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Understanding the Role of Overpotentials in Lithium Ion Conversion Reactions: Visualizing the Interface.

Guennadi EvmenenkoRobert E WarburtonHandan YildirimJeffrey P GreeleyMaria K Y ChanD Bruce BuchholzPaul FenterMichael J BedzykTimothy T Fister
Published in: ACS nano (2019)
Oxide conversion reactions are known to have substantially higher specific capacities than intercalation materials used in Li-ion batteries, but universally suffer from large overpotentials associated with the formation of interfaces between the resulting nanoscale metal and Li2O products. Here we use the interfacial sensitivity of operando X-ray reflectivity to visualize the structural evolution of ultrathin NiO electrodes and their interfaces during conversion. We observe two additional reactions prior to the well-known bulk, three-dimensional conversion occurring at 0.6 V: an accumulation of lithium at the buried metal/oxide interface (at 2.2 V) followed by interfacial lithiation of the buried NiO/Ni interface at the theoretical potential for conversion (at 1.9 V). To understand the mechanisms for bulk and interfacial lithiation, we calculate interfacial energies using density functional theory to build a potential-dependent nucleation model for conversion. These calculations show that the additional space charge layer of lithium is a crucial component for reducing energy barriers for conversion in NiO.
Keyphrases
  • density functional theory
  • ion batteries
  • molecular dynamics simulations
  • solid state
  • molecular dynamics
  • computed tomography
  • human health
  • climate change
  • risk assessment
  • living cells
  • atomic force microscopy