SOFC阳极纳米复合粉体及电池成型工艺的研究
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摘要
固体氧化物燃料电池(SOFC)是一种将化学能直接转化为电能的能量转换装置,具有能量转换效率高、对环境友好和操作简单等优点,在世界范围内得到了极大的关注和各国政府的大力支持。由于传统的机械混合造成Ni和YSZ(三氧化二钇稳定二氧化锆)两相分布不均,直接影响了SOFC性能的进一步提高。采用Pechini法合成了NiO/YSZ阳极纳米复合粉,实验结果表明,pH值和柠檬酸/金属阳离子物质的量配比是影响阳极复合粉粒径、团聚情况和阳极性能的主要因素。通过实验优化了阳极复合粉体的制备工艺(pH=7.0,柠檬酸/金属阳离子物质的量配比为2∶1),合成的复合粉体在阳极当中NiO、YSZ两相颗粒的分布最均匀。
将合成的复合粉体用压片法制备成阳极(面积为Φ20mm),涂敷电解质并组装模拟电池,800℃(H_2流量为50mL/min)时放电的最大功率密度达到850mW/cm~2;将复合粉作为阳极功能层通过流延工艺制备了半电池(面积为Φ20mm)并组装成模拟电池,在800℃(H2流量为50mL/min)具有最大的功率密度达到1000mW/cm~2。
为了组装SOFC电堆,需要制备大尺寸半电池,研究大尺寸半电池的流延成型工艺。首先,减小了造孔剂淀粉的含量,防止裂纹出现;其次,研究YSZ的粒径变化对半电池成型的影响,发现随煅烧温度的增加,YSZ颗粒的粒径加大,900℃煅烧2小时所得YSZ(颗粒粒径2.0μm)成型性最好(作为支撑层只有少量细微裂缝的产生);在YSZ确定的条件下,考察了北京建材NiO(颗粒粒径6.3μm)和上海国药NiO(颗粒粒径2.0μm)粒径变化对半电池成型的影响,发现采用上海国药NiO与YSZ匹配性最好,得到平整无缺陷的大尺寸半电池,并且通过改进流延浆料组分,于1300℃获得了致密的YSZ电解质,半电池800℃开路电压达到1.05V,接近理论电压。
采用优化的流延工艺,成功制备出面积为7.5×7.5cm~2的半电池及7×7cm~2的阳极。流延法制备的半电池所组装的模拟电池(面积为Φ20mm,丝网印刷阴极面积0.6×0.6cm~2)的放电性能,800℃(H_2流量为100mL/min)的最大功率密度为560mW/cm~2,以800mA/cm~2的电流密度放电,9小时无衰减。在7×7cm~2的阳极上涂敷电解质,将其制备成5×5cm~2的半电池,组装成单体电池。单体电池放电测试结果表明,当阳极面积为5.0×5.0cm~2 ,阴极面积为3.0×3.0cm~2时,800℃(H2流量为500mL/min)最大功率为1.32W,最大功率密度为146mW/cm~2。
Solid oxide fuel cell (SOFC) is considered as the electrochemical device that converts the chemical energy of reaction directly into electrical energy. It possesses the advantages of high conversion efficiency, environmental friendness, and abroad adaptive fuels. So, people worldwide focus on the research and development of SOFC. The anode performance obviously influences the cell performance. In order to advance the cell discharging performance, the NiO/YSZ (Yttrium oxide stabilized zirconium dioxide) composite nano-powders were synthesized by the Pechini method. Testing results showed that both the pH value and the citric acid/ metal cation mol ratio were the dominating factors which influence the gain size of the composite powders, the conglomerating phenomena and the anode performance. As the pH value increased, the particle size of the composite powders increased first, and then decreased. The optimum process of synthetizing NiO/YSZ composite powders was obtained when the pH value was 7.0 and the citric acid/ metal cation mol ratio was 2:1, the NiO and YSZ powders got the most uniform distribution in the anode.
The obtained NiO/YSZ composite powders were die-pressed and tape-casted into the anode pellets. Then the YSZ electrolyte thin films were dip-coated on the anodes, and the simulating cells were assembled and tested. When the H2 flux was 50mL/min, at 800℃, the maximum power density for the single cell with the die-pressed anode (Φ20mm) was 850mW/cm~2, and that for the single cell with the tape-casted anode (Φ20mm) was 1000 mW/cm~2.
Large-size planar cell was needed for the assembling the SOFC stack. In this paper, the tape-casting process for fabricating the large-size half cell was studied. First, the starch content was reduced, and the cracks on the cell were eliminated. Second, YSZ powders were calcined in order to change its particle size, and influence of the YSZ particle size on the molding of the half cell was studied. Testing results showed that the YSZ particle size increased with the increasing of the calcining temperature. After being calcined at 900℃for 2 h, the YSZ powders (with the particle size of 2.0μm) presented the best molding property, and only a few cracks occurred when the YSZ powders were used as the the supported layer. Keeping the YSZ conditions the same, influence of the NiO particle size on the molding of the half cell was studied. The Beijing Jiancai NiO (with the particle size of 6.3μm) and the Shanghai Guoyao NiO (with the particle size of 2.0μm) were investigated. Testing results showed that the Shanghai Guoyao NiO matched better with the YSZ, and the even and defect-free large-size half cell was obtained. Besides, by reducing the sintering temperature from 1500℃to 1300℃, dense YSZ electrolyte was obtained. At 800℃, the open circit voltage for the half cell reached 1.05V, which was close to the theoretical value.
After employing the optimized tape-casting process, the half cell with the area of 7.5×7.5cm~2 and the anode with the size of 7×7cm~2 were successfully fabricated. The simulating cell performance fabricated by tape-cating (with the diameter ofΦ20mm, and with the cathodic area of 6×0.6cm~2 prepared by screen-printing) was tested. At 800℃( with the H2 flux 100mL/min), the maximum power density was 550mW/cm~2, and when discharging with the current density of 800mA/cm~2, there is no attenuation in 9 h. YSZ electrolyte was dip-coated on the anode with the size of 7×7cm~2, and the half cell with the size of 5×5cm~2 was obtained. The single cell was assembled. The discharging performance for the single cell was tested. At 800℃( with the H_2 flux of 100mL/min),the maximum power was 1.32W, and the maximum power density was 146mW/cm~2, when the anode area was 5.0×5.0cm~2 and the cathode area was 3.0×3.0 cm~2.
将合成的复合粉体用压片法制备成阳极(面积为Φ20mm),涂敷电解质并组装模拟电池,800℃(H_2流量为50mL/min)时放电的最大功率密度达到850mW/cm~2;将复合粉作为阳极功能层通过流延工艺制备了半电池(面积为Φ20mm)并组装成模拟电池,在800℃(H2流量为50mL/min)具有最大的功率密度达到1000mW/cm~2。
为了组装SOFC电堆,需要制备大尺寸半电池,研究大尺寸半电池的流延成型工艺。首先,减小了造孔剂淀粉的含量,防止裂纹出现;其次,研究YSZ的粒径变化对半电池成型的影响,发现随煅烧温度的增加,YSZ颗粒的粒径加大,900℃煅烧2小时所得YSZ(颗粒粒径2.0μm)成型性最好(作为支撑层只有少量细微裂缝的产生);在YSZ确定的条件下,考察了北京建材NiO(颗粒粒径6.3μm)和上海国药NiO(颗粒粒径2.0μm)粒径变化对半电池成型的影响,发现采用上海国药NiO与YSZ匹配性最好,得到平整无缺陷的大尺寸半电池,并且通过改进流延浆料组分,于1300℃获得了致密的YSZ电解质,半电池800℃开路电压达到1.05V,接近理论电压。
采用优化的流延工艺,成功制备出面积为7.5×7.5cm~2的半电池及7×7cm~2的阳极。流延法制备的半电池所组装的模拟电池(面积为Φ20mm,丝网印刷阴极面积0.6×0.6cm~2)的放电性能,800℃(H_2流量为100mL/min)的最大功率密度为560mW/cm~2,以800mA/cm~2的电流密度放电,9小时无衰减。在7×7cm~2的阳极上涂敷电解质,将其制备成5×5cm~2的半电池,组装成单体电池。单体电池放电测试结果表明,当阳极面积为5.0×5.0cm~2 ,阴极面积为3.0×3.0cm~2时,800℃(H2流量为500mL/min)最大功率为1.32W,最大功率密度为146mW/cm~2。
Solid oxide fuel cell (SOFC) is considered as the electrochemical device that converts the chemical energy of reaction directly into electrical energy. It possesses the advantages of high conversion efficiency, environmental friendness, and abroad adaptive fuels. So, people worldwide focus on the research and development of SOFC. The anode performance obviously influences the cell performance. In order to advance the cell discharging performance, the NiO/YSZ (Yttrium oxide stabilized zirconium dioxide) composite nano-powders were synthesized by the Pechini method. Testing results showed that both the pH value and the citric acid/ metal cation mol ratio were the dominating factors which influence the gain size of the composite powders, the conglomerating phenomena and the anode performance. As the pH value increased, the particle size of the composite powders increased first, and then decreased. The optimum process of synthetizing NiO/YSZ composite powders was obtained when the pH value was 7.0 and the citric acid/ metal cation mol ratio was 2:1, the NiO and YSZ powders got the most uniform distribution in the anode.
The obtained NiO/YSZ composite powders were die-pressed and tape-casted into the anode pellets. Then the YSZ electrolyte thin films were dip-coated on the anodes, and the simulating cells were assembled and tested. When the H2 flux was 50mL/min, at 800℃, the maximum power density for the single cell with the die-pressed anode (Φ20mm) was 850mW/cm~2, and that for the single cell with the tape-casted anode (Φ20mm) was 1000 mW/cm~2.
Large-size planar cell was needed for the assembling the SOFC stack. In this paper, the tape-casting process for fabricating the large-size half cell was studied. First, the starch content was reduced, and the cracks on the cell were eliminated. Second, YSZ powders were calcined in order to change its particle size, and influence of the YSZ particle size on the molding of the half cell was studied. Testing results showed that the YSZ particle size increased with the increasing of the calcining temperature. After being calcined at 900℃for 2 h, the YSZ powders (with the particle size of 2.0μm) presented the best molding property, and only a few cracks occurred when the YSZ powders were used as the the supported layer. Keeping the YSZ conditions the same, influence of the NiO particle size on the molding of the half cell was studied. The Beijing Jiancai NiO (with the particle size of 6.3μm) and the Shanghai Guoyao NiO (with the particle size of 2.0μm) were investigated. Testing results showed that the Shanghai Guoyao NiO matched better with the YSZ, and the even and defect-free large-size half cell was obtained. Besides, by reducing the sintering temperature from 1500℃to 1300℃, dense YSZ electrolyte was obtained. At 800℃, the open circit voltage for the half cell reached 1.05V, which was close to the theoretical value.
After employing the optimized tape-casting process, the half cell with the area of 7.5×7.5cm~2 and the anode with the size of 7×7cm~2 were successfully fabricated. The simulating cell performance fabricated by tape-cating (with the diameter ofΦ20mm, and with the cathodic area of 6×0.6cm~2 prepared by screen-printing) was tested. At 800℃( with the H2 flux 100mL/min), the maximum power density was 550mW/cm~2, and when discharging with the current density of 800mA/cm~2, there is no attenuation in 9 h. YSZ electrolyte was dip-coated on the anode with the size of 7×7cm~2, and the half cell with the size of 5×5cm~2 was obtained. The single cell was assembled. The discharging performance for the single cell was tested. At 800℃( with the H_2 flux of 100mL/min),the maximum power was 1.32W, and the maximum power density was 146mW/cm~2, when the anode area was 5.0×5.0cm~2 and the cathode area was 3.0×3.0 cm~2.
引文
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2 N. Q. Minh and T. Takahashi. Science and Technology of Ceramic Fuel Cells. Elsevier Science B. V. Amsterdam, 1995:15
3 S. McIntosh, J. G. Raymond. Direct Hydrocarbon Solid Oxide Fuel Cells. Chemical Review. 2004, 104:4845-4865
4 M. Yokoo, Y. Tabata, Y. Yoshida, et al. Development of 1kW class SOFC stack using anode supported planar cells. Journal of Power Sources. 2008, 182(2):496-502
5程继贵,邓丽萍,孟光耀.固体氧化物燃料电池阳极材料制备及性能研究进展.兵器材料科学与工程. 2002, 25(6):45-49
6 T. L. Cable, S. W. Sofie. A symmetrical, planar SOFC design for NASA's high specific power density requirements. Journal of Power Sources. 2007, 174(1): 221-227
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