CN100456544C - Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method - Google Patents
Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method Download PDFInfo
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Abstract
This invention relates to solid oxidation fuel battery anode supportive electrolyte compound film, which comprises the following layers: anode supportive layer by NiO-YSZ of 3mol%Y<2>O<3; anode active layer by NiO-SSZ; solid electrolyte layer of SSZ 9mol% scandium oxide with total stable zircite and middle layer of CGO mixed with 20mol% cerium oxide.
Description
Technical field
The present invention relates to belong to the material preparation process field in the solid fuel cell with the large tracts of land anode support type electrolyte complex film of Solid Oxide Fuel Cell (SOFC) and the preparation method of multilayer The tape casting.
Background technology
SOFC is the high-efficient full solid-state electrochemical energy conversion equipment that chemical energy is converted into electric energy.The electric energy loss of its generating mainly concentrates on the internal resistance loss of electrolyte.For current density and the power density that improves battery, can reduce the working temperature of battery again, when selecting high conductivity novel electrolytes material, must adopt electrolytical filming preparation technology.As everyone knows, the preparation technology of ceramic membraneization is a lot, as air plasma spray (APS), electrochemical vapour deposition (EVD) (EVD) although etc. the preparation method can settle at one go by forming and sintering, because of the equipment price costliness, cost of manufacture is high and be difficult to apply.The curtain coating rule since technology simple, with low cost be the process that is suitable for making the Boping ceramic material of large tracts of land, sandwich construction most, plate intermediate temperature solid oxide fuel cell large-scale production is had vast market prospect.In field of solid oxide fuel; some researchs of the two-layer curtain coating of bibliographical information are arranged; they are first curtain coating one deck electrolyte and then curtain coating one deck anode support [Seungdoo Park; Raymond J.Gorte and John M.Vohs; Tape Cast Solid Oxide Fuel Cells for theDirect Oxidation of Hydrocarbons; Journal of The Electrochemical Society; 2001:A443-A444]; but do not see also at present that both at home and abroad relevant three layers of (comprising three layers) above The tape casting prepare the report of composite membrane; and three laminar flows prolong the technology in common burning and then dipping intermediate layer because many step sintering process; cost has also increased comparatively speaking; and the intermediate layer of dipping is difficult to sintering; cause it to combine relatively poorly with electrolytical, and this technology is not suitable for large-scale production.
Summary of the invention
At present situation, the purpose of this invention is to provide a kind of simple and practical and anode supporting type solid electrolyte complex film and preparation method thereof with Solid Oxide Fuel Cell of good electrical chemical property.
Anode supporting type solid electrolyte complex film provided by the present invention is made up of for four layers anode support, anode active layer, solid electrolyte layer and intermediate layer successively, and these four layers make by curtain coating, the area of composite membrane is 100mm * 100mm, thickness 0.5-1.0mm, and controllable.
Described anode support consists of NiO-YSZ, and wherein the quality percentage composition of NiO in the NiO-YSZ mixture is 30-70wt%, and YSZ then is by 3mol%Y
2O
3Partially stabilized cubic polycrystal zirconia and 8mol%Y
2O
3Complete stable cubic zirconia is formed, and the quality percentage composition in anode support is followed successively by 10-30wt% and 20-40wt%;
Described anode active layer consists of NiO-SSZ, and wherein the quality percentage composition of NiO in the NiO-SSZ mixture is 40-70wt%, and SSZ is the complete stable zirconia of 9mol% scandium oxide, and the quality percentage composition in described anode active layer is 60-30wt%;
Described solid electrolyte film consist of the complete stable zirconia of 9mol% scandium oxide;
The cerium oxide that consists of doping 20mol% gadolinium of described interlayer film.
Wherein anode support provides enough conductivity and intensity; Anode active layer improves chemical property by the length that increases three phase boundary; The SSZ electrolyte provides the conductivity higher than YSZ at low temperatures; The CGO intermediate layer also is a dielectric substrate, and it mainly acts on is to stop the reaction between the high activity negative electrode (perovskite cobaltatess) and SSZ electrolyte in the negative electrode sintering procedure and in the course of work of battery.Above-mentioned four layer materials are mixed with casting slurry respectively, press desired thickness curtain coating intermediate layer, dielectric substrate, anode active layer and anode support successively, after to be dried with the multilayer biscuit film at 1450 ℃ of following co-sinterings, the composite membrane size of making can be greater than 100mm * 100mm, the thickness 10-15 μ m in intermediate layer wherein, dielectric substrate thickness 15-20 μ m, anode active layer thickness 10-15 μ m, anode-supported layer thickness 600-700 μ m.(four laminar flows prolong sectional schematic diagram such as Fig. 2 of composite membrane)
The preparation method of anode supporting type solid electrolyte complex film of the present invention is:
The first step is produced the powder of four tunics respectively successively by the composition of four above-mentioned tunics, 3Y-TZP wherein, and 8YSZ and CGO powder are commercially available, are the TOSOH supply as 8YSZ, NiO is black Ni
2O
3Obtain through 800 ℃ of decomposition.The average grain diameter of 8YSZ powder is 0.2-0.4 μ m, and the average grain diameter of 3Y-TZP powder is 0.5-0.8 μ m, and the average grain diameter of NiO powder is 2.0-3.0 μ m.SSZ is the 9mol% scandium oxide.Complete stable zirconia, its manufacture method all has the report of its preparation method with complete to stablize 8YSZ identical on the document.
Second step, the powder of four layers of composite membrane is added butanone and alcohol mixed solvent and dispersant successively, use planetary ball mill respectively under 300-500 rev/min controlled condition, a ball milling 1-3 hour mixing is made slurry, wherein the mass ratio of butanone and ethanol is 2: 1, and dispersant is triethanolamine (TEA), adds 1-5wt%TEA in the anode support solution, and in other three kinds of composite membrane solution, adding 3-7wt%TEA, the amount of Jia Ruing all is benchmark with the solid mixture here.
The 3rd goes on foot, and goes on foot in the slurry of making second to add plastic agent and binding agent again, uses planetary ball mill more respectively under 300-500 rev/min controlled condition, makes uniform sizing material once more in ball milling 1-3 hour; Wherein, in the anode support slurry, add 4-8wt% dibutyl phthalate (being called for short DOP) and two kinds of plastic agents of Macrogol 200 (being called for short PEG) and 6-16wt% polyvinyl butyral resin (being called for short PVB) binding agent; Because the amount that PVB adds is bigger, so will add at twice; In anode active layer and solid electrolyte layer slurry, add 6-10wt% dibutyl phthalate (DOP) and Macrogol 200 (PEG) plastic agent and 3-7wt% polyvinyl butyral resin (being called for short PVB) binding agent; In the slurry of intermediate layer, add 6-10wt% dibutyl phthalate (DOP) and Macrogol 200 (PEG) plastic agent and 8-12wt% polyvinyl butyral resin (being called for short PVB) binding agent; The addition of above-described plastic agent and binding agent all is benchmark with the solid mixture.
The 4th step, the slurry of above-mentioned four kinds of mixings is sieved and after vacuum degassing handles through the 60-80 eye mesh screen respectively, successively curtain coating intermediate layer, electrolyte, anode active layer and anode support are made the composite membrane biscuit successively can to mix up the scraper height by desired thickness on casting machine, thereby make the compound biscuit film of desired thickness, wherein the scraper knife up in intermediate layer is 0.04-0.12mm, the scraper knife up of dielectric substrate is 0.08-0.16mm, the scraper knife up of anode active layer is 0.10-0.20mm, and the scraper knife up of anode support is 2.6-3.8mm.
The 5th step, dried composite membrane biscuit is cut into required dimensioned area employing Woelm Alumina pressing plate-composite membrane biscuit-Woelm Alumina pressing plate to be placed in the Muffle furnace like " sandwich style " structure and to burn altogether, 600 and 1400-1500 ℃ be incubated 2-6h respectively, plastic removal and sintering are once finished, after being cooled to 700 ℃ with 80-100 ℃/h speed then, cooling naturally; Speed is 30-150 ℃/h during intensification.
Composite membrane behind the sintering is coated the LSCF negative electrode after 1100 ℃ of sintering are made Solid Oxide Fuel Cell, carry out performance test.Test condition is: with H2, O2 is fuel, and working temperature is 800 ℃ and 850 ℃, and the composite membrane sintering temperature is 1450 ℃, and their performance is as shown in table 1.Can find out that from table the monocell performance that adopts four laminar flows provided by the invention to prolong the method preparation is better than the performance that three laminar flows prolong+flood the monocell of intermediate layer preparation.
The performance that table 1 different composite film constitutes relatively
This shows and the invention has the advantages that:
1, the simple efficient height of technology.Practicable batch process and can adjust the thickness that casting machine scraper height comes controlling diaphragm easily.
2, efficient height.Practicable batch process.
3, the composite membrane quality is good.Developed the smooth anode-supported electrolyte complex film that meets the SOFC instructions for use.
4, performance is good.The monocell performance that four laminar flows prolong the method preparation is better than the performance that three laminar flows prolong+flood the monocell of intermediate layer preparation.
Description of drawings
Fig. 1 is the schematic diagram of " sandwich style " perforated plate construction of composite membrane biscuit sintering employing provided by the invention
Fig. 2 prolongs the sectional schematic diagram of composite membrane for anode support type four laminar flows provided by the invention
Fig. 3 prolongs+floods the SEM photo that the intermediate layer composite membrane is coated the monocell after negative electrode generates electricity for three laminar flows provided by the invention
(a) solid electrolytic layer and intermediate layer; (b) anode support and intermediate layer
Fig. 4 prolongs the SEM photo that common burning composite membrane is coated the monocell after negative electrode generates electricity for four laminar flows provided by the invention
(a) intermediate layer and solid electrolyte layer; (b) anode support; (c) anode active layer
Embodiment
Describe below by specific embodiment, further specify substantial characteristics of the present invention and obvious improvement.
Embodiment 1
The multilayer The tape casting is made the preparation of large tracts of land anode support type electrolyte complex film biscuit
Taking by weighing 45g8YSZ respectively is the complete stable homemade 3mol%Y of zirconia, 30g of TOSOH (commerce) 8% yittrium oxide
2O
3The cubic polycrystal zirconia (3Y-TZP) and the 75g NiO that mix are black Ni
2O
3The anode support mixed powder that obtains through 800 ℃ of decomposition; Take by weighing complete stable zirconia (self-control) 20g of electrolyte powder 9mol% scandium oxide; The cerium oxide 20g that to take by weighing homemade intermediate layer powder CGO be doping 20mol% gadolinium, take by weighing the mixture 22g of anode active layer powder NiO-SSZ, mix butanone and ethanol (by 2: 1 mass ratioes) mixed solvent more respectively, add about 3wt% triethanolamine dispersant for anode support, add about 5wt% triethanolamine dispersant respectively for intermediate layer, electrolyte and anode active layer, use planetary ball mill 1 hour mixing of ball milling under 400 rev/mins of controlled conditions respectively.Mix the polyvinyl butyral resin binding agent of about 7wt% dibutyl phthalate and 200 two kinds of plastic agents of polyvinyl alcohol and about 10wt% then again for anode support, mix the polyvinyl butyral resin binding agent of about 8wt% dibutyl phthalate and 200 two kinds of plastic agents of polyvinyl alcohol and about 10wt% again for the intermediate layer, mix the polyvinyl butyral resin binding agent of about 8wt% dibutyl phthalate and 200 two kinds of plastic agents of polyvinyl alcohol and about 4wt% again for dielectric substrate, mix the polyvinyl butyral resin binding agent of about 8wt% dibutyl phthalate and 200 two kinds of plastic agents of polyvinyl alcohol and about 6wt% again for anode active layer, use planetary ball mill 2 hours mixings of ball milling again under 400 rev/mins of controlled conditions more respectively.Sieve and after vacuum degassing handles through 80 orders and 60 eye mesh screens, on casting machine by the scraper height that mixes up successively successively curtain coating make the composite membrane biscuit.
Embodiment 2
The multilayer The tape casting is made large tracts of land anode support type electrolyte complex film and is burnt till
Dried composite membrane biscuit is cut into required dimensioned area employing Woelm Alumina pressing plate-composite membrane biscuit-Woelm Alumina pressing plate this similar " sandwich style " structure to be placed in the Muffle furnace and to burn altogether, wherein the porosity of Woelm Alumina pressing plate is 50-60%, be warming up to 600 ℃ of insulation 2h with 30 ℃/h speed, be warming up to 1450 ℃ of insulation 4h with 120 ℃/h speed then, cooling is naturally once finished plastic removal and sintering after being cooled to 700 ℃ with 80 ℃/h speed again.
Embodiment 3
Four laminar flows prolong with three laminar flows and prolong+flood the SEM photo comparison that the intermediate layer composite membrane is coated the monocell after negative electrode generates electricity
By Fig. 3 and Fig. 4 as can be seen, four laminar flows prolong common burning composite membrane, and to coat intermediate layer, negative electrode generating back fine with combining of dielectric substrate, and the sintering in intermediate layer is fine, basically there is not layering after finishing generating, and three laminar flows prolong+flood the intermediate layer composite membrane and coat and obviously find out that the intermediate layer combines with dielectric substrate after the negative electrode generating and be not fine, almost do not have sintering just can not play the effect of reacting between prevention negative electrode and the SSZ dielectric substrate so topmost problem is the intermediate layer, Here it is causes the bad main cause of battery performance.
Claims (9)
1, the anode supporting type solid electrolyte complex film of Solid Oxide Fuel Cell is made up of anode support, anode active layer, solid electrolyte layer and intermediate layer successively, it is characterized in that:
(1) described anode support consists of NiO-YSZ, and wherein the quality percentage composition of NiO in the NiO-YSZ mixture is 30-70%, and YSZ then is by 3mol%Y
2O
3Partially stabilized cubic polycrystal zirconia and 8mol%Y
2O
3Complete stable cubic zirconia is formed, and the quality percentage composition in anode support is followed successively by 10-30% and 20-40%;
(2) described anode active layer consists of NiO-SSZ, and wherein the quality percentage composition of NiO in the NiO-SSZ mixture is 40-70%, and SSZ is the complete stable zirconia of 9mol% scandium oxide, and the quality percentage composition in described anode active layer is 60-30%;
(3) described solid electrolyte layer consists of the complete stable zirconia of 9mol% scandium oxide;
(4) cerium oxide that consists of doping 20mol% gadolinium in described intermediate layer.
2, press the anode supporting type solid electrolyte complex film of the described Solid Oxide Fuel Cell of claim 1, it is characterized in that intermediate layer thickness is 15-20 μ m, the solid electrolyte layer thickness is 15-20 μ m, and anode active layer thickness is 10-15 μ m, and the anode-supported layer thickness is 600-700 μ m.
3, by the anode supporting type solid electrolyte complex film of the described Solid Oxide Fuel Cell of claim 1, the area that it is characterized in that the composite membrane made is greater than 100mm * 100mm.
4, preparation is characterized in that as the method for the anode supporting type solid electrolyte complex film of claim 1,2 or 3 described Solid Oxide Fuel Cell preparation process is:
The first step takes by weighing the powder of four layers respectively successively by the composition of described four layers of claim 1;
Second step, the powder of four layers is added butanone and alcohol mixed solvent and dispersant successively, use planetary ball mill respectively under 300-500 rev/min controlled condition, a ball milling 1-3 hour mixing is made slurry, wherein the mass ratio of butanone and ethanol is 2: 1, dispersant is a triethanolamine, adding the quality percentage composition in the anode support solution is the triethanolamine of 1-5%, and add the quality percentage composition in the solution of other three layers is the triethanolamine of 3-7%, and addition all is benchmark with the solid mixture;
The 3rd goes on foot, and goes on foot in the slurry of making second to add plastic agent and binding agent again, uses planetary ball mill more respectively under 300-500 rev/min condition, makes uniform sizing material once more in ball milling 1-3 hour; Wherein, adding dibutyl phthalate that the quality percentage composition is 4-8% and two kinds of plastic agents of Macrogol 200 and quality percentage composition in the anode support slurry is the polyvinyl butyral resin binding agent of 6-16%; Adding dibutyl phthalate that the quality percentage composition is 6-10% and Macrogol 200 plastic agent and quality percentage composition in anode active layer and solid electrolyte layer slurry is the polyvinyl butyral resin binding agent of 3-7%; Adding dibutyl phthalate that the quality percentage composition is 6-10% and Macrogol 200 plastic agent and quality percentage composition in the slurry of intermediate layer is the polyvinyl butyral resin binding agent of 8-12%; The addition of above-described plastic agent and binding agent all is benchmark with the solid mixture;
The 4th step, the slurry of above-mentioned four kinds of mixings is sieved and after vacuum degassing handles through the 60-80 eye mesh screen respectively, on casting machine by desired thickness mix up the scraper height successively successively curtain coating intermediate layer, solid electrolyte layer, anode active layer and anode support make the composite membrane biscuit, thereby make the compound biscuit film of desired thickness; Wherein the scraper knife up in intermediate layer is 0.04-0.12mm, and the scraper knife up of solid electrolyte layer is 0.08-0.16mm, and the scraper knife up of anode active layer is 0.10-0.20mm, and the scraper knife up of anode support is 2.6-3.8mm;
The 5th step, dried composite membrane biscuit is cut into required dimensioned area, adopting Woelm Alumina pressing plate-composite membrane biscuit-Woelm Alumina pressing plate to be placed in the Muffle furnace like " sandwich style " structure burns altogether, 600 and 1400-1500 ℃ be incubated 2-6h respectively, plastic removal and sintering are once finished, after being cooled to 700 ℃ with 80-100 ℃/h speed then, cooling naturally.
5, press the preparation method of the anode supporting type solid electrolyte complex film of the described Solid Oxide Fuel Cell of claim 4, it is characterized in that described NiO is Ni
2O
3Make through 800 ℃ of decomposition, average grain diameter is 2.0-3.0 μ m.
6, press the preparation method of the anode supporting type solid electrolyte complex film of the described Solid Oxide Fuel Cell of claim 4, it is characterized in that 3mol%Y
2O
3Partially stabilized cubic polycrystal zirconia average grain diameter is 0.5-0.8 μ m; 8mol%Y
2O
3Complete stable cubic zirconia particle diameter is 0.2-0.4 μ m.
7, press the preparation method of the anode supporting type solid electrolyte complex film of the described Solid Oxide Fuel Cell of claim 4, it is characterized in that polyvinyl butyral resin is that the branch secondary adds in the described anode support slurry.
8, press the preparation method of the anode supporting type solid electrolyte complex film of the described Solid Oxide Fuel Cell of claim 4, the porosity of the Woelm Alumina pressing plate that uses when it is characterized in that sintering is 50-60%.
9, press the preparation method of the anode supporting type solid electrolyte complex film of the described Solid Oxide Fuel Cell of claim 4, the heating rate when it is characterized in that sintering is 30-150 ℃/h.
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| CN101399352B (en) * | 2007-09-25 | 2011-01-19 | 中国科学院宁波材料技术与工程研究所 | Producing method for a high strength ultra-thin anode supporting type solid oxide fuel cell |
| KR101175581B1 (en) * | 2009-03-26 | 2012-08-21 | 도요타 지도샤（주） | Electrolyte membrane formation method, membrane-electrode assembly, and membrane-electrode assembly manufacturing method |
| CN102683728A (en) * | 2012-05-14 | 2012-09-19 | 杨绍华 | Anode-supported solid oxide fuel cell and preparation method thereof |
| WO2013173981A1 (en) * | 2012-05-22 | 2013-11-28 | Yang Shaohua | Anode-supported solid oxide fuel cell and method for preparing same |
| CN103811787A (en) * | 2012-11-07 | 2014-05-21 | 中国科学院上海硅酸盐研究所 | Method for producing flat-plate-type solid oxide fuel cell anode support electrolyte composite membrane |
| CN104183860B (en) * | 2014-08-04 | 2016-08-17 | 景德镇陶瓷学院 | A kind of zirconium oxide plate burnt for planar anode-supported type SOFC half-cell pressure and surface modification method thereof |
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| TWI708747B (en) * | 2019-10-28 | 2020-11-01 | 行政院原子能委員會核能研究所 | A method of preparation and application for glass ceramic sealing thin strips |
| KR20210052820A (en) * | 2019-11-01 | 2021-05-11 | 현대자동차주식회사 | A membrane electrode assembly with excellent durability and proton conductivity and method of manufacturing thereof |
| CN111087239A (en) * | 2019-12-10 | 2020-05-01 | 神华新能源有限责任公司 | Water-based tape casting slurry, electrolyte film, preparation method and application thereof |
| CN113381041B (en) * | 2021-06-29 | 2022-11-04 | 清华四川能源互联网研究院 | Electrode supporting type solid oxide fuel cell and preparation method thereof |
| CN114561656A (en) * | 2022-04-06 | 2022-05-31 | 北京理工大学 | Medium-low temperature metal support solid oxide electrolytic cell |
| CN116826130A (en) * | 2023-06-30 | 2023-09-29 | 中国矿业大学 | Preparation method of solid oxide fuel cell |
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