固体氧化物燃料电池双钙钛矿陶瓷阳极缺陷结构设计与性能调控

研究了固体氧化物燃料电池Sr₂Fe Mo_0.6Mg_0.25Al_0.15O₆ (SFMMA)双钙钛矿阳极的晶体缺陷结构、热膨胀性能、电荷传输特性、氧化还原稳定性以及电化学性能。结果表明:SFMMA室温下为I 4/m四方结构,400℃时材料转变为F m 3 m立方结构。SFMMA材料的实际晶体结构式为Sr₂(Fe_0.75Mg_0.25)(Mo_0.6Fe_0.25Al_0.15)O6-δ,材料晶格中含有大量反位缺陷FeB’以及—Fe_B—O—Fe_B’—键,有利于氧空位的形成及氧离子的迁移扩散。SFMMA的热膨胀系数在25~400℃和400~900℃范围内分别为13.0×10^–6K^–1和17.6×10^–6K^–1,在氢气气氛下600~900℃温度范围内电导率超过35 S·cm^–1,并且具有较快的氧表面交换特性以及非常优异的氧化还原循环结构稳定性。在900,850,800℃和750℃时,湿润H₂(3%H₂O,50 m L/min)气氛中,SFMMA/La_0.4Ce_0.6O₂(LDC)/La_0.8Sr_0.2Ga_0.8Mg_0.2O₃(LSGM)/LDC/SFMMA对称半电池面比电阻分别为0.096,0.142,0.239Ω·cm²和0.447Ω·cm²。以SFMMA为阳极组装电解质支撑型单电池SFMMA/LDC/LSGM (300μm)/Pr Ba_0.5Sr_0.5Co_1.5Fe_0.5O₅+δ,850℃时电池最大功率密度可达886 m W·cm^–2。     

水热原位生长制备致密氧化铈基固体氧化物燃料电池隔离层

面向高性能固体氧化物燃料电池(SOFC)低成本制备及长寿命运行需求,提出了一种致密氧化铈基隔离层的制备方法。将阳极支撑半电池的Y₂O₃稳定ZrO₂(YSZ)电解质浸没于硝酸钆和硝酸铈水溶液中,并在180℃水热条件下处理36 h,获得了原位生长的致密Gd₂O₃掺杂CeO₂(GDC)薄膜;进一步将其与La_0.6Sr_0.4Co_0.2Fe_0.8O_3–δ阴极在1 075℃共烧结,得到阳极支撑SOFC单电池。结果表明,水热原位生长制备的GDC隔离层连续且致密,组成约为Gd_0.044Ce_0.956O_2–δ,厚度约为0.23μm;阳极支撑单电池在750℃的欧姆阻抗约为0.101Ω·cm²,相较于传统丝网印刷GDC隔离层单电池降低了约38%,在室温加湿氢气燃料下的最大功率密度达到...     

原位析出制备固体氧化物电解池的“氧化铈–金属–钙钛矿”复合阴极材料

固体氧化物电解池能够利用可再生电能将CO₂转化为CO等储存,但其阴极材料仍面临活性位易烧结和积碳等问题。通过原位析出策略在A位缺陷钙钛矿阴极材料La_0.4Ca_0.4Ti_0.94Ni_0.06O_3–δ表面构筑金属Ni纳米颗粒,并优化不同的合成手段(掺杂、浸渍、混合)引入CeO₂,构筑了“氧化铈–金属–钙钛矿”三相复合阴极。结果表明：机械混合CeO₂对阴极的抗积碳性能与电化学性能的提升最为显著：在800℃,70%(体积分数) CO₂/30%CO,1.4 V电解电压下,电流密度提高3倍,衰减速率降低58%,该改性结果与其表面氧空位浓度增加及CO₂吸附强化有关。     

Co掺杂SrTi0.3Fe0.7O3-δ 阳极SOFC在化工副产气燃料下的性能及稳定性

化工副产气是具有一定热值的可燃性复杂气体,但一直以来提纯再利用经济效益低,大多采用直接燃烧的方法处理。针对当前化学工业开展绿色低碳转型的需求,研究了固体氧化物燃料电池(SOFC)采用化工副产气发电的性能。以SrTi_0.3Fe_0.7O_3-δ (STF)钙钛矿氧化物为基础,采用高温固相合成法制备了B位Co掺杂的Sr_0.95Ti_0.33Fe_0.6Co_0.07O_3-δ (STFC)阳极,以不同种类和组成的模拟化工副产气作为燃料,系统研究了单电池的电化学性能和稳定性。结果表明,STFC钙钛矿氧化物在加湿氢气中还原后原位析出Co_0.28Fe_0.72纳米合金颗粒;以其为阳极的SOFC单电池在多种模拟化工副产气燃料下实现了高性能运行,表现出较小的极化阻抗和良好的电化学性能输出;在含有多种碳氢组分的复杂燃料下表现出卓越的长期运行稳定性。     

不同燃料SOFC的理论电池电动势及其性能

以NH₃以及3% H₂O增湿的H₂、CH₄、C₃H₈和煤炭地下气化(underground coal gasification,UCG)气为燃料,用最小Gibbs自由能法计算平衡气体组分和理论电池电动势,并测试在NiO-GDC‖GDC‖Ba_0.9Co_0.7Fe_0.2Nb_0.1O_3-δ(B_0.9CFN)阳极支撑固体氧化物燃料电池(SOFC)中的电池开路电压、电池性能和长期稳定性。结果表明,以上述气体作燃料的SOFC热力学计算理论电动势均高于1.05 V,而由于GDC电解质在还原气氛下存在电子电导,导致碳氢燃料在NiO-GDC‖GDC‖B_0.9CFN阳极支撑电池中的开路电压略小。中低温下,碳氢燃料相对缓慢的动力学过程和GDC电解质快速的氧离子传输速率,使得以UCG气、CH₄和C₃H₈为燃料的电池实际积炭比理论预测少。以UCG气为燃料的SOFC在500、550、600和650℃的最高功率密度分别高达0.151、0.299、0.537和0.729 W·cm^-2,在0.6 V恒压放电120 h后性能没有明显衰减,且阳极表面无积炭产生,表明直接UCG气SOFC具有广阔的应用前景。     

Co掺杂SrTi0.3Fe0.7O3-δ 阳极SOFC在化工副产气燃料下的性能及稳定性

化工副产气是具有一定热值的可燃性复杂气体,但一直以来提纯再利用经济效益低,大多采用直接燃烧的方法处理。针对当前化学工业开展绿色低碳转型的需求,研究了固体氧化物燃料电池(SOFC)采用化工副产气发电的性能。以SrTi_0.3Fe_0.7O_3-δ (STF)钙钛矿氧化物为基础,采用高温固相合成法制备了B位Co掺杂的Sr_0.95Ti_0.33Fe_0.6Co_0.07O_3-δ (STFC)阳极,以不同种类和组成的模拟化工副产气作为燃料,系统研究了单电池的电化学性能和稳定性。结果表明,STFC钙钛矿氧化物在加湿氢气中还原后原位析出Co_0.28Fe_0.72纳米合金颗粒;以其为阳极的SOFC单电池在多种模拟化工副产气燃料下实现了高性能运行,表现出较小的极化阻抗和良好的电化学性能输出;在含有多种碳氢组分的复杂燃料下表现出卓越的长期运行稳定性。     

固体氧化物燃料电池Cu/Ni-LSCM阳极中n(Cu)/n(Ni)对碳沉积影响数值模拟研究

固体氧化物燃料电池(SOFC)使用碳氢化合物为燃料时,多孔阳极易出现严重的积碳的现象,导致阳极催化活性降低,电池功率密度下降以及电池寿命急剧衰减。铬酸镧基钙钛矿材料在高温氧化和还原气氛下具有较好的稳定性、电催化活性和抗积碳性能。建立LSCM以及Cu/Ni-LSCM中CH₄与CO₂干重整动力学模型,模型耦合了动量传递、质量传递、化学反应动力学、域微分方程以及气体在多孔介质中的传质模型,并利用该模型研究了Cu/Ni-LSCM阳极材料的抗积碳性能、催化活性以及孔隙率随时间的变化情况。得出结论:Cu的引入可以明显降低碳沉积速率,在一定基础上增加燃料转化率。其中CH₄热分解是形成积碳的主要原因。与此同时,模拟结果显示阳极燃料入口处为碳沉积最为严重的区域。     

复合阳极Ni-Fe/Ce0.9Gd0.1O1.95在阴极支撑单电池的性能及其表征

为了提高固体氧化物燃料电池在中温条件下的电性能,探索了一种双金属阳极的阴极支撑单电池。单电池以La_0.6Sr_0.4CoO₃（LSC）-Ce_0.9Gd_0.1O_1.95（GDC）为阴极支撑体,旋涂了甘氨酸-硝酸盐法制备的La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ（LSGM）电解质及Sm_0.2Ce_0.8O_1.9（SDC）缓冲层,涂覆了由硬模板法和浸渍法结合制备的Ni-Fe/GDC双金属阳极。对制备材料进行了XRD和微观形貌分析,单电池电化学测试在800 ℃和750 ℃下,以氢气为燃料的最大功率密度达0.73 W/cm²和0.64 W/cm²,以甲烷为燃料时达0.41 W/cm²和0.40 W/cm²。测试后的SEM表明,阳极具有多孔的微观结构,金属颗粒均匀包覆蠕虫状GDC,保证了单电池具有较高的发电性能。     

硬模板法制备固体氧化物燃料电池复合阳极GDC–SrMoO_4–YSZ

以活性炭纤维为模板,用硬模板法合成钙钛矿材料Sr Mo O_4,并在Sr Mo O_4阳极上浸渍Gd_(0.2)Ce_(0.8)O_(1.9)(GDC),制备出GDC–Sr Mo O_4–YSZ复合阳极。分别以Sr Mo O_4–YSZ和GDC–Sr Mo O_4–YSZ为阳极,制备了固体氧化物燃料单电池,并测试了其电性能。探究了不同浸渍次序下,阳极的材料组成对电池发电性能的影响。结果表明,以CH4为燃料,工作温度为800℃时,Sr Mo O_4中浸渍GDC质量分数为50%,Sr Mo O_4与YSZ质量比为5:5的阳极材料,最大功率密度为317.15 m W/cm~2;Sr Mo O_4–YSZ中GDC浸渍量为50%时,单电池性能最佳,最大功率达到361.01 m W/cm~2。     

Ce掺杂La0.7Sr0.3Cr0.5Fe0.5O3-δ材料的制备及其电化学性能

近年来化石燃料大量消耗导致环境污染日益严重,固体氧化物电解池(SOEC)能够高效、环境友好地将CO₂转化为CO等高附加值化学品,因此受到广泛关注。开发高效稳定的SOEC需要采用性能优异的电极材料,La_0.7Sr_0.3Cr_0.5Fe_0.5O_3-δ(Sto-LSCrF)钙钛矿氧化物因其优异的氧化还原稳定性受到了高度重视。为进一步提高Sto-LSCrF燃料电极材料电解CO₂的能力,在Sto-LSCrF的A位掺杂Ce来调控Ce_0.08La_0.62Sr_0.3Cr_0.5Fe_0.5O_3-δ(Ce-LSCrF)中可移动氧空穴含量以便提高其对CO₂的吸附/活化能力,进而改善其电化学性能。同时对材料的相结构、氧空穴含量以及其对CO₂的吸附/脱附能力进行详细的表征和分析。此外,我们还探究了Ce-LSCrF的电化学性能,发现与Sto-LSCrF相比,Ce-LSCrF燃料电极表现出较高的电解性能,也显示出较好的恒压稳定性,电解性能的增强归因于Ce-LSCrF晶格中较多的可移动氧空位可有效吸附/活化CO₂,以上试验结果表明Ce-LSCrF是性能优异的CO₂电解材料。     

Comparative analysis of ceramic-carbonate nanocomposite fuel cells using composite GDC/NLC electrolyte with different perovskite structured cathode materials

A comparative analysis of perovskite structured cathode materials, La_0.65Sr_0.35MnO₃ (LSM), La_0.8Sr_0.2CoO₃ (LSC), La_0.6Sr_0.4FeO₃ (LSF) and La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF), was performed for a ceramic-carbonate nanocomposite fuel cell using composite electrolyte consisting of Gd_0.1Ce_0.9O_1.95 (GDC) and a eutectic mixture of Na₂CO₃ and Li₂CO₃. The compatibility of these nanocomposite electrode powder materials was investigated under air, CO₂ and air/CO₂ atmospheres at 550 °C. Microscopy measurements together with energy dispersive X-ray spectroscopy (EDS) elementary analysis revealed few spots with higher counts of manganese relative to lanthanum and strontium under pure CO₂ atmosphere. Furthermore, electrochemical impedance (EIS) analysis showed that LSC had the lowest resistance to oxygen reduction reaction (ORR) (14.12 Ω·cm²) followed by LSF (15.23 Ω·cm²), LSCF (19.38 Ω·cm²) and LSM (>300 Ω·cm²). In addition, low frequency EIS measurements (down to 50 µHz) revealed two additional semi-circles at frequencies around 1 Hz. These semicircles can yield additional information about electrochemical reactions in the device. Finally, a fuel cell was fabricated using GDC/NLC nanocomposite electrolyte and its composite with NiO and LSCF as anode and cathode, respectively. The cell produced an excellent power density of 1.06 W/cm² at 550 °C under fuel cell conditions.     

Enthalpy recovery of gases issued from H2 production processes: Activity and stability of oxide and noble metal catalysts in oxidation reaction under highly severe conditions

Oxidation activity and stability under reaction was investigated for a series of mixed oxide catalysts, doped or not by a precious metal (Pd, Pt). The reaction feedstock, containing CO, H₂, CH₄, CO₂ and H₂O, simulated gases issued from H₂ production processes for fuel cells. Contrarily to conventional noble metal catalysts, mixed oxide samples present generally good stability under reaction at high temperature. The activities measured for the perovskite and hexaaluminate catalysts, are however largely lower than that of the reference Pd/Al₂O₃ catalyst. High activities were obtained after impregnation of 1.1 wt.% Pd or 0.8 wt.% Pt on the hexaaluminates samples. Even if Pd/Al₂O₃ was found to present a high activity, this sample suffered from drastic deactivation at 700 °C. Better stability were obtained on perovskite. Furthermore, doping hexaaluminate by Pt led to samples with good activities and high stability. Even if better activities were obtained by doping the hexaaluminate samples by Pd, the Pd/BaAl₁₂O₁₉ strongly deactivated, as it was previously observed for the reference catalyst. Interestingly, this Pd deactivation was not observed when Pd was impregnated on the Mn substituted hexaaluminate, leading to a stable and active catalyst. This suggests that it is possible to stabilize the palladium in its oxidized form at high temperature (700 °C) on the surface of some supports.     

火焰喷雾合成法制备La0.8Sr0.2Mn1-xCuxO3催化氧化CO性能研究

采用火焰喷雾合成法制备了Sr²⁺、Cu²⁺分别取代A、B位的La_0.8Sr_0.2Mn_1-xCu_xO₃ （x=0,0.1,0.2,0.3,0.4）钙钛矿催化剂,并用于CO催化氧化实验,研究了水蒸气和CO₂对催化剂CO氧化活性的影响。对不同取代量La_0.8Sr_0.2Mn_1-xCu_xO₃ 催化剂进行了XRD、SEM、EDS、BET、XPS、H₂-TPR和O₂-TPD等表征测试。结果表明,火焰喷雾合成法制备的钙钛矿催化剂具有良好的钙钛矿相、疏松多孔结构和催化氧化活性。其中,La_0.8Sr_0.2Mn_0.9Cu_0.1O₃分别在119.4℃和133.3℃实现50%和90%的CO转化率。掺杂水蒸气和CO₂会与CO在催化剂表面形成竞争吸附,导致5种催化剂性能衰减,但La_0.8Sr_0.2Mn_0.9Cu_0.1O₃仍能在150.2℃实现90%的CO催化转化,在连续稳定性催化氧化测试中,5种催化剂性能衰减不超过10%。结合上述CO催化氧化实验,火焰喷雾合成法制备的催化剂具有良好的稳定性和催化活性,适合制备高CO催化氧化活性的钙钛矿催化剂。     

Chemical Effects of CO2 Concentration on Soot Formation in Jet-stirred/Plug-flow Reactor

Soot formation was investigated numerically with CO2 addition in a jet-stirred/plug-flow reactor （JSR/PFR） C2H4/OJN2 reactor （C/O ratio of 2.2） at atmospheric pressure. An updated Kazakov mechanism empha- sizes the effect of the O2/CO2 atmosphere instead of an O2/N2 one in the premixed flame. The soot formation was taken into account in the JSR/PFR for C2H4/O2/N2. The effects of CO2 addition on soot formation in different C2H4/O2/CO2/N2 atmospheres were studied, with special emphasis on the chemical effect. The simulation shows that the endothermic reaction CO2 ＋ H - CO ＋ OH is responsible of the reduction of hydrocarbon intermediates in the CO2 added combustion through the supplementary formation of hydroxyl radicals. The competition of CO2 for H radical through the above forward reaction with the single most important chain branching reaction H ＋ O2, ＇ O ＋ OH reduces significantly the fuel burning rate. The chemical effects of CO2 cause a significant increase in residence time and mole fractions of CO and OH, significant decreases in some intermediates （H, C2H2）, polycyclic aromatic hydrocarbons （PAHs, C6H6 and CI6H10, etc.） and soot volume fraction. The CO2 addition will leads to a decrease by only about 5% to 20% of the maximum mole fractions of some C3 to Clo hydrocarbon intermediates. The sensitivity analysis and reaction-path analysis results show that C2H4 reaction path and products are altered due to the CO2 addition.     

表面修饰对镧锶钴铁阴极材料电化学性能的影响

通过柠檬酸-EDTA络合法制备固体氧化物燃料电池阴极材料La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(LSCF)粉体。以Sm_0.2Ce_0.8O_1.9(SDC)为电解质,制备了LSCF/SDC/LSCF对称电极。采用浸渍法在LSCF/SDC/LSCF两侧浸渍La(NO₃)₃、Ni(NO₃)₂、Fe(NO₃)₃混合溶液,850℃烧结后得到表面修饰后的阴极材料。研究了浸渍烧结后表面修饰阴极材料的物相结构特征、电化学交流阻抗、电化学催化活性及单电池输出性能。结果表明:通过浸渍法在LSCF阴极表面形成了与LSCF结构相似的La_0.62Sr_0.38Ni_0.03Co_0.19Fe_0.78O_3-δ(LSNCF)固溶体,在表面产生的纳米颗粒提升了阴极材料对O2的吸附解离能力,并表现出较低的极化阻抗,在800℃时LSNCF阴极材料的极化面电阻为0.083Ω·cm²,在800℃连续工作7 200 min后,LSNCF阴极材料对称电池极化阻抗为0.117Ω·cm²。以Ni-SDC为阳极,SDC为电解质,LSNCF为阴极组装阳极支撑单电池,在750℃时最大功率密度为693 m W/cm²。     

Kinetics of the water–gas shift reaction on Pt catalysts supported on alumina and ceria

We report the kinetic parameters for the water–gas shift (WGS) reaction on Pt catalysts supported on ceria and alumina under fuel reformer conditions for fuel cell applications (6.8% CO, 8.5% CO₂, 22% H₂O, 37.3% H₂, and 25.4% Ar) at a total pressure of 1 atm and in the temperature range of 180–345 °C. When ceria was used as a support, the turnover rate (TOR) for WGS was 30 times that on alumina supported Pt catalysts. The overall WGS reaction rate (r) on Pt/alumina catalysts as a function of the forward rate (r_f) was found to be: r = r_f(1 − β), where r_f = k_f[CO]^0.1[H₂O]^1.0[CO₂]^−0.1[H₂]^−0.5, k_f is the forward rate constant, β = ([CO₂][H₂])/(K_eq[CO][H₂O]) is the approach to equilibrium, and K_eq is the equilibrium constant for the WGS reaction. The negative apparent reaction orders indicate inhibition of the forward rate by CO₂ and H₂. The surface is saturated with CO on Pt under reaction conditions as confirmed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The small positive apparent reaction order for CO, in concert with the negative order for H₂ and the high CO coverage is explained by a decrease in the heat of adsorption as the CO coverage increases. Kinetic models based on redox-type mechanisms can explain the observed reaction kinetics and can qualitatively predict the changes in CO coverage observed in the DRIFTS study.     

KINETIC AND STRUCTURAL STUDIES OF REGENERATION OF SULFIDED DOLOMITE IN CARBON DIOXIDE I THE FIRST CYCLE REGENERATION

(Communicated by H. L. Toor)

Half-calcined dolomite (CaCO₃ · MgO) is one of the most promising sorbents for desulfurizing fuel gas at high temperatures. For environmental reasons, the spent dolomite must be capable of regeneration for cyclic use. Regeneration by a mixed gas of H₂O/CO₂ has not met with success due mainly to the deterioration of sorbent reactivity with cycling. This research investigates an alternative method of regeneration using CO₂ alone and its application to cyclic use.

Kinetic data for first cycle regeneration are collected in a TGA system at 500 to 950°C and 1 to 21.4 atm. The effects of gas-composition, preconditioning and solid structure are also studied. The results show that regeneration by CO, is equally effective as by H₂O/CO₂ in terms of sorbenl reactivity. More significantly, the sorbent has shown a much slower deterioration upon cycling. Examination of solid structure by SEM and compositional profile of sulfur by XES reveals that the reaction proceeds topochemically above 700°C and homogeneously below 650°C. A transport-reaction model is developed and shown to agree closely with experimental results.