Thermodynamic properties of Ca–Pb electrodes determined by electromotive force measurements

Nathan D. Smith, Nicole E. Orabona, Jorge Paz Soldan Palma, Yuran Kong, Cameron Blanchard, Hojong Kim

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


Thermodynamic properties of Ca–Pb alloys are investigated by electromotive force (emf) measurements to determine equilibrium cell potentials and phase properties for their application in energy storage systems such as liquid metal batteries. Using the electrochemical cell Ca(s) | CaF2(s) | Ca(in Pb) at 700–1060 K, cell emf is measured for thirteen Ca–Pb alloys at mole fractions, xCa = 0.06–0.80. At 873 K, the equilibrium potentials of liquid Ca–Pb alloys are 0.57–0.62 V versus Ca and the activity values are as low as aCa = 6.2 × 10−8 at xCa = 0.06. In addition, the emf values as a function of temperature provide partial molar quantities (entropy and enthalpy) as well as phase transitions which are corroborated by determining transition temperatures and phase constituents using differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD). This work establishes the fundamental data necessary for the design of Pb-containing liquid metal electrodes through the integration of electrochemical, thermal, and structural properties of Ca–Pb electrodes.

Original languageEnglish (US)
Article number227745
JournalJournal of Power Sources
StatePublished - Mar 1 2020

All Science Journal Classification (ASJC) codes

  • Renewable Energy, Sustainability and the Environment
  • Energy Engineering and Power Technology
  • Physical and Theoretical Chemistry
  • Electrical and Electronic Engineering


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