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1.
《Ceramics International》2023,49(10):15276-15283
Ceramic electrolytes based on Yb and Sc stabilized zirconia enable efficient heat transfer and effective ionic conductivity. Here, the design and synthesis of Yb and Sc stabilized zirconia electrolyte is presented for intermediate temperature solid oxide fuel cells (SOFCs). Yb0.12Sc0.08Zr0.8O2–δ was synthesized using the sol-gel method, and a thorough characterization of the electrolyte properties was conducted including structural and electrical properties. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDS) confirmed the composition of the electrolyte. A single-phase cubic structure with a density of 6.7041 ± 0.0008 g cm−3 was obtained. The thermal expansion coefficient in the temperature range from 25 °C to 800 °C is equal to 1.17 × 10−6 K−1. The activation energy of 1.06 eV and 1.15 eV was obtained for the bulk and grain boundary conductivity, respectively. The ionic conductivity of approx. 2.10 S m−1 was achieved at 667 °C, thus it is suitable for efficient ionic conduction at intermediate temperatures.  相似文献   

2.
Yttrium stabilized zirconia (YSZ) used as the state-of-the-art electrolyte for solid oxide fuel cells (SOFCs) requires high temperature (over 800 °C) to realize sufficient oxygen ion conductivity. Thus, the high operational temperature is the main restriction for the commercial process of YSZ-based SOFCs. To obtain decent ionic conductivity at intermediate-low temperatures, Sr-free cathode LaNiO3 is introduced into YSZ to construct a novel LaNiO3-YSZ composite electrolyte, which is sandwiched by two Ni0.8Co0.15Al0.05LiO2-δ (NCAL) electrodes to assemble systematical fuel cells. This device presents an excellent peak output of 1045 mW cm-2 at 600 °C and even 399 mW cm-2 at 450 °C. A series of characterizations indicates that the oxygen ion conductivity of the LaNiO3-YSZ composite is significantly promoted in comparison with that of pure YSZ, and the LaNiO3 component has certain proton conductivity after hydrogenation. Both of the two factors contributes to the superior performance of such devices at intermediate-low temperatures. Furthermore, the sharp decrease in electronic conductivity for LaNiO3 in hydrogen atmosphere combined with Schottky junction at the anode-electrolyte interface eliminates the short-circuiting problem. Our work demonstrates that incorporating Sr-free cathode LaNiO3 into the YSZ electrolyte is an efficient strategy to boost the performance and reduce the operational temperature of YSZ-based SOFCs.  相似文献   

3.
Solid oxide fuel cells (SOFCs) operating at intermediate temperature (500°C‐700°C) provide advantages of better durability, lower cost, and wider target application market. In this work, we have studied Sc2O3 (5‐11 mol%) stabilized ZrO2–CeO2 as a potential solid electrolyte for application in IT‐SOFCs. Lower Sc2O3 doping range than the traditional 11 mol% Sc2O3‐stabilized ZrO2 is an interesting research topic as it could potentially lead to an electrolyte with reduced oxygen vacancy ordering, lower cost, and higher mechanical strength. XRD and Raman spectroscopy was used to study the phase equilibrium in ZrO2–CeO2–Sc2O3 system and impedance spectroscopy was done to estimate the grain, grain boundary, and total ionic conductivities. Maximum for the grain and grain‐boundary conductivities as well as the tetragonal‐cubic phase boundary was found at 8‐9 Sc2O3 mol% in ZrO2‐1 mol% CeO2 system. It is suggested that the addition of 1 mol% CeO2 in the ZrO2 host lattice has improved the phase stability of high‐conductivity cubic and tetragonal phases at the expense of low‐conductivity t′‐ and β‐phases.  相似文献   

4.
《Ceramics International》2017,43(15):11692-11698
Yttria-stabilized zirconia (YSZ) is a common solid electrolyte for solid oxide fuel cells (SOFCs) because of its high electrical conductivity and high ionic transference number in both oxidizing and reducing atmospheres. Samarium doped ceria (SDC) has also been considered as an alternative electrolyte material to YSZ for intermediate temperature SOFC because of its high conductivity at relatively low temperatures. Due to improved ionic conductivity of YSZ at high temperature (~ 800 °C) and good conductivity of SDC in the intermediate temperature range (600–800 °C), the electrical properties of YSZ-SDC composites were investigated. Composites of YSZ and SDC with weight ratio 9.5:0.5, 9:1 and 8.5:1.5 were synthesized via glycine-nitrate route. XRD pattern of the systems revealed the formation of composite phases. Biphasic electrolyte microstructures were observed, in which SDC grains are dispersed in YSZ matrix. Relative density of the compositions was found to be more than 92% to the theoretical density. It was observed that the interface provides a channel for ionic transport, leading to a notable ionic conductivity. With increase in SDC weight ratio the electrical conductivity was found to increase. For weight ratio 8.5:1.5 the electrical conductivity was found to be greater than that of YSZ in the temperature range 400–700 °C. Further, for weight ratio more than 8.5:1.5, conductivity was found to decreases due to the formation of a few other insulating impurity phases. The electrode polarisation was also found to reduce significantly with SDC in the composite electrolyte system. Thus, such composite system may be useful for improving the ionic conductivity of the composite electrolytes.  相似文献   

5.
《Ceramics International》2023,49(4):5637-5645
Yttrium stabilized zirconia (YSZ) as a typical oxygen ionic conductor has been widely used as the electrolyte for solid oxide fuel cell (SOFC) at the temperature higher than 1000 °C, but its poor ionic conductivity at lower temperature (500–800 °C) limits SOFC commercialization. Compared with oxide ionic transport, protons conduction are more transportable at low temperatures due to lower activation energy, which delivered enormous potential in the low-temperature SOFC application. In order to increase the proton conductivity of YSZ-based electrolyte, we introduced semiconductor ZnO into YSZ electrolyte layer to construct heterointerface between semiconductor and ionic conductor. Study results revealed that the heterointerface between ZnO and YSZ provided a large number of oxygen vacancies. When the mass ratio of YSZ to ZnO was 5:5, the fuel cell achieved the best performance. The maximum power density (Pmax) of this fuel cell achieved 721 mW cm?2 at 550 °C, whereas the Pmax of the fuel cell with pure YSZ electrolyte was only 290 mW cm?2. Further investigation revealed that this composite electrolyte possessed poor O2? conductivity but good proton conductivity of 0.047 S cm?1 at 550 °C. The ionic conduction activation energy of 5YSZ-5ZnO composite in fuel cell atmosphere was only 0.62 eV. This work provides an alternative way to improve the ionic conductivity of YSZ-based electrolytes at low operating temperatures.  相似文献   

6.
Z. Ding  R. Guo  W. Guo  Z. Liu  G. Cai  H. Jiang 《Fuel Cells》2016,16(2):252-257
A novel K2NiF4‐type oxide Pr1.7Sr0.3CuO4 (PSCu) is studied to obtain its electrochemical properties as the cathode for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs). The PSCu cathode powder and Ce0.8Sm0.2O1.9 (SDC) electrolyte powder were synthesized by sol‐gel method and glycine‐nitrate method, respectively. The crystal structure of PSCu powder and PSCu‐SDC composite powder were identified with X‐ray diffraction (XRD). It is shown that PSCu belongs to tetragonal K2NiF4‐type and has good chemical compatibility with SDC. The thermal expansion coefficient (TEC) of PSCu is close to that of SDC. The conductivity of PSCu tested with four‐probe method exhibits a semiconductor‐pseudometal transformation at 400–450 °C, where the maximum conductivity of 103.6 S cm−1 is obtained. The polarization test indicates the area specific resistance (ASR) of PSCu decreases with increasing temperature, reaching 0.11 Ω cm2 at 800 °C. The activation energy of oxygen reduction reaction during 600–800 °C is 1.19 eV. The single fuel cell performance test reveals the open circuit voltage (OCV) and resistivity of PSCu reduce with increasing temperature, but the power density ascends with increasing temperature. The maximal power density is 243 mW cm−2 at 800 °C, and the corresponding current density and OCV are 633 mA cm−2 and 0.77 V, respectively.  相似文献   

7.
(Sc2O3)0.1(CeO2)0.01(ZrO2)0.89 (SCSZ) ceramic electrolyte has superior ionic conductivity in the intermediate temperature range (700–800 °C), but it does not exhibit good phase and chemical stability in comparison with 8 mol% Y2O3–ZrO2 (YSZ). To maintain high ionic conductivity and improve the stability in the whole electrolyte, layered structures with YSZ outer layers and SCSZ inner layers were designed. Because of a mismatch of coefficients of thermal expansion and Young's moduli of SCSZ and YSZ phases, upon cooling of the electrolytes after sintering, thermal residual stresses will arise, leading to a possible strengthening of the layered composite and, therefore, an increase in the reliability of the electrolyte. Laminated electrolytes with three, four, and six layers design were manufactured using tape‐casting, lamination, and sintering techniques. After sintering, while the thickness of YSZ outer layers remained constant at ∼30 μm, the thickness of the SCSZ inner layer varied from ∼30 μm for a Y–SC–Y three‐layered electrolyte, ∼60 μm for a Y–2SC–Y four‐layered electrolyte, and ∼120 μm for a Y–4SC–Y six‐layered electrolyte. The microstructure, crystal structure, impurities present, and the density of the sintered electrolytes were characterized by scanning and transmission electron microscopy, X‐ray and neutron diffraction, secondary ion mass spectroscopy, and water immersion techniques.  相似文献   

8.
《Ceramics International》2021,47(23):32490-32504
The shortcomings of high-temperature solid oxide fuel cells necessitate research on SOFCs designs that are capable of operation at intermediate temperatures (600–800 °C), the so-called intermediate-temperature SOFCs. One of the limitations for the efficient operation of these fuel cells lies in insufficient ionic conductivity of the electrolyte material. This review briefly covers the types of ceramic electrolytes used in intermediate-temperature SOFCs and focuses on scandia-stabilized zirconia (ScSZ) electrolytes. It explores possibilities of control of phase stability and ionic conductivity of ScSZ by co-doping by various oxides, such as ceria, bismuth oxide, yttria, ytterbia, and several other co-dopants. It also covers a range of novel techniques applied to preparation of ScSZ electrolytes, which can be used to influence microstructure and phase composition of the electrolytes. The recommendations on the optimal ScSZ co-doping scheme are developed in the course of the present work.  相似文献   

9.
Ionic conduction of oxygen in the ceria-samarium oxide system was investigated as a function of temperature, partial pressure of oxygen and the oxide composition, together with its crystal structure, density and defect structure. The ionic conductivity of (CeO2)1–x(SmO1.5)x was the highest in ZrO2-, ThO2- and CeO2-based oxide systems. The system CeO2-SmO1.5 consisted of the solid solution with a fluorite structure atx<50 at.%. The ionic transference number was nearly unity between 600 and 900°C. With an increase in Sm2O3 content, the ionic conductivity gradually decreased due to a decrease in mobility of oxygen ions. The samarium oxide-doped ceria was less reducible than pure and alkaline earth oxide-doped ceria.  相似文献   

10.
Low temperature densification and improving the ionic conductivity of doped ceria electrolyte is important for the realization of efficient intermediate temperature solid oxide fuel cell system. Herein, we report the effect of lithium co-doping (1, 3, 5 and 7?mol%) in 20?mol% samarium doped ceria on the low temperature sinterability and conductivity. The synthesized nanoparticles by citrate-nitrate combustion method showed a decrease in lattice parameter and increase in oxygen vacancy with lithium content after calcination due to the substitution of Li+ into CeO2 lattice. Upon sintering at 900?°C, the density improved and reached a maximum value of 98.6% for 5% Li which exhibited a dense microstructure than at 7% Li. 5%Li co-doping exhibited the best conductivity of 3.65?×?10?04–1.81?×?10?3 S?cm?1 in the operative temperature range of IT-SOFC (550–700?°C).Our results demonstrate the significance of lithium as co-dopant for efficient low temperature sintering as well as improving the electrolyte conductivity.  相似文献   

11.
The performance of low-to-intermediate temperature (400–800?°C) solid oxide fuel cells (SOFCs) depends on the properties of electrolyte used. SOFC performance can be enhanced by replacing electrolyte materials from conventional oxide ion (O2-) conductors with proton (H+) conductors because H+ conductors have higher ionic conductivity and theoretical electrical efficiency than O2- conductors within the target temperature range. Electrolytes based on cerate and/or zirconate have been proposed as potential H+ conductors. Cerate-based electrolytes have the highest H+ conductivity, but they are chemically and thermally unstable during redox cycles, whereas zirconate-based electrolytes exhibit the opposite properties. Thus, tailoring the properties of cerate and/or zirconate electrolytes by doping with rare-earth metals has become a main concern for many researchers to further improve the ionic conductivity and stability of electrolytes. This article provides an overview on the properties of four types of cerate and/or zirconate electrolytes including cerate-based, zirconate-based, single-doped ceratezirconate and hybrid-doped ceratezirconate. The properties of the proton electrolytes such as ionic conductivity, chemical stability and sinterability are also systematically discussed. This review further provides a summary of the performance of SOFCs operated with cerate and/or zirconate proton conductors and the actual potential of these materials as alternative electrolytes for proton-conducting SOFC application.  相似文献   

12.
Diffusion behavior of Ni during high temperature co-sintering was quantitatively investigated for anode-supported solid oxide fuel cells (SOFCs) that had BaZr0.1Ce0.7Y0.1Yb0.1O3?δ (BZCYYb) proton-conducting electrolyte and NiO-BZCYYb anode. Although diffused Ni in such SOFCs effectively acts as a sintering aid to densify the BZCYYb electrolyte layer, it often negatively affects the electrolyte conductivity. In the present study, field emission electron probe microanalysis (with wavelength dispersive X-ray spectroscopy) clearly revealed that Ni diffused into the BZCYYb electrolyte layer, and that the amount of diffused Ni increased with increasing co-sintering temperature. In particular, relatively high Ni concentration within the electrolyte layer was observed near the electrolyte/anode interface, e.g., approximately 1.5 and 2.8 wt% at co-sintering temperature of 1300 and 1400 °C, respectively. Electrochemical measurements showed that, compared with the lower co-sintering temperatures (1300–1350 °C), the highest co-sintering temperature (1400 °C) led to the highest ohmic resistance because of lower electrolyte conductivity. These results suggest that high co-sintering temperature causes excessive Ni diffusion into the BZCYYb electrolyte layer, thus degrading the intrinsic electrolyte conductivity and consequently degrading the SOFC performance.  相似文献   

13.
《Ceramics International》2020,46(14):22727-22732
Nd0.2Ce0.8O3-δ (NDC) is one of the most common solid electrolyte materials used in solid oxide fuel cells (SOFCs). However, the densification temperature of NDC electrolyte is above 1400 °C. In this work, Bi2O3 and CoO sintering aids were individually or synergistically added to Nd0.2Ce0.8O3-δ (NDC) electrolytes through the sol-gel method to lower its sintering temperature. Effects of Bi2O3-CoO dual sintering aid on the sintering behavior, phase composition, microstructure, and electrochemical properties of NDC electrolyte were all investigated. The data revealed that Bi2O3-CoO dual-sintering aid doped-NDC (labeled as NDC-CB) possessed high density and superior conductivity at low temperatures, better than that of Bi2O3 or CoO single sintering aid. NDC electrolyte doped with Bi2O3-CoO dual-sintering aid achieved highest relative density of 95.3% at 1100 °C and total conductivity of 5.765 × 10-2 S cm-1 at 800 °C. Furthermore, NDC-CB displayed excellent physical and chemical compatibility with La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF) cathode and NiO-NDC anode. Oxygen reduction reaction at LSCF/NDC-CB interface was improved by about 40% when compared to NDC. In sum, Bi2O3-CoO looks promising as dual-sintering additive for lowing sintering temperature and increasing electrical conductivity of NDC. Therefore, NDC-CB might be potential electrolyte for future intermediate-temperature solid oxide fuel cells (IT-SOFCs).  相似文献   

14.
It has been demonstrated that the samarium and neodymium codoped ceria (Ce0.8Sm0.1Nd0.1O2?δ abbreviated SNDC) shows high ionic conductivity at intermediate operating temperature (0.012 S/cm at 500°C. However, the poor mechanical properties limited its applications in solid fuel cells and oxygen sensors. Present research reports an approach to improve the mechanical properties of SNDC by adding another kind of oxide solid electrolyte, the apatite‐type lanthanum silicate (La10Si6O27 abbreviated LSO). The SNDC/LSO composites were prepared by mixing the powders with different proportion, and sintered at 1600°C. Their structure, morphology, mechanical, and electrical properties were characterized. It was found that with the 5wt%‐7wt% LSO addition, both the flexural strength and the fracture toughness were improved. The improvement of flexural strength for the SNDC reached as high as 71%. It is also seen that the ionic conductivity of SNDC was enhanced with the adding of 5wt% LSO. The enhanced mechanical properties and electrical conductivity of SNDC/LSO composites make them a promising candidates for high‐performance SOFCs and oxygen sensors.  相似文献   

15.
Electrolyte powders with low sintering temperature and high-ionic conductivity can considerably facilitate the fabrication and performance of solid oxide fuel cells (SOFCs). Gadolinia-doped ceria (GDC) is a promising electrolyte for developing intermediate- and low-temperature (IT and LT) SOFCs. However, the conventional sintering temperature for GDC is usually above 1200 °C unless additives are used. In this work, a nanocrystalline powder of GDC, (10 mol% Gd dopant, Gd0.1Ce0.9O1.95) with low-sintering temperature has been synthesized using ammonium benzoate as a novel, environmentally friendly and cost-effective precursor/precipitant. The synthesized benzoate powders (termed washed- and non-washed samples) were calcined at a relatively low temperature of 500 °C for 6 h. Physicochemical characteristics were determined using thermal analysis (TG/DTA), Raman spectroscopy, FT-IR, SEM/EDX, XRD, nitrogen absorptiometry, and dilatometry. Dilatometry showed that the newly synthesized GDC samples (washed and non-washed routes) start to shrink at temperatures of 500 and 600 °C (respectively), reaching their maximum sintering rate at 650 and 750 °C. Sintering of pelletized electrolyte substrates at the sintering onset temperature for commercial GDC powder (950 °C) for 6 h, showed densification of washed- and non-washed samples, obtaining 97.48 and 98.43% respectively, relative to theoretical density. The electrochemical impedance spectroscopy (EIS) analysis for the electrolyte pellets sintered at 950 °C showed a total electrical conductivity of 3.83 × 10?2 and 5.90 × 10?2 S cm?1 (under air atmosphere at 750 °C) for washed- and non-washed samples, respectively. This is the first report of a GDC synthesis, where a considerable improvement in sinterability and electrical conductivity of the product GDC is observed at 950 °C without additives addition.  相似文献   

16.
Rare-earth-doped CeO2 have been found to enhance the ionic conductivity of ceria-based electrolytes in solid oxide fuel cells (SOFCs) because trivalent rare-earth cations can spontaneously induce oxygen vacancies. Experimentally, it has been shown that the rare-earth elements La, Nd, Sm, Gd, Tb, Dy, and Er are likely candidates for electrolyte doping. However, the performances differ for the trivalent cations, suggesting that rare-earth doping plays multiple roles instead of only increasing the oxygen vacancies. First-principles calculations are performed on a series of rare-earth-doped CeO2 systems to study the doping effects on the ionic conductivity. It is found that the migration barriers of the oxygen ions are significantly different for the different dopants and depend on the dopant's radius. Gd-, Dy-, Er-, and Tb-doping results in small migration barriers and enhances the ionic conductivity. We also calculate the formation energies (Evac) of the intrinsic oxygen vacancies due to thermal excitation. It is found that the Sm- and Gd-doped ceria systems have the smallest Evac values. The electronic structures indicate that the band gaps are not sensitive to the dopant elements but are very sensitive to the fluctuations in the oxygen content.  相似文献   

17.
Co-doped CeO2 (Ba0.10Ga0.10Ce0.80O3–δ) was synthesized via a cost-effective co-precipitation technique, and the electrochemical properties of the solid oxide fuel cell were studied. The microstructural and surface morphological properties were investigated by XRD and SEM, respectively. The structure of the prepared material was found to be cubic fluorite with an average crystallite size of 36?nm. The ionic conductivity of the prepared BGC (Ba0.10Ga0.10Ce0.80O3–δ) electrolyte material was measured as 0.071?S?cm?1. The activation energy was found to be 0.46?eV using an Arrhenius plot. The maximum power density and current density achieved were 375?mW?cm?2 and 893?mA?cm?2, respectively, at 650?°C with hydrogen as a fuel. This study shows that the prepared co-doped electrolyte material could be used as a potential electrolyte to lower the operating temperature of solid oxide fuel cells.  相似文献   

18.
《Ceramics International》2022,48(7):9673-9680
Solid oxide fuel cells (SOFCs) have strong potential for next-generation energy conversion systems. However, their high processing temperature due to multi-layer ceramic components has been a major challenge for commercialization. In particular, the constrained sintering effect due to the rigid substrate in the fabrication process is a main reason to increase the sintering temperature of ceramic electrolyte. Herein, we develop a bi-layer sintering method composed of a Bi2O3 sintering sacrificial layer and YSZ main electrolyte layer to effectively lower the sintering temperature of the YSZ electrolyte even under the constrained sintering conditions. The Bi2O3 sintering functional layer applied on the YSZ electrolyte is designed to facilitate the densification of YSZ electrolyte at the significantly lowered sintering temperature and is removed after the sintering process to prevent the detrimental effects of residual sintering aids. Subsequent sublimation of Bi2O3 was confirmed after the sintering process and a dense YSZ monolayer was formed as a result of the sintering functional layer-assisted sintering process. The sintering behavior of the Bi2O3/YSZ bi-layer system was systematically analyzed, and material properties including the microstructure, crystallinity, and ionic conductivity were analyzed. The developed bi-layer sintered YSZ electrolyte was employed to fabricate anode-supported SOFCs, and a cell performance comparable to a conventional high temperature sintered (1400 °C) YSZ electrolyte was successfully demonstrated with significantly reduced sintering temperature (<1200 °C).  相似文献   

19.
Samarium-doped CeO2 is a leading electrolyte for applications in solid oxide fuel cells (SOFCs), which requires a typical sintering temperature of 1400–1600 °C. In this work, fully dense CeO2 ceramics doped with 10–20 at.% samarium have been fabricated by a simple polyol process. The XRD and SEM results show that a complete solid solution between CeO2 and samarium was obtained at the sintering temperature of 1300 °C. And also the densification temperature is significantly lower than those (1400–1600 °C) reported for the SDC powders processed by modified sol–gel process and hydrothermal treatment. The resultant ceramics show the sizes of ultrafine grain are lower than 1 μm.  相似文献   

20.
《Ceramics International》2017,43(14):10934-10938
The ionic conductivity and the crystalline structure of ZrO2−10 mol% Sc2O3- x mol% Nb2O5 solid electrolytes were investigated for x=0.25, 0.5 and 1. Dense specimens with relative densities higher than 95% were prepared by solid state reaction and sintered at 1500 °C for 5 h. Full stabilization of the cubic structure at room temperature was obtained for compounds with x=0.5 and 1, whereas the cubic and rhombohedric structures coexist for x=0.25. The highest ionic conductivity in codoped system was found for specimen containing 0.5 mol% niobium pentoxide, with the same order of magnitude as that of the parent solid electrolyte (zirconia-10 mol% scandia) in the high temperature range (above 600 °C). Preliminary investigation on phase stability shows that the isothermal conductivity of the new solid electrolyte remained constant up to 100 h at 600 °C. Niobium pentoxide addition was found to improve the overall ionic conductivity of zirconia-scandia solid electrolyte.  相似文献   

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