CN101306954B - Method for preparing porous ceramic support - Google Patents
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Abstract
The invention discloses a method for making a porous ceramic support body. The method comprises the following steps that: (1) a step of ceramic powder pretreatment, during which, ceramic powder and a pore-forming material are evenly ground with the weight of the pore-forming material is 5 to 30 percent of that of the ceramic powder; (2) a step of slurry preparing, during which, a forming agent is dissolved in a solvent and then is added in the pretreated ceramic powder so as to be ground evenly; the forming agent is polysulfone or polyethersulfone and the solvent can dissolve the forming agent; moreover, the weight percent of the forming agent, the solvent and the pretreated ceramic powder is 1 to 15 percent : 2 to 30 percent : 55 to 97 percent; (3) a step of making green compact, during which, slurry is made into green compact and then is dipped in pure water so as to carry out forming; and (4) a step of high-temperature sintering. The method has high rate of finished products and quick making speed and can be used in the solid oxide fuel cell field.
Description
Technical field
The present invention relates to the preparation method of porous ceramic, specifically is the preparation method of porous ceramic support.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of novel power generation device, the three-in-one structure that the SOFC cell is made up of porous ceramic anode (fuel electrode), electrolyte and porous ceramic negative electrode (oxidant electrode), cell forms battery pile by the connecting plate series connection, and battery pile can outwards be powered separately or behind series and parallel.In each types of fuel cells, Solid Oxide Fuel Cell has: 1. structure of whole solid state, and volume is little, is convenient to structure and scale design and amplification, and does not have the leakage problem of electrolyte; 2. suitable cogeneration, energy utilization efficiency is up to more than 85%; 3. fuel gas is applied widely waits unique advantage, thereby in large, medium and small type power station, portable, compact power, and there is wide application prospect in fields such as military affairs, Aero-Space.For practical application, the SOFC cell need be made battery pile to increase the output of voltage and power.The structural design of SOFC battery pile has multiple, as flat, tubular type, bushing type and corrugated etc.But through the constantly survival of the fittest, what research also had most application prospect at most at present mainly is tubular type and flat.
One of key technology of Solid Oxide Fuel Cell is exactly the preparation of porous ceramic anode support.
The patent No. is that 99108725.9 Chinese invention patent discloses and adopts the gypsum mould grouting legal system to be equipped with the method for YSZ electrolyte thin wall tube, this method is in casting process, the uniformity of slurry and suspension are very big to the quality influence of slip casting product, thereby this method only is fit to preparation one pack system light wall pipe.And shortcomings such as slip casting also exists demoulding difficulty, and process is loaded down with trivial details, and rate of finished products is low.The patent No. be 01104146.3 and application number be that 200710099624.3 Chinese invention patent has been reported a kind of novel forming method-gel forming method, it comes from the achievement in research of U.S. Oak Ridge National Laboratory Mark A.Janner professor in the nineties in 20th century, be by being that ceramic powder particle is dispersed in and makes low viscosity in the medium with the organic polymer monomer, the dense suspension of high solid volume fraction, and adding initator and catalyst, then concentrate suspension (slurry) is injected non-porous mould, effect by initator and catalyst makes that the organic polymer thing is monomer crosslinked to aggregate into three-dimensional netted polymer gel, and with ceramic particle original position bonding and be solidified into base substrate.This method belongs to formed in situ, but thereby dead size forming shape complexity, intensity height, microstructure is even, density is high base substrate.But the gel forming method needs to use some to the prejudicial organic chemical of human nerve in application process, and the initiation of reaction control is comparatively difficult, can not utilize this method to prepare the tubular type device at present.Utilize double screw extruder also can prepare long tube formula base substrate, but will expect that high-quality base substrate need pass through a series of preliminary preparations such as pugging, ageing, has prolonged experimental period like this, and, double screw extruder costs an arm and a leg, and inlet amount is also bigger, only is fit to produce in enormous quantities.
Summary of the invention:
The object of the present invention is to provide the preparation method of a kind of easy demoulding, rate of finished products height, the fireballing porous ceramic support of preparation, and it is applied in field of solid oxide fuel.
As follows for realizing the technical scheme that purpose of the present invention adopts:
A kind of preparation method of porous ceramic support, its material composition is mainly: ceramic powder, pore creating material, forming agent, solvent; May further comprise the steps:
(1) preliminary treatment of ceramic powder: ceramic powder and pore creating material are ground evenly, and the weight of described pore creating material is 5%～30% of ceramic powder weight; Described ceramic powder is zirconia, samarium doping of cerium oxide, gadolinium doping of cerium oxide, the zirconia of 3%mol stabilized with yttrium oxide, the aluminium oxide of nickel oxide, 8%mol stabilized with yttrium oxide, or the binary or the multicomponent mixture of the zirconia of nickel oxide and 8%mol stabilized with yttrium oxide, samarium doping of cerium oxide, gadolinium doping of cerium oxide;
(2) allotment of slurry: forming agent is dissolved in the solvent, adds the good ceramic powder of preliminary treatment then, grind evenly; Described forming agent is polysulfones or polyether sulfone, and described solvent is for dissolving the solvent of forming agent; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 1～15%: 2～30%: 55～97%;
(3) preparation of green compact: pulp preparation is become green compact, be immersed in moulding in the pure water then;
(4) high temperature sintering.
The preferred N-methyl pyrrolidone of described solvent.
Described pore creating material is that the general pore creating material among the porous ceramic preparation method gets final product, preferred active carbon, flour, corn flour, methylcellulose or ethyl cellulose.
In order to guarantee do not have slight crack when the sintering, heating rate was preferably less than 2 ℃/minute when temperature was lower than 400 ℃ in described step (4) high-temperature sintering process.If heating rate is too fast when being lower than 400 ℃, may make the porous ceramic behind the sintering produce slight crack.
In order to prepare the porous ceramic anode support that is suitable for Solid Oxide Fuel Cell, green compact are the tubular type green compact described in the step (3), and the porous ceramic for preparing like this is fit to be applied to the anode support of fuel cell.
Compare with existing porous ceramic preparation method, beneficial effect of the present invention is as follows:
(1) green compact of making according to the inventive method are immersed in just energy moulding at once in the water, and shaping speed is fast;
When (2) preparing porous ceramic support according to the inventive method, rate of finished products is more than 95%;
The supporter that not only can prepare single ceramic species when (3) preparing porous ceramic support according to the inventive method can also prepare the supporter of binary or polynary ceramic species;
Porosity can arbitrarily be adjusted as required when (4) preparing porous ceramic support according to the inventive method, and method of adjustment is that the pore creating material mixing that adds requirement when the preliminary treatment ceramic powder gets final product, and the porosity that obtains can reach 30%～80%;
(5) according to the porous ceramic anode support that is used for Solid Oxide Fuel Cell of the inventive method preparation, its shape is not limited to tubular type, and it can prepare difform porous ceramic support as required.
Description of drawings
Fig. 1 is the generalized section of fuel cell, and 1 is the porous ceramic anode support, and 2 is dielectric substrate, and 3 is negative electrode.
Fig. 2 prepares the metal die schematic diagram of long tube formula porous ceramic support for extrustion process, and 21 for having the funnel-shaped container of under shed, and 22 is the axis concentric with under shed, and 23 is air inlet, and 24 is the container of splendid attire pure water.
Embodiment
The invention will be further described below in conjunction with drawings and Examples, but the present invention's scope required for protection is not limited to the described scope of embodiment.
Accurately zirconia (PSZ) ceramic powders of weighing 15g3%mol stabilized with yttrium oxide adds 3g flour then and grinds evenly in agate mortar earlier.Weighing 0.75g polysulfones (PSF) is dissolved in the 2.25g N-methyl pyrrolidone (NMP), be added to then in the good PSZ ceramic powders of preliminary treatment, evenly obtain mud shape slurry with the mortar grinding, slurry evenly is coated in the glass bar surface, coming rollback to press on the glass plate about 5 minutes with rolling process afterwards, treat become after the even tube wall of pipe it to be immersed in the pure water 3 minutes, take out glass bar subsequently and just obtained the tubular type green compact.At last resulting green compact being placed in the high temperature furnace 1200 ℃ of sintering just obtained porosity in 4 hours and has been about 74% PSZ tubular type porous ceramic support.
In the present embodiment: the weight of described pore creating material is 20% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 3.57%: 10.71%: 85.72%.
On glass bar, apply different length and thickness, can obtain the tubulose green compact that length, wall thickness do not wait.
Embodiment 2
Zirconia (YSZ) ceramic powders of accurate weighing 7.5g nickel oxide (NiO) and 7.5g 8%mol stabilized with yttrium oxide is in ball grinder respectively, add 1.5g flour then, add an amount of absolute ethyl alcohol again, be placed on ball milling 1h on the planetary ball mill, it is standby to be placed on drying in oven at last.Weighing 1.0g polyether sulfone (PES) is dissolved in the 2.5g N-methyl pyrrolidone (NMP), be added to then in the good NiO-YSZ hybrid ceramic powder of preliminary treatment, evenly obtain mud shape slurry with the mortar grinding, slurry evenly is coated in the glass bar surface, coming rollback to press on the glass plate about 5 minutes with rolling process afterwards, treat become after the even tube wall of pipe it to be immersed in the pure water 10 minutes, take out the tubular type green compact that glass bar just obtains the about 1.0mm of wall thickness at last.
In the present embodiment: the weight of described pore creating material is 10% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 5%: 12.5%: 87.5%.
The NiO-YSZ tubular type green compact that will obtain with said method make it that certain intensity be arranged 1150 ℃ of following pre-burnings 4 hours, obtain the NiO-YSZ anode support tube 1 of presintering.Adopt infusion process at the NiO-YSZ of presintering anode support tube 1 surface preparation YSZ electrolytic thin-membrane 2 afterwards again, subsequently NiO-YSZ anode support tube/YSZ dielectric film was put into 1400 ℃ of sintering of high temperature Muffle furnace 4 hours.At last, be coated with one deck La on YSZ dielectric film 2 surfaces that sintering is crossed with the method for brushing
0.8Sr
0.2MnO
3(LSM)/and LSM-YSZ composite cathode 3, just obtained the SOFC monocell of long tube formula NiO-YSZ anode-supported after 2 hours through 1200 ℃ of sintering, as shown in Figure 1.The porosity of anode is about 40% in this monocell.
Adopt four electrode method that the output performance of this monocell is measured, silver-colored line is as lead in the test, and the silver slurry is as connecting material, is fuel with the hydrogen of saturated water vapour under the room temperature, and free-pouring air is an oxidant.Test shows, the output voltage of monocell is about 1V in the time of 800 ℃, and peak power output is at 800mW/cm
2About, demonstrated excellent properties.
Embodiment 3
The first PSZ long tube porous ceramic support for preparing the about 15cm of length according to composition proportion and the method for embodiment 1, utilize the film of infusion process again at its surface preparation nickel oxide (NiO) and gadolinium doped cerium oxide (GDC) mixture, obtained the NiO-GDC anode in 4 hours through 1150 ℃ of pre-burnings, and then utilize infusion process at its surface preparation GDC film, with after 1450 ℃ of sintering 4 hours, form the GDC dielectric substrate, the GDC dielectric substrate external coating barium strontium ferro-cobalt (Ba that crosses at sintering more at last
0.5Sr
0.5Co
0.8Fe
0.2O
3) negative electrode, just obtain the filming SOFC monocell that the PSZ porous ceramic supports after 2 hours through 970 ℃ of sintering.
Adopt four electrode method that the output performance of this monocell is measured, silver-colored line is as lead in the test, and the silver slurry is as connecting material, is fuel with the hydrogen of saturated water vapour under the room temperature, and free-pouring air is an oxidant.Test shows, the output voltage of monocell is about 1V in the time of 650 ℃, and peak power output is at 700mW/cm
2About, demonstrated excellent properties.
Embodiment 4
Take by weighing 12g aluminium oxide ceramics powder in mortar, add 1.5g flour again and grind evenly standby.Take by weighing 1.5g polysulfones (PSF) and be dissolved in the 9g N-methyl pyrrolidone (NMP), add the good ceramic powders of preliminary treatment then, stirring obtains viscous paste.This slurry is transferred in the graduated cylinder, adopt infusion process to do long tube formula green compact, specific practice is: test tube or glass bar are inserted in the slurry, lentamente it is lifted out from slurry then, and rapid soaking is in pure water, after 10 minutes, take out the long tube formula green compact that test tube or glass bar just obtain end sealing, these green compact just obtain porosity through 1400 ℃ of sintering and are about 45% porous alumina ceramic supporting body after 4 hours.
In the present embodiment: the weight of described pore creating material is 12.5% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 6.25%: 37.5%: 56.25%.
Embodiment 5
Adopt extrustion process to prepare long tube formula porous ceramic support in conjunction with mould shown in Figure 2.Concrete steps are as follows:
The first step is made an opening funnel-shaped container that has axis according to shown in Figure 2;
In second step, zirconia (PSZ) ceramic powders that takes by weighing the 16.3g3%mol stabilized with yttrium oxide adds 2g flour then and grinds evenly in agate mortar, and the mixed powder after will grinding is subsequently transferred in the beaker standby;
The 3rd step took by weighing 4.9g polyether sulfone (PES) and is dissolved in the 9.8g N-methyl pyrrolidone (NMP), poured into then in the above-mentioned beaker that mixed powder is housed, and stirred, and obtained the slurry that needs;
The 4th step, above-mentioned slurry is transferred in the metal die shown in Figure 2 21, fix axis 22, in mould, feed high pressure N by air inlet 23 then
2Gas, the while puts the container 24 of a splendid attire pure water under hopper outlet, through N
2The slurry that air pressure is gone into falls into and promptly may be molded to elongated tubular in the pure water; The present embodiment consumption can ensure that obtaining one is about 20cm, external diameter 6mm, the tubular type green compact of wall thickness 1.5mm;
The 5th step was placed in the high temperature furnace 1400 ℃ of sintering 4 hours with the tubular type green compact that obtain, and finally obtained being about 15cm, external diameter 4mm, wall thickness 1.0mm, the PSZ earthenware of porosity about 43%.
In the present embodiment: the weight of described pore creating material is 12.3% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 14.8%: 29.7%: 55.5%.
Embodiment 6
Chinese invention patent ZL200510101487.3 discloses solid oxide fuel cell monomer and the battery pack that a kind of conical tube type positive electrode supports, monomer whose comprises porous anode supporter, dense electrolyte film and porous cathode film, the porous anode supporter is that an end opening is big, the Taper Pipe shape that one end opening is little, the outer rim of little openend are arc; The dense electrolyte film covers porous anode supporter outer; The dense electrolyte upper strata of cathode layer between the arc outer rim of the little openend of Taper Pipe and big openend end edge.Battery pack be by in the big openend of the little openend outer of a conical tube type positive electrode support solid oxide fuel cell monomer and another monomer along by being connected and encapsulating material is tightly connected and constitutes.Battery cell bulk is little, the battery power output big, making easily, is specially adapted to small-sized SOFC pile.The negative electrode of battery cell is contacted with the mode of another Taper Pipe socket by a Taper Pipe easily with the anode of another battery cell and is connected, and sealing also is easier to realize.
It is big that present embodiment promptly prepares an end opening, the porous ceramic anode support of the Taper Pipe shape that an end opening is little.
Accurate weighing 3.75g nickel oxide (NiO) and 3.75g samarium doping of cerium oxide (SDC) ceramic powders are in ball grinder respectively, add the 1.0g active carbon then, add an amount of absolute ethyl alcohol again, be placed on the planetary ball mill ball milling 1 hour, it is standby to be placed on drying in oven at last.Weighing 0.75g polyether sulfone (PES) is dissolved in the 2.25g N-methyl pyrrolidone (NMP), be added to then in the good NiO-SDC hybrid ceramic powder of preliminary treatment, add 0.25g ethyl cellulose and 0.5g terpinol again, evenly obtain sposh shape slurry with the mortar grinding, with small brushes slurry is brushed inwall at coniform mould equably then, wait to brush to certain thickness, it is immersed in the pure water 10 minutes, behind the taking-up mould is exactly the coniform green compact of NiO-SDC, these green compact are placed on 1400 ℃ of sintering just obtained coniform NiO-SDC porous ceramic in 4 hours in the high temperature furnace, porosity is about 60%.The porous ceramic of present embodiment preparation promptly can be used for solid oxide fuel cell monomer and the battery pack that Chinese invention patent ZL200510101487.3 conical tube type positive electrode supports.
In the present embodiment: the weight of described pore creating material is 16.7% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 6.3%: 23.6%: 75.1%.
Embodiment 7
The zirconia (YSZ) of elder generation's weighing 5g nickel oxide (NiO), 7g8%mol stabilized with yttrium oxide, 3g gadolinium doping of cerium oxide (GDC) ceramic powders add the 0.75g corn flour then and grind evenly in agate mortar.Weighing 1g polysulfones (PSF) is dissolved in the 2.25g N-methyl pyrrolidone (NMP), be added to then in the good ceramic powders of preliminary treatment, evenly obtain mud shape slurry with the mortar grinding, slurry evenly is coated in the glass bar surface, coated length is 20cm, coming rollback to press on the glass plate about 5 minutes with rolling process afterwards, treat become after the even tube wall of pipe it to be immersed in the pure water 5 minutes, take out glass bar at last and just obtained the tubular type green compact.At last resulting green compact being placed in the high temperature furnace 1200 ℃ of sintering just obtained porosity in 4 hours and has been about 30% tubular type porous ceramic support.
In the present embodiment: the weight of described pore creating material is 5% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 5.26%: 11.84%: 82.9%.
Embodiment 8
Elder generation's weighing 10g nickel oxide (NiO) ceramic powders adds 3g flour then and grinds evenly in agate mortar.Weighing 1g polysulfones (PSF) is dissolved in the 2g N-methyl pyrrolidone (NMP), is added to then in the good ceramic powders of preliminary treatment, grinds with mortar and evenly obtains mud shape slurry, utilizes mould shown in Figure 2 to prepare the tubular type green compact, soaks 3 hours in pure water.At last resulting green compact being placed in the high temperature furnace 1200 ℃ of sintering just obtained porosity in 4 hours and has been about 80% tubular type porous ceramic support.
In the present embodiment: the weight of described pore creating material is 30% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 6.25%: 12.5%: 81.25%.
Embodiment 9
Zirconia (YSZ) ceramic powders of the weighing 80g8%mol of elder generation stabilized with yttrium oxide adds 10g flour then and grinds evenly in agate mortar.Weighing 1g polysulfones (PSF) is dissolved in the 9g N-methyl pyrrolidone (NMP), is added to then in the good ceramic powders of preliminary treatment, grinds with mortar and evenly obtains mud shape slurry, utilizes mould shown in Figure 2 to prepare the tubular type green compact, soaks 30 minutes in pure water.At last resulting green compact being placed in the high temperature furnace 1200 ℃ of sintering just obtained porosity in 4 hours and has been about 45% YSZ tubular type porous ceramic support.
In the present embodiment: the weight of described pore creating material is 14.1% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 1%: 7%: 90%.
Embodiment 10
Elder generation's weighing 72g samarium doping of cerium oxide (SDC) ceramic powders adds 8g flour then and grinds evenly in agate mortar.Weighing 6g polysulfones (PSF) is dissolved in the 14g N-methyl pyrrolidone (NMP), be added to then in the good ceramic powders of preliminary treatment, evenly obtain mud shape slurry with the mortar grinding, utilize mould shown in Figure 2 to prepare the first tubular type green compact, in pure water, soaked 10 minutes.At last resulting green compact being placed in the high temperature furnace 1400 ℃ of sintering just obtained porosity in 4 hours and has been about 43% SDC tubular type porous ceramic support.
Utilize second tubular type green compact of mould preparation shown in Figure 2, in pure water, soaked 10 hours.At last resulting green compact being placed in the high temperature furnace 1400 ℃ of sintering just obtained porosity in 4 hours and has been about 35% SDC tubular type porous ceramic support.
Soak 10 hours with soak the pipe that 10 minutes institutes finally prepare, its difference is that the green compact soak time is long more, pipe porosity behind the sintering is low more, and also easy more appearance pipe outer wall and inwall hole are little on microstructure, the sandwich sandwich structure that middle hole is big.
In the present embodiment: the weight of described pore creating material is 11.11% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 6%: 14%: 80%.
Embodiment 11
Elder generation's weighing 60g gadolinium doping of cerium oxide (GDC) ceramic powders adds 5g flour then and grinds evenly in agate mortar.Weighing 10g polysulfones (PSF) is dissolved in the 25gN-methyl pyrrolidone (NMP), is added to then in the good ceramic powders of preliminary treatment, grinds with mortar and evenly obtains mud shape slurry, utilizes mould shown in Figure 2 to prepare the tubular type green compact, soaks 20 minutes in pure water.At last resulting green compact being placed in the high temperature furnace 1400 ℃ of sintering just obtained porosity in 4 hours and has been about 38% GDC tubular type porous ceramic support.
In the present embodiment: the weight of described pore creating material is 8.33% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 10%: 25%: 65%.
Embodiment 12
Elder generation's weighing 20g nickel oxide (NiO), zirconia of 20g8%mol stabilized with yttrium oxide (YSZ) and 10g gadolinium doping of cerium oxide (GDC) ceramic powders add 5g flour then and grind evenly in agate mortar.Weighing 15g polysulfones (PSF) is dissolved in the 30g N-methyl pyrrolidone (NMP), is added to then in the good ceramic powders of preliminary treatment, grinds with mortar and evenly obtains mud shape slurry, utilizes mould shown in Figure 2 to prepare the tubular type green compact, soaks 5 minutes in pure water.At last resulting green compact being placed in the high temperature furnace 1400 ℃ of sintering just obtained porosity in 4 hours and has been about 46% polynary ceramic pipe type porous ceramic support.
In the present embodiment: the weight of described pore creating material is 10% of ceramic powder weight; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 15%: 30%: 55%.
Claims (4)
1. the preparation method of a porous ceramic support may further comprise the steps:
(1) preliminary treatment of ceramic powder: ceramic powder and pore creating material are ground evenly, and the weight of described pore creating material is 5%～30% of ceramic powder weight; Described ceramic powder is zirconia, samarium doping of cerium oxide, the gadolinium doping of cerium oxide of nickel oxide, 8%mol stabilized with yttrium oxide, the zirconia or the aluminium oxide of 3%mol stabilized with yttrium oxide, or the binary or the multicomponent mixture of nickel oxide and following three kinds of materials: the zirconia of 8%mol stabilized with yttrium oxide, samarium doping of cerium oxide, gadolinium doping of cerium oxide;
(2) allotment of slurry: forming agent is dissolved in the solvent, adds the good ceramic powder of preliminary treatment then, grind evenly; Described forming agent is polysulfones or polyether sulfone, and described solvent is the N-methyl pyrrolidone; The percentage by weight of described forming agent, solvent, ceramic powder that preliminary treatment is good is 1～15%: 2～30%: 55～97%;
(3) preparation of green compact: pulp preparation is become green compact, be immersed in moulding in the pure water then;
(4) high temperature sintering.
2. the preparation method of porous ceramic support according to claim 1 is characterized in that described pore creating material is active carbon, flour, corn flour, methylcellulose or ethyl cellulose.
3. the preparation method of porous ceramic support according to claim 1, heating rate is less than 2 ℃/minute when it is characterized in that temperature is lower than 400 ℃ in described step (4) high-temperature sintering process.
4. according to the preparation method of each described porous ceramic support of claim 1 to 3, it is characterized in that green compact are the tubular type green compact described in the step (3).
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| CN1180249A (en) * | 1996-08-27 | 1998-04-29 | 纽约州立大学研究基金会 | Gas diffusion electrodes based on polyethersulfone carbon blends |
| CN1964111A (en) * | 2005-11-10 | 2007-05-16 | 中国科学院大连化学物理研究所 | Electrode and membrane electrode of proton exchange membrane fuel cell, and making method and application |
| CN1971990A (en) * | 2005-11-25 | 2007-05-30 | 新光电气工业株式会社 | Solid electrolyte fuel cell |
| CN101162779A (en) * | 2007-10-26 | 2008-04-16 | 华南理工大学 | Preparation method of anode supporter of tube-type solid-oxide fuel battery |
-
2008
- 2008-07-01 CN CN2008100291529A patent/CN101306954B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3899354A (en) * | 1973-09-10 | 1975-08-12 | Union Carbide Corp | Gas electrodes and a process for producing them |
| CN1180249A (en) * | 1996-08-27 | 1998-04-29 | 纽约州立大学研究基金会 | Gas diffusion electrodes based on polyethersulfone carbon blends |
| CN1964111A (en) * | 2005-11-10 | 2007-05-16 | 中国科学院大连化学物理研究所 | Electrode and membrane electrode of proton exchange membrane fuel cell, and making method and application |
| CN1971990A (en) * | 2005-11-25 | 2007-05-30 | 新光电气工业株式会社 | Solid electrolyte fuel cell |
| CN101162779A (en) * | 2007-10-26 | 2008-04-16 | 华南理工大学 | Preparation method of anode supporter of tube-type solid-oxide fuel battery |
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| CN101306954A (en) | 2008-11-19 |
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