Predicting Thermochemical Equilibria with Interacting Defects: Alloys for Water Splitting: Article No. 013008

Anuj Goyal, Michael Sanders, Ryan O'Hayre, Stephan Lany

Research output: Contribution to journalArticlepeer-review


Solar thermochemical hydrogen is one of the few potential routes towards direct fuel production from renewable energy sources, but the thermodynamic boundary conditions for efficient and economic energy conversion are challenging. Success or failure of a given oxide working material depends on the subtle balance between enthalpy and entropy contributions in the redox processes. Developing a mechanistic understanding of the behavior of materials on the basis of atomistic models and first-principles calculations is an important part of advancing the technology. One challenge is to quantitatively predict thermochemical equilibria at high concentrations when the redox-active defects start to interact with each other, thereby impeding the formation of additional defects. This problem is of more general importance to applications that rely on high levels of off-stoichiometry or doping, including, for example, batteries, thermoelectrics, and ceramic fuel cells. To account for such repulsive defect interactions, we introduce a statistical mechanics approach, defining an expression for the free energy of defect interaction based on limited sampling of defect configurations in density functional theory supercell calculations. The parameterization of this energy contribution as a function of defect concentration and temperature allows on-the-fly simulation of thermochemical equilibria. The approach consistently incorporates finite temperature effects by including the leading contributions to the temperature-dependent free energy for the case at hand, i.e., the ideal gas and configurational enthalpies and entropies. We demonstrate the capability and utility of the approach by simulating the water splitting redox processes for alloys.
Original languageAmerican English
Number of pages16
JournalPRX Energy
Issue number1
StatePublished - 2024

NREL Publication Number

  • NREL/JA-5K00-87302


  • defect equilibria
  • density functional theory
  • solar thermochemical hydrogen


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