基于第一性原理的密度泛函理论,分别对钙钛矿型氧化物BaFeO3、BaCoO3和BaNbO3的电子结构和氧空位形成能进行了理论模拟,经优化后得到的晶胞参数与实验文献值吻合良好.通过比较密度泛函理论计算得到的晶格能和氧空位形成能,发现体系稳定性表现为BaCoO3＜ BaFeO3＜ BaNbO3.对于B位含有多种元素的体系,在实验研究中通过1130℃煅烧10 h的条件下得到了BaCo0.5 Fe0.25 Nb0.25O3-(δ)纯相并分析了其晶胞参数.理论研究中以BaCoO3为基构造了钙钛矿型复合氧化物BaCo0.5Fe0.25Nb0.25O3,并通过第一性原理计算优化了其结构,理论计算得到的晶胞参数0.397nm与实验测定的0.407 nm相接近；通过分析此晶体态密度证实了它是电子导体；本文还分析和比较了晶体中两个B位原子间的氧空位形成能差异,发现钴离子附近的氧空位形成能非常小,在0.5～0.6eV左右.
参考文献
| [1] | Maignan A;Martin C;Pelloquin D et al.Structuer and Magnetic Studies of Ordered Oxygen-Deficinet Perovakite LnBaCo2O5+(8),Closely Related the "112” Structure[J].Solide State Chemistry,1999,142(02):247-260. |
| [2] | Henrich V E .The Surfaces of Metal Oxide[J].Reports on Progress in Physics,1985,48(11):1481. |
| [3] | Frederikse H P R;Thurber W R;Hosler W R .Electronic Transport in Strontium Titanatee[J].Phyiew Review,1964,134(2A):A442-A445. |
| [4] | Makoto Harada;Kazunari Domen;Michikazu Hara .Oxygen-permeable Membranes of Ba_(1.0))Co_(0.7)Fe_(0.2)Nb_(0.1)O__(3-delta)for Preparation of Synthesis Gas from Methane by Partial Oxidation[J].Chemistry Letters,2006(8):968-969. |
| [5] | Ze Liu;Ling-zhi Cheng;Min-Fang Han .A-site deficient Ba(1_x)Co_(0.7)Fe_(0.2)Ni_(0.1)O_(3-δ) cathode for intermediate temperature SOFC[J].Journal of Power Sources,2011(2):868-871. |
| [6] | Zhu C J;Liu X M;Yi C S et al.Novel BaCo0.7Fe0.3NbyO3-δ(y =0-0.12) as a Cathode for Intermediate Temperature Solid Oxide Fuel Cell[J].Electrochemistry Communications,2009,11(05):958-961. |
| [7] | Cheng Y;Zhao H;Teng D et al.Investigation of Ba Fully Occupied A-site BaCo0.7Fe0.3-xNbxO3-δ Perovskite Stabilized by Low Concentration of Nb for Oxygen Permeation Membrane[J].Journal of Membrane Science,2008,322:484-490. |
| [8] | Pardo V;Blaha P;Iglesias M et al.Magnetic Structure and Orbital Ordering in BaCoO3 from First-principles Calculations[J].Physical Review B,2004,70:14442-14449. |
| [9] | Jones A;Islam MS .Atomic-scale insight into LaFeO3 perovskite: Defect nanoclusters and ion migration[J].The journal of physical chemistry, C. Nanomaterials and interfaces,2008(12):4455-4462. |
| [10] | Zener C .Interaction between the D-shells in the Transition Metals. Ⅱ. Ferromagnetic Compounds of Manganese with Perovskite Structure[J].Physical Review,1951,82:403-405. |
| [11] | Kresse G.;Furthmuller J. .EFFICIENT ITERATIVE SCHEMES FOR AB INITIO TOTAL-ENERGY CALCULATIONS USING A PLANE-WAVE BASIS SET[J].Physical Review.B.Condensed Matter,1996(16):11169-11186. |
| [12] | Kresse G;Hefner J .Ab Initio Molecular Dynamics for Open-shell Transition Metals[J].Physical Review B,1993,47:558. |
| [13] | Bl(o)chl P E .Projector Augmented-wave Method[J].Physical Review B,1994,50:17953. |
| [14] | Kresse G.;Joubert D. .From ultrasoft pseudopotentials to the projector augmented-wave method[J].Physical Review.B.Condensed Matter,1999(3):1758-1775. |
| [15] | Perdew J P;Burke K;Ernzerhof M .Generalized Gradient Approximation Made Simple[J].Physical Review Letters,1996,77(18):3865-3868. |
| [16] | Dudarev SL.;Savrasov SY.;Szotek Z.;Temmerman WM.;Sutton AP.;Botton GA. .Electronic structure and elastic properties of strongly correlated metal oxides from first principles: LSDA+U, SIC-LSDA and EELS study of UO2 and NiO[J].Physica Status Solidi, A. Applied Research,1998(1):429-443. |
| [17] | Feng Hong-Jian,Liu Fa-Min.Electronic structures and magnetoelectric properties of tetragonal BaFeO3:an ab initio density functional theory study[J].中国物理B（英文版）,2008(05):1874-1880. |
| [18] | Erchak M;Fankuchen I;Ward R .Reaction Between Ferric Oxide and Barium Carbonate in the Solid Phase. Identification of Phases by X-Ray Diffraction[J].Journal of the American Chemical Society,1946,68:2085-2093. |
| [19] | Kopnin E M;Istomin S Ya;Dyachenko O G .Synthesis,Structure and Resistivity Properties of K1-xBaxNbO3(0.2≤x≤0.5) and Kj0.5Sr0.5NbO0.5[J].Materials Research Bulletin,1995,30(11):1379-1386. |
| [20] | Shen P J;Liu X;Wang H H et al.Niobium Doping Effects on Performance of BaCo0.7 Fe0.3-xNbxO3-8 Perovskite[J].Journal of Physical Chemistry C,2010,114:22338-22345. |
| [21] | Felser C;Fecher G H;Balke B .Spintronics:A Challenge for Material Science and Solid-State Chemistry[J].Angewandte Chemie-inemational Edition,2007,46:668-699. |
| [22] | Pardo V;Blaha P;Iglesias M .Magnetic Structure an D Orbital Ordering in BaCoO3 from First-Principles Calculations[J].Physical Review B,2004,70:144422-144429. |
| [23] | Tang Y H;Zhang H;Shi S Q et al.First-principles Investigation on Redox Properties of M-doped CeO2(M =Mn,Pr,Sn,Zr)[J].Physical Review B,2010,82(125104):l-9. |
| [24] | Zhukovskii, YF;Kotomin, EA;Piskunov, S;Ellis, DE .A comparative ab initio study of bulk and surface oxygen vacancies in PbTiO3, PbZrO3 and SrTiO3 perovskites[J].Solid State Communications,2009(33/34):1359-1362. |
| [25] | Yuri A. Mastrikov;Rotraut Merkle;Eugene Heifets .Pathways for Oxygen Incorporation in Mixed Conducting Perovskites: A DFT-Based Mechanistic Analysis for (La, Sr)MnO_(3δ)[J].The journal of physical chemistry, C. Nanomaterials and interfaces,2010(7):3017-3027. |
| [26] | Kotomin, E.A.;Mastrikov, Y.A.;Kuklja, M.M.;Merkle, R.;Roytburd, A.;Maier, J. .First principles calculations of oxygen vacancy formation and migration in mixed conducting Ba_(0.5)Sr_(0.5)Co_(1-y)Fe _yO_(3-δ) perovskites[J].Solid state ionics,2011(1):1-5. |
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