CN115241471B - Cathode material of solid oxide fuel cell and preparation method and application thereof - Google Patents
Cathode material of solid oxide fuel cell and preparation method and application thereof Download PDFInfo
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Abstract
Description
技术领域Technical Field
本发明属于阴极材料及其制法与应用,具体为一种固体氧化物燃料电池阴极材料及其制法与应用。The present invention relates to cathode materials and a preparation method and application thereof, and in particular to a solid oxide fuel cell cathode material and a preparation method and application thereof.
背景技术Background Art
固体氧化物燃料电池(SOFC)以高效、无污染、环境友好等特点成为发展清洁能源的佼佼者,被认为是最具发展潜力的能源转换装置之一,在缓解能源危机和环境污染等方面具有重要意义。虽然SOFC在较高的操作温度下表现出理想的电化学性能,但是过高的温度也带来了诸多问题,比如密封成本过高、电极材料烧结以及热膨胀不匹配等,影响电池的使用寿命。因此降低操作温度是SOFC的发展趋势。Solid oxide fuel cells (SOFCs) have become the leaders in the development of clean energy with their high efficiency, pollution-free and environmentally friendly features. They are considered to be one of the most promising energy conversion devices and are of great significance in alleviating energy crises and environmental pollution. Although SOFCs exhibit ideal electrochemical performance at higher operating temperatures, excessively high temperatures also bring many problems, such as high sealing costs, electrode material sintering, and thermal expansion mismatch, which affect the service life of the battery. Therefore, lowering the operating temperature is the development trend of SOFCs.
随着操作温度的降低,尤其在低于600℃的工作温度下,阴极材料的极化阻抗急剧增大,催化活性显著降低,影响SOFC的输出功率,从而限制了SOFC的实际应用,因此开发在低于600℃的工作温度下具备高氧还原活性以及长时间稳定性的固体氧化物燃料电池的阴极材料成为了研究热点。As the operating temperature decreases, especially at operating temperatures below 600°C, the polarization impedance of the cathode material increases sharply and the catalytic activity decreases significantly, affecting the output power of SOFC, thereby limiting the practical application of SOFC. Therefore, the development of cathode materials for solid oxide fuel cells with high oxygen reduction activity and long-term stability at operating temperatures below 600°C has become a research hotspot.
发明内容Summary of the invention
发明目的:为了克服现有技术中存在的不足,本发明目的是提供一种长时间高效稳定的固体氧化物燃料电池阴极材料,本发明的另一目的是提供一种简单高效、成本低廉的固体氧化物燃料电池阴极材料的制备方法,本发明的再一目的是提供一种固体氧化物燃料电池阴极材料在低温氧离子导体基固体氧化物燃料电池中的应用,本发明的又一目的是提供一种固体氧化物燃料电池阴极材料在低温质子陶瓷燃料电池中的应用。Purpose of the invention: In order to overcome the deficiencies in the prior art, the purpose of the present invention is to provide a long-term, efficient and stable solid oxide fuel cell cathode material. Another purpose of the present invention is to provide a simple, efficient and low-cost method for preparing a solid oxide fuel cell cathode material. Another purpose of the present invention is to provide an application of a solid oxide fuel cell cathode material in a low-temperature oxygen ion conductor-based solid oxide fuel cell. Another purpose of the present invention is to provide an application of a solid oxide fuel cell cathode material in a low-temperature proton ceramic fuel cell.
技术方案:本发明的所述的一种固体氧化物燃料电池阴极材料,化学式为Sr4FexCoyO13+δ(SFC4),其中0<x<4,2<y<6,δ为氧空位浓度,0<δ<1。Technical solution: The solid oxide fuel cell cathode material of the present invention has a chemical formula of Sr 4 Fe x Co y O 13+δ (SFC4), wherein 0<x<4, 2<y<6, δ is the oxygen vacancy concentration, and 0<δ<1.
进一步地,阴极材料的平均粒径为300~500nm。Furthermore, the average particle size of the cathode material is 300-500 nm.
上述固体氧化物燃料电池阴极材料的制备方法,包括如下步骤:The method for preparing the solid oxide fuel cell cathode material comprises the following steps:
步骤一,按照化学计量比,分别称取硝酸锶、九水硝酸铁、六水硝酸钴、乙二胺四乙酸、一水合柠檬酸和氨水;Step 1, weighing strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediaminetetraacetic acid, citric acid monohydrate and ammonia water respectively according to the stoichiometric ratio;
步骤二,将上述原料依次溶解于去离子水中,在加热搅拌至凝胶状;Step 2, dissolving the above raw materials in deionized water in sequence, and heating and stirring until they are in a gel state;
步骤三,将步骤二所得物置于烘箱中烘干,得到前驱体;Step 3, drying the product obtained in step 2 in an oven to obtain a precursor;
步骤四,将步骤三所得前驱体置于马弗炉中进行除碳处理,再进行氧分压煅烧,得到粉体;Step 4, placing the precursor obtained in step 3 in a muffle furnace for decarbonization, and then calcining under oxygen partial pressure to obtain a powder;
步骤五,将步骤四所得粉体进行研磨,得到Sr4FexCoyO13+δ阴极材料粉末。Step 5: Grind the powder obtained in step 4 to obtain Sr 4 Fe x Co y O 13+δ cathode material powder.
进一步地,步骤一中,乙二胺四乙酸:一水合柠檬酸:金属阳离子的摩尔比为1:2:1~2,所述金属阳离子的摩尔数为硝酸锶、九水硝酸铁、六水硝酸钴的摩尔数之和。Furthermore, in step 1, the molar ratio of ethylenediaminetetraacetic acid: citric acid monohydrate: metal cation is 1:2:1-2, and the molar number of the metal cation is the sum of the molar numbers of strontium nitrate, ferric nitrate nonahydrate, and cobalt nitrate hexahydrate.
进一步地,步骤二中,先将硝酸锶、九水硝酸铁、六水硝酸钴溶解于去离子水中,加热搅拌,得到金属硝酸盐溶液,再将乙二胺四乙酸溶解于氨水中,将溶有乙二胺四乙酸的氨水、一水合柠檬酸加入金属硝酸盐溶液中,继续加热搅拌至凝胶状。加热温度为80~100℃,搅拌速度为200~300r·min-1。加热温度低于80℃,会延缓凝胶形成速率;加热温度高于100℃,会导致搅拌时间缩短,高温下凝胶易发泡。搅拌速度低于200r·min-1,会影响金属离子的络合均匀度;搅拌速度高于300r·min-1,会导致溶液飞溅。Furthermore, in step 2, strontium nitrate, ferric nitrate nonahydrate, and cobalt nitrate hexahydrate are first dissolved in deionized water, heated and stirred to obtain a metal nitrate solution, and then ethylenediaminetetraacetic acid is dissolved in ammonia water, and ammonia water and citric acid monohydrate dissolved in ethylenediaminetetraacetic acid are added to the metal nitrate solution, and heating and stirring are continued until it is in a gel state. The heating temperature is 80-100°C, and the stirring speed is 200-300r·min -1 . If the heating temperature is lower than 80°C, the gel formation rate will be slowed down; if the heating temperature is higher than 100°C, the stirring time will be shortened, and the gel will easily foam at high temperature. If the stirring speed is lower than 200r·min -1 , the uniformity of the complexation of metal ions will be affected; if the stirring speed is higher than 300r·min -1 , the solution will splash.
进一步地,步骤三中,烘干温度为200~300℃,时间为200~300min。烘干温度低于200℃,会导致凝胶中有机物碳化不足;烘干温度高于300℃,会导致碳骨架燃烧。Furthermore, in step 3, the drying temperature is 200-300°C and the time is 200-300 minutes. A drying temperature lower than 200°C will result in insufficient carbonization of organic matter in the gel; a drying temperature higher than 300°C will result in combustion of the carbon skeleton.
进一步地,步骤五中,研磨后用200~400目筛过筛。Furthermore, in step five, the powder is sieved with a 200-400 mesh sieve after grinding.
上述固体氧化物燃料电池阴极材料在低温氧离子导体基固体氧化物燃料电池中的应用,以Sr4FexCoyO13+δ作为阴极,以氧化钐掺杂的氧化铈作为电解质,以NiO和SDC的混合物作为阳极。The solid oxide fuel cell cathode material is used in a low-temperature oxygen ion conductor-based solid oxide fuel cell, using Sr 4 Fe x Co y O 13+δ as the cathode, samarium oxide-doped cerium oxide as the electrolyte, and a mixture of NiO and SDC as the anode.
上述固体氧化物燃料电池阴极材料在低温质子陶瓷燃料电池中的应用,以Sr4FexCoyO13+δ作为阴极,以BaZr0.1Ce0.7Y0.1Yb0.1O3-δ作为电解质,以NiO和BZCYYb的混合物作为阳极。The solid oxide fuel cell cathode material is used in a low-temperature proton ceramic fuel cell, with Sr 4 Fe x Co y O 13+δ as the cathode, BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ as the electrolyte, and a mixture of NiO and BZCYYb as the anode.
制备原理:Sr4FexCoyO13+δ材料由纳米级的单钙钛矿相Sr(Co,Fe)O3、尖晶石相(Co,Fe)3O4、氧化钴CoO以及碳酸锶SrCO3构成。单钙钛矿相、尖晶石相以及与碳酸锶和氧化钴的自组装混合,其中单钙钛矿相具有优异的电导率和较好的氧还原活性,尖晶石相的电导率较低但氧还原催化活性高,碳酸锶和氧化钴的存在降低了热膨胀系数,保障长时间的操作稳定性。通过以上体系的纳米级催化剂的自组装混合,协同效应的影响,促进该材料制备的电池能拥有优异的输出功率和长时间的稳定性,在低温范围内结构稳定,应用在O-SOFC和PCFC上均能表现出良好的ORR催化活性。Preparation principle: Sr 4 Fe x Co y O 13+δ material is composed of nano-scale single perovskite phase Sr(Co,Fe)O 3 , spinel phase (Co,Fe) 3 O 4 , cobalt oxide CoO and strontium carbonate SrCO 3. The single perovskite phase, spinel phase and self-assembly mixture with strontium carbonate and cobalt oxide, among which the single perovskite phase has excellent conductivity and good oxygen reduction activity, the spinel phase has low conductivity but high oxygen reduction catalytic activity, and the presence of strontium carbonate and cobalt oxide reduces the thermal expansion coefficient, ensuring long-term operational stability. Through the self-assembly mixing of the nano-scale catalysts of the above system and the influence of the synergistic effect, the battery prepared by the material can have excellent output power and long-term stability, and the structure is stable in the low temperature range. It can show good ORR catalytic activity when applied to O-SOFC and PCFC.
有益效果:本发明和现有技术相比,具有如下显著性特点:Beneficial effects: Compared with the prior art, the present invention has the following significant features:
1、所制得的固体氧化物燃料电池阴极材料具有优异的电池输出性能,所制备的低温质子陶瓷燃料电池在550℃下的输出功率达到了645mW·cm-2,所制备的氧离子导体基燃料电池在600℃下的输出功率达到了1250mW·cm-2;1. The prepared solid oxide fuel cell cathode material has excellent battery output performance. The output power of the prepared low-temperature proton ceramic fuel cell at 550°C reaches 645mW·cm -2 , and the output power of the prepared oxygen ion conductor-based fuel cell at 600°C reaches 1250mW·cm -2 ;
2、所制得的固体氧化物燃料电池阴极材料具有优异的长时间热化学稳定性,质子基对称电池和质子陶瓷燃料电池可在550℃下分别持续工作1000h和3100h,其阻抗和输出功率没有明显衰减,所制备的氧离子基对称电池可在550℃下持续工作1000h,其阻抗没有明显衰减,具有良好的热稳定性;2. The prepared solid oxide fuel cell cathode material has excellent long-term thermochemical stability. The proton-based symmetric battery and proton ceramic fuel cell can work continuously for 1000 hours and 3100 hours at 550°C respectively, and their impedance and output power have no obvious attenuation. The prepared oxygen ion-based symmetric battery can work continuously for 1000 hours at 550°C, and its impedance has no obvious attenuation, which shows good thermal stability.
3、所制得的阴极材料适用范围广,具备一定的质子传导性能,因此该材料不仅可作为O-SOFC阴极使用,还适用于PCFC;3. The prepared cathode material has a wide range of applications and has certain proton conductivity properties. Therefore, the material can be used not only as an O-SOFC cathode, but also as a PCFC cathode.
4、阴极材料通过简单的溶胶凝胶一步法合成,制备方法简单高效,原料成本低廉,适合于工业化大规模生产;4. The cathode material is synthesized by a simple sol-gel one-step method. The preparation method is simple and efficient, the raw material cost is low, and it is suitable for industrial large-scale production;
5、阴极材料SFC4的平均颗粒大小在纳米尺度上,使得结构内部的有效三相线长度增加,从而具有更大的电化学反应范围;5. The average particle size of the cathode material SFC4 is at the nanoscale, which increases the effective three-phase line length inside the structure, thus having a larger electrochemical reaction range;
6、采用氧分压煅烧,即在封闭环境中氧气随着煅烧逐渐减少,能够生成碳酸盐,从而使阴极材料能够保持长时间稳定工作;6. Use oxygen partial pressure calcination, that is, in a closed environment, oxygen gradually decreases with calcination, and carbonates can be generated, so that the cathode material can maintain stable operation for a long time;
7、阴极材料SFC4制备时,会有层状钙钛矿相生成,该结构具有良好的化学灵活性、较高的电导率和强大的结构稳定性,从而使阴极材料能够保持长时间稳定工作。7. When the cathode material SFC4 is prepared, a layered perovskite phase will be generated. This structure has good chemical flexibility, high electrical conductivity and strong structural stability, so that the cathode material can maintain stable operation for a long time.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明SFC4阴极材料的XRD图;Fig. 1 is an XRD diagram of the SFC4 cathode material of the present invention;
图2是本发明氧离子基对称电池SFC4|SDC|SFC4在550℃下的阻抗图;FIG2 is an impedance diagram of the oxygen ion-based symmetrical battery SFC4|SDC|SFC4 of the present invention at 550° C.;
图3是本发明氧离子基对称电池SFC4|SDC|SFC4在550℃下的长期稳定性图;FIG3 is a long-term stability diagram of the oxygen ion-based symmetrical battery SFC4|SDC|SFC4 of the present invention at 550° C.;
图4是本发明氧离子基燃料电池SFC4|SDC|NiO-SDC在400℃、500℃和600℃的温度下的功率输出性能图;4 is a power output performance diagram of the oxygen ion-based fuel cell SFC4|SDC|NiO-SDC of the present invention at temperatures of 400° C., 500° C. and 600° C.;
图5是本发明氧离子基燃料电池SFC4|SDC|NiO-SDC横截面的SEM图;5 is a SEM image of a cross section of an oxygen ion-based fuel cell SFC4|SDC|NiO-SDC of the present invention;
图6是本发明质子基对称电池SFC4|BZCYYb|SFC4在550℃下的阻抗图;FIG6 is an impedance diagram of the proton-based symmetric battery SFC4|BZCYYb|SFC4 of the present invention at 550° C.;
图7是本发明质子基对称电池SFC4|BZCYYb|SFC4在550℃下的长期稳定性图;FIG7 is a long-term stability diagram of the proton-based symmetric battery SFC4|BZCYYb|SFC4 of the present invention at 550° C.;
图8是本发明质子陶瓷燃料电池SFC4|BZCYYb|NiO-BZCYYb在350℃、450℃和550℃的温度下的功率输出性能图;8 is a graph showing the power output performance of the proton ceramic fuel cell SFC4|BZCYYb|NiO-BZCYYb of the present invention at temperatures of 350° C., 450° C. and 550° C.;
图9是本发明质子陶瓷燃料电池SFC4|BZCYYb|NiO-BZCYYb横截面的SEM图;9 is a SEM image of a cross section of a proton ceramic fuel cell SFC4|BZCYYb|NiO-BZCYYb of the present invention;
图10是本发明质子陶瓷燃料电池SFC4|BZCYYb|NiO-BZCYYb在550℃下的长期稳定性图。FIG. 10 is a graph showing the long-term stability of the proton ceramic fuel cell SFC4|BZCYYb|NiO-BZCYYb of the present invention at 550° C.
具体实施方式DETAILED DESCRIPTION
以下各实施例中,除碳处理为将前驱体置于马弗炉中700℃煅烧5小时。金属阳离子的摩尔数为硝酸锶、九水硝酸铁、六水硝酸钴的摩尔数之和。In the following examples, the carbon removal treatment is to place the precursor in a muffle furnace and calcine it at 700° C. for 5 hours. The molar number of the metal cation is the sum of the molar numbers of strontium nitrate, ferric nitrate nonahydrate, and cobalt nitrate hexahydrate.
实施例1Example 1
一种固体氧化物燃料电池阴极材料的制备方法,包括如下步骤:A method for preparing a cathode material for a solid oxide fuel cell comprises the following steps:
a、按照化学计量比,分别称取硝酸锶、九水硝酸铁、六水硝酸钴、乙二胺四乙酸、一水合柠檬酸和氨水,乙二胺四乙酸:一水合柠檬酸:金属阳离子的摩尔比为1:2:1;a. According to the stoichiometric ratio, weigh strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediaminetetraacetic acid, citric acid monohydrate and ammonia water respectively, and the molar ratio of ethylenediaminetetraacetic acid: citric acid monohydrate: metal cation is 1:2:1;
b、先将硝酸锶、九水硝酸铁、六水硝酸钴溶解于去离子水中,以80℃的温度和300r·min-1的转速进行加热搅拌,得到金属硝酸盐溶液,同时在乙二胺四乙酸中加入去离子水以及氨水,将溶有乙二胺四乙酸的氨水、一水合柠檬酸加入金属硝酸盐溶液中,继续以80℃的温度和300r·min-1的转速进行加热搅拌,直至溶液成为凝胶状;b. First, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, and heated and stirred at a temperature of 80°C and a rotation speed of 300 r·min -1 to obtain a metal nitrate solution. At the same time, deionized water and ammonia water are added to ethylenediaminetetraacetic acid, and ammonia water and citric acid monohydrate dissolved in ethylenediaminetetraacetic acid are added to the metal nitrate solution, and the temperature is continued to be 80°C and the rotation speed is 300 r·min -1 . Stirring until the solution becomes a gel;
c、将步骤b所得凝胶置于200℃烘箱中烘干300min,得到前驱体;c. drying the gel obtained in step b in an oven at 200° C. for 300 min to obtain a precursor;
d、将步骤c所得前驱体置于马弗炉中进行除碳处理,再进行氧分压煅烧,得到粉体;d. placing the precursor obtained in step c in a muffle furnace for carbon removal, and then calcining under oxygen partial pressure to obtain a powder;
e、将步骤四所得粉体进行研磨,并用200目筛过筛,得到Sr4Fe0.5Co5.5O13+δ(SFC4)阴极材料粉末,其平均粒径为300nm。e. Grind the powder obtained in step 4, and sieve it with a 200-mesh sieve to obtain Sr 4 Fe 0.5 Co 5.5 O 13+δ (SFC4) cathode material powder with an average particle size of 300 nm.
实施例2Example 2
一种固体氧化物燃料电池阴极材料的制备方法,包括如下步骤:A method for preparing a cathode material for a solid oxide fuel cell comprises the following steps:
a、按照化学计量比,分别称取硝酸锶、九水硝酸铁、六水硝酸钴、乙二胺四乙酸、一水合柠檬酸和氨水,乙二胺四乙酸:一水合柠檬酸:金属阳离子的摩尔比为1:2:2;a. According to the stoichiometric ratio, weigh strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediaminetetraacetic acid, citric acid monohydrate and ammonia water respectively, and the molar ratio of ethylenediaminetetraacetic acid: citric acid monohydrate: metal cation is 1:2:2;
b、先将硝酸锶、九水硝酸铁、六水硝酸钴溶解于去离子水中,以100℃的温度和200r·min-1的转速进行加热搅拌,得到金属硝酸盐溶液,同时在乙二胺四乙酸中加入去离子水以及氨水,将溶有乙二胺四乙酸的氨水、一水合柠檬酸加入金属硝酸盐溶液中,继续以100℃的温度和200r·min-1的转速进行加热搅拌,直至溶液成为凝胶状;b. First, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, and heated and stirred at a temperature of 100°C and a rotation speed of 200 r·min -1 to obtain a metal nitrate solution. At the same time, deionized water and ammonia water are added to ethylenediaminetetraacetic acid, and ammonia water and citric acid monohydrate dissolved in ethylenediaminetetraacetic acid are added to the metal nitrate solution, and the temperature is continued to be 100°C and the rotation speed is 200 r·min -1 . Stirring until the solution becomes a gel;
c、将步骤b所得凝胶置于300℃烘箱中烘干200min,得到前驱体;c. drying the gel obtained in step b in an oven at 300° C. for 200 min to obtain a precursor;
d、将步骤c所得前驱体置于马弗炉中进行除碳处理,再进行氧分压煅烧,得到粉体;d. placing the precursor obtained in step c in a muffle furnace for carbon removal, and then calcining under oxygen partial pressure to obtain a powder;
e、将步骤四所得粉体进行研磨,并用400目筛过筛,得到Sr4Fe3.5Co2.5O13+δ(SFC4)阴极材料粉末,其平均粒径为500nm。e. Grind the powder obtained in step 4, and sieve it with a 400-mesh sieve to obtain Sr 4 Fe 3.5 Co 2.5 O 13+δ (SFC4) cathode material powder with an average particle size of 500 nm.
实施例3Example 3
一种固体氧化物燃料电池阴极材料的制备方法,包括如下步骤:A method for preparing a cathode material for a solid oxide fuel cell comprises the following steps:
a、按照化学计量比,分别称取硝酸锶、九水硝酸铁、六水硝酸钴、乙二胺四乙酸、一水合柠檬酸和氨水,乙二胺四乙酸:一水合柠檬酸:金属阳离子的摩尔比为1:2:1.5;a. According to the stoichiometric ratio, weigh strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediaminetetraacetic acid, citric acid monohydrate and ammonia water respectively, and the molar ratio of ethylenediaminetetraacetic acid: citric acid monohydrate: metal cation is 1:2:1.5;
b、先将硝酸锶、九水硝酸铁、六水硝酸钴溶解于去离子水中,以95℃的温度和230r·min-1的转速进行加热搅拌,得到金属硝酸盐溶液,同时在乙二胺四乙酸中加入去离子水以及氨水,将溶有乙二胺四乙酸的氨水、一水合柠檬酸加入金属硝酸盐溶液中,继续以95℃的温度和230r·min-1的转速进行加热搅拌,直至溶液成为凝胶状;b. First, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, and heated and stirred at a temperature of 95° C. and a rotation speed of 230 r·min -1 to obtain a metal nitrate solution. At the same time, deionized water and ammonia water are added to ethylenediaminetetraacetic acid, and ammonia water and citric acid monohydrate dissolved in ethylenediaminetetraacetic acid are added to the metal nitrate solution, and the temperature is continued to be 95° C. and the rotation speed is 230 r·min -1. Stirring until the solution becomes a gel;
c、将步骤b所得凝胶置于220℃烘箱中烘干230min,得到前驱体;c. drying the gel obtained in step b in an oven at 220° C. for 230 min to obtain a precursor;
d、将步骤c所得前驱体置于马弗炉中进行除碳处理,再进行氧分压煅烧,得到粉体;d. placing the precursor obtained in step c in a muffle furnace for carbon removal, and then calcining under oxygen partial pressure to obtain a powder;
e、将步骤四所得粉体进行研磨,并用300目筛过筛,得到Sr4Fe3Co5O13+δ(SFC4)阴极材料粉末,其平均粒径为350nm。e. Grind the powder obtained in step 4 and sieve it through a 300-mesh sieve to obtain Sr 4 Fe 3 Co 5 O 13+δ (SFC4) cathode material powder with an average particle size of 350 nm.
实施例4Example 4
一种固体氧化物燃料电池阴极材料的制备方法,包括如下步骤:A method for preparing a cathode material for a solid oxide fuel cell comprises the following steps:
a、按照化学计量比,分别称取硝酸锶、九水硝酸铁、六水硝酸钴、乙二胺四乙酸、一水合柠檬酸和氨水,乙二胺四乙酸:一水合柠檬酸:金属阳离子的摩尔比为1:2:1;a. According to the stoichiometric ratio, weigh strontium nitrate, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ethylenediaminetetraacetic acid, citric acid monohydrate and ammonia water respectively, and the molar ratio of ethylenediaminetetraacetic acid: citric acid monohydrate: metal cation is 1:2:1;
b、先将硝酸锶、九水硝酸铁、六水硝酸钴溶解于去离子水中,以90℃的温度和300r·min-1的转速进行加热搅拌,得到金属硝酸盐溶液,同时在乙二胺四乙酸中加入去离子水以及氨水,将溶有乙二胺四乙酸的氨水、一水合柠檬酸加入金属硝酸盐溶液中,继续以90℃的温度和300r·min-1的转速进行加热搅拌,直至溶液成为凝胶状;b. First, strontium nitrate, ferric nitrate nonahydrate and cobalt nitrate hexahydrate are dissolved in deionized water, and heated and stirred at a temperature of 90°C and a rotation speed of 300 r·min -1 to obtain a metal nitrate solution. At the same time, deionized water and ammonia water are added to ethylenediaminetetraacetic acid, and ammonia water and citric acid monohydrate dissolved in ethylenediaminetetraacetic acid are added to the metal nitrate solution, and the temperature is continued to be 90°C and the rotation speed is 300 r·min -1 . Stirring until the solution becomes a gel;
c、将步骤b所得凝胶置于250℃烘箱中烘干250min,得到前驱体;c. drying the gel obtained in step b in an oven at 250° C. for 250 min to obtain a precursor;
d、将步骤c所得前驱体置于马弗炉中进行除碳处理,再进行氧分压煅烧,得到粉体;d. placing the precursor obtained in step c in a muffle furnace for carbon removal, and then calcining under oxygen partial pressure to obtain a powder;
e、将步骤四所得粉体进行研磨,并用300目筛过筛,得到Sr4Fe3Co4O13+δ(SFC4)阴极材料粉末,其平均粒径为400nm。e. Grind the powder obtained in step 4 and sieve it with a 300-mesh sieve to obtain Sr 4 Fe 3 Co 4 O 13+δ (SFC4) cathode material powder with an average particle size of 400 nm.
对本实施例合成的SFC4阴极材料进行X射线衍射(XRD)表征,结果如图1所示。由图1中结果可知,SFC4阴极材料由由纳米级的单钙钛矿相Sr(Co,Fe)O3、尖晶石相(Co,Fe)3O4、氧化钴CoO以及碳酸锶SrCO3构成。图1中的Pmcn相为碳酸锶的空间群,占据材料的4.1%。碳酸盐可以提高电极材料的氧活化性能以及稳定性,这是该材料制备的单电池能拥有较高的输出性能和长时间的稳定性能的重要原因之一。另外单钙钛矿相具有良好的电导率,层状钙钛矿相具有较高的电导率和长时间的性能稳定性,这是该材料制备的单电池能拥有较高的输出性能和长时间的稳定性能的根本原因。The SFC4 cathode material synthesized in this embodiment was characterized by X-ray diffraction (XRD), and the results are shown in Figure 1. As shown in Figure 1, the SFC4 cathode material is composed of a nanoscale single perovskite phase Sr(Co,Fe)O 3 , a spinel phase (Co,Fe) 3 O 4 , cobalt oxide CoO and strontium carbonate SrCO 3. The Pmcn phase in Figure 1 is the space group of strontium carbonate, which occupies 4.1% of the material. Carbonates can improve the oxygen activation performance and stability of electrode materials, which is one of the important reasons why the single cell prepared by the material can have higher output performance and long-term stable performance. In addition, the single perovskite phase has good electrical conductivity, and the layered perovskite phase has higher electrical conductivity and long-term performance stability, which is the fundamental reason why the single cell prepared by the material can have higher output performance and long-term stable performance.
对比例1Comparative Example 1
本对比例其余步骤均与实施例4相同,区别仅仅在于:将步骤b中的温度替换为70℃。结果发现:凝胶形成速率大幅下降。The remaining steps of this comparative example are the same as those of Example 4, except that the temperature in step b is replaced with 70° C. As a result, it is found that the gel formation rate is greatly reduced.
对比例2Comparative Example 2
本对比例其余步骤均与实施例4相同,区别仅仅在于:将步骤b中的温度替换为110℃。结果发现:搅拌时间缩短,高温下凝胶易发泡。The remaining steps of this comparative example are the same as those of Example 4, except that the temperature in step b is replaced with 110° C. The results show that the gel is easy to foam at high temperature due to shortened stirring time.
对比例3Comparative Example 3
本对比例其余步骤均与实施例4相同,区别仅仅在于:将步骤c中烘箱的温度替换为180℃。结果发现:凝胶中有机物碳化不足。The remaining steps of this comparative example are the same as those of Example 4, except that the temperature of the oven in step c is changed to 180° C. The results show that the organic matter in the gel is insufficiently carbonized.
对比例4Comparative Example 4
本对比例其余步骤均与实施例4相同,区别仅仅在于:将步骤c中烘箱的温度替换为320℃。结果发现:碳骨架过度燃烧。The remaining steps of this comparative example are the same as those of Example 4, except that the temperature of the oven in step c is replaced with 320° C. The results show that the carbon skeleton is excessively burned.
实施例5Example 5
采用实施例4的SFC4阴极材料,制备SFC4|SDC|SFC4氧离子基对称电池,具体步骤如下:The SFC4 cathode material of Example 4 was used to prepare a SFC4|SDC|SFC4 oxygen ion-based symmetrical battery, and the specific steps were as follows:
(1)量取10ml异丙醇、2ml乙二醇以及0.6ml丙三醇,并称取1gSFC4阴极粉体,并置于行星式球磨机上球磨,球磨机转速为400r min-1,球磨时间为2h,制得阴极粉体浆料;(1) 10 ml of isopropanol, 2 ml of ethylene glycol and 0.6 ml of propylene glycol were weighed, and 1 g of SFC4 cathode powder was weighed and placed on a planetary ball mill for ball milling at a speed of 400 r min -1 for 2 h to obtain cathode powder slurry;
(2)称取0.5g的SDC电解质粉体,并利用压片机将其压成15mm的圆片,置于约为1400℃的高温炉中煅烧5h,制得电解质片。(2) Weigh 0.5 g of SDC electrolyte powder and press it into a 15 mm disc using a tablet press. Then, calcine it in a high-temperature furnace at about 1400° C. for 5 h to obtain an electrolyte sheet.
(3)利用喷枪将上述浆料均匀的喷在电解质片的两侧,并置于约为800℃的马弗炉中煅烧2h,制得对称电池;(3) using a spray gun to evenly spray the slurry on both sides of the electrolyte sheet, and calcining it in a muffle furnace at about 800° C. for 2 h to obtain a symmetrical battery;
(4)在上述氧离子基对称电池两侧刷上集流层,连上银线。(4) Apply a current collecting layer on both sides of the above oxygen ion-based symmetrical battery and connect them with silver wires.
对本实施例制备的SFC4|SDC|SFC4氧离子基对称电池在550℃的空气氛围中进行电化学阻抗的测试,结果如图2所示。由图2中结果可知,SFC4|SDC|SFC4氧离子基对称电池在550℃的测试温度下,其阻值为0.04Ωcm2。The SFC4|SDC|SFC4 oxygen ion based symmetric battery prepared in this example was subjected to electrochemical impedance test in air at 550°C, and the result is shown in Figure 2. As shown in Figure 2, the resistance of the SFC4|SDC|SFC4 oxygen ion based symmetric battery at the test temperature of 550°C is 0.04Ωcm2 .
对本实施例制备的SFC4|SDC|SFC4氧离子基对称电池进行热化学稳定性的测试,结果如图3所示。由图3中结果可知,SFC4阴极材料所制备的氧离子基对称电池在550℃的测试温度下可以持续工作1000h,其阻抗没有明显的增加。The thermochemical stability of the SFC4|SDC|SFC4 oxygen ion-based symmetrical battery prepared in this embodiment was tested, and the results are shown in Figure 3. As can be seen from the results in Figure 3, the oxygen ion-based symmetrical battery prepared with the SFC4 cathode material can continue to work for 1000 hours at a test temperature of 550°C, and its impedance does not increase significantly.
实施例6Example 6
采用实施例4的SFC4阴极材料,制备SFC4|SDC|NiO-SDC氧离子基燃料电池,具体步骤如下:The SFC4 cathode material of Example 4 is used to prepare a SFC4|SDC|NiO-SDC oxygen ion-based fuel cell, and the specific steps are as follows:
(1)量取10ml异丙醇、2ml乙二醇以及0.6ml丙三醇,并称取1g的SFC4阴极粉体,并置于行星式球磨机上球磨,球磨机转速为400r min-1,球磨时间为2h,制得阴极粉体浆料;(1) 10 ml of isopropanol, 2 ml of ethylene glycol and 0.6 ml of propylene glycol were weighed, and 1 g of SFC4 cathode powder was weighed and placed on a planetary ball mill for ball milling at a speed of 400 r min -1 for 2 h to obtain cathode powder slurry;
(2)称取7g NiO粉体、3g SDC粉体以及0.7g PVB置于研钵中,并倒入适量的酒精,研磨直到酒精全部挥发,接着放置于烘箱中烘干,再置于研钵中研磨成NiO-SDC阳极粉体。(2) Weigh 7 g of NiO powder, 3 g of SDC powder and 0.7 g of PVB into a mortar, add an appropriate amount of alcohol, grind until the alcohol is completely evaporated, then place in an oven to dry, and then place in a mortar and grind into NiO-SDC anode powder.
(3)称取0.35g的NiO-SDC阳极粉体,利用压片机将其压成15mm的圆片,再称取0.015g的SDC电解质粉体,并用300目的筛子均匀过筛到阳极粉体圆片的一侧表面上,继续压,压好的圆片置于1400℃的高温炉中煅烧5h,制得半电池片。(3) Weigh 0.35 g of NiO-SDC anode powder and press it into a 15 mm disc using a tablet press. Then weigh 0.015 g of SDC electrolyte powder and evenly sieve it onto one side of the anode powder disc using a 300-mesh sieve. Continue pressing and calcine the pressed disc in a high-temperature furnace at 1400°C for 5 h to obtain a half-cell.
(4)利用喷枪将上述阴极粉体浆料均匀的喷在半电池的电解质一侧,并置于800℃的马弗炉中煅烧2h,制得氧离子基燃料电池;(4) using a spray gun to evenly spray the cathode powder slurry onto the electrolyte side of the half-cell, and calcining it in a muffle furnace at 800° C. for 2 h to obtain an oxygen ion-based fuel cell;
(5)在上述氧离子基燃料电池阴极侧刷上集流层,在两侧连上银线,并封装在石英玻璃管上。(5) A current collecting layer is applied on the cathode side of the oxygen ion-based fuel cell, silver wires are connected on both sides, and the fuel cell is packaged on a quartz glass tube.
对本实施例制备的氧离子基燃料电池进行输出性能测试,具体方法为:以干的H2为燃料,以空气为氧化剂分别在400℃、500℃和600℃的温度下采用数字源表(Keithley2440)进行测试,测试温度间隔为50℃,结果如图4所示,在600℃下最大功率密度可达1250mW cm-2。The output performance of the oxygen ion-based fuel cell prepared in this embodiment was tested by using dry H2 as fuel and air as oxidant at 400°C, 500°C and 600°C respectively using a digital source meter (Keithley2440). The test temperature interval was 50°C. The results are shown in FIG4 . At 600°C, the maximum power density can reach 1250 mW cm -2 .
图5显示了本实施例制备的氧离子基燃料电池的SEM图,包含了SFC4多孔阴极,致密的SDC电解质和NiO-SDC复合阳极的横截面图像形状。从图5中可以看出,SFC4阴极(厚度约为25μm)与SDC电解质(厚度约为20μm)之间的粘附很紧密,从而证明了氧离子基燃料电池性能测试结果的可靠性。Figure 5 shows the SEM image of the oxygen ion-based fuel cell prepared in this embodiment, including the cross-sectional image shape of the SFC4 porous cathode, the dense SDC electrolyte and the NiO-SDC composite anode. As can be seen from Figure 5, the adhesion between the SFC4 cathode (thickness of about 25 μm) and the SDC electrolyte (thickness of about 20 μm) is very close, thus proving the reliability of the oxygen ion-based fuel cell performance test results.
实施例7Example 7
采用实施例4的SFC4阴极材料,制备SFC4|BZCYYb|SFC4质子基对称电池,具体步骤如下:The SFC4 cathode material of Example 4 was used to prepare a SFC4|BZCYYb|SFC4 proton-based symmetric battery, and the specific steps were as follows:
(1)量取10ml异丙醇、2ml乙二醇以及0.6ml丙三醇,并称取1g的SFC4阴极粉体,并置于行星式球磨机上球磨,球磨机转速为400r min-1,球磨时间为2h,制得阴极粉体浆料;(1) 10 ml of isopropanol, 2 ml of ethylene glycol and 0.6 ml of propylene glycol were weighed, and 1 g of SFC4 cathode powder was weighed and placed on a planetary ball mill for ball milling at a speed of 400 r min -1 for 2 h to obtain cathode powder slurry;
(2)称取约0.5g的BZCYYb电解质粉体,并利用压片机将其压成直径为15mm的圆片,置于约为1450℃的高温炉中煅烧5h,制得电解质片。(2) About 0.5 g of BZCYYb electrolyte powder was weighed and pressed into a disc with a diameter of 15 mm using a tablet press, and then placed in a high-temperature furnace at about 1450° C. and calcined for 5 h to obtain an electrolyte sheet.
(3)利用喷枪将上述浆料均匀的喷在电解质片的两侧,并置于约为800℃的马弗炉中煅烧2h,制得对称电池;(3) using a spray gun to evenly spray the slurry on both sides of the electrolyte sheet, and calcining it in a muffle furnace at about 800° C. for 2 h to obtain a symmetrical battery;
(4)在上述质子基对称电池两侧刷上集流层,连上银线。(4) Apply current collecting layer on both sides of the above-mentioned proton-based symmetrical battery and connect them with silver wires.
对本实施例制备的SFC4|BZCYYb|SFC4质子基对称电池在550℃的湿空气(3%H2O)氛围中进行电化学阻抗的测试,结果如图6所示。由图6中结果可知,SFC4阴极材料所制备的对称电池在550℃的测试温度下,其阻值为0.774Ωcm2。The SFC4|BZCYYb|SFC4 proton-based symmetric battery prepared in this example was subjected to electrochemical impedance testing in a humid air (3% H 2 O) atmosphere at 550°C, and the results are shown in Figure 6. As shown in Figure 6, the resistance of the symmetric battery prepared with the SFC4 cathode material at a test temperature of 550°C is 0.774Ωcm 2 .
对本实施例制备的SFC4|BZCYYb|SFC4质子基对称电池进行热化学稳定性的测试,结果如图7所示。由图7中结果可知,SFC4|BZCYYb|SFC4质子基对称电池在550℃的测试温度下可以持续工作1000h,其阻抗以4/10000Ωcm2/h的速率在增大。The thermochemical stability of the SFC4|BZCYYb|SFC4 proton-based symmetric battery prepared in this example was tested, and the results are shown in Figure 7. As shown in Figure 7, the SFC4|BZCYYb|SFC4 proton-based symmetric battery can continue to work for 1000 hours at a test temperature of 550°C, and its impedance increases at a rate of 4/10000Ωcm2 / h.
实施例8Example 8
本实施例SFC4|BZCYYb|SFC4质子陶瓷燃料电池的制备方法,具体步骤如下:The preparation method of the SFC4|BZCYYb|SFC4 proton ceramic fuel cell in this embodiment has the following specific steps:
(1)量取10ml异丙醇、2ml乙二醇以及0.6ml丙三醇,并称取1g的SFC4阴极粉体,并置于行星式球磨机上球磨,球磨机转速为400r min-1,球磨时间为2h,制得阴极粉体浆料;(1) 10 ml of isopropanol, 2 ml of ethylene glycol and 0.6 ml of propylene glycol were weighed, and 1 g of SFC4 cathode powder was weighed and placed on a planetary ball mill for ball milling at a speed of 400 r min -1 for 2 h to obtain cathode powder slurry;
(2)称取6g NiO粉体、4g BZCYYb粉体以及1g淀粉置于球磨罐中,并倒入适量的酒精,放在行星式球磨机上以400r min-1的转速球磨40min,球磨后的浆料倒入研钵中研磨直到酒精全部挥发,接着放置于烘箱中烘干,再置于研钵中研磨成NiO-BZCYYb阳极粉体。(2) Weigh 6 g of NiO powder, 4 g of BZCYYb powder and 1 g of starch into a ball mill, add an appropriate amount of alcohol, and place the mixture on a planetary ball mill at a speed of 400 r min -1 for 40 min. Pour the milled slurry into a mortar and grind until all the alcohol is evaporated. Then place the mixture in an oven to dry, and then place the mixture in a mortar and grind it into NiO-BZCYYb anode powder.
(3)称取0.35g的NiO-BZCYYb阳极粉体,利用压片机将其压成15mm的圆片,再称取0.015g的BZCYYb电解质粉体,并用300目的筛子均匀过筛到阳极粉体圆片的一侧表面上,继续压,压好的圆片置于1450℃的高温炉中煅烧10h,制得半电池片。(3) Weigh 0.35 g of NiO-BZCYYb anode powder and press it into a 15 mm disc using a tablet press. Then weigh 0.015 g of BZCYYb electrolyte powder and evenly sieve it onto one side of the anode powder disc using a 300-mesh sieve. Continue pressing. The pressed disc is placed in a high-temperature furnace at 1450°C and calcined for 10 h to obtain a half-cell.
(4)利用喷枪将上述阴极粉体浆料均匀的喷在半电池的电解质一侧,并置于800℃的马弗炉中煅烧2h,制得质子陶瓷燃料电池;(4) using a spray gun to evenly spray the cathode powder slurry onto the electrolyte side of the half-cell, and calcining it in a muffle furnace at 800° C. for 2 h to obtain a proton ceramic fuel cell;
(5)在上述单电池阴极侧刷上集流层,在两侧连上银线,并封装在石英玻璃管上。(5) Apply a current collecting layer on the cathode side of the above single cell, connect silver wires on both sides, and encapsulate it in a quartz glass tube.
对本实施例制备的质子陶瓷燃料电池进行输出性能测试,具体方法为:以湿H2(3%H2O)为燃料,以空气为氧化剂分别在350℃、450℃和550℃的温度下采用数字源表(Keithley 2440)进行测试,结果如图8所示,在550℃下最大功率密度可达645mW cm-2。The output performance of the proton ceramic fuel cell prepared in this embodiment was tested by using wet H 2 (3% H 2 O) as fuel and air as oxidant at 350°C, 450°C and 550°C respectively using a digital source meter (Keithley 2440). The results are shown in FIG8 . At 550°C, the maximum power density can reach 645 mW cm -2 .
图9显示了本实施例制备的质子陶瓷燃料电池的SEM图,包含了SFC4多孔阴极,致密的BZCYYb电解质和NiO-BZCYYb复合阳极的横截面图像形状。从图中可以明显看出,SFC4阴极(厚度约为30μm)与BZCYYb电解质(厚度约为25μm)之间的粘附仍然很紧密,这也证明了质子陶瓷燃料电池性能测试结果的可靠性。Figure 9 shows the SEM image of the proton ceramic fuel cell prepared in this embodiment, including the cross-sectional image shape of the SFC4 porous cathode, the dense BZCYYb electrolyte and the NiO-BZCYYb composite anode. It can be clearly seen from the figure that the adhesion between the SFC4 cathode (thickness of about 30μm) and the BZCYYb electrolyte (thickness of about 25μm) is still very close, which also proves the reliability of the proton ceramic fuel cell performance test results.
对本实施例制备的质子陶瓷燃料电池进行热化学稳定性测试,具体方法为:以干的H2为燃料,以空气为氧化剂在550℃的温度下采用数字源表(Keithley 2440)进行稳定性测试,结果如图10所示,在550℃的测试温度下可以持续稳定的工作3100h。The proton ceramic fuel cell prepared in this embodiment was subjected to a thermochemical stability test. The specific method is: using dry H2 as fuel and air as oxidant at a temperature of 550°C using a digital source meter (Keithley 2440) to perform a stability test. The results are shown in FIG10 . At a test temperature of 550°C, the fuel cell can continue to work stably for 3100 hours.
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