Pr_(1-x)SrCo_(0.5)Ni_(0.5)O_(4+δ)阴极材料的合成及电化学性质
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摘要
采用固相法合成中温固体氧化物燃料电池(IT-SOFC)阴极材料Pr_(1-x)SrCo_(0.5)Ni_(0.5)O_(4+δ)(P_(1-x)SCN,x=0.00,0.05,0.10,0.15,0.20),并对材料的物相、热膨胀系数(TEC)、电导率、电极的微观形貌以及电化学性质进行表征。XRD结果表明,该材料形成单一的K_2NiF_4结构,空间群为I4/mmm,并与电解质材料Ce_(0.9)Gd_(0.1)O_(1.95)(CGO)具有良好的高温化学相容性。碘量法分析表明随着Pr离子缺位浓度增加,P_(1-x)SCN中Co/Ni离子平均化合价随着x的增加而升高,至x=0.10后逐渐降低,而氧空位含量逐渐升高。引入Pr离子缺位使材料的电导率明显提高,其中P_(0.90)SCN在700℃空气中电导率值为309 S·cm~(-1)。TEC测试结果显示,随着Pr缺位的增加,热膨胀系数逐渐增大,最大值为1.51×10~(-5)K~(-1)。交流阻抗谱(EIS)测试结果表明,Pr缺位明显降低了电极的极化阻抗值,P_(0.90)SCN阴极在700℃空气中的极化阻抗值为0.21Ω·cm~2。电解质支撑NiO-CGO/CGO/P_(0.90)SCN单电池在700℃最大输出功率密度为197.8 mW·cm~(-2)。
Intermediate temperature solid oxide fuel cells(IT-SOFCs)cathode materials Pr_(1-x)SrCo_(0.5)Ni_(0.5)O_(4+δ)(P_(1-x)SCN,x=0.0,0.05,0.10,0.15,0.20)are synthesized by solid-state reaction method.The phase,thermal expansion coefficient(TEC),conductivity,electrode morphology and electrochemical properties are characterized.XRD results show that the oxides crystallize in a single K_2NiF_4structure with a space group of I4/mmm.The cathode materials exhibited good high temperature chemical compatibility with electrolyte Ce_(0.9)Gd_(0.1)O_(1.95)(CGO).Iodometry analysis shows that with the increase of Pr~(3+)vacancy concentration,the average valence of Co/Ni ions in oxides increased stepwise with the increase of x and then decreased after x=0.10,while the content of oxygen vacancy increased gradually.Introducing Pr~(3+)vacancy significantly improved the conductivity of the material.The highest conductivity of 309 S·cm~(-1)was found in P_(0.90)SCN at 700℃in air.The thermal expansion measurement results show that TEC increased with the increase of Pr~(3+)deficiency,and the maximum value is 1.51×10~(-5)K~(-1).Electrochemical impedance spectroscopy(EIS)measurements show that Pr vacancy significantly reduced the polarization resistance of the electrode,and the smallest polarization resistance of 0.21Ω·cm~2was obtained on P_(0.90)SCN cathode at700℃in air.The maximum output power density of electrolyte supported single cell NiO-CGO/CGO/P_(0.90)SCN was197.8 mW·cm~(-2)at 700℃.
Intermediate temperature solid oxide fuel cells(IT-SOFCs)cathode materials Pr_(1-x)SrCo_(0.5)Ni_(0.5)O_(4+δ)(P_(1-x)SCN,x=0.0,0.05,0.10,0.15,0.20)are synthesized by solid-state reaction method.The phase,thermal expansion coefficient(TEC),conductivity,electrode morphology and electrochemical properties are characterized.XRD results show that the oxides crystallize in a single K_2NiF_4structure with a space group of I4/mmm.The cathode materials exhibited good high temperature chemical compatibility with electrolyte Ce_(0.9)Gd_(0.1)O_(1.95)(CGO).Iodometry analysis shows that with the increase of Pr~(3+)vacancy concentration,the average valence of Co/Ni ions in oxides increased stepwise with the increase of x and then decreased after x=0.10,while the content of oxygen vacancy increased gradually.Introducing Pr~(3+)vacancy significantly improved the conductivity of the material.The highest conductivity of 309 S·cm~(-1)was found in P_(0.90)SCN at 700℃in air.The thermal expansion measurement results show that TEC increased with the increase of Pr~(3+)deficiency,and the maximum value is 1.51×10~(-5)K~(-1).Electrochemical impedance spectroscopy(EIS)measurements show that Pr vacancy significantly reduced the polarization resistance of the electrode,and the smallest polarization resistance of 0.21Ω·cm~2was obtained on P_(0.90)SCN cathode at700℃in air.The maximum output power density of electrolyte supported single cell NiO-CGO/CGO/P_(0.90)SCN was197.8 mW·cm~(-2)at 700℃.
引文
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[2] FAN Yu-Hang(范宇航), SUN Li-Ping(孙丽萍), HUO Li-Hua(霍丽华),et al. Chinese J. Inorg. Chem.(无机化学学报),2016,32(10):1730-1738
[3] Shen J, Yang G M, Zhang Z B, et al. J. Mater. Chem. A,2016,4(27):10641-10649
[4] KimY B, Holme T P, Gür T M, et al. Adv. Funct. Mater.,2011,21:4684-4690
[5] Sharma R K, Djurado E. J. Mater. Chem. A, 2018,6(23):10787-10802
[6] Kaluzhskikha M S, Kazakova S M, Mazoa G N, et al. J. Solid State Chem., 2011,184:698-704
[7] SHENG Shuang(盛双), ZHAO Hui(赵辉), HAO Ju-Hong(郝举红), et al. Chinese J. Inorg. Chem.(无机化学学报), 2016,32(12):2143-2150
[8] Gao Z, Mogni L V, Miller E C, et al. Energy Environ. Sci.,2016,9:1602-1644
[9] CAO Yue(曹悦), GU Hai-Tao(顾海涛),CHEN Han(陈涵),et al. J. Inorg. Mater.(无机材料学报), 2010,25(7):738-742
[10]Mazo G N, Mamaev Y A, Galin M Z, et al. Inorg. Mater.,2011,47:1218-1226
[11]Kharton V V, Viskup A P, Kovalevsky A V, et al. Solid State Ionics, 2001,143:337-353
[12]Khandale A P, Bhoga S S. J. Alloys Compd., 2009,509:6955-6961
[13]Soorie M, Skinner S J. Solid State Ionic, 2006,177:2081-2086
[14]Li Q, Zhao H, Huo L H, et al. Electrochem. Commun.,2007,9:1508-1512
[15]Ding X F, Kong X, Jiang J G, et al. Int. J. Hydrogen Energy,2009,34:6869-6975
[16]Flura A, Dru S, Nicollet C, et al. J. Solid State Chem., 2015,228:189-198
[17]Nie H W, Wen T L, Wang S R, et al. Solid State Ionic,2006,177:1929-1932
[18]Zhao H, Li Q, Sun L P. Sci. China-Chem., 2011,54:898-910
[19]Munnings C N, Skinner S J, Amow G, et al. Solid State Ionics, 2005,176:1895-1901
[20]Wang J K, Zhou J, Fan W W, et al. J. Solid State Chem.,2017,247:24-30
[21]Hu Y, Bouffanais Y, Almar L, et al. Int. J. Hydrogen Energy,2013,38:3064-3072
[22]Zharikova E V, Rozova M G, Kazakov S M, et al. Solid State Commun., 2016,245:31-35
[23]Boulahya K, Gil D M, Hassan M, et al. Dalton Trans., 2017,46(4):1283-1289
[24]Laguna-Bercero M A, Kinadjan N, Sayers R, et al. Fuel Cells,2011,1:102-107
[25]Riza F, Ftikos C. J. Eur. Ceram. Soc., 2007,27:571-573
[26]Istomin S Y, Karakulina O M, Rozova M G, et al. RSC Adv.,2016,6:33951-33958
[27]Zhao F, Wang X F, Wang Z Y, et al. Solid State Ionics,2008,179:1450-1453
[28]Laguna-Bercero M A, Luebbe H, Silva J, et al. Fuel Cells,2015,15:98-104
[29]Lalanne C, Prosperi G, Bassat J M, et al. J. Power Sources,2008,185:1218-1224
[30]Zhao H, Mauvy F, Lalanne C, et al. Solid State Ionic, 2008,179:2000-2005
[31]Ferkhi M, Ahmed Yahia H. Mater. Res. Bull., 2016,83:268-274
[32]Hassen A, Ali A I, Kim B G, et al. American Journal of Condensed Matter Physics, 2012,2(4):93-100
[33]Song H S, Min J H, Kim J, et al. J. Power Sources, 2009,191:269-274
[34]JIANG Tao(姜涛), DING Tie-Zhu(丁铁柱), CHAO LuoMeng(潮洛蒙), et al. J. Funct. Mater.(功能材料), 2008,39:521-523
[35]Chen Y, Zhang L, Niu B B, et al. Int. J. Hydrogen Energy,2017,42:6231-6242
[36]Jin F J, Xu H W, Long W, et al. J. Power Sources, 2013,243:10-18
[37]Dai N N, Feng J, Wang Z H, et al. J. Mater. Chem. A, 2013,1:14147-14153
[38]Somacescu S, Florea M, Osiceanu P, et al. J. Nanopart. Res.,2015,17:426(16 Pages)
[39]Yang Z B, Han M F, Zhu P Y, et al. Int. J. Hydrogen Energy, 2011,36:9162-9168
[40]Pang S L, Jiang X N, Li X N, et al. J. Power Sources, 2012,204:53-59
[41]Fu D W, Jin F J, He T M. J. Power Sources, 2016,313:134-141
[42]Jiang X N, Shi Y C, Zhou W L, et al. J. Power Sources,2014,272:371-377
[43]Li Q, Zeng X, Sun L P, et al. Int. J. Hydrogen Energy, 2012,37:2552-2558
[44]Kim J D, Kim G D, Moon J W, et al. Solid State Ionics,2001,143(3):379-389
[45]Souza R A D, Kilner J A. Solid State Ionics, 1998,106(3):175-187
[46]Souza R A D, Kilner J A. Solid State Ionics, 1999,126(1):153-161
[47]Gao Z, Liu X M, Bergman B. J. Power Sources, 2011,196:9195-9203
[48]Gao L, Li Q, Sun L P, et al. J. Power Sources, 2017,371:86-95
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