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1.
Protonic ceramic membrane fuel cells (PCMFCs) based on proton-conducting electrolytes have attracted much attention because of many advantages, such as low activation energy and high energy efficiency. BaZr0.1Ce0.7Y0.2O3−δ (BZCY7) electrolyte based PCMFCs with stable Ba0.5Sr0.5Zn0.2Fe0.8O3−δ (BSZF) perovskite cathode were investigated. Using thin membrane BZCY7 electrolyte (about 15 μm in thickness) synthesized by a modified Pechini method on NiO-BZCY7 anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.015 V, a maximum power density of 486 mW cm−2, and a low polarization resistance of the electrodes of 0.08 Ω cm2 was achieved at 700 °C. The results have indicated that BZCY7 proton-conducting electrolyte with BSZF cathode is a promising material system for the next generation solid oxide fuel cells.  相似文献   

2.
A novel BaCe0.4Zr0.3 Sn0.1Y0.2O3−δ (BSY) electrolyte membrane with thickness of 20 μm was fabricated on NiO-based anode substrate via a one-step all-solid-state method followed by a co-sintering at 1450 °C for 5 h. Chemical stability test demonstrated that BSY electrolyte showed adequate chemical stability against CO2 and H2O at intermediate temperature. Besides, the doping of Sn also enhanced the conductivity in humidified hydrogen. With Nd0.7Sr0.3MnO3−σ cathode and hydrogen fuel, the fuel cell generated maximum output of 320, 185 and 105 mW cm−2 at 700, 650 and 600 °C, respectively. The interfacial resistance of the fuel cell was studied under open circuit conditions and the short-term cell performance also confirmed the stability of BSY electrolyte membrane.  相似文献   

3.
The structure, conductivity and water uptake of the oxygen-deficient perovskite-type compound Ba4Ca2Ta2O11 have been investigated. Ba4Ca2Ta2O11 crystallizes in the cryolite structure (cubic, Fm3m SG) with a = 8.4508(2) Å, under dry air. The compound can be partially hydrated up to a maximum water content of approximately 0.52 mol H2O per mol Ba4Ca2Ta2O11. In moist air, the structure symmetry becomes monoclinic (C2/m) and the temperature dependence of total conductivity shows a different behavior because of changes in transport mechanism. Three regions can be observed as a function of temperature. For the low temperature range 200–400 °C, the protonic conduction is prevailing with an activation energy EA = 0.85 eV. In the intermediate temperature range (400–600 °C), O2− anionic and protonic conductions are mixed with an activation energy EA = 0.45 eV and in the third region, for temperatures above 600 °C, O2−conduction is prevailing with an activation energy EA = 0.85 eV.  相似文献   

4.
The formation of perovskite nanopowders of the common proton-conducting, electrolyte material Ba(Zr1−xYx)O3−δ is demonstrated by room temperature mechanosynthesis for the compositional range x=0, 0.058 and 0.148. This is achieved with a planetary ball mill at 650 rpm in zirconia vials, starting from BaO2 with ZrO2, (ZrO2)0.97(Y2O3)0.03 or (ZrO2)0.92(Y2O3)0.08 precursors, respectively. Powder X-ray diffraction (XRD) reveals the formation of the perovskite phase in the early stages of milling with phase purity being achieved after milling times of 240 min for composition x=0.058 whereas 420 min is necessary for composition x=0.148. In contrast, traces of ZrO2 are apparent in composition x=0 even after milling times of 420 min. The use of BaCO3 as precursor does not allow the formation of the perovskite phase for any composition. The perovskite crystallites are spherical in shape with an average size determined from XRD of ca. 30 nm in agreement with transmission electron microscopy observations. FTIR spectra demonstrate that contamination levels of BaCO3 in the mechanosynthesized powders are very low. The spherical shape and nanoscale of the crystallites allow densification levels that are highly competitive when compared to BaZrO3-based materials formed by alternative synthesis techniques documented in the literature.  相似文献   

5.
The phase relations in the system In2O3–TiO2–MgO at 1100 and 1350°C are determined by a classical quenching method. In this system, there are four pseudobinary compounds, In2TiO5, MgTi2O5 (pseudobrookite type), MgTiO3 (ilmenite type), and Mg2TiO4 (spinel type) at 1100°C. At 1350°C, in addition to these compounds there exist a spinel-type solid solution Mg2−xIn2xTi1−xO4 (0≤x≤1) and a compound In6Ti6MgO22 with lattice constants a=5.9236(7) Å, b=3.3862(4) Å, c=6.3609(7) Å, β=108.15(1)°, and q=0.369, which is isostructural with the monoclinic In3Ti2FeO10 in the system In2O3–TiO2–MgO. The relation between the lattice constants of the spinel phase and the composition nearly satisfies Vegard's law. In6Ti6MgO22 extends a solid solution range to In20Ti17Mg3O67 with lattice constants of a=5.9230(5) Å, b=3.3823(3) Å, c=6.3698(6) Å, β=108.10(5)°, and q=0.360. The distributions of constituent cations in the solid solutions are discussed in terms of their ionic radius and site preference effect.  相似文献   

6.
Differential scanning calorimetry and high temperature oxide melt solution calorimetry are used to study enthalpy of phase transition and enthalpies of formation of Cu2P2O7 and Cu3(P2O6OH)2. α-Cu2P2O7 is reversibly transformed to β-Cu2P2O7 at 338–363 K with an enthalpy of phase transition of 0.15 ± 0.03 kJ mol−1. Enthalpies of formation from oxides of α-Cu2P2O7 and Cu3(P2O6OH)2 are −279.0 ± 1.4 kJ mol−1 and −538.8 ± 2.7 kJ mol−1, and their standard enthalpies of formation (enthalpy of formation from elements) are −2096.1 ± 4.3 kJ mol−1 and −4302.7 ± 6.7 kJ mol−1, respectively. The presence of hydrogen in diphosphate groups changes the geometry of Cu(II) and decreases acid–base interaction between oxide components in Cu3(P2O6OH)2, thus decreasing its thermodynamic stability.  相似文献   

7.
LiFe0.5Ti1.5O4 was synthesized by solid-state reaction carried out at 900 °C in flowing argon atmosphere, followed by rapid quenching of the reaction product to room temperature. The compound has been characterized by X-ray powder diffraction (XRD) and 57Fe Mössbauer effect spectroscopy (MES). It crystallizes in the space group P4332, a = 8.4048(1) Å. Results from Rietveld structural refinement indicated 1:3 cation ordering on the octahedral sites: Li occupies the octahedral (4b) sites, Ti occupies the octahedral (12d) sites, while the tetrahedral (8c) sites have mixed (Fe/Li) occupancy. A small, about 5%, inversion of Fe on the (4b) sites has been detected. The MES data is consistent with cation distribution and oxidation state of Fe, determined from the structural data.The title compound is thermally unstable in air atmosphere. At 800 °C it transforms to a mixture of two Fe3+ containing phases – a face centred cubic spinel Li(1+y)/2Fe(5−3y)/2TiyO4 and a Li(z−1)/2Fe(7−3z)/2TizO5 – pseudobrookite. The major product of thermal treatment at 1000 °C is a ramsdellite type lithium titanium iron(III) oxide, accompanied by traces of rutile and pseudobrookite.  相似文献   

8.
Asymmetrical thin membranes of SrCe0.95Y0.05O3−δ (SCY) were prepared by a conventional and cost-effective dry pressing method. The substrate consisted of SCY, NiO and soluble starch (SS), and the top layer was the SCY. NiO was used as a pore former and soluble starch was used to control the shrinkage of the substrate to match that of the top layer. Crack-free asymmetrical thin membranes with thicknesses of about 50 μm and grain sizes of 5–10 μm were successfully pressed on to the substrates. Hydrogen permeation fluxes (JH2) of these thin membranes were measured under different operating conditions. At 950 °C, JH2 of the 50 μm SCY asymmetrical membrane towards a mixture of 80% H2/He was as high as 7.6 × 10−8 mol/cm2 s, which was about 7 times higher than that of the symmetrical membranes with a thickness of about 620 μm. The hydrogen permeation properties of SCY asymmetrical membranes were investigated and activation energies for hydrogen permeation fluxes were calculated. The slope of the relationship between the hydrogen permeation fluxes and the thickness of the membranes was −0.72, indicating that permeation in SCY asymmetric membranes was controlled by both bulk diffusion and surface reaction in the range investigated.  相似文献   

9.
Remarkable power density was obtained for anode-supported solid oxide fuel cells (SOFCs) based on La0.8Sr0.2Ga0.8Mg0.2O3−δ (LSGM) electrolyte films, fabricated following an original procedure that allowed avoiding undesired reactions between LSGM and electrode materials, especially Ni. Electrophoretic deposition (EPD) was used for the fabrication of 30 μm-thick electrolyte films. Anode supports were made of La0.4Ce0.6O2−x (LDC). The LSGM powder was deposited by EPD on an LDC green tape-cast membrane added with carbon powder, both as pore former and substrate conductivity booster. A subsequent co-firing step at 1490 °C produced dense electrolyte films on porous LDC skeletons. Then, a La0.8Sr0.2Fe0.8Co0.2O3−δ (LSFC) cathode was applied by slurry-coating and calcined at 1100 °C. Finally, the porous LDC layer was impregnated with molten Ni nitrate to obtain, after calcination at 900 °C, a composite NiO–LDC anode. Maximum power densities of 780, 450, 275, 175, and 100 mW/cm2 at 700, 650, 600, 550, and 500 °C, respectively, were obtained using H2 as fuel and air as oxidant, demonstrating the success of the processing strategy. As a comparison, electrolyte-supported SOFCs made of the same materials were tested, showing a maximum power density of 150 mW/cm2 at 700 °C, more than 5 times smaller than the anode-supported counterpart.  相似文献   

10.
We have successfully synthesized a high-purity polycrystalline sample of tetragonal Li7La3Zr2O12. Single crystals have been also grown by a flux method. The single-crystal X-ray diffraction analysis verifies that tetragonal Li7La3Zr2O12 has the garnet-related type structure with a space group of I41/acd (no. 142). The lattice constants are a=13.134(4) Å and c=12.663(8) Å. The garnet-type framework structure is composed of two types of dodecahedral LaO8 and octahedral ZrO6. Li atoms occupy three crystallographic sites in the interstices of this framework structure, where Li(1), Li(2), and Li(3) atoms are located at the tetrahedral 8a site and the distorted octahedral 16f and 32g sites, respectively. The structure is also investigated by the Rietveld method with X-ray and neutron powder diffraction data. These diffraction patterns are identified as the tetragonal Li7La3Zr2O12 structure determined from the single-crystal data. The present tetragonal Li7La3Zr2O12 sample exhibits a bulk Li-ion conductivity of σb=1.63×10−6 S cm−1 and grain-boundary Li-ion conductivity of σgb=5.59×10−7 S cm−1 at 300 K. The activation energy is estimated to be Ea=0.54 eV in the temperature range of 300–560 K.  相似文献   

11.
Cu2+ binding on γ-Al2O3 is modulated by common electrolyte ions such as Mg2+, , and in a complex manner: (a) At high concentrations of electrolyte ions, Cu2+ uptake by γ-Al2O3 is inhibited. This is partially due to bulk ionic strength effects and, mostly, due to direct competition between Mg2+ and Cu2+ ions for the SO surface sites of γ-Al2O3. (b) At low concentrations of electrolyte ions, Cu2+ uptake by γ-Al2O3 can be enhanced. This is due to synergistic coadsorption of Cu2+ and electrolyte anions, and . This results in the formation of ternary surface species (SOH2SO4Cu)+, (SOH2PO4Cu), and (SOH2HPO4Cu)+ which enhance Cu2+ uptake at pH < 6. The effect of phosphate ions may be particularly strong resulting in a 100% Cu uptake by the oxide surface. (c) EPR spectroscopy shows that at pH  pHPZC, Cu2+ coordinates to one SO group. Phosphate anions form stronger, binary or ternary, surface species than sulfate anions. At pH  pHPZC Cu2+ may coordinate to two SO groups. At pH  pHPZC electrolyte ions and are bridging one O-atom from the γ-Al2O3 surface and one Cu2+ ion forming ternary [γ-Al2O3/elecrolyte/Cu2+] species.  相似文献   

12.
Li2O–Cr2O3–GeO2–P2O5 based glasses were synthesized by a conventional melt-quenching method and successfully converted into glass-ceramics through heat treatment. Experimental results of DTA, XRD, ac impedance techniques and FESEM indicated that Li1.4Cr0.4Ge1.6(PO4)3 glass-ceramics treated at 900 °C for 12 h in the Li1 + xCrxGe2 − x(PO4)3 (x = 0–0.8) system exhibited the best glass stability against crystallization and the highest ambient conductivity value of 6.81 × 10−4 S/cm with an activation energy as low as 26.9 kJ/mol. In addition, the Li1.4Cr0.4Ge1.6(PO4)3 glass-ceramics displayed good chemical stability against lithium metal at room temperature. The good thermal and chemical stability, excellent conducting property, easy preparation and low cost make it promising to be used as solid-state electrolytes for all-solid-state lithium batteries.  相似文献   

13.
Values of partial conductions (ionic: protonic, oxygen, hole) and their activation energies in LaYO3 are determined at 700–1050°C, pO2 ranging from air to 10−15 Pa, and pH2O = 0.04–13.5 kPa for different versions of doping with calcium (when introduced into the lanthanum or yttrium sublattices, or into both sublattices simultaneously). The conductivity increases in the series La0.97Ca0.03YO3 − α < LaY0.97Ca0.03O3 − α < La0.985Y0.985Ca0.03O3 − α, which means that the stoichiometric composition with a 1 : 1 ratio between Y and La has the highest conductivity.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 610–615.Original Russian Text Copyright © 2005 by Balakireva, Stroeva, Gorelov.  相似文献   

14.
The double-perovskite Sr2NiMoO6−δ (SNMO) was investigated as an anode material of a solid oxide fuel cell (SOFC). With a 300 μm thick La0.9Sr0.1Ga0.8Mg0.2O3−σ (LSGM) disk as electrolyte and Ba0.5Sr0.5Co0.8Fe0.2O3−δ as the cathode, the SNMO anode showed power densities of 819 mW cm−2 in hydrogen at 1123 K. Moreover, there was no buffer layer between anode and electrolyte, which would reduce design techniques and save design cost. After test no chemical reaction was discovered between anode and electrolyte. The anode exhibited good conductivity and the value was around 60 S cm−1 in H2. Also it had almost linear thermal expansion from room temperature to 1253 K and the average thermal expansion coefficient was about 12.14 × 10−6 K−1, which was quite close to that of La0.9Sr0.lGa0.8Mg0.2O3 (12.17 × 10−6 K−1) electrolyte.  相似文献   

15.
The thermal evolution and structural properties of fluorite-related δ-Bi2O3-type Bi9ReO17 were studied with variable temperature neutron powder diffraction, synchrotron X-ray powder diffraction and electron diffraction. The thermodynamically stable room-temperature crystal structure is monoclinic P21/c, a=9.89917(5), b=19.70356(10), c=11.61597(6) Å, β=125.302(2)° (Rp=3.51%, wRp=3.60%) and features clusters of ReO4 tetrahedra embedded in a distorted Bi–O fluorite-like network. This phase is stable up to 725 °C whereupon it transforms to a disordered δ-Bi2O3-like phase, which was modeled with δ-Bi2O3 in cubic Fmm with a=5.7809(1) Å (Rp=2.49%, wRp=2.44%) at 750 °C. Quenching from above 725 °C leads to a different phase, the structure of which has not been solved but appears on the basis of spectroscopic evidence to contain both ReO4 tetrahedra and ReO6 octahedra.  相似文献   

16.
We report that glass–ceramic Li2S–P2S5 electrolytes can be prepared by a single step ball milling (SSBM) process. Mechanical ball milling of the xLi2S·(100 − x)P2S5 system at 55 °C produced crystalline glass–ceramic materials exhibiting high Li-ion conductivity over 10−3 S cm−1 at room temperature with a wide electrochemical stability window of 5 V. Silicon nanoparticles were evaluated as anode material in a solid-state Li battery employing the glass–ceramic electrolyte produced by the SSBM process and showed outstanding cycling stability.  相似文献   

17.
Fluorescein (HFin) emitted strong and stable room temperature phosphorescence (RTP) on filter paper after set at 50 °C for 10 min using Li+ as the ion perturber. HFin existed as Fin when the pH value was in the range of 5.45–7.36. Fin could react with [Cu(BPY)2]2+ (BPY: α,α-bipyridyl) to produce ion association complex [Cu(BPY)2]2+·[(Fin)2]2−, which could enhance the RTP signal of Hfin. In the presence of bovine serum albumin (BSA), the –COOH group of Fin in the [Cu(BPY)2]2+·[(Fin)2]2− could react with the –NH2 group of BSA to form the ion association complex [Cu(BPY)2]2+·[(Fin-BSA)2]2−, which contained –CO–NH– bond. This complex could sharply enhance the RTP signal of Hfin and the ΔIp was directly proportional to the content of BSA. According to the facts above, a new solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace protein had been established using the ion association complex [Cu(BPY)2]2+·[(Fin)2]2−as a phosphorescent probe. This method had wide linear range (0.40 × 10−9–280 × 10−9 mg l−1), high sensitivity (the detection limit (LD) was 1.4 × 10−10 mg l−1), good precision (RSD: 3.4–4.9%) and high selectivity (the allowed concentration of coexistent ions or coexistent materials was high). It had been applied to the determination of the content of protein in 10 kinds of real samples, and the result agreed well with pyrocatechol violet-Mo (VI) method (P.V.M.M.), which indicated it had high accuracy. Meanwhile, reaction mechanism for the determination of trace protein with [Cu(BPY)2]2+·[(Fin)2]2− phosphorescent probe was also discussed. The academic thought of this research could not only be used to develop many kinds of ion association complex phosphorescent probes, but also provided a new way to promote the sensitivity of SS-RTP.  相似文献   

18.
A new class of M(II)–Hg(II) (M=Cu(II), Co(II), Ni(II)) mixed-metal coordination polymers, Cu(2-pyrazinecarboxylate)2HgCl2 (4), [Co(2-pyrazinecarboxylate)2(HgCl2)2] · 0.61H2O (5) and [Ni(2-pyrazinecarboxylate)2(HgCl2)2] · 0.77H2O (6), have been prepared by self assembly of metal-containing building blocks, M(2-pyrazinecarboxylate)2 · (H2O)2(M=Cu(II), Co(II), Ni(II)), with HgCl2. Compounds 46 were characterized fully by IR, elemental analysis and single crystal X-ray diffraction. Compound 4 crystallized in the monoclinic space group C2/c, with a=17.916(5) Å, b=7.223(2) Å, c=13.335(4) Å, β=128.726(3)°, V=1346.2(6) Å3, Z=4. It contains alternating Hg(II) and Cu(II) metal centers that are cross-linked by 2-pyrazinecarboxylate spacers and chlorine co-ligands to generate a unique three-dimensional Hg(II)–Cu(II) mixed metal framework. Compound 5 crystallized in the triclinic space group P , with a=6.3879(7) Å, b=6.6626(8) Å, c=13.2286(15) Å, α=96.339(2)°, β=91.590(2)°, γ=113.462(2)°, V=511.71(10) Å3, Z=1. Compound 6 also crystallized in the triclinic space group P , with a=6.3543(8) Å, b=6.6194(8) Å, c=13.2801(16) Å, α=96.449(2)°, β=92.263(2)°, γ=113.541(2)°, V=506.67(11) Å3, Z=1. Compounds 5 and 6 are isostructural and in the solid state the Hg(II)M(II)Hg(II) units are connected by Hg2Cl2 linkages to produce a novel M(II)–Hg(II) (M=Co(II), Ni(II)) zigzag mixed-metal chain, in which a new type of M–M′–M′–M array was observed. The metal containing building blocks, M(2-pyrazinecarboxylate)2 · (H2O)2 (M=Cu(II), Co(II), Ni(II)), exhibit different connectivities to HgCl2 depending on the metal cation contained within them.  相似文献   

19.
Two oxoborates, (Pb3O)2(BO3)2MO4 (M=Cr, Mo), have been prepared by solid-state reactions below 700 °C. Single-crystal XRD analyses showed that the Cr compound crystallizes in the orthorhombic group Pnma with a=6.4160(13) Å, b=11.635(2) Å, c=18.164(4) Å, Z=4 and the Mo analog in the group Cmcm with a=18.446(4) Å, b=6.3557(13) Å, c=11.657(2) Å, Z=4. Both compounds are characterized by one-dimensional chains formed by corner-sharing OPb4 tetrahedra. BO3 and CrO4 (MoO4) groups are located around the chains to hold them together via Pb–O bonds. The IR spectra further confirmed the presence of BO3 groups in both structures and UV–vis diffuse reflectance spectra showed band gaps of about 1.8 and 2.9 eV for the Cr and Mo compounds, respectively. Band structure calculations indicated that (Pb3O)2(BO3)2MoO4 is a direct semiconductor with the calculated energy gap of about 2.4 eV.  相似文献   

20.
D.F. Zhou  Y.J. Xia  J.X. Zhu  J. Meng   《Solid State Sciences》2009,11(9):1587-1591
Ce6−xDyxMoO15−δ (0.0 ≤ x ≤ 1.8) were synthesized by modified sol–gel method. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The XRD patterns showed that the materials were single phase with a cubic fluorite structure. Impedance spectroscopy measurement in the temperature range between 350 °C and 800 °C indicated a sharp increase in conductivity for the system containing small amount of Dy2O3. The Ce5.6Dy0.4MoO15−δ detected to be the best conducting phase with the highest conductivity (σt = 8.93 × 10−3 S cm−1) is higher than that of Ce5.6Sm0.4MoO15−δ (σt = 2.93 × 10−3 S cm−1) at 800 °C, and the corresponding activation energy of Ce5.6Dy0.4MoO15−δ (0.994 eV) is lower than that of Ce5.6Sm0.4MoO15−δ (1.002 eV).  相似文献   

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