Ion-transport engineering of alkaline-earth hydrides for hydride electrolyte applications

Rowberg, Andrew J. E.; Weston, Leigh; Van de Walle, Chris G.

doi:10.1021/acs.chemmater.8b01593

Title: Ion-transport engineering of alkaline-earth hydrides for hydride electrolyte applications

Journal Article · Mon Aug 13 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b01593· OSTI ID:1464502

^[1]; Weston, Leigh ^[2]; Van de Walle, Chris G. ^[1]

Univ. of California, Santa Barbara, CA (United States)
Univ. of California, Santa Barbara, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The heavier alkaline-earth hydrides (AeH₂; Ae = Ca, Sr, Ba) are promising materials for hydrogen energy applications, due to their excellent ionic conductivity and thermal stability. We use first-principles calculations to elucidate their defect chemistry and ion-transport mechanisms. Based on calculated formation energies, we find that hydrogen vacancies (V_H) are present in large concentrations, and hence, transport is vacancy-mediated. The vacancy migration barrier depends strongly on the charge state of the vacancy, with V_H⁺ yielding the lowest barriers. The activation energy for ionic transport, which is the sum of the migration barrier and formation energy, can be further reduced by lowering the formation energy of the vacancies. This goal can be achieved by doping with acceptors, such as alkali-metal impurities, which induces larger concentrations of V_H⁺. We show that, with optimized conditions for doping, ionic conductivities can be improved by several orders of magnitude; for BaH₂, the conductivity is on par with proton conductivity in the best proton-conducting oxides. For BaH₂, we find K to be the optimal dopant for enhancing conductivity, and for CaH₂ and SrH₂, we find Na to be optimal. Here, the resulting large ionic conductivity of hydrogen makes the heavier alkaline-earth hydrides strong candidates for electrolytes in hydrogen fuel cells.

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Research Organization:: Univ. of California, Santa Barbara, CA (United States). Materials Dept.

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Organization:: Center for Scientific Computing at the California NanoSystems Institute and Materials Research Laboratory; National Energy Research Scientific Computing Center

Grant/Contract Number:: FG02-07ER46434

OSTI ID:: 1464502

Journal Information:: Chemistry of Materials, Vol. 30, Issue 17; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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