【摘要】：固體氧化物燃料電池(SOFC)作為一種高效、清潔的能量轉(zhuǎn)換裝置而倍受關(guān)注。然而,傳統(tǒng)鎳基陽極在碳?xì)浠衔锶剂系闹苯舆\行過程存在嚴(yán)重的積碳問題,成為制約其應(yīng)用的瓶頸。本文針對鎳基陽極的積碳難題,采用熱分解法制備鎳鐵功能層,研究鐵的摻雜對功能層的相結(jié)構(gòu)、抗積碳能力及單電池性能的影響；并在此基礎(chǔ)上,系統(tǒng)考察了熱分解溫度、熱分解時間、螯合劑種類與添加量以及摻雜元素等因素對Ni0.75Fe0.25功能層抗積碳性能的影響；結(jié)合相結(jié)構(gòu)的分析,探討功能層的相結(jié)構(gòu)與抗積碳性能的相關(guān)性規(guī)律。首先,對鎳鐵功能層的相結(jié)構(gòu)、抗積碳性能及單電池性能的研究表明：鐵的摻雜能夠改善鎳的抗積碳性能,Ni0.75Fe0.25功能層的抗積碳性能最好。在650℃甲烷燃料運行下,具有Ni0.75Fe0.25功能層的單電池最大功率密度為326 mW·cm-2,高于其他成分的鎳鐵功能層制作的單電池；并且該單電池具有最佳的穩(wěn)定性(運行260分鐘后其電壓僅衰減9%)。其次,對不同熱分解溫度和時間制備的Ni0.75Fe0.25功能層的相結(jié)構(gòu)、抗積碳性能及單電池性能的研究表明：705℃1小時制備的Ni0.75Fe0.25功能層的抗積碳性能優(yōu)于675和735℃1小時制備的功能層；在650℃甲烷燃料運行下,具有705℃制備的Ni0.75Fe0.25功能層的單電池的功率密度和穩(wěn)定性均高于具有其他溫度制備的功能層的單電池。第一性原理計算結(jié)果表明,該功能層的FeNi3相各晶面具有最低的表面能,從而改善其抗積碳性能。對705℃下不同熱分解時間制備的功能層的研究表明,熱分解8小時制得的功能層抗積碳能力最佳,此結(jié)果也通過第一性原理計算獲得驗證。添加不同螯合劑(檸檬酸、乙醇酸和D-葡萄糖酸)制備的Ni0.75Fe0.25功能層,其晶相均為FeNi3相。含D-葡萄糖酸的功能層具有最佳的抗積碳能力；具有該功能層的單電池在650℃甲烷燃料中最大功率達(dá)289 mW·cm-2,以600 mA·cm-2的電流密度下運行540分鐘后電壓仍保持初始電壓的61%,高于未添加螯合劑的功能層制作的單電池(53%)。添加不同含量檸檬酸(CA)的功能層中,添加金屬離子摩爾量1.5倍的檸檬酸(CA1.5)制備的功能層其各晶面的表面能最低且晶粒尺寸最大,因此具有最佳的抗積碳性能；具有CA1.5功能層的單電池在650℃甲烷中運行540分鐘后依然保持74%的電壓。此外,本文還研究了Co摻雜對Ni0.75Fe0.25功能層的相結(jié)構(gòu)和抗積碳性能的影響。結(jié)果表明：三元功能層的物相為類似FeNi3的尖晶石立方結(jié)構(gòu)；在三元功能層中,(Ni0.75Fe0.25)0.6Co0.4的抗積碳性能最好,此結(jié)果也通過第一性原理計算獲得了驗證。
[Abstract]:Solid oxide fuel cell (SOFC) (SOFC) has attracted much attention as an efficient and clean energy conversion device. However, there is a serious problem of carbon deposition in the direct operation of traditional nickel based anodes in hydrocarbon fuels, which has become the bottleneck of its application. In order to solve the problem of carbon deposition of nickel based anode, the functional layer of nickel iron was prepared by thermal decomposition method. The effect of iron doping on the phase structure, carbon deposition resistance and single cell performance of the functional layer was studied, and the thermal decomposition temperature was investigated systematically. The effects of thermal decomposition time, chelating agent type and amount of chelating agent and doping elements on the anti-carbon deposition performance of Ni0.75Fe0.25 functional layer were discussed, and the correlation between the phase structure and the anti-carbon deposition property of functional layer was discussed by the analysis of phase structure. Firstly, the phase structure, carbon deposition resistance and single cell performance of Ni-Fe functional layer are studied. The results show that Fe doping can improve the carbon deposition performance of Ni 0.75Fe 0.25 functional layer. The maximum power density of the single cell with Ni0.75Fe0.25 functional layer is 326 mW cm-2, higher than that of Ni-Fe functional layer at 650 鈩，

本文編號：2211498