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Redox processes in sodium vanadium phosphate cathodes - insights from operando magnetometry.

Gregor Klinser1, Roman Zettl, Martin Wilkening

  • 1Institute of Material Physics, Graz University of Technology, Petersgasse 16, A-8010 Graz, Austria. wuerschum@tugraz.at g.klinser@tugraz.at.

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Operando magnetic susceptibility measurements reveal vanadium

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-State Chemistry

Background:

  • Sodium-ion batteries are a promising alternative to lithium-ion batteries.
  • Understanding cathode material behavior during cycling is crucial for battery performance.
  • Transition metal oxidation state changes are key to battery operation.

Purpose of the Study:

  • To monitor transition metal oxidation states in sodium-ion cathode materials during electrochemical cycling.
  • To investigate the operational mechanisms of NaxV2(PO4)3 cathodes.
  • To identify potential parasitic side reactions affecting battery performance.

Main Methods:

  • Utilizing operando magnetic susceptibility measurements.
  • Performing continuous and bulk-sensitive monitoring.
  • Conducting repetitive electrochemical cycling of NaxV2(PO4)3.

Main Results:

  • Vanadium was identified as the sole ion undergoing oxidation/reduction in NaxV2(PO4)3 during battery operation.
  • Magnetic susceptibility data revealed anomalies during the initial charge-discharge cycle and after storage.
  • These anomalies suggest parasitic side reactions occurring on the cathode surface.

Conclusions:

  • Operando magnetic susceptibility is effective for tracking oxidation states in sodium-ion cathodes.
  • Parasitic side reactions can occur on NaxV2(PO4)3 cathodes, particularly during initial cycles and after storage.
  • Further investigation into surface chemistry is needed to mitigate these side reactions and improve battery longevity.