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Title: Exsolution and electrochemistry in perovskite solid oxide fuel cell anodes: Role of stoichiometry in Sr(Ti,Fe,Ni)O 3

Abstract

The exsolution of metal cations from oxides under reducing fuel conditions ends in the formation of surface metallic nanoparticles, which can reduce Solid Oxide Fuel Cell anode polarization resistance. However, the loss of the B-site cations shifts the stoichiometry of the perovskite oxide. Depending on the amount exsolved and the initial stoichiometry, the exsolution can presumably shift the oxide away from its single-phase perovskite region. Herein, the direct comparison of initially stoichiometric composition Sr(Ti 0.3Fe 0.63Ni 0.07)O 3-δ (STFN0) with initially A-site deficient Sr 0.95(Ti 0.3Fe 0.63Ni 0.07)O 3-δ (STFN5) is conducted and reported. X-ray diffraction along with scanning and transmission electron microscopy analysis of the oxides, which are both reduced at 850 °C in H 2/H 2O/Ar, demonstrates a similar size and density of exsolved Fe–Ni alloy nanoparticles, albeit with slightly different alloy compositions. Whereas the oxide phase in reduced STFN5 shows a well-ordered perovskite structure, the greater B-site deficiency in reduced STFN0 results in a highly disordered and strained structure. The electrochemical performance of STFN0 anodes is inferior to that of STFN5 anodes, and even worse than SrTi 0.3Fe 0.7O 3-δ (Ni-free) anodes. It appears that an initial Sr deficiency is important to avoid a too-high B-site deficiencymore » after exsolution, which distorts the perovskite structure and impairs electrochemical processes.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [2];  [3]; ORCiD logo [4]
  1. Northwestern Univ., Evanston, IL (United States); Nanjing Univ. (China)
  2. Comision Nacional de Energia Atomica (CNEA), Rio Negro (Argentina). Centro Atomico Bariloche (CAB)
  3. Tsinghua Univ., Beijing (China)
  4. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Natural Science Foundation of China (NNSFC); National Key R&D Program of China; Keck Foundation; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF)
Contributing Org.:
International Institute for Nanotechnology (IIN)
OSTI Identifier:
1599125
Alternate Identifier(s):
OSTI ID: 1560700; OSTI ID: 1658924
Grant/Contract Number:  
SC0016965; DMR-1121262; NNCI-1542205; 51702163; 2018YFB1502203
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 439; Journal Issue: C; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Solid oxide fuel cell; Sr(Ti,Fe,Ni)O3; Perovskite anode; Exsolution; Stoichiometry; 30 DIRECT ENERGY CONVERSION

Citation Formats

Zhu, Tenglong, Troiani, Horacio, Mogni, Liliana V., Santaya, Mariano, Han, Minfang, and Barnett, Scott A. Exsolution and electrochemistry in perovskite solid oxide fuel cell anodes: Role of stoichiometry in Sr(Ti,Fe,Ni)O3. United States: N. p., 2019. Web. doi:10.1016/j.jpowsour.2019.227077.
Zhu, Tenglong, Troiani, Horacio, Mogni, Liliana V., Santaya, Mariano, Han, Minfang, & Barnett, Scott A. Exsolution and electrochemistry in perovskite solid oxide fuel cell anodes: Role of stoichiometry in Sr(Ti,Fe,Ni)O3. United States. https://doi.org/10.1016/j.jpowsour.2019.227077
Zhu, Tenglong, Troiani, Horacio, Mogni, Liliana V., Santaya, Mariano, Han, Minfang, and Barnett, Scott A. Thu . "Exsolution and electrochemistry in perovskite solid oxide fuel cell anodes: Role of stoichiometry in Sr(Ti,Fe,Ni)O3". United States. https://doi.org/10.1016/j.jpowsour.2019.227077. https://www.osti.gov/servlets/purl/1599125.
@article{osti_1599125,
title = {Exsolution and electrochemistry in perovskite solid oxide fuel cell anodes: Role of stoichiometry in Sr(Ti,Fe,Ni)O3},
author = {Zhu, Tenglong and Troiani, Horacio and Mogni, Liliana V. and Santaya, Mariano and Han, Minfang and Barnett, Scott A.},
abstractNote = {The exsolution of metal cations from oxides under reducing fuel conditions ends in the formation of surface metallic nanoparticles, which can reduce Solid Oxide Fuel Cell anode polarization resistance. However, the loss of the B-site cations shifts the stoichiometry of the perovskite oxide. Depending on the amount exsolved and the initial stoichiometry, the exsolution can presumably shift the oxide away from its single-phase perovskite region. Herein, the direct comparison of initially stoichiometric composition Sr(Ti0.3Fe0.63Ni0.07)O3-δ (STFN0) with initially A-site deficient Sr0.95(Ti0.3Fe0.63Ni0.07)O3-δ (STFN5) is conducted and reported. X-ray diffraction along with scanning and transmission electron microscopy analysis of the oxides, which are both reduced at 850 °C in H2/H2O/Ar, demonstrates a similar size and density of exsolved Fe–Ni alloy nanoparticles, albeit with slightly different alloy compositions. Whereas the oxide phase in reduced STFN5 shows a well-ordered perovskite structure, the greater B-site deficiency in reduced STFN0 results in a highly disordered and strained structure. The electrochemical performance of STFN0 anodes is inferior to that of STFN5 anodes, and even worse than SrTi0.3Fe0.7O3-δ (Ni-free) anodes. It appears that an initial Sr deficiency is important to avoid a too-high B-site deficiency after exsolution, which distorts the perovskite structure and impairs electrochemical processes.},
doi = {10.1016/j.jpowsour.2019.227077},
url = {https://www.osti.gov/biblio/1599125}, journal = {Journal of Power Sources},
issn = {0378-7753},
number = C,
volume = 439,
place = {United States},
year = {2019},
month = {9}
}

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