反向滴定共沉淀法合成新型中温固体氧化物燃料电池阴极材料La_(0.7)Sr_(0.3-x)Ca_xCo_(1-y)Fe_yO_(3-δ)SYNTHESIS OF NEWCATHODE MATERIALS La_(0.7)Sr_(0.3-x)Ca_xCo_(1-y)Fe_yO_(3-δ) BY REVERSE-TITRATION CO-PRECIPITATION METHOD FOR ITSOFC
郎业鹏,高文元,隋新国,李长敏,胡志强
摘要(Abstract)：
以氢氧化钠和碳酸钠混合碱为沉淀剂,金属硝酸盐为原料,共沉淀法合成了中温固体氧化物燃料电池阴极材料La0.7Sr0.3-xCaxCo1-yFeyO3-δ(简称:LSCCF,x=0.05、0.10、0.15、0.20;y=0.10、0.20、0.40)的前躯体。讨论了共沉淀的最佳pH值范围以及加料顺序,TG-DSC研究了LSCCF粉料的形成过程,XRD和SEM对其前驱体在600℃,800℃,1000℃煅烧4h后的晶体结构和粒度形貌进行了研究和表征;并通过与固相合成LSCCF的条件比较可知:pH值在9.1～9.5范围内,反向滴定共沉淀法得到的前驱体在800℃煅烧4h可以合成出纯度高、组份均匀的单一钙钛矿相的LSCCF粉料。使用直流四极探针法在空气气氛下研究不同烧结温度下LSCCF样品从100℃到800℃时的电导率发现:电导率随着烧结温度的升高在增大;随着x从0.05到0.20以及y从0.10到0.40,1200℃烧结3h后样品的电导率却在减少;当x=0.10或0.15时,Ca2+和Sr2+掺杂对电导率产生"混合"效应,致使其值基本相等。且在500～800℃范围所有样品的电导率都超过了100S/cm。合成的阴极材料LSCCF与电解质Ce0.8Sm0.2O2两者间有良好的相容性。
关键词(KeyWords)： 中温固体氧化物燃料电池;反向滴定共沉淀法;La0.7Sr0.3-xCaxCo1-yFeyO3-δ;电导率;相容性
基金项目(Foundation): 辽宁省教育厅高等学校科学研究项目(编号:05L073);; 辽宁省自然科学基金项目(编号:20062145)
作者(Author): 郎业鹏,高文元,隋新国,李长敏,胡志强
参考文献(References)：
- 1T.Tsai,E.Perry and S.Barnet.J.Electrochem.Soc.,1997,144:130
- 2E.P.Murray,T.Tsai and S.A.Barnett.Nature,1999,400:649
- 3P.Charpentier,P.Fragnaud,D.M.Schleich and C.Lunot.Ionics,1996,2:312
- 4S.de Souza,S.J.Visco and L.C.DeJonghe.Solid State Ionics,1997,98:57
- 5B.C.H.Steele.Solid State Ionics,1996,92:86
- 6C.Milliken,S.Guruswamy and A.Khandkar.J.Electrochem.Soc.,1999,146:872
- 7N.Maffei and A.K.Kuriakose.J.Power Sources,1998,75:162
- 8R.Maric,S.Ohara,T.Fukui,H.Yoshida,M.Nishimura,T.Inagaki and K.Miura.J.Electrochem.Soc.,1999,146:2006
- 9R.Doshi,Von L.Richards,J.D.Carter,X.P.Wang and M.Krumpelt.J.Electrochem.Soc.,1999,146:1273
- 10K.Huang,M.Feng and J.B.Goodenough.J.Electrochem.Soc.,1997,144:3620
- 11Bin Zhu,Xiangrong Liu,Mingtao Sun,et al.Solid State Ionics,2003,5:1127
- 12R.Doshi,V.L.Richards,J.D.Carter,X.P.Wang and M.Krumpelt.J.Electrochem.Soc.,1999,146:1273
- 13Y.Teraoka,H.M.Zhang,K.Okamoto and N.Yamazoe.Mater.Res.Bull.,1988,23:51
- 14Y.Teraoka,H.M.Zhang,S.Furukawa and N.Yamazoe.Chem.Lett.,1985,167:1743
- 15Y.Matsumoto,S.Yamada,T.Nishida and E.Sato.J.Electrochem.Soc.,1980,127:2360
- 16L.-W.Tai,M.M.Nasrallah,H.U.Anderson,D.M.Sparlin and S.R.Sehlin.Solid State Ionics,1995,76:259
- 17Anthony Petric,Peng Huang and Frank Tietz,Solid State Ionics,2000,135,719
- 18M.Mori,Y.Hiei,N.M.Sammes,et al.Journal of the Electrochemical Society,2000,147[4]:1295
- 19Liang Yingjiao[梁英教],Che Yinchang[车荫昌]and Liu Xiaoxia[刘晓霞].Handbook of Inorganic Heat Mechanics Data[无机物热力学数据手册].Shenyang:Northeastern University Press,1994
- 20Ni Jingan[倪静安].Inorganic and Analysis Chemistry[无机及分析化学].Beijing:Chemistry Industry Press,1999
- 21M.Mori,N.M.Sammes and G.A.Tompstett.Journal of Power Sources,2000,86:395
- 22M.Katsuki,Shaorong Wang,M.Dokiya,et al.Solid State Ionics,2003,156:453
- 23Rune Bredesen and Truls Norby.Solid State Ionics,2000,129:285
- 24G.Ch.Kostogloudis and Ch.Ftikos.Solid State Ionics.1999,126:143
- 25A.R.Ruffa.J.Mater.Sci.,1980,15:2258