固体氧化物燃料电池新型阳极材料的制备及性能研究
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摘要
传统的固体氧化物燃料电池(SOFC)采用镍氧化钇稳定的氧化锆Ni／YSZ作阳极材料，电池操作温度较高(约1000℃)，给电池组装及材料选择带来了很多困难。并且这种阳极材料对燃料的选择较强，对含硫燃料的容忍性较差，还会在阳极上形成严重的碳沉积现象。钙钛矿型氧化物LaCrO_3基掺杂材料具有较高的电子—离子混合电导率、优良的催化性能及较好的对硫容忍性。因此，LaCrO_3基掺杂材料是潜在的适用于以碳氢化合物为燃料的SOFC阳极材料。作者用差热-热重(TG-DTA)、X射线衍射分析(XRD)、扫描电子显微镜(SEM)、能谱分析(EDS)、程序升温还原(TPR)、粒度分析、交流阻抗、直流四探针等技术对材料的合成过程及性能进行了系统的研究。
采用固相法合成La_(1-x)Sr_xCr_(1-y)Mn_yO_(3-δ)(LSCM)阳极材料，在高于1250℃的温度下烧结15h后，均得到了具有单一钙钛矿结构的LSCM材料。在250-850℃范围内，LSCM材料在空气中的电导率符合小极化子绝热导电机理，在850℃时，最大的电导率为25S／cm。在H_2和CH_4气氛中，LSCM样品的电导率下降约两个数量级，其中，La_(0．7)Sr_(0．3)Cr_(．5)Mn_(0．5)O_(3-δ)(LSCM7355)样品在850℃时的电导率约为0．2S／cm。此外，还用甘氨酸-硝酸(GNP)法合成了LSCM材料，其前躯体在1200℃烧结5h后，得到了具有单一钙钛矿结构的LSCM材料。使用GNP法所得LSCM材料的导电性能与固相法所得材料相近，但GNP法合成材料温度较低，材料的催化性能较好。
当在LaCrO_3基材料中掺入部分Co元素，材料的电导性能就会提高。设计并采用GNP法合成La_(1-x)Sr_xCr_(1-y-z)Mn_yCo_zO_(3-δ)(LSCMCo)阳极材料，其前驱体在高于1300℃烧结后，才能得到单一钙钛矿结构的材料。在H_2和CH_4气氛中，LSCMCo73541样品在850℃时的电导率分别为0．4S／cm和4．5S／cm。
采用GNP法合成La_(0．7)Sr_(0．3)Cr_(0．5)Mn_(0．5)O_(3-δ)-Ce_(0．8)Ca_(0．2)O_(1．8)(LSCM-CDC)复合阳极材料。在1200℃下烧结5h后，分别得到了个钙钛矿-萤石复合结构的LSCM-CDC材料，在250-850℃范围内，LSCM-CDC样品配比为3：7时在空气下的电导率最高，在H_2气氛中850℃时的电导率约为1．0S／cm。
阳极材料(LSCM，LSCMCo)与LSGM电解质具有较好的化学相容性，上述电极材料与LSGM电解质的热匹配效果较好。
Traditional Solid Oxide Fuel Cell (SOFC) use Ni-yttria stabilzed ziroonia (Ni/YSZ) as its anode material, which leads the operation temperature is high (about 1000℃), and it is difficult for the choice of the electrode material and the cell stack contain materials. This anode has strong dependence of fuel gas, bad tolerance for fuels containing sulfur, and there maybe serious carbon deposit on the anode. LaCrO_3-based materials have high ionic-electronic conductivity, good catalytic and tolerance to sulfur properties. So, the LaCrO_3-based materials are a promising anode in SOFC system which using hydrocarbon as fuel. The above materials was prepared and tested by thermodynamic analysis (TG), differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microcopy (SEM), energy dispersive spectroscopy (EDS), temperature process reduction (TPR), the characterization on the diameters of particles, AC impedance and direct current four-electrode techniques.
The La_(1-x)Sr_xCr_(1-y)Mn-yO_(3-d)(LSCM) anode materials with single phase were identified after sintering above 1250℃for 15h using solid state reaction method. The electrical conductivities of all the LSCM samples increase linearly with temperature over the range of 250℃～850℃in air, and the maximum values is 25S/cm. The conductivities of LSCM7355 sample decrease about two orders of magnitude when the atmosphere changes from air to pure hydrogen and methane, and they are both about 0.2 S/cm in the above reducing atmospheres. The LSCM materials with single phase were obtained after sintering at 1200℃5h using Glycine-Nitrate (GNP) method, and the conductivity of the LSCM materials obtained by GNP method is similar to that of the LSCM materials prepared using solid state reaction method. But it need lower temperature to synthesize materials using GNP method, and the catalytic performance is preferably.
For Co element can improve the electrical conductivity of anode materials, so mixed part of Co into LaCrO_3-based materials can increase. the conductivity of anode materials. The La_(1-x)Sr_xCr_(1-y-z)Mn_yCo_xO_(3-d) (LSCMCo) anode materials were designed and synthesized by GNP method, and the LSCMCo materials with single phase were obtained after sintering at least 1300℃for 5h. Comparing to LSCM materials, the conductivities of the LSCMCo samples did not improve in air, but the conductivities of LSCMCo73541 sample are 0.4S/cm and 4.5S/cm at 850℃in pure hydrogen and methane, respectively. So LSCMCo is more suitable used as anode material of SOFC.
The La_(0.7)Sr_(0.3)Cr_(0.5)Mn_(0.5)O_(3-d)-Ce_(0.8)Ca_(0.2)O_(1.8)(LSCM-CDC) anode materials with pervskite-fluorite structure were obtained after sintering at 1200℃for 5h by GNP method. The optimum composition of the composite anode of LSCM and CDC was 7 to 3 at molar ratio. At 850℃, the electrical conductivity is 6.49S/cm in air and 1 S/cm in the reduction atmosphere, respectively.
The chemical compatibilities between anode (LSCM, LSCMCo) materials and LSGM electrolyte are very good. The above electrode materials but LSCM-CDC have good thermal capabilities with LSGM electrolyte material.
采用固相法合成La_(1-x)Sr_xCr_(1-y)Mn_yO_(3-δ)(LSCM)阳极材料，在高于1250℃的温度下烧结15h后，均得到了具有单一钙钛矿结构的LSCM材料。在250-850℃范围内，LSCM材料在空气中的电导率符合小极化子绝热导电机理，在850℃时，最大的电导率为25S／cm。在H_2和CH_4气氛中，LSCM样品的电导率下降约两个数量级，其中，La_(0．7)Sr_(0．3)Cr_(．5)Mn_(0．5)O_(3-δ)(LSCM7355)样品在850℃时的电导率约为0．2S／cm。此外，还用甘氨酸-硝酸(GNP)法合成了LSCM材料，其前躯体在1200℃烧结5h后，得到了具有单一钙钛矿结构的LSCM材料。使用GNP法所得LSCM材料的导电性能与固相法所得材料相近，但GNP法合成材料温度较低，材料的催化性能较好。
当在LaCrO_3基材料中掺入部分Co元素，材料的电导性能就会提高。设计并采用GNP法合成La_(1-x)Sr_xCr_(1-y-z)Mn_yCo_zO_(3-δ)(LSCMCo)阳极材料，其前驱体在高于1300℃烧结后，才能得到单一钙钛矿结构的材料。在H_2和CH_4气氛中，LSCMCo73541样品在850℃时的电导率分别为0．4S／cm和4．5S／cm。
采用GNP法合成La_(0．7)Sr_(0．3)Cr_(0．5)Mn_(0．5)O_(3-δ)-Ce_(0．8)Ca_(0．2)O_(1．8)(LSCM-CDC)复合阳极材料。在1200℃下烧结5h后，分别得到了个钙钛矿-萤石复合结构的LSCM-CDC材料，在250-850℃范围内，LSCM-CDC样品配比为3：7时在空气下的电导率最高，在H_2气氛中850℃时的电导率约为1．0S／cm。
阳极材料(LSCM，LSCMCo)与LSGM电解质具有较好的化学相容性，上述电极材料与LSGM电解质的热匹配效果较好。
Traditional Solid Oxide Fuel Cell (SOFC) use Ni-yttria stabilzed ziroonia (Ni/YSZ) as its anode material, which leads the operation temperature is high (about 1000℃), and it is difficult for the choice of the electrode material and the cell stack contain materials. This anode has strong dependence of fuel gas, bad tolerance for fuels containing sulfur, and there maybe serious carbon deposit on the anode. LaCrO_3-based materials have high ionic-electronic conductivity, good catalytic and tolerance to sulfur properties. So, the LaCrO_3-based materials are a promising anode in SOFC system which using hydrocarbon as fuel. The above materials was prepared and tested by thermodynamic analysis (TG), differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microcopy (SEM), energy dispersive spectroscopy (EDS), temperature process reduction (TPR), the characterization on the diameters of particles, AC impedance and direct current four-electrode techniques.
The La_(1-x)Sr_xCr_(1-y)Mn-yO_(3-d)(LSCM) anode materials with single phase were identified after sintering above 1250℃for 15h using solid state reaction method. The electrical conductivities of all the LSCM samples increase linearly with temperature over the range of 250℃～850℃in air, and the maximum values is 25S/cm. The conductivities of LSCM7355 sample decrease about two orders of magnitude when the atmosphere changes from air to pure hydrogen and methane, and they are both about 0.2 S/cm in the above reducing atmospheres. The LSCM materials with single phase were obtained after sintering at 1200℃5h using Glycine-Nitrate (GNP) method, and the conductivity of the LSCM materials obtained by GNP method is similar to that of the LSCM materials prepared using solid state reaction method. But it need lower temperature to synthesize materials using GNP method, and the catalytic performance is preferably.
For Co element can improve the electrical conductivity of anode materials, so mixed part of Co into LaCrO_3-based materials can increase. the conductivity of anode materials. The La_(1-x)Sr_xCr_(1-y-z)Mn_yCo_xO_(3-d) (LSCMCo) anode materials were designed and synthesized by GNP method, and the LSCMCo materials with single phase were obtained after sintering at least 1300℃for 5h. Comparing to LSCM materials, the conductivities of the LSCMCo samples did not improve in air, but the conductivities of LSCMCo73541 sample are 0.4S/cm and 4.5S/cm at 850℃in pure hydrogen and methane, respectively. So LSCMCo is more suitable used as anode material of SOFC.
The La_(0.7)Sr_(0.3)Cr_(0.5)Mn_(0.5)O_(3-d)-Ce_(0.8)Ca_(0.2)O_(1.8)(LSCM-CDC) anode materials with pervskite-fluorite structure were obtained after sintering at 1200℃for 5h by GNP method. The optimum composition of the composite anode of LSCM and CDC was 7 to 3 at molar ratio. At 850℃, the electrical conductivity is 6.49S/cm in air and 1 S/cm in the reduction atmosphere, respectively.
The chemical compatibilities between anode (LSCM, LSCMCo) materials and LSGM electrolyte are very good. The above electrode materials but LSCM-CDC have good thermal capabilities with LSGM electrolyte material.
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