CN102185148A - NiO-based SOFC (Solid Oxide Fuel Cell) composite anode film material with nano-sheet microcellular structure and preparation method thereof - Google Patents
NiO-based SOFC (Solid Oxide Fuel Cell) composite anode film material with nano-sheet microcellular structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing a NiO-based SOFC (Solid Oxide Fuel Cell) with a nano-sheet microcellular structure by soaking and synthesizing in porous YSZ (Yttria Stabilized Zirconia) frameworks, belonging to the field of flat-plate solid oxide fuel cells (SOFC). The preparation method comprises the following steps of: soaking and synthesizing a nickel hydroxide precursor with a nano-sheet microcellular structure in porous YSZ frameworks which are communicated with one another by taking porous YSZ as frameworks (one face is provided with compact YSZ electrolyte of 15mum in thickness) on the basis of a soaking and synthesizing method; and sintering to obtain a support body film material half-cell. The method disclosed by the invention has the advantages of simple process and low cost, and is suitable for industrial production; and a prepared anode film material has high electro-catalytic performance.
Description
Technical field
NiO base anode film material of dipping synthesis of nano sheet microcellular structure and preparation method thereof belongs to flat-plate-type solid-oxide fuel battery (SOFC) field in the YSZ skeleton that the present invention relates in porous.
Background technology
The energy and environment are increasing to the mankind's pressure, and the cry that requirement improves existent environment of people as early as possible is more and more higher.The capacity usage ratio of the Solid Oxide Fuel Cell of environment-friendly type (SOFC) can reach more than 70%～80%, and to be that SOFC is high efficiency demonstrate fully for this, also is that other any generation technologies are incomparable.As new and effective clear energy sources, the generation technology of SOFC has worldwide caused common concern, and countries in the world are all competitively conducting a research.Compare with the Solid Oxide Fuel Cell of other structure, flat solid oxide fuel cell energy density height, battery pack structure is flexible, and technology is easy, and is easy to control the quality.The anode support type flat solid oxide fuel cell carries out co-sintering with anode support and electrolytic thin-membrane usually, after silk screen printing and the sintered cathode, obtains the monocell diaphragm again.
The anode catalyst material that present SOFC is most widely used is the lower nickel oxide of price, nickel oxide in the time of in working order in the anode is reduced to metallic nickel, metallic nickel has higher electric conductivity and catalytic activity, the overpotential that causes at anode is very little, and the catalysis of its antianode plays a decisive role.Nickel oxide in the time of in working order in the anode is reduced to metallic nickel, and metallic nickel has higher electric conductivity and catalytic activity.Usually NiO is that form with solid powder is incorporated into anode, selects the suitable particle diameter and the primary of particle size distribution, can optimize the microstructure of electrode.Catalyst size nanometer and pattern special efficacyization are the important development directions of new high-efficiency eelctro-catalyst research among the SOFC.Because the surface provides catalytic reaction required place, thereby always trend towards using the catalyst on high surface.Generally there are two kinds of approach on the surface of improving catalyst: the one, reduce the granularity (but the particle of solid construction but easily causes problem such as battery performance instability, catalyst granules reunion in running when being reduced to a certain degree especially the nanometer size) of catalyst; The 2nd, catalyst is made porous material.This research is noticed: compare with the catalyst of solid construction, the catalyst of nanometer sheet microcellular structure has than better catalytic performance of the catalyst of solid construction and structural stability.At present we developed in alcohol-aqueous medium can cheap a large amount of preparation nanometer sheet microcellular structure NiO and the preparation method of the nano particle of ordered micro-cellular structures such as tiny balloon, and can regulate and control [Wei Fei to the size of two-dimentional curved surface and the gap length and the surface state of curved surface, Wu is also all, the preparation and the sign of flower-shape Ni O nanometer sheet self-assembly, silicate journal, 2009,37 (12): 19～25; Wei Fei, Wu Yefan, the scale preparation of NiO tiny balloon and sign. electronic component and material, 2009,28 (12): 49～51; Wei Fei, Wu Yefan, the preparation and the sign of NiO nanometer sheet self-assembly in the methanol-water medium, ceramic journal, 2009,30 (2): 213-216].The powder of the NiO nanometer sheet microcellular structure of being made up of a large amount of two-dimentional curved surfaces with tripartite phase structure for example, the size of its two-dimentional curved surface are about that 2 μ m * 3 μ m, curve clearance are about 100nm, specific area is 104m
2/ g, such microcellular structure extremely helps the diffusion of anode reaction gas.A large amount of literature research show, the oxide of nickel or the hydroxide thermal decomposition product metallic nickel through obtaining after the thermal reduction under hydrogen atmosphere has " inheritance " [Liu Zhihong to its presoma on pattern, pattern in the preparation of nickel cobalt oxalates and granularity control (doctorate paper), Central South University, 2007], our early-stage Study also shows, the nickel oxide of nanometer sheet microcellular structure is the nanometer sheet microcellular structure still after 800 ℃ of hydrogen heat reduction, on pattern its presoma is also had " inheritance ".
Because the catalyst surface area of nanometer sheet microcellular structure is big, catalytic activity is high, the microcellular structure of hollow also helps and constitutes electron conduction phase continuous frame, compare with the catalyst of solid construction, the catalyst of nanometer sheet microcellular structure is the catalytic activity height not only, and consumption is few.The nickel oxide (this microcellular structure extremely helps the diffusion of anode reaction gas) that this patent takes the lead in having the nanometer sheet microcellular structure is incorporated in the anode preparation of SOFC.
Summary of the invention
At the deficiencies in the prior art, the present invention is flooded the NiO base anode catalyst of synthesis of nano sheet microcellular structure based on environment-friendly type water system The tape casting on the support film material that makes, thus the NiO based composite anode film material of preparation nanometer sheet microcellular structure.This method technology is simple, with low cost, easily realizes large tracts of land, large-scale production.
The present invention includes preparation, dipping, drying and the heat treatment process of batching, ball milling, degasification, curtain coating, plastic removal, sintering, maceration extract, comprise the steps:
(1) Zirconium powder, starch pore creating material, ammonium polyacrylate, polyvinyl alcohol, the water with stabilized with yttrium oxide is mixed with slurry A;
(2) ball milling mixed slurry A, degasification is made the anode biscuit film with slurry A flow casting molding;
(3) with Zirconium powder, ammonium polyacrylate, polyvinyl alcohol, the water form slurry B of stabilized with yttrium oxide;
(4) ball milling mixed slurry B, degasification is made the electrolyte biscuit film with slurry B flow casting molding;
(5) the electrolyte biscuit film is become anode support type-compound biscuit film of thin layer electrolyte with the anode biscuit film through hot pressing;
(6) anode support type-compound biscuit film of thin layer electrolyte that makes is carried out high temperature sintering behind the plastic removal, make anode support type-thin layer electrolyte composite material;
(7) nickel nitrate is mixed with the saturated aqueous solution;
(8) anode support type-thin layer electrolyte composite material is immersed in the saturated nickel nitrate aqueous solution, vacuumizes the gas in eliminating anode support type-thin layer electrolyte composite material duct then, flood;
(9) anode support type-thin layer electrolyte composite material that will flood through the nickel nitrate aqueous solution of supersaturation dries in the shade;
(10) in volume ratio be the urea liquid of preparation 2mol/L in 7: 3 the ethanol-water media;
(11) in the water-bath 85 ℃ the time, to be immersed in through the anode support type that the contains nickel nitrate-thin layer electrolyte composite material that dries in the shade in the urea liquid of 2mol/L (volume ratio is 7: 3 a ethanol-water media), the nickel hydroxide of synthesis of nano sheet microcellular structure in the zirconia framework material of porous stabilized with yttrium oxide makes anode film material precursor;
(12) the anode film material precursor that makes is heat-treated, make the anode film material.
Preferred plastic removal condition is 450-600 ℃, and programming rate is 0.5-1 ℃/minute.The preferred elevated temperature sintering condition is 1350-1500 ℃ of following sintering 2-10 hour.Preferred heat-treat condition is 600-800 ℃ of following sintering 2 hours.Preferred electrolyte biscuit film flow casting molding condition is knife up 100-130 μ m, and preferred anode biscuit film flow casting molding condition is knife up 1.0-1.8mm, and at room temperature dry 20-30 hour.
The raw material of selecting of the NiO catalyst of dipping synthesis of nano sheet microcellular structure in the YSZ of porous skeleton is nickel nitrate, urea, water.
In the slurry of above-mentioned steps (1), add dispersant, bridging agent and plasticizer.
In an embodiment of the present invention, with starch be pore creating material;
With water is solvent;
(PAA, molecular weight 5000g/mol) is dispersant with polyacrylic acid;
With polyvinyl alcohol (PVA-1788) is binding agent;
With polyethylene glycol (PEG400) is plasticizer;
The mass percent of each component specifically consists of in the slurry:
Anode diaphragm (skeleton) slurry: anode powder 17.5～30wt.%, pore creating material 20～30wt.%, water 4～10wt.%, PAA 0.1～0.8wt.%, PVA 2～7wt.%, PEG1.2～6wt.% at different powders, can take different proportioning modes.
The compound nickel oxide Catalytic Layer of nanometer sheet microcellular structure in the zirconia anode material hole of the stabilized with yttrium oxide that the present invention makes, be that catalyst material is compound in the zirconia material of porous stabilized with yttrium oxide and forms compound film material, and catalyst material is the nickel oxide of nanometer sheet microcellular structure.
The invention has the advantages that:
(1) The tape casting technology is simple, with low cost, pollution-free, and easily realizes large tracts of land production;
(2) by changing the content that adds pore creating material in the anode slurry, can control the porosity of porous anode supporter, help improving the chemical property of research;
(3) by changing kind and the granular size that adds pore creating material in the anode slurry, can change pore opening and shape, help improving the anode microstructure, reduce concentration polarization;
(4) by changing composition, concentration and the number of times of maceration extract, can change anode-catalyzed layer thickness, help to improve (raising) chemical property.
Description of drawings
Fig. 1 represent respectively by the anode film material of embodiment one preparation (curve a) and the anode film material (curve b) of solid NiO powder preparing under different Ni content situation with the graph of a relation of conductivity.
Specific embodiments
In order more to be expressly understood the present invention, illustrate that below in conjunction with specific embodiments the present invention substantially makes progress and obvious improvement, the application example that provides the inventor is so that the present invention is further illustrated, but not only is confined to embodiment.
Embodiment 1
The NiO based composite anode film material of dipping synthesis of nano sheet microcellular structure in the preparation large tracts of land porous YSZ skeleton
Get YSZ (8molY
2O
3Stable ZrO
2) 50g, starch 20g, zirconium oxide balls 180g, PAA0.5g adds in the polytetrafluoroethylene ball grinder, and ball milling is 24 hours on planetary ball mill; Add PVA5g in above-mentioned slurry, PEG 3.6g continued ball milling 24 hours, obtained the anode support slurry.
Get YSZ (8molY
2O
3Stable ZrO
2) 20g, zirconium oxide balls 50g, PAA0.2g adds in the polytetrafluoroethylene ball grinder, and ball milling is 24 hours on planetary ball mill; Add PVA1.8g in above-mentioned slurry, PEG1.2g continued ball milling 24 hours, obtained electrolyte slurry.
The anode support slurry was vacuumized 10 minutes, on casting machine with knife up 1.8mm flow casting molding, the demoulding after dry 24 hours under the room temperature.
Electrolyte slurry was vacuumized 10 minutes, on casting machine with knife up 120 μ m flow casting moldings, the demoulding after dry 24 hours under the room temperature.
With anode support diaphragm and electrolyte membrane lamination, heat-insulation pressure keeping half an hour under 70 ℃, 20Mpa pressure, make anode support type-compound biscuit film of thin layer electrolyte.
Anode support type-compound the biscuit film of thin layer electrolyte that makes is carried out sintering: the plastic removal condition optimization is 450-600 ℃, and programming rate is preferably 0.5-1 ℃/minute.The high temperature sintering condition optimization is 1350-1500 ℃ of following sintering 2-10 hour, and programming rate is 2 ℃/minute.Behind sintering, make anode support type-thin layer electrolyte composite material.
Anode support type-thin layer electrolyte composite material is immersed in the saturated nickel nitrate aqueous solution, vacuumizes the gas in eliminating anode support type-thin layer electrolyte composite material duct simultaneously, flood half an hour.To place at room temperature 12 hours through the anode support type-thin layer electrolyte composite material of dipping, it is dried in the shade.The anode support type that will dry in the shade-thin layer electrolyte composite material is immersed in the saturated nickel nitrate aqueous solution once more, and vacuumizes the gas of getting rid of in its duct, and dipping with its taking-up, was placed 12 hours after half an hour at room temperature, and it is dried in the shade.Aforesaid operations is carried out 11 times repeatedly, it is placed at room temperature it was dried in the shade in 12 hours then, the back insulation 3 hours in 80 ℃ of air of drying in the shade.
In volume ratio is in 7: 3 the ethanol-water media 85 ℃ the time, above-mentioned anode support type-thin layer the electrolyte composite material that contains nickel nitrate was immersed in the urea liquid of 2mol/L (volume ratio is 7: 3 a ethanol-water media) reaction 24 hours, the Ni (OH) of synthesis of nano sheet microcellular structure in the zirconia framework material of porous stabilized with yttrium oxide
2, make anode film material precursor.With anode film material precursor soaked in absolute ethyl alcohol 3 times that make, take out and dried in the shade 8 hours, to heat-treat then, heat-treat condition is 600 ℃ of following sintering 2 hours, programming rate is 1 ℃/minute, makes composite anode film material.
Fig. 1 represent respectively by the anode film material of embodiment one preparation (curve a) and the anode film material (curve b) of solid NiO powder preparing under different Ni content situation with the graph of a relation of conductivity, as can be seen from the figure, under the identical situation of NiO content, anode film material of the present invention has higher conductivity.
Embodiment 2
The fine and close ScSZ film of preparation large tracts of land anode support type
Get YSZ (8molY
2O
3Stable ZrO
2) 50g, starch 20g, zirconium oxide balls 180g, PAA0.5g adds in the polytetrafluoroethylene ball grinder, and ball milling is 24 hours on planetary ball mill; Add PVA5g in above-mentioned slurry, PEG 3.6g continued ball milling 24 hours, obtained the anode support slurry.
Get ScSZ (8molSc
2O
3Stable ZrO
2) 20g, zirconium oxide balls 50g, PAA0.2g adds in the polytetrafluoroethylene ball grinder, and ball milling is 24 hours on planetary ball mill; Add PVA1.8g in above-mentioned slurry, PEG1.2g continued ball milling 24 hours, obtained electrolyte slurry.
The anode support slurry was vacuumized 10 minutes, on casting machine with knife up 1.8mm flow casting molding, the demoulding after dry 24 hours under the room temperature.
Electrolyte slurry was vacuumized 10 minutes, on casting machine with knife up 120 μ m flow casting moldings, the demoulding after dry 24 hours under the room temperature.
With anode support diaphragm and electrolyte membrane lamination, heat-insulation pressure keeping half an hour under 70 ℃, 20Mpa pressure, make the fine and close ScSZ film composite material of large tracts of land anode support type biscuit film.
Anode support type-compound the biscuit film of thin layer electrolyte that makes is carried out sintering: the plastic removal condition optimization is 450-600 ℃, and programming rate is preferably 0.5-1 ℃/minute.The high temperature sintering condition optimization is 1350-1500 ℃ of following sintering 2-10 hour, makes the electrolyte densification, and programming rate is 2 ℃/minute.Behind sintering, make the fine and close ScSZ film composite material of anode support type.
The fine and close ScSZ film composite material of anode support type is immersed in the saturated nickel nitrate aqueous solution, vacuumizes the gas in eliminating anode support type-thin layer electrolyte composite material duct simultaneously, flood half an hour.To place at room temperature 12 hours through the fine and close ScSZ film composite material of the anode support type of dipping, it is dried in the shade.The fine and close ScSZ film composite material of the anode support type that will dry in the shade is immersed in the saturated nickel nitrate aqueous solution once more, and vacuumizes the gas of getting rid of in its duct, and dipping with its taking-up, was placed 12 hours after half an hour at room temperature, and it is dried in the shade.Aforesaid operations is carried out 11 times repeatedly, it is placed at room temperature it was dried in the shade in 12 hours then, the back insulation 3 hours in 80 ℃ of air of drying in the shade.
In volume ratio is in 7: 3 the ethanol-water media 85 ℃ the time, the fine and close ScSZ film composite material of the above-mentioned anode support type that contains nickel nitrate was immersed in the urea liquid of 2mol/L (volume ratio is 7: 3 a ethanol-water media) reaction 24 hours, the Ni (OH) of synthesis of nano sheet microcellular structure in the zirconia framework material of porous stabilized with yttrium oxide
2, make anode film material precursor.With anode film material precursor soaked in absolute ethyl alcohol 3 times that make, take out and dried in the shade 8 hours, to heat-treat then, heat-treat condition is 600 ℃ of following sintering 2 hours, programming rate is 1 ℃/minute.Finally make the half-cell of large tracts of land anode support type/fine and close ScSZ dielectric film.
Embodiment 3
Preparation nanometer sheet microcellular structure NiO-YSZ/ScSZ/Pr
0.7Ca
0.3Mn
0.3(PCM) flat-plate SOFC single battery
Method according to embodiment 2 prepares the fine and close ScSZ film composite material of large tracts of land anode support type, the disk of cutting diameter 3cm.
Get PCM 1g, terpineol solution 0.7g fully grinds in agate Lao mortar, and the gained slurry is screen-printed to dielectric film one side of composite film material, and in 1200 ℃ of sintering 3 hours, programming rate was 1 ℃/minute then.Side at the fine and close ScSZ film composite material of large tracts of land anode support type makes negative electrode.
With above-mentioned cathode side epoxy sealing.
The anode support type composite material of cathode side sealing is immersed in the saturated nickel nitrate aqueous solution, vacuumizes the gas in eliminating anode support type-thin layer electrolyte composite material duct simultaneously, flood half an hour.To place at room temperature 12 hours through the anode support type composite material of dipping, it is dried in the shade.The anode support type composite material that will dry in the shade is immersed in the saturated nickel nitrate aqueous solution once more, and vacuumizes the gas of getting rid of in its duct, and dipping with its taking-up, was placed 12 hours after half an hour at room temperature, and it is dried in the shade.Aforesaid operations is carried out 11 times repeatedly, it is placed at room temperature it was dried in the shade in 12 hours then, the back insulation 3 hours in 80 ℃ of air of drying in the shade.
In volume ratio is in 7: 3 the ethanol-water media 85 ℃ the time, the above-mentioned anode support type composite material that contains nickel nitrate was immersed in the urea liquid of 2mol/L (volume ratio is 7: 3 a ethanol-water media) reaction 24 hours, the Ni (OH) of synthesis of nano sheet microcellular structure in the zirconia framework material of porous stabilized with yttrium oxide
2, make anode film material precursor.With anode film material precursor soaked in absolute ethyl alcohol 3 times that make, taking-up was dried in the shade 8 hours, heat-treated then, and heat-treat condition is 600 ℃ of following sintering 2 hours, programming rate is 1 ℃/minute, finally makes nanometer sheet microcellular structure NiO-YSZ/ScSZ/PCM flat-plate SOFC single battery.
The cell power generation experiment
Anode one side at monocell is coated the platinum grid with collected current, and draws Pt silk electricity at the two poles of the earth, seals with glass ring.
Behind 750 ℃ of NiO, be that fuel carries out generator experimental with hydrogen with the nanometer sheet microcellular structure in the hydrogen reducing anode.The result shows that this monocell has preferable performance, H
2Under maximum power density reached 1.2W/cm
2
Claims (6)
1. a SOFC anode film material is characterized in that, comprises the zirconia stephanoporate framework material of stabilized with yttrium oxide and is compound in the nickel oxide of the nanometer sheet microcellular structure in the zirconia stephanoporate framework material of described stabilized with yttrium oxide.
2. by the preparation method of the described anode film material of claim 1, comprise preparation, dipping, drying and the heat treatment process of batching, ball milling, degasification, curtain coating, plastic removal, sintering, maceration extract, it is characterized in that following step:
(1) Zirconium powder, starch pore creating material, ammonium polyacrylate, polyvinyl alcohol, polyethylene glycol, the water with stabilized with yttrium oxide is mixed with slurry A;
(2) ball milling mixed slurry A, degasification is made the anode biscuit film with slurry A flow casting molding;
(3) with Zirconium powder, ammonium polyacrylate, polyvinyl alcohol, polyethylene glycol, the water form slurry B of stabilized with yttrium oxide;
(4) ball milling mixed slurry B, degasification is made the electrolyte biscuit film with slurry B flow casting molding;
(5) with electrolyte biscuit film and anode biscuit film through the hot pressing lamination, make anode support type-compound biscuit film of thin layer electrolyte;
(6) anode support type-compound biscuit film of thin layer electrolyte that makes is carried out high temperature sintering behind the plastic removal, make anode support type-thin layer electrolyte composite material;
(7) nickel nitrate is mixed with saturated aqueous solution;
(8) anode support type-thin layer electrolyte composite material is immersed in the saturated nickel nitrate aqueous solution, vacuumizes the gas in eliminating anode support type-thin layer electrolyte composite material duct then, flood;
(9) will dry in the shade through the anode support type-thin layer electrolyte composite material of supersaturation nickel nitrate aqueous solution dipping;
(10) in volume ratio be the urea liquid of preparation 2mol/L in 7: 3 the ethanol-water media;
(11) in the water-bath 85 ℃ the time, to be immersed in through the anode support type that the contains nickel nitrate-thin layer electrolyte composite material that dries in the shade in the urea liquid of 2mol/L (volume ratio is 7: 3 a ethanol-water media), the nickel hydroxide of synthesis of nano sheet microcellular structure makes anode film material precursor in the zirconia stephanoporate framework material of stabilized with yttrium oxide;
(12) the anode film material precursor that makes is heat-treated, make the anode film material.
3. by the preparation method of the described anode film material of claim 2, it is characterized in that described step (6) high temperature sintering condition is 1350-1500 ℃ of following sintering 2-10 hour.
4. by the preparation method of the described anode film material of claim 2, it is characterized in that described plastic removal condition is 450-600 ℃, programming rate is 0.5-1 ℃/minute.
5. by the preparation method of the described anode film material of claim 2, it is characterized in that the catalyst in the described anode film material is the nickel oxide of nanometer sheet microcellular structure.
6. by the preparation method of the described anode film material of claim 2, it is characterized in that, also add dispersant, binding agent and plasticizer in the slurry of described step (1).
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| CN102437358A (en) * | 2011-11-30 | 2012-05-02 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN104766983A (en) * | 2015-03-31 | 2015-07-08 | 昆山艾可芬能源科技有限公司 | Current collection layer structure of solid oxide fuel cell |
| CN106025315A (en) * | 2016-07-25 | 2016-10-12 | 合肥工业大学 | Improved LSCM (Laser Scanning Confocal Microscope) electrode and preparation method thereof |
| CN110429285A (en) * | 2019-07-15 | 2019-11-08 | 合肥国轩高科动力能源有限公司 | A kind of SOFC anode electrode and preparation method thereof with sulfur resistance |
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| CN102394307A (en) * | 2011-10-12 | 2012-03-28 | 景德镇陶瓷学院 | Preparation method for anode support layer of solid oxide fuel cell |
| CN102437358A (en) * | 2011-11-30 | 2012-05-02 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN102437358B (en) * | 2011-11-30 | 2013-12-11 | 中国科学技术大学 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
| CN104766983A (en) * | 2015-03-31 | 2015-07-08 | 昆山艾可芬能源科技有限公司 | Current collection layer structure of solid oxide fuel cell |
| CN106025315A (en) * | 2016-07-25 | 2016-10-12 | 合肥工业大学 | Improved LSCM (Laser Scanning Confocal Microscope) electrode and preparation method thereof |
| CN106025315B (en) * | 2016-07-25 | 2019-03-29 | 合肥工业大学 | A kind of modified LS CM electrode and preparation method thereof |
| CN111819720A (en) * | 2018-03-06 | 2020-10-23 | 住友电气工业株式会社 | Electrolyte layer-anode composite member for fuel cell, cell structure, fuel cell, and method for producing composite member |
| CN111819720B (en) * | 2018-03-06 | 2023-10-20 | 住友电气工业株式会社 | Electrolyte layer-anode composite member for fuel cell, cell structure, fuel cell, and method for manufacturing composite member |
| CN110429285A (en) * | 2019-07-15 | 2019-11-08 | 合肥国轩高科动力能源有限公司 | A kind of SOFC anode electrode and preparation method thereof with sulfur resistance |
| CN115142087A (en) * | 2022-06-27 | 2022-10-04 | 上海嘉氢源科技有限公司 | Porous bifunctional decomposition water-electricity catalyst, preparation method thereof, electrolytic cell and application |
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Application publication date: 20110914 |