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Energy

Ion Migration In Electrodes Revealed

Fluorosulfate materials reveal differences in Na+ and Li+ movement, a finding that could improve rechargeable batteries

by Jyllian N. Kemsley
April 18, 2011 | A version of this story appeared in Volume 89, Issue 16

In a family of fluorosulfate materials of interest for rechargeable battery cathodes, higher calculated activation energies for sodium-ion movement in NaFeSO4F 
compared with lithium-ion movement in LiFeSO4F help explain the poor performance of NaFeSO4F as an electrode material (Chem. Mater., DOI: 10.1021/cm200683n). A better understanding of the differences between sodium- and lithium-based materials could point the way to development of sodium-based cathodes, reducing pressure on global lithium supplies. Linda F. Nazar of Canada’s University of Waterloo, M. Saiful Islam of England’s University of Bath, and colleagues studied ion migration pathways within LiFeSO4F and NaFeSO4F. They calculated that the paths for Na+ migration in NaFeSO4F all have higher activation energies than the paths for Li+ migration in 
LiFeSO4F. Additionally, only one migration path is likely in NaFeSO4F, whereas Li+ can migrate along paths in multiple directions. Such differences in ion mobility, along with the fact that the crystal lattice has to expand more to accommodate the larger Na+ ions, would explain the differences in electrode performance observed experimentally, the researchers say.

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Credit: Adapted from Chem. Mater.
According to a theoretical analysis, sodium ions (black) can only migrate through NaFeSO4F along a single zigzag path (red); FeO4F2 is gray, SO4 is yellow.
Credit: Adapted from Chem. Mater.
According to a theoretical analysis, sodium ions (black) can only migrate through NaFeSO4F along a single zigzag path (red); FeO4F2 is gray, SO4 is yellow.

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