本文選題：固體氧化物燃料電池 + 鈣鈦礦��； 參考：《北京科技大學》2016年博士論文

【摘要】：固體氧化物燃料電池(SOFCs)址一種將燃氣中的化學能直接轉化為電能的裝置。憑借其清潔、高效、燃料適用性廣以及全固態(tài)結構的特點,SOFCs被視為最具商業(yè)潛質(zhì)的新型能源技術傳統(tǒng)的Ni/YSZ陽極在使用碳氫燃料時會出現(xiàn)嚴重的碳沉積和硫中毒問題,導致電池性能嚴重衰減,因此需要開發(fā)新型高性能替代陽極材料。鈣鈦礦型陽極,在還原氣氛下具有良好的結構穩(wěn)定性,較強的抗積碳和硫中毒能力,是一類很有潛力的陽極替代材料。但該類材料存在催化活性差、離子電導率低、氧化還原結構穩(wěn)定性差、電池性能不理想等問題。本論文圍繞上述問題開展了系統(tǒng)研究。首先結合缺陷化學、材料晶體結構及元素特性,設計并合成了Sr2FeMo2/3Mg1/3O6-δ陽極材料,該材料具有優(yōu)異的氧化還原結構穩(wěn)定性、高的電導率、合適的熱膨脹系數(shù)、高的氧表面交換系數(shù)以及優(yōu)越的催化活性。由于Mg與Mo在離子電價和半徑上存較大差異,Mg與Mo分別占據(jù)雙鈣鈦礦結構中的B和B'位,導致過渡金屬Fe同時占據(jù)雙鈣鈦礦的B、B'位置,在材料晶格中形成高濃度的FeB-O-FeB鍵,因而該材料的實際晶體結構應為Sr2(Fe2/3Mg1/3)(Mo2/3Fe1/3)O6-δ。第一性原理計算結果表明材料中FeB-O-FeB鍵的形成有利于降低材料氧空位形成能以及遷移能,從而有效提高材料的氧離子電導率,改善材料的氧表面交換動力學過程,增強材料的電化學催化活性。以Sr2FeMo2/3Mg1/3O6-δ為陽極的電解質(zhì)支撐型單電池在800,850和900℃時的最大功率分別為637,866和1044 mW cm-2,表明Sr2FeMo2/3Mg1/3O6-δ是一種非常有發(fā)展前途的SOFCs陽極候選材料。為進一步開發(fā)高性能陽極材料,我們首次將原位析出技術應用于雙鈣鈦礦材料,設計并制備了Sr2FeMo0.65M0.3506 (M=Co, Ni)陽極材料。首先在空氣中制備單相材料,然后在還原條件下實現(xiàn)Co-Fe、Ni-Fe納米金屬催化顆粒在該材料顆粒表面的原位析出,材料表層轉變?yōu)镽P相Sr3FeMoO7以及鈣鈦礦相SrFe1-XMoxO3,獲得納米金屬顆粒修飾的鈣鈦礦陽極材料Sr2FeMo0.65Mo.3506 (M=Co, Ni)材料對H2和CH4表現(xiàn)出優(yōu)異的電化學催化活性,以其為陽極的單電池功率在850℃純H2中分別達到820和960mWcm-2;當以CH4為燃料時,電池功率分別達到430和500 mW cm-2。結果表明Sr2FeMo0.65Mo.3506 (M=Co, Ni)材料是一種非常有潛力的高性能SOFCs陽極材料。研究發(fā)現(xiàn),上述雙鈣鈦礦材料合成中極易出現(xiàn)的SrMoO4雜質(zhì),在陽極還原環(huán)境中可以轉變成SrMoO3鈣鈦礦相,將之與電解質(zhì)復合,制備的SrMoO3-60GDC復合陽極表現(xiàn)出良好的結構穩(wěn)定性以及電化學催化活性。為建立結構與性能之間的關聯(lián)性,本文從陽極材料Lao.3Sr0.7Ti03基體出發(fā),通過在Ti位摻雜Co成功將其由陽極材料轉變成一種結構穩(wěn)定的高性能陰極材料Lao.3Sr0.7Ti1-xCoxO3-δ(x=0.3,0.45,0.6)。LSTC(x=0.45,0.6)材料具有高的電導率,優(yōu)異的電化學催化活性以及與LSGM電解質(zhì)具有優(yōu)異的化學相容性。800℃時,LSTC(x=0.45,0.6)材料的極化電阻僅為0.0575和0.0233Ωcm2。通過實驗與第一性原理計算相結合,揭示了LSTC材料電導性能、催化活性的演變原因。LSTC對氧還原反應的催化性能與其結構中的O 2p軌道中心具有良好的線性對應關系。通過第一性原理計算分析材料電子結構可預測材料催化活性的變化規(guī)律,從而實現(xiàn)高性能電極材料的理論設計。
[Abstract]:Solid oxide fuel cell (SOFCs) is a device for direct conversion of chemical energy in gas to electrical energy. By virtue of its cleaning, high efficiency, wide application of fuel and the characteristics of all solid state structures, SOFCs is regarded as the most commercial potential of new energy technology, the traditional Ni/YSZ anode will have serious carbon deposition in the use of hydrocarbon fuel. The problem of sulfur poisoning leads to the serious attenuation of battery performance, so a new type of high performance substitute anode material is needed. The perovskite type anode has good structural stability in the reduction atmosphere and strong ability to resist carbon and sulfur poisoning. It is a kind of potential anode substitute material. However, there are poor catalytic activity and ionic conductivity in this kind of material. Low stability of redox structure and poor battery performance. This paper has carried out a systematic study on the above problems. Firstly, the Sr2FeMo2/3Mg1/3O6- delta anode material was designed and synthesized by combining defect chemistry, crystal structure and element properties. The material has excellent stability of redox structure, high conductivity and suitable for this material. The thermal expansion coefficient, high oxygen surface exchange coefficient and superior catalytic activity. Due to the large difference between Mg and Mo in the ionic valence and radius, Mg and Mo occupy B and B'positions in the double perovskite structure respectively, causing the transition metal Fe to occupy the B of the double perovskite, B' position, and the high concentration FeB-O-FeB bond in the lattice of the material, so that the high concentration of the FeB-O-FeB bond is formed in the lattice. The actual crystal structure of the material should be Sr2 (Fe2/3Mg1/3) (Mo2/3Fe1/3) O6- Delta. The first principle calculation shows that the formation of FeB-O-FeB bond in the material is beneficial to reduce the formation energy of oxygen vacancy and the transfer energy, thus effectively improve the oxygen ion conductivity of the material, improve the oxygen surface exchange kinetics of the material, and enhance the electrification of the material. The maximum power of the electrolyte supported single cell with Sr2FeMo2/3Mg1/3O6- Delta as the anode is 637866 and 1044 mW cm-2 respectively at 800850 and 900 C, indicating that Sr2FeMo2/3Mg1/3O6- delta is a very promising candidate for the SOFCs anode. For the further development of high energy anode materials, we first precipitated in situ. The Sr2FeMo0.65M0.3506 (M=Co, Ni) anode materials were designed and prepared in the double perovskite materials. The single-phase materials were prepared in the air, and then Co-Fe was realized under the reduction conditions. The Ni-Fe nanoparticles were precipitated in situ on the surface of the material, and the surface of the material was transformed into RP phase Sr3FeMoO7 and perovskite SrFe1-XMox. O3, Sr2FeMo0.65Mo.3506 (M=Co, Ni) materials modified by nano metal particles showed excellent electrochemical catalytic activity for H2 and CH4. The single battery power of the anode was 820 and 960mWcm-2 in pure H2 at 850 degrees C. When CH4 was used as fuel, the battery power was 430 and 500 mW cm-2. showed Sr. The 2FeMo0.65Mo.3506 (M=Co, Ni) material is a highly potential high performance SOFCs anode material. It is found that the SrMoO4 impurity which is very easy to appear in the synthesis of the two perovskite materials can be transformed into the SrMoO3 perovskite phase in the anodic reduction environment, which is combined with the electrolyte, and the prepared SrMoO3-60GDC composite anode shows a good knot. Structure stability and electrochemical catalytic activity. In order to establish the relationship between structure and properties, this paper, starting from the anode material Lao.3Sr0.7Ti03 matrix, successfully transformed the anode material from the anode material into a stable high performance cathode material Lao.3Sr0.7Ti1-xCoxO3- Delta (x=0.3,0.45,0.6).LSTC (x=0.45,0.6) material by the Ti bit doping Co. High conductivity, excellent electrochemical catalytic activity and excellent chemical compatibility with LSGM electrolytes at.800 C, the polarization resistance of LSTC (x=0.45,0.6) material is only 0.0575 and 0.0233 Omega cm2. combined by experiment and first principle calculation, which reveals the conductivity of LSTC materials and the evolution of catalytic activity by.LSTC to oxygen reduction reaction. There is a good linear relationship between the catalytic properties and the O 2p orbit center in the structure. Through the first principle, the analysis of the change law of the catalytic activity of the material can be calculated and analyzed, thus the theoretical design of the high performance electrode material is realized.

【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2016
【分類號】：O646.54;TM911.4

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