes, which are difficult to analyze using traditional diffractometry and analytical techniques.

AB - Electrochemical properties of batteries are closely related to phase transition behaviors at alloying anodes. This transition process in many cases occurs in a continuous and reversible manner with the formation of multiple phases with similar compositions and structures, making it difficult to identify the transition behaviors using conventional techniques. In this study, a combination of first-principles calculations and voltammetric measurements is used to identify multiple and continuous phase transition behaviors at an Sb anode during Na-Sb battery cycles. Calculations reveal that inflowing Na ions transform the fundamental structural motifs of NaxSb and generate various stable and metastable NaxSb phases. Plausible phases are selected by comparing the calculated formation energies with those determined from experimentally obtained polarization curves. The identities of the phases are verified by reproducing the experimental polarization curves by thermodynamic modeling. The formation of metastable phases during charging and discharging of the Sb anode is responsible for the hysteresis loss indicated in the polarization curve. The present model provides a simple yet effective means of identifying both stable and metastable phases formed during successive phase transition processes, which are difficult to analyze using traditional diffractometry and analytical techniques.

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