Co/Ni掺杂SrTi_(0.3)Fe_(0.7)O_(3–δ)钙钛矿电极材料制备及性能
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摘要
以Sr Ti_(0.3)Fe_(0.7)O_(3–δ)(STF)为基础,研究了B位Co、Ni掺杂Sr Ti_(0.3)(Fe_(1–x)Co_x)_(0.7)O_(3–δ)(STFC)和Sr Ti_(0.3)(Fe_(1–y)Ni_y)_(0.7)O_(3–δ)(STFN)钙钛矿氧化物的成相过程及其在还原气氛中的结构演变规律,并进一步表征了其用于固体氧化物燃料电池(SOFC)对称电极的电化学性能。结果表明:Co和Fe可以在B位无限互溶,形成Sr Ti_(0.3)Fe_(0.7)O_(3–δ)–Sr Ti_(0.3)Co_(0.7)O_(3–δ)固溶体系;但当Ni替换Fe的比例超过约30%时就会出现明显的Sr_2Fe_2O_5杂相。在还原气氛中,STFC和STFN的结构稳定性随Co或Ni掺杂量的增加而降低,并逐渐由ABO_3结构转变为富AO相的钙钛矿衍生结构,同时伴随着Co基或Ni基金属相的生成。在850℃和加湿氢气燃料下,La_(0.8)Sr_(0.2)Ga_(0.83)Mg_(0.17)O_(3–δ)电解质支撑SrTi_(0.3)(Fe_(0.9)Ni_(0.1))_(0.7)O_(3–δ)和Sr Ti_(0.3)(Fe_(0.9)Co_(0.1))_(0.7)O_(3–δ)对称电池的最大功率密度分别达到约1.00和0.87 W/cm~2,表现出较好的电化学性能和实用前景。
Cobalt and nickel substituted SrTi_(0.3)Fe_(0.7)O_(3–δ)perovskite oxides,i.e.,Sr Ti_(0.3)(Fe_(1–x)Co_x)_(0.7)O_(3–δ)(STFC)and Sr Ti_(0.3)(Fe_(1–y)Ni_y)_(0.7)O_(3–δ)(STFN),were synthesized.Their structure evolutions in reducing atmospheres were investigated,and their electrochemical properties as symmetrical electrodes in solid oxide fuel cell were characterized.The results show that solid solutions from Sr Ti_(0.3)Fe_(0.7)O_(3–δ)to Sr Ti_(0.3)Co_(0.7)O_(3–δ)are effectively synthesized,and impurity phases of Sr_2Fe_2O_(5 )occur in STFN system with a substituted nickel ratio of>30%to iron.After reduction in reducing atmosphere,the structure stability of STFC and STFN decreases with the increase of doping amount of Co or Ni,and the ABO_(3 )structurechanges to AO-rich perovskite-derived structure and cobalt-or nickel-based metallic phases appear.Sr Ti_(0.3)(Fe_(0.9)Ni_(0.1))_(0.7)O_(3–δ)and SrTi_(0.3)(Fe_(0.9)Co_(0.1))_(0.7)O_(3–δ)symmetrical cells with La_(0.8)Sr_(0.2)Ga_(0.83)Mg_(0.17)O_(3–δ)electrolyte supports both have the maximum power densities of 1.00 and 0.87W/cm~2,respectively,in wet hydrogen fuel,which could be used for the promising applications.
Cobalt and nickel substituted SrTi_(0.3)Fe_(0.7)O_(3–δ)perovskite oxides,i.e.,Sr Ti_(0.3)(Fe_(1–x)Co_x)_(0.7)O_(3–δ)(STFC)and Sr Ti_(0.3)(Fe_(1–y)Ni_y)_(0.7)O_(3–δ)(STFN),were synthesized.Their structure evolutions in reducing atmospheres were investigated,and their electrochemical properties as symmetrical electrodes in solid oxide fuel cell were characterized.The results show that solid solutions from Sr Ti_(0.3)Fe_(0.7)O_(3–δ)to Sr Ti_(0.3)Co_(0.7)O_(3–δ)are effectively synthesized,and impurity phases of Sr_2Fe_2O_(5 )occur in STFN system with a substituted nickel ratio of>30%to iron.After reduction in reducing atmosphere,the structure stability of STFC and STFN decreases with the increase of doping amount of Co or Ni,and the ABO_(3 )structurechanges to AO-rich perovskite-derived structure and cobalt-or nickel-based metallic phases appear.Sr Ti_(0.3)(Fe_(0.9)Ni_(0.1))_(0.7)O_(3–δ)and SrTi_(0.3)(Fe_(0.9)Co_(0.1))_(0.7)O_(3–δ)symmetrical cells with La_(0.8)Sr_(0.2)Ga_(0.83)Mg_(0.17)O_(3–δ)electrolyte supports both have the maximum power densities of 1.00 and 0.87W/cm~2,respectively,in wet hydrogen fuel,which could be used for the promising applications.
引文
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[24]NENNING A,VOLGGER L,MILLER E,et al.The electrochemical properties of Sr(Ti,Fe)O3-δfor anodes in solid oxide fuel cells[J].JElectrochem Soc,2017,164:F364-F371.
[25]CHEN X,NI W,WANG J,et al.Exploration of Co-Fe alloy precipitation and electrochemical behavior hysteresis using Lanthanum and cobalt co-substituted SrFeO3-δSOFC anode[J].Electrochim Acta,2018,277:226-234.
[2]韩敏芳,张永亮.固体氧化物燃料电池中的陶瓷材料[J].硅酸盐学报,2017,45:1548-1554.HAN Minfang,ZHANG Yongliang.J Chin Ceram Soc,2017,45:1548-1554.
[3]TAO S,IRVINE J T.A redox-stable efficient anode for solid-oxide fuel cells[J].Nat Mater,2003,2:320-323.
[4]GOODENOUGH J B,HUANG Y H.Alternative anode materials for solid oxide fuel cells[J].J Power Sources,2007,173:1-10.
[5]LIU Q,DONG X,XIAO G,et al.A novel electrode material for symmetrical SOFCs[J].Adv Mater,2010,22:5478-5482.
[6]SENGODAN S,CHOI S,JUN A,et al.Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells[J].Nat Mater,2015,14:205-209.
[7]CHO S,FOWLER D E,MILLER E C,et al.Fe-substituted SrTiO3-δ-Ce0.9Gd0.1O2 composite anodes for solid oxide fuel cells[J].Energy Environme Sci,2013,6:1850.
[8]ZHU T,FOWLER D E,POEPPELMEIER K R,et al.Hydrogen oxidation mechanisms on perovskite solid oxide fuel cell anodes[J].JElectrochem Soc,2016,163:F952-F961.
[9]KIM G,LEE S,SHIN J Y,et al.Investigation of the structural and catalytic requirements for high-performance SOFC anodes formed by infiltration of LSCM[J].Electrochem Solid-State Lett,2009,12:B48.
[10]IRVINE J T S,NEAGU D,VERBRAEKEN M C,et al.Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers[J].Nat Energy,2016,1:15014.
[11]XIAO G,JIN C,LIU Q,et al.Ni modified ceramic anodes for solid oxide fuel cells[J].J Power Sources,2012,201:43-48.
[12]MADSEN B D,KOBSIRIPHAT W,WANG Y,et al.Nucleation of nanometer-scale electrocatalyst particles in solid oxide fuel cell anodes[J].J Power Sources,2007,166:64-67.
[13]SHIN T H,OKAMOTO Y,IDA S,et al.Self-recovery of Pd nanoparticles that were dispersed over La(Sr)Fe(Mn)O3 for intelligent oxide anodes of solid-oxide fuel cells[J].Chemistry,2012,18:11695-11702.
[14]YANG C,YANG Z,JIN C,et al.Sulfur-tolerant redox-reversible anode material for direct hydrocarbon solid oxide fuel cells[J].Adv Mater,2012,24:1439-1443.
[15]NEAGU D,TSEKOURAS G,MILLER D N,et al.In situ growth of nanoparticles through control of non-stoichiometry[J].Nat Chem,2013,5:916-923.
[16]SUN Y,LI J,ZENG Y,et al.A-site deficient perovskite:the parent for in situ exsolution of highly active,regenerable nano-particles as SOFCanodes[J].J Mater Chem A,2015,3:11048-11056.
[17]DU Z,ZHAO H,YI S,et al.High-performance anode material Sr2FeMo0.65Ni0.35O6-δwith in situ exsolved nanoparticle catalyst[J].ACS nano,2016,10:8660-8669.
[18]ZHU T,TROIANI H E,MOGNI L V,et al.Ni-substituted Sr(Ti,Fe)O3SOFC anodes:achieving high performance via metal alloy nanoparticle exsolution[J].Joule,2018,2:478-496.
[19]NEAGU D,OH T S,MILLER D N,et al.Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution[J].Nat Communicat,2015,6:8120.
[20]BIERSCHENK D M,POTTER-NELSON E,HOEL C,et al.Pd-substituted(La,Sr)CrO3-δ-Ce0.9Gd0.1O2-δsolid oxide fuel cell anodes exhibiting regenerative behavior[J].J Power Sources,2011,196:3089-3094.
[21]ROTHSCHILD A,MENESKLOU W,TULLER H L,et al.Electronic structure,defect chemistry,and transport properties of SrTi1-x Fex O3-y solid solutions[J].Chem Mater,2006,18:3651-3659.
[22]GLASER R,ZHU T,TROIANI H,et al.The enhanced electrochemical response of Sr(Ti0.3Fe0.7Ru0.07)O3-δanodes due to exsolved Ru-Fe nanoparticles[J].J Mater Chem A,2018,6:5193-5201.
[23]ZHANG S-L,WANG H,LU M Y,et al.Cobalt-substituted SrTi0.3Fe0.7O3-δ:a stable high-performance oxygen electrode material for intermediate-temperature solid oxide electrochemical cells[J].Energy Environm Sci,2018
[24]NENNING A,VOLGGER L,MILLER E,et al.The electrochemical properties of Sr(Ti,Fe)O3-δfor anodes in solid oxide fuel cells[J].JElectrochem Soc,2017,164:F364-F371.
[25]CHEN X,NI W,WANG J,et al.Exploration of Co-Fe alloy precipitation and electrochemical behavior hysteresis using Lanthanum and cobalt co-substituted SrFeO3-δSOFC anode[J].Electrochim Acta,2018,277:226-234.