skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Thermodynamic Stability and Defect Chemistry of Bismuth-Based Lead-Free Double Perovskites

Authors:
 [1];  [2];  [3];  [1]
  1. Department of Physics and Astronomy, Wright Center for Photovoltaic Innovation and Commercialization, The University of Toledo, Toledo Ohio 43606 USA
  2. Department of Physics and Astronomy, Wright Center for Photovoltaic Innovation and Commercialization, The University of Toledo, Toledo Ohio 43606 USA, School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, Institute for Advanced Studies, Wuhan University, Wuhan 430072 China
  3. School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, Institute for Advanced Studies, Wuhan University, Wuhan 430072 China
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400784
Grant/Contract Number:
EE0006712; AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 9; Journal Issue: 18; Related Information: CHORUS Timestamp: 2017-10-20 15:54:23; Journal ID: ISSN 1864-5631
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Xiao, Zewen, Meng, Weiwei, Wang, Jianbo, and Yan, Yanfa. Thermodynamic Stability and Defect Chemistry of Bismuth-Based Lead-Free Double Perovskites. Germany: N. p., 2016. Web. doi:10.1002/cssc.201600771.
Xiao, Zewen, Meng, Weiwei, Wang, Jianbo, & Yan, Yanfa. Thermodynamic Stability and Defect Chemistry of Bismuth-Based Lead-Free Double Perovskites. Germany. doi:10.1002/cssc.201600771.
Xiao, Zewen, Meng, Weiwei, Wang, Jianbo, and Yan, Yanfa. Thu . "Thermodynamic Stability and Defect Chemistry of Bismuth-Based Lead-Free Double Perovskites". Germany. doi:10.1002/cssc.201600771.
@article{osti_1400784,
title = {Thermodynamic Stability and Defect Chemistry of Bismuth-Based Lead-Free Double Perovskites},
author = {Xiao, Zewen and Meng, Weiwei and Wang, Jianbo and Yan, Yanfa},
abstractNote = {},
doi = {10.1002/cssc.201600771},
journal = {ChemSusChem},
number = 18,
volume = 9,
place = {Germany},
year = {Thu Aug 04 00:00:00 EDT 2016},
month = {Thu Aug 04 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/cssc.201600771

Citation Metrics:
Cited by: 31works
Citation information provided by
Web of Science

Save / Share:
  • Cited by 1
  • Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made on lead-doped and lead-free Bi{sub 2-z}Pb{sub z}Sr{sub 2}Ca{sub 1}Cu{sub 2}O{sub x} superconducting ceramics in the temperature range {approx} 700-815 C by means of an oxygen-titration technique that employs an yttria-stabilized zirconia electrolyte. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Thermodynamic assessments of the partial molar quantities {Delta}{bar H} (O{sub 2}) and {Delta}{bar S}(O{sub 2}) for lead-doped Bi-2212 and lead-free Bi-2212 indicate that the solid-state decomposition of these bismuth cuprates at low oxygen partial pressuremore » can be represented by the diphasic CuO---Cu{sub 2}O system.« less
  • The oxygen nonstoichiometry of La{sub 2-x}Sr{sub x}CuO{sub 4-{delta}} (x = 0-0.3) was measured as a function of Sr content, temperature (400-1000{degrees}C), and oxygen partial pressure (P(O{sub 2})=1-1x10{sup -10} atm) using high-temperature gravimetry and coulometric titration. The oxygen nonstoichiometry ranges from oxygen excess to oxygen deficiency one depending on P(O{sub 2}) and the Sr content, x. Oxygen excess was observed for specimens with x less than 0.05. The dependence of oxygen excess non-stoichiometry on oxygen partial pressures was found to be explained by a model with interstitial oxygen as a predominant defect. In oxygen-deficient regions, partial molar enthalpy and partial molarmore » entropy of oxygen were calculated from the non-stoichiometry data. It was revealed from the variation in partial molar enthalpy that a strong interaction between the oxygen and its vacancy exists in oxygen-deficient La{sub 2-x}SrCuO{sub 4-{delta}}. The experimentally obtained partial molar entropy of oxygen was compared with those calculated assuming a so-called metal model, a hopping conduction model, and a narrow band conduction model, where the increase in oxygen vacancies hardly influences the carrier concentration, the holes generated by oxidation of the specimen are trapped by Cu ions, and the holes generated are itinerant, respectively. The variation in partial molar entropy of oxygen could be explained well by either the hopping model or the narrow band conduction model. The oxygen partial pressures required for the decomposition of La{sub 2-x}Sr{sub x}CuO{sub 4-{delta}} were also measured through the nonstoichiometry measurement. Discontinuity was observed in the dependence of oxygen partial pressures for decomposition on Sr content between x = 0.05 and 0.10, suggesting an abrupt variation in the thermodynamic behavior of La{sub 2-x}Sr{sub x}CuO{sub 4-{delta}} with the Sr content in this region.« less