CN103319182B - High-performance solid oxide electrolytic tank support - Google Patents
High-performance solid oxide electrolytic tank support Download PDFInfo
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- CN103319182B CN103319182B CN201310279789.4A CN201310279789A CN103319182B CN 103319182 B CN103319182 B CN 103319182B CN 201310279789 A CN201310279789 A CN 201310279789A CN 103319182 B CN103319182 B CN 103319182B
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- 239000007787 solid Substances 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 claims abstract description 25
- 230000008014 freezing Effects 0.000 claims abstract description 24
- 238000007710 freezing Methods 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000007767 bonding agent Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 abstract 1
- 230000010287 polarization Effects 0.000 abstract 1
- 239000011343 solid material Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000007789 gas Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 8
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a novel high-performance solid oxide electrolytic tank support which belongs to the technical field of a solid oxide electrolytic tank. The support is provided with a continuous gradient porous structure with the porosity of 60%-80%. A support preparation method comprises the following steps of: preparing water-based paste by using 8YSZ powder or NiO-8YSZ as a solid material and an ammonium polyacrylate dispersing agent and a water-based emulsion bonding agent, molding through the combination of a freezing pouring process and a freeze drying method, and finally sintering at high temperature to obtain the target support. As the support is provided with the continuous gradient porous structure, the area of the three-phase interface is greatly enlarged, meanwhile, the resistance of gas diffusing toward the surface of electrolyte from the surface of an electrode is reduced, and therefore, the polarization impedance of a solid oxide battery can be greatly reduced, thus the performance of the solid oxide battery is improved. The method has the advantages of simple operation, flexibility, controllable pore passage morphology and the like.
Description
Technical field
The invention belongs to electrolytic tank of solid oxide technical field, particularly a kind of novel high-performance solid oxidate electrolytic cell supporter.
Background technology
Solid Oxide Fuel Cell (Solid Oxide Fuel Cells, SOFC) be a kind of device chemical energy of fuel directly being changed into electric energy, by SOFC antikinesis, be the chemical energy of hydrogen or hydrocarbon fuel by electric energy conversion by the electrochemical reaction under high temperature, be called electrolytic tank of solid oxide (Solid Oxide Electrolytic Cells, SOEC).Use the efficiency of electrolytic tank of solid oxide at high temperature electrolysis of water steam hydrogen manufacturing can up to 45 ~ 59% (ratios of the total energy that the energy content that hydrogen production efficiency is defined as obtained hydrogen consumes with hydrogen manufacturing), being considered to 21 century substitutes one of route of the extensive hydrogen manufacturing of fossil energy.Meanwhile, in recent years by the common electrolytic reaction in electrolytic tank of solid oxide system by CO
2and H
2o is converted into H
2with CO (i.e. synthetic gas), simultaneously in conjunction with the existing catalyzed reaction flow process (as Fischer-Tropsch reaction, methanolizing reaction etc.) having realized suitability for industrialized production, the technology that is clean, sustainable, scale operation realizing liquid carbon hydrogen fuel receives much concern.High-temperature electrolysis hydrogen manufacturing and high temperature altogether electrolytic preparation synthol technology have become the study hotspot in current international energy field.
As core component, the structure design of electrolytic tank of solid oxide and technology of preparing are the focus of research both at home and abroad all the time.The reduction reaction no matter occurring in the water of hydrogen electrode or the oxidizing reaction of the oxonium ion occurring in oxygen electrode is gas-solid reaction, namely occur on the three phase boundary that is made up of electrode materials, ionogen and the gas space, therefore the length of three phase boundary directly can affect electrochemical reaction speed.In electrolytic reaction process, hydrogen electrode constantly consumes water vapour and discharges hydrogen simultaneously, and oxygen electrode disengages oxygen.Because gas transfer is generally divided into convection current and diffusion two kinds, and electrode interior is to be diffused as master.Therefore, three phase boundary area can be increased by the microtexture optimizing SOEC, improves gas diffusion properties.At present, common SOEC generally adopts ionogen or hydrogen electrode to make supporting layer.And the SOEC that hydrogen electrode supports is owing to have employed the higher hydrogen electrode of electronic conductance as supporting layer, greatly reduces the thickness of dielectric substrate, improve performance.Current hydrogen electrode supports SOEC many employings casting method or dry pressing preparation.For ensureing effective transmission of gas, generally in casting slurry or powder, add pore-forming material, through high temperature binder removal, organism burn off, leaves hole, then is obtained the support electrode with certain porosity by high temperature sintering.But the wettability of Ni particle to YSZ particle of hydrogen electrode is poor result in long-time running the phenomenon that there will be Ni particle agglomeration, the porosity of supporting layer reduces, thus three phase boundary area reduces gas condition of divergence deterioration simultaneously, finally causes the decay of electrolytic tank of solid oxide performance.
The SOEC of electrolyte-supported, owing to adopting thicker dense electrolyte layer as support, has stronger physical strength and more stable performance.Consider that the thickness of SOEC supporter is about 0.4-0.6mm, freezing casting ultimate principle is similar to freezing casting method principle and to have preparation method simple, be more suitable for the advantage of laboratory scale research, the present invention adopts freezing casting to prepare the electrolytic tank of solid oxide supporting structure with gradient duct feature.The aqueous-based ceramic slurry be mixed to get by additive by ceramic powder, dispersion agent and binding agent and necessity injects the mould of specified shape, and after freeze forming, vacuum-drying except anhydrating, then obtains through high temperature sintering the pottery remaining with water crystallization pattern duct.Be expected to increase three phase boundary area, strengthening gas spreads and improves the performance degradation problem because Ni particle agglomeration causes.
Summary of the invention:
The object of the present invention is to provide a kind of novel high-performance electrolytic tank of solid oxide supporter.
Above-mentioned supporter has gradient pore passage structure, adds reaction three phase boundary area, strengthening gas diffusion path.Freezing casting utilizes suitable thermograde to lure ice crystallization the characteristic of oriented growth prepares electrolytic tank of solid oxide gradient duct supporting structure in ceramic aqueous slurry into.The thickness of supporting layer and the diameter in directed duct regulate and control by regulating mold thickness, slurry solid content, freezing temp and time etc.The formation in directed duct by reaction interface by a few to tens of micron thickness range extension of bath surface ten in whole supporting structure, considerably increase three phase boundary area, enhance gas simultaneously and spread.
A kind of high-performance solid oxidate electrolytic cell supporter, described supporter has continuous gradient pore passage structure, and porosity is 60% ~ 80%, is to adopt following methods to be prepared from, and concrete steps are as follows:
1) prepare water-based slurry: by formation dispersion liquid soluble in water for ammonium polyacrylate dispersion agent, regulate pH be 6 ~ 10, add ceramic powder, stir and ultrasonic after add binding agent, ball milling 1 ~ 5h, prepares water-based slurry;
2) pour into a mould: with anti-low temperature water-proof silica-gel acrylic resin mould is fixed on metal freezing plate and makes casting mold, by step 1) in water-based slurry be cast in above-mentioned mould;
3) water crystallographic orientation growth: cryogenic thermostat stirring reaction bath provide low-temperature receiver, by step 2) in metal freezing plate be placed in one, slurry freeze forming;
4) lyophilize: the sample of freeze forming is placed in vacuum freeze drier, takes out the demoulding after vacuum lyophilization, obtain ceramic green sheet;
5) binder removal sinter molding: above-mentioned ceramic green sheet is placed in High Temperature Furnaces Heating Apparatus, heat up carry out binder removal, electrolytic tank of solid oxide supporter that sintering obtains having continuous gradient duct.
Step 1) described in ceramic powder be 8YSZ (zirconium white of 8mol% stabilized with yttrium oxide) or NiO-8YSZ powder, described NiO-8YSZ powder be NiO and 8YSZ powder in mass ratio 55:45 mixing, alcohol dampening ball milling 8h, oven dry obtains.
The particle diameter of described 8YSZ or NiO-8YSZ powder is 0.02 ~ 1 μm, and specific surface is 1 ~ 10m
2/ g.
Step 1) described in the consumption of ceramic powder be 15 ~ 30% of the volume of water.
Step 1) described in the consumption of ammonium polyacrylate dispersion agent be 1% ~ 10% of the quality of water.
Step 1) described in the consumption of binding agent be 1% ~ 10% of the quality of water.
Step 3) in freezing temp be-80 ~-10 DEG C, freezing time is 0.5 ~ 2h.
Step 4) described in lyophilize temperature be-50 ~-10 DEG C, sublimation drying is 24 ~ 48h.
Step 5) described in dump temperature be 300-600 DEG C, the binder removal time is 1 ~ 5h.
Step 5) described in sintering temperature be 1000 ~ 1500 DEG C, sintering time is 2 ~ 10h.
Beneficial effect of the present invention is: the pore structure that electrolytic tank of solid oxide supporter of the present invention has gradient orientation not only can increase reaction three phase boundary area but also can strengthen gas condition of divergence, thus improves the electrical property of SOEC and improve the stable of long-time running.Medium side surface is dense structure, can save the step that dense electrolyte layer is prepared in silk screen printing, thus simplify operation in the preparation process of complete S OEC.When particularly adopting NiO-8YSZ to be powder raw material, obtained supporting structure can directly use as the hydrogen electrode supporter of electrolytic tank of solid oxide.
Accompanying drawing illustrates:
Fig. 1 is the principle schematic of the freezing casting that the present invention adopts;
Wherein each label is: the freezing metal sheet of 1-, the heat insulation mould of 2-, 3-refrigerant, 4-ceramic size.
Fig. 2 is embodiment 1 gained 8YSZ supporting structure medium side surface SEM photo scanning Electronic Speculum (SEM) figure.
Fig. 3 is embodiment 1 gained 8YSZ supporting structure side partial sweep Electronic Speculum (SEM) figure.
Fig. 4 is embodiment 2 gained 8YSZ supporting structure side scanning electron microscope (SEM) figure.
Fig. 5 is embodiment 3 gained NiO-8YSZ supporting structure side scanning electron microscope (SEM) figure.
Embodiment:
Freezing cast ratio juris of the present invention as described in Figure 1, low-temperature receiver is the bath of cryogenic thermostat stirring reaction, it act as heat-conducting medium as freezing metal sheet to adopt copper coin, make copper coin surface temperature distribution even, heat insulation mould is fixed on copper coin surface, slurry is poured in mould, due to the effect of thermograde (in figure shown in arrow), water crystallographic orientation grows, final formation gradient pore passage structure.
Embodiment 1
1) by ammonium polyacrylate dispersion agent (DURAMAX D-3019) the formation dispersion liquid soluble in water of quality 2%, pH is regulated to be 9, add the 8YSZ (TZ-8YS that Tosoh company produces, the 25vol% of water) powder, stir and ultrasonic after add 5% binding agent (DURAMAX B-1000) of quality, ball milling 2h.Described 8YSZ powder median size is 0.258 μm, and specific surface is 6.271m
2/ g.
2) pour into a mould.With 704 water-proof silica-gels acrylic resin mould is fixed on metal freezing plate and makes casting mold, by step 1) in water-based slurry be cast in above-mentioned mould.
3) water crystallographic orientation growth.Cryogenic thermostat stirring reaction bath (DHJF-8002 that Beijing auspicious one-tenth great achievement plant and instrument company limited produces minimumly reaches-80 DEG C) provides low-temperature receiver, and alcohol is as refrigerant, and temperature is-60 DEG C.Metal freezing plate in step 2 is placed in one, treats 1h disposed slurry freeze forming.
3) lyophilize.The sample of abundant freeze forming is placed in vacuum freeze drier (the VFD-2000 freeze drier that Beijing Bo Yikang laboratory apparatus company limited produces) and after 48h vacuum lyophilization, takes out the demoulding at-30 DEG C.
4) binder removal sinter molding.Above-mentioned ceramic green sheet is placed in High Temperature Furnaces Heating Apparatus, is warming up to 600 DEG C of insulation 2h binder removals, be then warming up to the electrolytic tank of solid oxide supporter that 1400 DEG C of insulation 4h sintering obtain having gradient duct.
Described supporter porosity after high temperature sintering reduction is 70%, and its scanning electron microscope (SEM) photograph is for shown in Fig. 1-2.
Embodiment 2:
1) by ammonium polyacrylate dispersion agent (DURAMAX D-3019) the formation dispersion liquid soluble in water of quality 3%, pH is regulated to be 9, add the 8YSZ (TZ-8YS that Tosoh company produces, 30vol% take water as benchmark) powder, stir and ultrasonic after add 5% binding agent (DURAMAX B-1000) of quality, ball milling 2h.Described 8YSZ powder median size is 0.258 μm, and specific surface is 6.271m
2/ g.
2) pour into a mould.With 704 water-proof silica-gels acrylic resin mould is fixed on metal freezing plate and makes casting mold.Water-based slurry in step 1 is cast in above-mentioned mould.
3) water crystallographic orientation growth.Cryogenic thermostat stirring reaction bath (DHJF-8002 that Beijing auspicious one-tenth great achievement plant and instrument company limited produces minimumly reaches-80 DEG C) provides low-temperature receiver, and alcohol is as refrigerant, and temperature is-40 DEG C.Metal freezing plate in step 2 is placed in one, treats 1h disposed slurry freeze forming.
3) lyophilize.The sample of abundant freeze forming is placed in vacuum freeze drier (the VFD-2000 freeze drier that Beijing Bo Yikang laboratory apparatus company limited produces) and after 48h vacuum lyophilization, takes out the demoulding at-30 DEG C.
4) binder removal sinter molding.Above-mentioned ceramic green sheet is placed in High Temperature Furnaces Heating Apparatus, is warming up to 600 DEG C of insulation 2h binder removals, be then warming up to the electrolytic tank of solid oxide supporter that 1400 DEG C of insulation 4h sintering obtain having gradient duct.Described supporter porosity after high temperature sintering reduction is 65%, and its scanning electron microscope (SEM) photograph as shown in Figure 4.
Embodiment 3:
1) by ammonium polyacrylate dispersion agent (DURAMAX D-3019) the formation dispersion liquid soluble in water of quality 3%, regulate pH to be 9, (oven dry obtains for the powder quality 55:45 of NiO and 8YSZ, alcohol dampening ball milling 8h to add NiO-8YSZ; 30vol% take water as benchmark) powder, stir and ultrasonic after add the binding agent (DURAMAX B-1000) of quality 5%, ball milling 2h.
2) pour into a mould.With anti-low temperature water-proof silica-gel (704 water-proof silica-gel) acrylic resin mould is fixed on metal freezing plate and makes casting mold.Water-based slurry in step 1 is cast in above-mentioned mould.
3) water crystallographic orientation growth.Cryogenic thermostat stirring reaction bath (DHJF-8002 that Beijing auspicious one-tenth great achievement plant and instrument company limited produces minimumly reaches-80 DEG C) provides low-temperature receiver, and alcohol is as refrigerant, and temperature is-40 DEG C.Metal freezing plate in step 2 is placed in one, treats 1h disposed slurry freeze forming.
3) lyophilize.The sample of abundant freeze forming is placed in vacuum freeze drier (the VFD-2000 freeze drier that Beijing Bo Yikang laboratory apparatus company limited produces) and after 48h vacuum lyophilization, takes out the demoulding at-30 DEG C.
4) binder removal sinter molding.Above-mentioned ceramic green sheet is placed in High Temperature Furnaces Heating Apparatus, is warming up to 600 DEG C of insulation 2h binder removals, be then warming up to the electrolytic tank of solid oxide supporting structure that 1000 DEG C of insulation 4h sintering obtain having gradient duct.Described NiO-YSZ hydrogen electrode supporter porosity after high temperature sintering reduction is 65%, and its scanning electron microscope (SEM) photograph as shown in Figure 5.
Claims (10)
1. a high-performance solid oxidate electrolytic cell supporter, is characterized in that, described supporter has continuous gradient pore passage structure, and porosity is 60% ~ 80%, is to adopt following methods to be prepared from, and concrete steps are as follows:
1) prepare water-based slurry: by formation dispersion liquid soluble in water for ammonium polyacrylate dispersion agent, regulate pH be 6 ~ 10, add ceramic powder, stir and ultrasonic after add binding agent, ball milling 1 ~ 5h, prepares water-based slurry;
2) pour into a mould: with anti-low temperature water-proof silica-gel acrylic resin mould is fixed on metal freezing plate and makes casting mold, by step 1) in water-based slurry be cast in above-mentioned mould;
3) water crystallographic orientation growth: cryogenic thermostat stirring reaction bath provide low-temperature receiver, by step 2) in metal freezing plate be placed in one, slurry freeze forming;
4) lyophilize: the sample of freeze forming is placed in vacuum freeze drier, takes out the demoulding after vacuum lyophilization, obtain ceramic green sheet;
5) binder removal sinter molding: above-mentioned ceramic green sheet is placed in High Temperature Furnaces Heating Apparatus, heat up carry out binder removal, electrolytic tank of solid oxide supporter that sintering obtains having continuous gradient duct.
2. electrolytic tank of solid oxide supporter according to claim 1, it is characterized in that, step 1) described in ceramic powder be 8YSZ or NiO-8YSZ powder, described NiO-8YSZ be NiO and 8YSZ powder in mass ratio 55:45 mixing, alcohol dampening ball milling 8h, oven dry obtains.
3. electrolytic tank of solid oxide supporter according to claim 2, is characterized in that, the particle diameter of described 8YSZ or NiO-8YSZ powder is 0.02 ~ 1 μm, and specific surface is 1 ~ 10m
2/ g.
4. electrolytic tank of solid oxide supporter according to claim 1, is characterized in that, step 1) described in the consumption of ceramic powder be 15 ~ 30% of the volume of water.
5. electrolytic tank of solid oxide supporter according to claim 1, is characterized in that, step 1) described in the consumption of ammonium polyacrylate dispersion agent be 1% ~ 10% of the quality of water.
6. electrolytic tank of solid oxide supporter according to claim 1, is characterized in that, step 1) described in the consumption of binding agent be 1% ~ 10% of the quality of water.
7. electrolytic tank of solid oxide supporter according to claim 1, is characterized in that, step 3) in freezing temp be-80 ~-10 DEG C, freezing time is 0.5 ~ 2h.
8. electrolytic tank of solid oxide supporter according to claim 1, is characterized in that, step 4) described in lyophilize temperature be-50 ~-10 DEG C, sublimation drying is 24 ~ 48h.
9. electrolytic tank of solid oxide supporter according to claim 1, is characterized in that, step 5) described in dump temperature be 300-600 DEG C, the binder removal time is 1 ~ 5h.
10. electrolytic tank of solid oxide supporter according to claim 1, is characterized in that, step 5) described in sintering temperature be 1000 ~ 1500 DEG C, sintering time is 2 ~ 10h.
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| CN106631044A (en) * | 2016-09-19 | 2017-05-10 | 武汉大学 | Method for shaping gradient-straight-hole double-layer asymmetric ceramic oxygen separation membrane |
| CN108054393A (en) * | 2017-12-25 | 2018-05-18 | 河南工业大学 | A kind of preparation method of the intermediate temperature solid oxide fuel cell cathode with novel nano structure |
| CN109852988B (en) * | 2019-04-12 | 2021-05-25 | 清华大学 | Micro-nano tree-shaped solid oxide electrolytic cell anode and preparation method thereof |
| CN110078502B (en) * | 2019-05-17 | 2021-07-13 | 福州大学 | Method for improving hardness of 8YSZ |
| CN113745531A (en) * | 2021-09-14 | 2021-12-03 | 北京思伟特新能源科技有限公司 | High-performance solid oxide electrolytic cell and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503518A (en) * | 2011-11-16 | 2012-06-20 | 黑龙江大学 | Preparation method of porous crystalline TiO2 foamed ceramic |
| CN102807391A (en) * | 2012-08-29 | 2012-12-05 | 哈尔滨工业大学 | Method for preparing porous silicon carbide ceramic |
| CN102951922A (en) * | 2012-11-27 | 2013-03-06 | 陕西科技大学 | Method for preparing barium titanate porous ceramic by freeze pouring method |
-
2013
- 2013-07-04 CN CN201310279789.4A patent/CN103319182B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503518A (en) * | 2011-11-16 | 2012-06-20 | 黑龙江大学 | Preparation method of porous crystalline TiO2 foamed ceramic |
| CN102807391A (en) * | 2012-08-29 | 2012-12-05 | 哈尔滨工业大学 | Method for preparing porous silicon carbide ceramic |
| CN102951922A (en) * | 2012-11-27 | 2013-03-06 | 陕西科技大学 | Method for preparing barium titanate porous ceramic by freeze pouring method |
Non-Patent Citations (3)
| Title |
|---|
| Novel functionally graded acicular electrode for solid oxide cells fabricated by the freeze-tape-casting process;Yu Chen et al.;《Journal of Power Sources》;20120416;第213卷;第94页右栏第2段至第95页左栏第1段 * |
| 中温固体氧化物燃料电池电解质材料及其制备工艺的研究发展趋势;史可顺;《硅酸盐学报》;20081130;第36卷(第11期);第1684页 * |
| 冷冻浇注成型法制备可固体氧化物电解池的微通道支撑结构;王雪等;《第十七届全国高技术陶瓷学术年会摘要集》;20120930;第98页 * |
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