固體氧化物燃料電池材料和鎳基甲烷干重整催化劑的制備與性能研究
發(fā)布時(shí)間：2018-07-24 17:31
【摘要】：本論文主要圍繞固體氧化物燃料電池(solid oxide fuel cell, SOFC)材料和甲烷干重整(dry reforming of methane, DRM)催化劑的制備與性能開展研究。SOFC是一種將化學(xué)能直接轉(zhuǎn)化為電能的裝置,具有清潔、高效、全固態(tài)設(shè)計(jì)、模塊化等特點(diǎn)。降低SOFC的生產(chǎn)成本,提高其工作效率和穩(wěn)定性是目前研究的主要問題。DRM將兩種溫室氣體(CH4和C02)轉(zhuǎn)化為兩種重要的合成氣(H2和CO),對(duì)于提高CH4利用率、減少污染以及化工合成產(chǎn)業(yè)都有重要意義。當(dāng)前的許多相關(guān)工作都著重于尋找和制備穩(wěn)定、高效和抗積碳能力強(qiáng)的催化劑。論文主要工作包括(1)開發(fā)了一種適用于大規(guī)模生產(chǎn)、操作簡(jiǎn)單、生產(chǎn)周期短且成本低的高性能SOFC制備技術(shù),對(duì)其中的關(guān)鍵參數(shù)進(jìn)行了優(yōu)化；(2)對(duì)SOFC陽(yáng)極材料進(jìn)行優(yōu)化,通過加入納米氧化鋁改善陽(yáng)極燒結(jié)性能,提高SOFCs的發(fā)電效率和穩(wěn)定性；(3)使用濕法浸漬制備甲烷干重整催化劑,通過材料表征和性能測(cè)試對(duì)碳沉積機(jī)理進(jìn)行分析,得到了比較理想的鈣鈦礦型Ni基催化劑前軀體材料。具體結(jié)果如下：論文第二章的主要工作是開發(fā)了利用濕粉噴霧法(wet powder spraying, WPS)制備YSZ電解質(zhì)層(electrolyte layer, EI)、NiO-YSZ陽(yáng)極功能曾(anode functional layer, AFL)和流延法(tape casting, TC)制備NiO-YSZ陽(yáng)極支撐層(anode support Layer, ASL)的SOFC半電池制備技術(shù),并優(yōu)化了工藝參數(shù)。研究表明在WPS制備YSZ薄膜時(shí),襯底溫度、噴霧速率和漿料中的粘結(jié)劑(聚乙烯醇縮丁醛,PVB)濃度對(duì)薄膜生坯中的YSZ粉體分散與堆積情況影響很大。通過對(duì)制備出的YSZ薄膜的表征和分析,我們優(yōu)化了噴霧條件和漿料配比,成功利用自動(dòng)式噴霧設(shè)備制備出了平整、厚度均勻且致密的YSZ電解質(zhì)薄膜,此方法也被應(yīng)用于NiO-YSZ AFL的制備。另一方面,使用TC制備ASL時(shí),我們研究了ASL漿料中NiO粉體比表面積和PVB粘結(jié)劑含量對(duì)ASL燒結(jié)性能的影響,進(jìn)一步完善了使用商業(yè)粉體制備ASL的技術(shù)。在此基礎(chǔ)之上,我們將WPS和TC結(jié)合起來,開發(fā)出了一次共燒制備具有ASL/AFL/EL三層結(jié)構(gòu)的半電池生坯的方法。以LSM-YSZ為陰極、以H2為燃料、空氣為氧化劑時(shí),活化面積為4×4 cm2的單電池在750℃下的輸出功率達(dá)到5.6 W,開路電壓大于1.00 V。半電池成品率達(dá)到95%以上。論文第三章主要研究了向NiO-YSZ陽(yáng)極中加入A1203對(duì)陽(yáng)極燒結(jié)性質(zhì)的影響。本章報(bào)道了一種兩步燒結(jié)制備具有三層結(jié)構(gòu)半電池的方法。第一步是生坯在(?)(1280℃)下的自由燒結(jié),第二步是在1400℃下的受限燒結(jié)。ASL(?)率和SOFC半電池的平整度可以通過向陽(yáng)極支撐層中添加氧化鋁進(jìn)行調(diào)三.我們也研究了氧化鋁添加劑對(duì)NiO-YSZ陽(yáng)極材料的影響。在燒結(jié)初期,NiO(?)Al2O3反應(yīng)生成NiAl2O4尖晶石,這一過程短暫地促進(jìn)了NiO的晶粒生長(zhǎng)；當(dāng)這一反應(yīng)結(jié)束并且NiAl2O4生成后,即使燒至更高溫度,NiO的進(jìn)一步燒結(jié)將受到NiAl2O4的抑制。我們的結(jié)果表明通過添加適量的A1203(約0.2%),可以得到更小的NiO顆粒,NiAl2O4的副作用可以忽略。這有利于提高陽(yáng)極電導(dǎo)率和穩(wěn)定性,并且提高SOFC的性能。以LSM-YSZ為陰極、以H2為燃料、空氣為氧化劑時(shí),活化面積為4×4 cm2的ASL添加A1203的單電池在750℃下,輸出電壓為0.7 V時(shí)的輸出功率達(dá)到6.0 W以上,開路電壓大于1.05 V。論文第四章的主要工作是甲烷干重整催化劑的制備與表征,研究甲烷干重整催化劑的積碳機(jī)理,提高催化劑的抗積碳能力。對(duì)于Ni-Al2O3甲烷干重整催化劑來說,Ni與γ-Al2O3的相互作用要強(qiáng)于Ni與α-Al2O3的相互作用。這是由于在前驅(qū)體中,NiO更容易與γ-Al2O3反應(yīng)生成比較穩(wěn)定的NiAl2O4尖晶石結(jié)構(gòu)。金屬與載體之間的強(qiáng)相互作用有利于吸附在載體上的CO2與Ni表面吸附的碳物質(zhì)反應(yīng),提高CO2轉(zhuǎn)化率。但是在干重整過程中,Ni仍然會(huì)發(fā)生燒結(jié)團(tuán)聚,導(dǎo)致Ni顆粒長(zhǎng)大,使催化劑的活性降低,并且發(fā)生嚴(yán)重的積碳。利用含Ni鈣鈦礦前軀體可以改善Ni基催化劑抗積碳能力。我們采用濕法浸漬法制備了名義組分為L(zhǎng)a2NiO4和LaNiO3的Ni基鈣鈦礦前軀體,以及對(duì)應(yīng)的Fe部分取代樣品(La2Ni0.5Fe0.5O4和LaNi0.5Fe0.5O3)。不含F(xiàn)e的鈣鈦礦在DRM測(cè)試中不穩(wěn)定,會(huì)完全分解成活性組分Ni和載體La203。我們的結(jié)果表明鈣鈦礦的穩(wěn)定性通過Fe部分取代得到顯著提高,并且在這些樣品的催化性能測(cè)試中觀察到了抗積碳能力的明顯改善。這是由于更強(qiáng)的金屬-載體關(guān)聯(lián)使Ni具有更小的顆粒和更高的分散度。LaNixFe1-xO3鈣鈦礦相對(duì)催化劑在還原氣氛中的結(jié)構(gòu)穩(wěn)定性和金屬-載體關(guān)聯(lián)強(qiáng)度起到重要的作用。利用濕法浸漬制備的名義組分為L(zhǎng)aNi0.5Fe0.5O3的前軀體,可以得到穩(wěn)定且抗積碳能力強(qiáng)的甲烷干重整催化劑。這種催化劑在750℃下,通入CH4和CO2摩爾比為1：1,空速為1.2×104ml/gcat.h時(shí),CH4和CO2的轉(zhuǎn)化率在60%以上,經(jīng)過8hDRM測(cè)試后,催化劑中的積碳量小于0.03 gc/gcat。
[Abstract]:This paper mainly focuses on the preparation and performance of solid oxide fuel cell (solid oxide fuel cell, SOFC) and methane dry reforming (dry reforming of methane, DRM) catalyst..SOFC is a device that converts chemical energy directly into electrical energy. It has the characteristics of cleaning, high efficiency, all solid state design, modularization and so on. Production cost, improving its efficiency and stability is the main problem of current research.DRM converting two kinds of greenhouse gases (CH4 and C02) into two important syngas (H2 and CO). It is of great significance for improving CH4 utilization, reducing pollution and chemical industry. The main work of this paper is (1) the development of a high performance SOFC preparation technology suitable for large-scale production, simple operation, short production cycle and low cost. The key parameters were optimized. (2) the anode material was optimized and the anode sintering performance was improved by adding nano alumina. The power generation efficiency and stability of SOFCs were improved; (3) the methane dry reforming catalyst was prepared by wet impregnation and the mechanism of carbon deposition was analyzed through material characterization and performance testing. The ideal precursor material for perovskite type Ni based catalyst was obtained. The concrete results are as follows: the main work of the second chapter of the article is to develop wet powder The YSZ electrolyte layer (electrolyte layer, EI) was prepared by wet powder spraying (WPS). The preparation technology of the semi battery for the NiO-YSZ anode function was prepared by the NiO-YSZ anode function (anode functional layer, WPS), and the process parameters were optimized. At the film, the substrate temperature, the spray rate and the concentration of the binder (polyvinyl butyral, PVB) in the slurry have a great influence on the dispersion and accumulation of the YSZ powder in the thin film. Through the characterization and analysis of the prepared YSZ films, we optimized the spray conditions and the proportion of the slurry, and successfully made the smoothness by using the automatic spray equipment. YSZ electrolyte thin film with uniform thickness and dense thickness is also applied to the preparation of NiO-YSZ AFL. On the other hand, when using TC to prepare ASL, we have studied the effect of the specific surface area of NiO powder and the content of PVB binder on the ASL sintering properties in ASL slurry, and further improved the technology of using the commercial powder system to prepare ASL. Based on this, we have further improved the technology of using the commercial powder system to prepare ASL. Combining WPS with TC, a method of CO burning a semi battery with ASL/AFL/EL three layer structure is developed. With LSM-YSZ as the cathode, H2 as the fuel and air as oxidant, the output power of the single cell with an activated area of 4 x 4 cm2 at 750 C is 5.6 W, and the open circuit voltage is more than 1 V. half the battery rate of over 95%. The third chapter mainly studies the effect of adding A1203 to the anode sintering properties of the NiO-YSZ anode. This chapter reports a two step sintering method for the preparation of a three layer structure half battery. The first step is the free sintering of the blank at (?) (1280), the second step is the limited sintering.ASL (?) rate and the smoothness of the SOFC half battery at 1400. It can be adjusted to three by adding alumina to the anode support layer. We also studied the effect of the alumina additive on the NiO-YSZ anode material. At the beginning of the sintering, the NiO (?) Al2O3 reaction generated NiAl2O4 spinel. This process briefly promoted the grain growth of NiO; when this reaction ended and NiAl2O4 was generated, even higher to higher temperature. At temperature, further sintering of NiO will be suppressed by NiAl2O4. Our results show that a smaller NiO particle can be obtained by adding a proper amount of A1203 (about 0.2%), and the side effects of NiAl2O4 can be ignored. This will help improve the conductivity and stability of the anode and improve the sexual energy of SOFC. LSM-YSZ is the cathode, H2 is the fuel, air is oxidant. When the activation area is 4 * 4 cm2, the single cell of ASL adding A1203 at 750 C and the output voltage of 0.7 V is more than 6 W, the main work of the open circuit voltage greater than 1.05 V. is the preparation and characterization of the methane dry reforming catalyst. The carbon deposition mechanism of the methane dry reforming catalyst is studied and the carbon deposition of the catalyst is improved. Ability. For Ni-Al2O3 methane dry reforming catalyst, the interaction between Ni and gamma -Al2O3 is stronger than the interaction between Ni and alpha -Al2O3. This is because in the precursor, NiO is more likely to react with gamma -Al2O3 to produce a more stable NiAl2O4 spinel structure. The strong phase interaction between the metal and the carrier is beneficial to the CO2 and Ni table adsorbed on the carrier. The reaction of carbon material adsorbed by the surface improves the conversion rate of CO2. But in the process of dry reforming, Ni will still have sintering agglomerate, which leads to the growth of Ni particles, the decrease of the activity of the catalyst and the serious carbon deposition. The use of Ni perovskite precursor can improve the carbon resistance of the Ni based catalyst. We have prepared a nominal group by wet impregnation method. The Ni based perovskite precursor is divided into La2NiO4 and LaNiO3, as well as the corresponding Fe partially substituted samples (La2Ni0.5Fe0.5O4 and LaNi0.5Fe0.5O3). The perovskite without Fe is unstable in DRM test and will be completely decomposed into active component Ni and carrier La203.. The results show that the stability of perovskite is significantly improved by the Fe partial substitution. A significant improvement in carbon resistance has been observed in the catalytic performance tests of these samples. This is due to a stronger metal carrier association that makes the Ni with smaller particles and higher dispersion.LaNixFe1-xO3 perovskite relative catalysts play an important role in the structural stability of the reduction atmosphere and the bond strength of the metal body. The nominal component of the wet impregnation is LaNi0.5Fe0.5O3's precursor, and a stable and carbon resistant methane dry reforming catalyst can be obtained. At 750 centigrade, the molar ratio of CH4 and CO2 is 1:1 and the velocity of air velocity is 1.2 x 104ml/gcat.h, the conversion rate of CH4 and CO2 is above 60%. After 8hDRM test, carbon deposition in the catalyst The amount is less than 0.03 gc/gcat.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：O643.36;TM911.4
本文編號(hào)：2142122
[Abstract]:This paper mainly focuses on the preparation and performance of solid oxide fuel cell (solid oxide fuel cell, SOFC) and methane dry reforming (dry reforming of methane, DRM) catalyst..SOFC is a device that converts chemical energy directly into electrical energy. It has the characteristics of cleaning, high efficiency, all solid state design, modularization and so on. Production cost, improving its efficiency and stability is the main problem of current research.DRM converting two kinds of greenhouse gases (CH4 and C02) into two important syngas (H2 and CO). It is of great significance for improving CH4 utilization, reducing pollution and chemical industry. The main work of this paper is (1) the development of a high performance SOFC preparation technology suitable for large-scale production, simple operation, short production cycle and low cost. The key parameters were optimized. (2) the anode material was optimized and the anode sintering performance was improved by adding nano alumina. The power generation efficiency and stability of SOFCs were improved; (3) the methane dry reforming catalyst was prepared by wet impregnation and the mechanism of carbon deposition was analyzed through material characterization and performance testing. The ideal precursor material for perovskite type Ni based catalyst was obtained. The concrete results are as follows: the main work of the second chapter of the article is to develop wet powder The YSZ electrolyte layer (electrolyte layer, EI) was prepared by wet powder spraying (WPS). The preparation technology of the semi battery for the NiO-YSZ anode function was prepared by the NiO-YSZ anode function (anode functional layer, WPS), and the process parameters were optimized. At the film, the substrate temperature, the spray rate and the concentration of the binder (polyvinyl butyral, PVB) in the slurry have a great influence on the dispersion and accumulation of the YSZ powder in the thin film. Through the characterization and analysis of the prepared YSZ films, we optimized the spray conditions and the proportion of the slurry, and successfully made the smoothness by using the automatic spray equipment. YSZ electrolyte thin film with uniform thickness and dense thickness is also applied to the preparation of NiO-YSZ AFL. On the other hand, when using TC to prepare ASL, we have studied the effect of the specific surface area of NiO powder and the content of PVB binder on the ASL sintering properties in ASL slurry, and further improved the technology of using the commercial powder system to prepare ASL. Based on this, we have further improved the technology of using the commercial powder system to prepare ASL. Combining WPS with TC, a method of CO burning a semi battery with ASL/AFL/EL three layer structure is developed. With LSM-YSZ as the cathode, H2 as the fuel and air as oxidant, the output power of the single cell with an activated area of 4 x 4 cm2 at 750 C is 5.6 W, and the open circuit voltage is more than 1 V. half the battery rate of over 95%. The third chapter mainly studies the effect of adding A1203 to the anode sintering properties of the NiO-YSZ anode. This chapter reports a two step sintering method for the preparation of a three layer structure half battery. The first step is the free sintering of the blank at (?) (1280), the second step is the limited sintering.ASL (?) rate and the smoothness of the SOFC half battery at 1400. It can be adjusted to three by adding alumina to the anode support layer. We also studied the effect of the alumina additive on the NiO-YSZ anode material. At the beginning of the sintering, the NiO (?) Al2O3 reaction generated NiAl2O4 spinel. This process briefly promoted the grain growth of NiO; when this reaction ended and NiAl2O4 was generated, even higher to higher temperature. At temperature, further sintering of NiO will be suppressed by NiAl2O4. Our results show that a smaller NiO particle can be obtained by adding a proper amount of A1203 (about 0.2%), and the side effects of NiAl2O4 can be ignored. This will help improve the conductivity and stability of the anode and improve the sexual energy of SOFC. LSM-YSZ is the cathode, H2 is the fuel, air is oxidant. When the activation area is 4 * 4 cm2, the single cell of ASL adding A1203 at 750 C and the output voltage of 0.7 V is more than 6 W, the main work of the open circuit voltage greater than 1.05 V. is the preparation and characterization of the methane dry reforming catalyst. The carbon deposition mechanism of the methane dry reforming catalyst is studied and the carbon deposition of the catalyst is improved. Ability. For Ni-Al2O3 methane dry reforming catalyst, the interaction between Ni and gamma -Al2O3 is stronger than the interaction between Ni and alpha -Al2O3. This is because in the precursor, NiO is more likely to react with gamma -Al2O3 to produce a more stable NiAl2O4 spinel structure. The strong phase interaction between the metal and the carrier is beneficial to the CO2 and Ni table adsorbed on the carrier. The reaction of carbon material adsorbed by the surface improves the conversion rate of CO2. But in the process of dry reforming, Ni will still have sintering agglomerate, which leads to the growth of Ni particles, the decrease of the activity of the catalyst and the serious carbon deposition. The use of Ni perovskite precursor can improve the carbon resistance of the Ni based catalyst. We have prepared a nominal group by wet impregnation method. The Ni based perovskite precursor is divided into La2NiO4 and LaNiO3, as well as the corresponding Fe partially substituted samples (La2Ni0.5Fe0.5O4 and LaNi0.5Fe0.5O3). The perovskite without Fe is unstable in DRM test and will be completely decomposed into active component Ni and carrier La203.. The results show that the stability of perovskite is significantly improved by the Fe partial substitution. A significant improvement in carbon resistance has been observed in the catalytic performance tests of these samples. This is due to a stronger metal carrier association that makes the Ni with smaller particles and higher dispersion.LaNixFe1-xO3 perovskite relative catalysts play an important role in the structural stability of the reduction atmosphere and the bond strength of the metal body. The nominal component of the wet impregnation is LaNi0.5Fe0.5O3's precursor, and a stable and carbon resistant methane dry reforming catalyst can be obtained. At 750 centigrade, the molar ratio of CH4 and CO2 is 1:1 and the velocity of air velocity is 1.2 x 104ml/gcat.h, the conversion rate of CH4 and CO2 is above 60%. After 8hDRM test, carbon deposition in the catalyst The amount is less than 0.03 gc/gcat.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：O643.36;TM911.4
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 ;Carbon dioxide reforming of methane over Ni/Mo/SBA-15-La_2O_3 catalyst:Its characterization and catalytic performance[J];Journal of Natural Gas Chemistry;2011年05期
，本文編號(hào)：2142122
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