固体氧化物燃料电池材料和镍基甲烷干重整催化剂的制备与性能研究
发布时间：2018-07-24 17:31
【摘要】：本论文主要围绕固体氧化物燃料电池(solid oxide fuel cell, SOFC)材料和甲烷干重整(dry reforming of methane, DRM)催化剂的制备与性能开展研究。SOFC是一种将化学能直接转化为电能的装置,具有清洁、高效、全固态设计、模块化等特点。降低SOFC的生产成本,提高其工作效率和稳定性是目前研究的主要问题。DRM将两种温室气体(CH4和C02)转化为两种重要的合成气(H2和CO),对于提高CH4利用率、减少污染以及化工合成产业都有重要意义。当前的许多相关工作都着重于寻找和制备稳定、高效和抗积碳能力强的催化剂。论文主要工作包括(1)开发了一种适用于大规模生产、操作简单、生产周期短且成本低的高性能SOFC制备技术,对其中的关键参数进行了优化；(2)对SOFC阳极材料进行优化,通过加入纳米氧化铝改善阳极烧结性能,提高SOFCs的发电效率和稳定性；(3)使用湿法浸渍制备甲烷干重整催化剂,通过材料表征和性能测试对碳沉积机理进行分析,得到了比较理想的钙钛矿型Ni基催化剂前躯体材料。具体结果如下：论文第二章的主要工作是开发了利用湿粉喷雾法(wet powder spraying, WPS)制备YSZ电解质层(electrolyte layer, EI)、NiO-YSZ阳极功能曾(anode functional layer, AFL)和流延法(tape casting, TC)制备NiO-YSZ阳极支撑层(anode support Layer, ASL)的SOFC半电池制备技术,并优化了工艺参数。研究表明在WPS制备YSZ薄膜时,衬底温度、喷雾速率和浆料中的粘结剂(聚乙烯醇缩丁醛,PVB)浓度对薄膜生坯中的YSZ粉体分散与堆积情况影响很大。通过对制备出的YSZ薄膜的表征和分析,我们优化了喷雾条件和浆料配比,成功利用自动式喷雾设备制备出了平整、厚度均匀且致密的YSZ电解质薄膜,此方法也被应用于NiO-YSZ AFL的制备。另一方面,使用TC制备ASL时,我们研究了ASL浆料中NiO粉体比表面积和PVB粘结剂含量对ASL烧结性能的影响,进一步完善了使用商业粉体制备ASL的技术。在此基础之上,我们将WPS和TC结合起来,开发出了一次共烧制备具有ASL/AFL/EL三层结构的半电池生坯的方法。以LSM-YSZ为阴极、以H2为燃料、空气为氧化剂时,活化面积为4×4 cm2的单电池在750℃下的输出功率达到5.6 W,开路电压大于1.00 V。半电池成品率达到95%以上。论文第三章主要研究了向NiO-YSZ阳极中加入A1203对阳极烧结性质的影响。本章报道了一种两步烧结制备具有三层结构半电池的方法。第一步是生坯在(?)(1280℃)下的自由烧结,第二步是在1400℃下的受限烧结。ASL(?)率和SOFC半电池的平整度可以通过向阳极支撑层中添加氧化铝进行调三.我们也研究了氧化铝添加剂对NiO-YSZ阳极材料的影响。在烧结初期,NiO(?)Al2O3反应生成NiAl2O4尖晶石,这一过程短暂地促进了NiO的晶粒生长；当这一反应结束并且NiAl2O4生成后,即使烧至更高温度,NiO的进一步烧结将受到NiAl2O4的抑制。我们的结果表明通过添加适量的A1203(约0.2%),可以得到更小的NiO颗粒,NiAl2O4的副作用可以忽略。这有利于提高阳极电导率和稳定性,并且提高SOFC的性能。以LSM-YSZ为阴极、以H2为燃料、空气为氧化剂时,活化面积为4×4 cm2的ASL添加A1203的单电池在750℃下,输出电压为0.7 V时的输出功率达到6.0 W以上,开路电压大于1.05 V。论文第四章的主要工作是甲烷干重整催化剂的制备与表征,研究甲烷干重整催化剂的积碳机理,提高催化剂的抗积碳能力。对于Ni-Al2O3甲烷干重整催化剂来说,Ni与γ-Al2O3的相互作用要强于Ni与α-Al2O3的相互作用。这是由于在前驱体中,NiO更容易与γ-Al2O3反应生成比较稳定的NiAl2O4尖晶石结构。金属与载体之间的强相互作用有利于吸附在载体上的CO2与Ni表面吸附的碳物质反应,提高CO2转化率。但是在干重整过程中,Ni仍然会发生烧结团聚,导致Ni颗粒长大,使催化剂的活性降低,并且发生严重的积碳。利用含Ni钙钛矿前躯体可以改善Ni基催化剂抗积碳能力。我们采用湿法浸渍法制备了名义组分为La2NiO4和LaNiO3的Ni基钙钛矿前躯体,以及对应的Fe部分取代样品(La2Ni0.5Fe0.5O4和LaNi0.5Fe0.5O3)。不含Fe的钙钛矿在DRM测试中不稳定,会完全分解成活性组分Ni和载体La203。我们的结果表明钙钛矿的稳定性通过Fe部分取代得到显著提高,并且在这些样品的催化性能测试中观察到了抗积碳能力的明显改善。这是由于更强的金属-载体关联使Ni具有更小的颗粒和更高的分散度。LaNixFe1-xO3钙钛矿相对催化剂在还原气氛中的结构稳定性和金属-载体关联强度起到重要的作用。利用湿法浸渍制备的名义组分为LaNi0.5Fe0.5O3的前躯体,可以得到稳定且抗积碳能力强的甲烷干重整催化剂。这种催化剂在750℃下,通入CH4和CO2摩尔比为1：1,空速为1.2×104ml/gcat.h时,CH4和CO2的转化率在60%以上,经过8hDRM测试后,催化剂中的积碳量小于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.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：O643.36;TM911.4
本文编号：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.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：O643.36;TM911.4
【参考文献】
相关期刊论文 前1条
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
，本文编号：2142122
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