CN101183716A - Preparation method of three-in-one electrode for solid oxide fuel cell - Google Patents
Preparation method of three-in-one electrode for solid oxide fuel cell Download PDFInfo
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Abstract
固体氧化物燃料电池三合一电极的制备方法，属于表面工程领域的等离子喷涂方法，用于固体氧化物燃料电池核心部件的制备，其目的是制备致密、薄膜厚度较小、物质成分分布均匀的电解质层，有效改善电解质电导率，降低SOFC内阻，提高输出功率；同时又能制备多孔隙，且分布均匀的电极。本发明包括：配制步骤、喷涂支撑电极步骤、喷涂电解质层步骤和喷涂阴极或者阳极步骤。本发明可直接采用细纳米或超微粉末进行喷涂，无需造粒；功能层间材质变化呈连续渐变梯度分布，可减小界面电阻、避免界面分层；成形与烧结过程一体化一次连续成形、无需多次烧结，尤其适合平板、管状、MOLB(Mono－Block Layer Built)、瓦楞等形式SOFC电极、纳米结构大面积涂层及纳米器件的短流程制造。
The preparation method of the solid oxide fuel cell three-in-one electrode belongs to the plasma spraying method in the field of surface engineering, and is used for the preparation of the core components of the solid oxide fuel cell. The electrolyte layer can effectively improve the conductivity of the electrolyte, reduce the internal resistance of SOFC, and increase the output power; at the same time, it can prepare porous and uniformly distributed electrodes. The invention comprises: preparation step, spraying supporting electrode step, spraying electrolyte layer step and spraying cathode or anode step. The invention can directly use fine nanometer or ultrafine powder for spraying without granulation; the material change between functional layers is distributed in a continuous gradient gradient, which can reduce interface resistance and avoid interface delamination; the forming and sintering process is integrated into one continuous forming, No need for multiple sintering, especially suitable for flat, tubular, MOLB (Mono-Block Layer Built), corrugated and other forms of SOFC electrodes, nanostructured large-area coatings and short-process manufacturing of nanodevices.
Description
Technical field
The invention belongs to the plasma spraying method in Surface Engineering field, be used for the preparation of Solid Oxide Fuel Cell core component.
Background technology
(Solid Oxide Fuel Cell SOFC) with its solid-state structure, high-energy conversion efficiency with to characteristics such as the extensive adaptability of fuel gas, has become one of focus of various countries' research and development to Solid Oxide Fuel Cell.But, existing manufacturing technology long flow path and efficient is low, manufacturing cost is high, properties of product poor reliability, percent defective height, power are not taken into account mutually with volume, the problems such as hot matching difference between the parts have hindered its commercialized development.Promote the commercialization of SOFC, not only need to study the SOFC material component, also proposed challenge with traditional manufacturing mode that shaping processing separates simultaneously to the design of SOFC structural system, material preparation.
According to the performance requirement of SOFC long-time steady operation to each parts, utilize film-forming process its core component that is shaped, must guarantee: it is thin and fine and close that membrane structure can meet dielectric substrate, the performance requirement of electrode porous; Technology is workable, good reproducibility; The film forming efficiency height, with low cost, pollute for a short time, be fit to large-scale commercial applications production.Existing at present conventional air plasma spraying (the Atmospheric Plasma Spraying that adopts, APS) report of prepared anode, negative electrode and connecting plate sees that the clothing treasured is honest and clean: " fuel cell-efficient, eco-friendly generation mode ", Beijing, Chemical Industry Press, 2000,5-8.But, the employing gas delivery solid state powder mode that matches with air plasma spraying is difficult to applying nano and attritive powder carries out air plasma spraying, have following shortcoming: 1) minuteness particle causes being difficult to realize even powder feeding because the adsorptivity of particle surface is mobile poor; 2) minuteness particle of light specific gravity is difficult for sending into flame stream center, is difficult to realize particle is evenly heated; 3) phase structure takes place and changes and grain growth under the elevated temperature heat action condition in minuteness particle easily.Above factor has determined the stratiform micro-structural characteristics of air plasma spraying layer, the about 100 μ m-1mm of general thickness, and porosity 1-20% is difficult to prepare the dielectric substrate that requires high-compactness.Therefore how to prepare thin and 8% (molar fraction) yttria-stabilized zirconia (8YSZ fine and close (15-30 μ m), Zirconium Oxide Stabilized Yttrium Trioxide) dielectric substrate has become one of key problem of present SOFC research, see P.Fauchais, V.Rat, C.Delbos, et al.Understanding of suspension DC plasma spraying of finely structuredcoatings for SOFC[J] .IEEE Transactions on Plasma Science, 2005,33 (2): 920-930.At present, seen the correlative study of adopting discharge plasma sintering (Spark Plasma Sintering), chemistry infiltration densification heat treatment or other additional process improving and improving its performance, see Khor, K.A., Yu, L.G., Chan, S.H., et al.Densification of plasma sprayed YSZelectrolytes by spark plasma sintering.Journal of the European CeramicSociety, 2003,23 (11): 1885-1863; Yang Hongwei, Luan Weiling, Tu Shandong; " new development of plasma spraying technology ", sufacing, 2005,34 (6): 7-9; Li Chengxin, peaceful advanced, Li Changjiu, plasma spraying prepares the SOFC dielectric substrate in conjunction with densification process, power technology, 2004,28 (9): 565-568; But this process can increase the complexity and the cost of manufacture of forming technology, and serious the obstruction made SOFC and commercialized development thereof in batches.
For this reason, (Suspension Plasma Spraying SPS) has been subjected to extensive concern to a kind of technology-liquid material plasma spraying of effective preparation YSZ dielectric substrate.This technology can directly utilize attritive powder, nanometer or ultra-micro powder as the sprayed coating material, and the mobile property of fluent material is good, by rational liquor charging parts of project organization and atomizer, and can be with the uniform atomizing of liquid material sprayed on material; Secondly, easily send into the jet-core region, realize evenly heating through the liquid fluid capacitance of atomizing; Once more, the microstructure of coating forms in spraying process, by control atomization parameter and the flight path of powder particle in plasma jet, the both phase structure of may command coating and crystallite dimension.Correlative study has at present shown that this technology can prepare the YSZ coating of compact texture.This technology also can prepare mushy SOFC negative electrode simultaneously, sees C.Monterrubio-Badillo, H.Ageorges, T.Chartier, et al.Preparation of LaMnO
3Perovskite thin films by suspensionplasma spraying for SOFC cathodes.Surface and Coatings Technology, 2006,200 (12-13): 3743-3756.The document of correlative study has simultaneously also been reported and has been adopted this technology successfully to prepare the SOFC electrolyte layers, see C.Hwang, C.C.Tzeng.A nanostructured YSZ film coatingby liquid suspension injection into an APS plasma flame.Joumal ofAdvanced Oxidation Technologies, 2005,8 (1): 85-89; C.Monterrubio-Badillo, H.Ageorges, T.Chartier, et al.Chemical composition optimisation ofperovskite coatings by suspension plasma spraying for SOFC cathodes.in:Proceedings of the International Thermal Spray Conference.2004.562-567.But,, be not suitable for spraying the bigger metal material of proportion (as anode material) though liquid material plasma spraying is suitable for the spray formation of the ceramic material of light specific gravity.
In sum, single air plasma spraying or liquid material plasma spraying all are difficult to adapt to the continuous once-forming of SOFC three-in-one electrode.
Summary of the invention
The invention provides a kind of preparation method of three-in-one electrode of solid oxide fuel battery, its objective is the dielectric substrate that preparation is fine and close, film thickness is less, material composition is evenly distributed, effectively improve electrolytic conductivity, reduce the SOFC internal resistance, improve power output; Simultaneously can prepare the porous crack again, and the electrode that is evenly distributed.
The preparation method of a kind of three-in-one electrode of solid oxide fuel battery of the present invention comprises:
(1) preparation steps, absolute ethyl alcohol, 8YSZ dusty material, dispersant are become electrolyte suspension with binder making, wherein to account for suspension quality percentage be 5～15% to the 8YSZ dusty material, it is 0.5～5% that dispersant accounts for suspension vol percentage, and it is 1～10% that binding agent accounts for suspension vol percentage;
(2) spraying support electrode step sprays anode material or cathode material with air plasma spraying on matrix, makes anode or negative electrode, and anode or cathode thickness are 450～700 μ m;
(3) spraying dielectric substrate step on anode that has been shaped or negative electrode, adopts the described electrolyte suspension of liquid material plasma spraying to form dielectric substrate, and its thickness is 20～45 μ m;
(4) sprayed cathode or anode step, on dielectric substrate, continue sprayed cathode material or anode material with air plasma spraying, preparation negative electrode or anode, negative electrode or anode thickness are that 50～100 μ m finally make anode-supported three-in-one electrode or cathode support three-in-one electrode.
The preparation method of described three-in-one electrode of solid oxide fuel battery, it is characterized in that: after described spraying support electrode step, on the anode or negative electrode of spray formation, first gradient transitional lay when adopting solid, liquid identical between spraying preparation anode and dielectric substrate or second gradient transitional lay between negative electrode and dielectric substrate; On first gradient transitional lay or second gradient transitional lay, adopt liquid material plasma spraying to carry the suspension spraying to form dielectric substrate; The 3rd gradient transitional lay when on dielectric substrate, adopting solid, liquid identical between spray formation dielectric substrate and negative electrode or the 4th gradient transitional lay between dielectric substrate and anode; On the 3rd transition zone or the 4th gradient transitional lay, continue spraying preparation negative electrode or anode with air plasma spraying again, finally make the three-in-one electrode that comprises two gradient transitional lay.
The preparation method of described three-in-one electrode of solid oxide fuel battery is characterized in that: described anode material is the mixed-powder of NiO and 8YSZ, and its percent by volume is NiO 35～50%, and 8YSZ 65～50%; Described cathode material is lanthanum manganate or La
1-xSr
xCo
1-yFe
yO
3, x=0.1～0.6, y=0～1.0; Described matrix is a kind of in hole pottery, fine and close stainless steel, nickel foam or the foamed aluminium; Described dispersant is polyethylene glycol or phosphoglyceride; Described binding agent is polyvinyl alcohol or glycerine.
The preparation method of described three-in-one electrode of solid oxide fuel battery is characterized in that:
The described first or the 3rd gradient transitional lay adopts air plasma spraying NiO powder, liquid material plasma spraying electrolyte suspension preparation, and the first or the 3rd gradient transition layer thickness is 20～35 μ m; The powder feed rate of NiO powder is constantly adjusted in the first gradient transitional lay preparation process, the percent by volume of NiO carries out the transition to 0% from described anode material, the speed of sending into of electrolyte suspension is also constantly adjusted, and the percent by volume of 8YSZ carries out the transition to 100% from described anode material; The powder feed rate of NiO powder is constantly adjusted in the 3rd gradient transitional lay preparation process, from 0% percent by volume that carries out the transition to NiO the described anode material, the speed of sending into of electrolyte suspension is also constantly adjusted, from 100% percent by volume that carries out the transition to 8YSZ the described anode material;
The described second or the 4th gradient transitional lay adopts the described cathode material of air plasma spraying, the described electrolyte suspension preparation of liquid material plasma spraying, and the second or the 4th gradient transition layer thickness is 20～35 μ m; The speed of sending into of the powder feed rate of cathode powder and electrolyte suspension is all constantly adjusted in the preparation process, guarantees the mass percent 70～50% of cathode material in the gradient transitional lay, and the mass percent of 8YSZ is 30～50%.
The present invention adopts the mixed phase plasma spraying to prepare the SOFC three-in-one electrode, promptly adopts air plasma spraying to prepare anode layer and cathode layer, prepare dielectric substrate with liquid material plasma spraying, the mixed phase plasma spraying of the gradient transitional lay between electrode and dielectric substrate.In the preparation process, switch easily by sending at different sprayed on material between mode (solid phase, liquid phase) and technological parameter, can be easy to three-in-one electrode quick, efficient, integral forming SOFC, thereby it is thin and fine and close to satisfy dielectric substrate, the preparation requirement of electrode porous, shorten manufacturing cycle greatly, and can effectively improve the runnability of SOFC.
Advantage of the present invention is: according to the performance requirement of different electrode layers, change the air plasma spraying technological parameter, thereby obtain needed porosity of each parts and density; Can be in atmospheric environment continuously, fast, separate or do not need discretely matrix or forming on the coating of material at need in high quality, form the three-in-one electrode of anode, dielectric substrate and cathode layer or negative electrode, dielectric substrate and anode layer in regular turn; Liquid material plasma spray coating process can suppress the nano particle trend of growing up in preparation process, obtain the dense electrolyte coating of complete nanophase structure, helps improving the ionic conductance of dielectric substrate.
The present invention can directly adopt thin nanometer or ultra-micro powder to spray, and need not granulation; The material variation is the continuous gradation Gradient distribution between functional layer, can reduce interface resistance, avoid interface debonding; Be shaped with the integrated one-time continuous shaping of sintering process, need not repeatedly sintering, especially be fit to the short flow process manufacturing of various ways SOFC electrode, nanostructure large tracts of land coating and nano-devices such as flat board, tubulose, MOLB (Mono-Block Layer Built), corrugation.
Description of drawings
Fig. 1 forms for the mixed phase plasma spray system;
Fig. 2 is an anode-supported SOFC three-in-one electrode structural representation;
Fig. 3 is a cathode support SOFC three-in-one electrode structural representation;
Fig. 4 is the anode-supported SOFC three-in-one electrode structural representation that comprises gradient transitional lay;
Fig. 5 is the cathode support SOFC three-in-one electrode structural representation that comprises gradient transitional lay.
Embodiment
Below in conjunction with accompanying drawing implementation step of the present invention is described.
The present invention adopts mixed phase plasma spray system as shown in Figure 1, comprises liquid material conveying system 1, plasma gun 2, and conventional solid-state powder feeder 3, plasma gun 2 produces plasma jet 4, sprays on matrix 5.
Embodiment 1: as shown in Figure 2, absolute ethyl alcohol, 8YSZ dusty material, polyethylene glycol and polyvinyl alcohol are mixed with electrolyte suspension, wherein to account for suspension quality percentage be 5% to the 8YSZ dusty material, it is 0.5% that the dispersant polyethylene glycol accounts for suspension vol percentage, and it is 1% that the binding agent polyvinyl alcohol accounts for suspension vol percentage.At first use NiO+8YSZ anode material (the NiO percent by volume is 35%, and the 8YSZ percent by volume is 65%), use the method for air plasma spraying, spraying forms anode 6 on matrix 5, and thickness is 550 μ m, and matrix 5 is the hole pottery; Secondly the 8YSZ suspension that will dispose with liquid material conveying system 1 is sent in the plasma jet 4, adopts liquid material plasma spraying method to continue the fine and close dielectric substrate 7 of spraying preparation on the anode 6 of spray formation, and thickness is 25 μ m; Adopt the cathode material lanthanum manganate at last, adopt air plasma spraying to continue spraying on dielectric substrate 7 and form negative electrode 8, thickness is 75 μ m; Obtain the anode-supported three-in-one electrode thus.
Embodiment 2: as shown in Figure 3, absolute ethyl alcohol, 8YSZ dusty material, phosphoglyceride and polyvinyl alcohol are mixed with electrolyte suspension, wherein to account for suspension quality percentage be 10% to the 8YSZ dusty material, it is 0.5% that the dispersant phosphoglyceride accounts for suspension vol percentage, and it is 1% that the binding agent polyvinyl alcohol accounts for suspension vol percentage.Use the method for air plasma spraying, at first adopt cathode material La
1-xSr
xCo
1-yFe
yO
3, x=0.1, y=1.0, spraying forms negative electrode 8 on matrix 5, and thickness is 700 μ m, and matrix 5 is fine and close stainless steel; Secondly the 8YSZ suspension that will dispose with liquid material conveying system 1 is sent in the plasma jet 4, adopts liquid material plasma spraying method to continue the fine and close dielectric substrate 7 of spraying preparation on the negative electrode 8 of spray formation, and thickness is 35 μ m; Adopt NiO+8YSZ anode material (the NiO percent by volume is 50%, and the 8YSZ percent by volume is 50%) at last, adopt air plasma spraying to continue spraying on dielectric substrate 7 and form anode 6, thickness is 90 μ m; Obtain the cathode support three-in-one electrode thus.
Embodiment 3: as shown in Figure 2, absolute ethyl alcohol, 8YSZ dusty material, polyethylene glycol and glycerine are mixed with electrolyte suspension, wherein to account for suspension quality percentage be 7.5% to the 8YSZ dusty material, it is 2.5% that the dispersant polyethylene glycol accounts for suspension vol percentage, and it is 5% that binding agent glycerine accounts for suspension vol percentage.At first use NiO+8YSZ anode material (the NiO percent by volume is 40%, and the 8YSZ percent by volume is 60%), use the method for air plasma spraying, spraying forms anode 6 on matrix 5, and thickness is 600 μ m, and matrix 5 is a nickel foam; Secondly the 8YSZ suspension that will dispose with liquid material conveying system 1 is sent in the plasma jet 4, adopts liquid material plasma spraying method to continue the fine and close dielectric substrate 7 of spraying preparation on the anode 6 of spray formation, and thickness is 30 μ m; Adopt cathode material La at last
1-xSr
xCo
1-yFe
yO
3, x=0.3, y=0.5 adopts air plasma spraying to continue spraying on dielectric substrate 7 and forms negative electrode 8, and thickness is 80 μ m; Obtain the anode-supported three-in-one electrode thus.
Embodiment 4: as shown in Figure 3, absolute ethyl alcohol, 8YSZ dusty material, polyethylene glycol and polyvinyl alcohol are mixed with electrolyte suspension, wherein to account for suspension quality percentage be 5% to the 8YSZ dusty material, it is 1% that the dispersant polyethylene glycol accounts for suspension vol percentage, and it is 1% that the binding agent polyvinyl alcohol accounts for suspension vol percentage.Use the method for air plasma spraying, at first adopt the cathode material lanthanum manganate, spraying forms negative electrode 8 on matrix 5, and thickness is 450 μ m, and matrix 5 is a foamed aluminium; Secondly the 8YSZ suspension that will dispose with liquid material conveying system 1 is sent in the plasma jet 4, adopts liquid material plasma spraying method to continue the fine and close dielectric substrate 7 of spraying preparation on the negative electrode 8 of spray formation, and thickness is 20 μ m; Adopt NiO+8YSZ anode material (the NiO percent by volume is 45%, and the 8YSZ percent by volume is 55%) at last, adopt air plasma spraying to continue spraying on dielectric substrate 7 and form anode 6, thickness is 50 μ m; Obtain the cathode support three-in-one electrode thus.
Embodiment 5: as shown in Figure 2, absolute ethyl alcohol, 8YSZ dusty material, phosphoglyceride and polyvinyl alcohol are mixed with electrolyte suspension, wherein to account for suspension quality percentage be 15% to the 8YSZ dusty material, it is 5% that the dispersant phosphoglyceride accounts for suspension vol percentage, and it is 10% that the binding agent polyvinyl alcohol accounts for suspension vol percentage.At first use NiO+8YSZ anode material (the NiO percent by volume is 35%, and the 8YSZ percent by volume is 65%), use the method for air plasma spraying, spraying forms anode 6 on matrix 5, and thickness is 500 μ m, and matrix 5 is a nickel foam; Secondly the 8YSZ suspension that will dispose with liquid material conveying system 1 is sent in the plasma jet 4, adopts liquid material plasma spraying method to continue the fine and close dielectric substrate 7 of spraying preparation on the anode 6 of spray formation, and thickness is 45 μ m; Adopt cathode material La at last
1-xSr
xCo
1-yFe
yO
3, x=0.6, y=0 adopts air plasma spraying to continue spraying on dielectric substrate 7 and forms negative electrode 8, and thickness is 100 μ m; Obtain the anode-supported three-in-one electrode thus.
Embodiment 6: as shown in Figure 4, difference from Example 1 is, spraying preparation the first and the 4th gradient transitional lay when adopting solid, liquid identical.The thickness 20 μ m of first gradient transitional lay 9 wherein, NiO powder volume percentage carries out the transition to 0% from 35% in the preparation process, and 8YSZ powder volume percentage carries out the transition to 100% from 65%; The thickness 35 μ m of the 4th gradient transitional lay 10, the mass percent of cathode material lanthanum manganate is 70% in the preparation process, the mass percent of 8YSZ powder is 30%.All the other same respective embodiments.Finally obtain comprising the anode-supported SOFC three-in-one electrode of gradient transitional lay.
Embodiment 7: as shown in Figure 4, difference from Example 3 is, spraying preparation the first and the 4th gradient transitional lay when adopting solid, liquid identical.The thickness 35 μ m of first gradient transitional lay 9 wherein, NiO powder volume percentage carries out the transition to 0% from 40% in the preparation process, and 8YSZ powder volume percentage carries out the transition to 100% from 60%; The thickness 25 μ m of the 4th gradient transitional lay 10, cathode material La in the preparation process
1-xSr
xCo
1-yFe
yO
3(x=0.3, mass percent y=0.5) is 60%, the mass percent of 8YSZ powder is 40%.All the other same respective embodiments.Finally obtain comprising the anode-supported SOFC three-in-one electrode of gradient transitional lay.
Embodiment 8: as shown in Figure 4, difference from Example 5 is, spraying preparation the first and the 4th gradient transitional lay when adopting solid, liquid identical.The thickness 25 μ m of first gradient transitional lay 9 wherein, NiO powder volume percentage carries out the transition to 0% from 35% in the preparation process, and 8YSZ powder volume percentage carries out the transition to 100% from 65%; The thickness 20 μ m of the 4th gradient transitional lay 10, cathode material La in the preparation process
1-xSr
xCo
1-yFe
yO
3(x=0.6, mass percent y=0) is 50%, the mass percent of 8YSZ powder is 50%.All the other same respective embodiments.Finally obtain comprising the anode-supported SOFC three-in-one electrode of gradient transitional lay.
Embodiment 9: as shown in Figure 5, difference from Example 2 is, spraying preparation the second and the 3rd gradient transitional lay when adopting solid, liquid identical.The thickness 35 μ m of second gradient transitional lay 11 wherein, cathode material La in the preparation process
1-xSr
xCo
1-yFe
yO
3(x=0.1, mass percent y=1.0) is 70%, the mass percent of 8YSZ powder is 30%; The thickness 20 μ m of the 3rd gradient transitional lay 12, NiO powder volume percentage carries out the transition to 50% from 0% in the preparation process, and 8YSZ powder volume percentage carries out the transition to 50% from 100%.All the other same respective embodiments.Finally obtain comprising the cathode support SOFC three-in-one electrode of gradient transitional lay.
Embodiment 10: as shown in Figure 5, difference from Example 4 is, spraying preparation the second and the 3rd gradient transitional lay when adopting solid, liquid identical.The thickness 30 μ m of second gradient transitional lay 11 wherein, the mass percent of cathode material lanthanum manganate is 50% in the preparation process, the mass percent of 8YSZ powder is 50%; The thickness 35 μ m of the 3rd gradient transitional lay 12, NiO powder volume percentage carries out the transition to 45% from 0% in the preparation process, and 8YSZ powder volume percentage carries out the transition to 55% from 100%.All the other same respective embodiments.Finally obtain comprising the cathode support SOFC three-in-one electrode of gradient transitional lay.
Embodiment 11: as shown in Figure 5, difference from Example 10 is, the thickness 20 μ m of second gradient transitional lay 11; The thickness 30 μ m of the 3rd gradient transitional lay 12.All the other same respective embodiments.Finally obtain comprising the cathode support SOFC three-in-one electrode of gradient transitional lay.
Claims (5)
1. the preparation method of a three-in-one electrode of solid oxide fuel battery comprises:
(1) preparation steps, absolute ethyl alcohol, 8YSZ dusty material, dispersant are become electrolyte suspension with binder making, wherein to account for suspension quality percentage be 5～15% to the 8YSZ dusty material, it is 0.5～5% that dispersant accounts for suspension vol percentage, and it is 1～10% that binding agent accounts for suspension vol percentage;
(2) spraying support electrode step sprays anode material or cathode material with air plasma spraying on matrix, makes anode or negative electrode, and anode or cathode thickness are 450～700 μ m;
(3) spraying dielectric substrate step on anode that has been shaped or negative electrode, adopts the described electrolyte suspension of liquid material plasma spraying to form dielectric substrate, and its thickness is 20～45 μ m;
(4) sprayed cathode or anode step continue sprayed cathode material or anode material with air plasma spraying on dielectric substrate, preparation negative electrode or anode, and negative electrode or anode thickness are 50～100 μ m; Finally make anode-supported three-in-one electrode or cathode support three-in-one electrode.
2. the preparation method of three-in-one electrode of solid oxide fuel battery as claimed in claim 1, it is characterized in that: after described spraying support electrode step, on the anode or negative electrode of spray formation, first gradient transitional lay when adopting solid, liquid identical between spraying preparation anode and dielectric substrate or second gradient transitional lay between negative electrode and dielectric substrate; On first gradient transitional lay or second gradient transitional lay, adopt liquid material plasma spraying to carry the suspension spraying to form dielectric substrate; The 3rd gradient transitional lay when on dielectric substrate, adopting solid, liquid identical between spray formation dielectric substrate and negative electrode or the 4th gradient transitional lay between dielectric substrate and anode; On the 3rd transition zone or the 4th gradient transitional lay, continue spraying preparation negative electrode or anode with air plasma spraying again, finally make the three-in-one electrode that comprises two gradient transitional lay.
3. the preparation method of three-in-one electrode of solid oxide fuel battery as claimed in claim 1 or 2, it is characterized in that: described anode material is the mixed-powder of NiO and 8YSZ, and its percent by volume is NiO 35～50%, and 8YSZ 65～50%; Described cathode material is lanthanum manganate or La
1-xSr
xCo
1-yFe
yO
3, x=0.1～0.6, y=0～1.0; Described matrix is a kind of in hole pottery, fine and close stainless steel, nickel foam or the foamed aluminium; Described dispersant is polyethylene glycol or phosphoglyceride; Described binding agent is polyvinyl alcohol or glycerine.
4. the preparation method of three-in-one electrode of solid oxide fuel battery as claimed in claim 2 is characterized in that:
The described first or the 3rd gradient transitional lay adopts air plasma spraying NiO powder, liquid material plasma spraying electrolyte suspension preparation, and the first or the 3rd gradient transition layer thickness is 20～35 μ m; The powder feed rate of NiO powder is constantly adjusted in the first gradient transitional lay preparation process, the percent by volume of NiO carries out the transition to 0% from described anode material, the speed of sending into of electrolyte suspension is also constantly adjusted, and the percent by volume of 8YSZ carries out the transition to 100% from described anode material; The powder feed rate of NiO powder is constantly adjusted in the 3rd gradient transitional lay preparation process, from 0% percent by volume that carries out the transition to NiO the described anode material, the speed of sending into of electrolyte suspension is also constantly adjusted, from 100% percent by volume that carries out the transition to 8YSZ the described anode material;
The described second or the 4th gradient transitional lay adopts the described cathode material of air plasma spraying, the described electrolyte suspension preparation of liquid material plasma spraying, and the second or the 4th gradient transition layer thickness is 20～35 μ m; The speed of sending into of the powder feed rate of cathode powder and electrolyte suspension is all constantly adjusted in the preparation process, guarantees the mass percent 70～50% of cathode material in the gradient transitional lay, and the mass percent of 8YSZ is 30～50%.
5. the preparation method of three-in-one electrode of solid oxide fuel battery as claimed in claim 3 is characterized in that:
The described first or the 3rd gradient transitional lay adopts air plasma spraying NiO powder, liquid material plasma spraying electrolyte suspension preparation, and the first or the 3rd gradient transition layer thickness is 20～35 μ m; The powder feed rate of NiO powder is constantly adjusted in the first gradient transitional lay preparation process, the percent by volume of NiO carries out the transition to 0% from described anode material, the speed of sending into of electrolyte suspension is also constantly adjusted, and the percent by volume of 8YSZ carries out the transition to 100% from described anode material; The powder feed rate of NiO powder is constantly adjusted in the 3rd gradient transitional lay preparation process, from 0% percent by volume that carries out the transition to NiO the described anode material, the speed of sending into of electrolyte suspension is also constantly adjusted, from 100% percent by volume that carries out the transition to 8YSZ the described anode material;
The described second or the 4th gradient transitional lay adopts the described cathode material of air plasma spraying, the described electrolyte suspension preparation of liquid material plasma spraying, and the second or the 4th gradient transition layer thickness is 20～35 μ m; The speed of sending into of the powder feed rate of cathode powder and electrolyte suspension is all constantly adjusted in the preparation process, guarantees the mass percent 70～50% of cathode material in the gradient transitional lay, and the mass percent of 8YSZ is 30～50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101686757A CN101183716B (en) | 2007-12-07 | 2007-12-07 | Method of producing three-in-one electrode of solid oxide fuel battery |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN2007101686757A CN101183716B (en) | 2007-12-07 | 2007-12-07 | Method of producing three-in-one electrode of solid oxide fuel battery |
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| CN101183716A true CN101183716A (en) | 2008-05-21 |
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| CN101515651B (en) * | 2009-03-16 | 2011-01-05 | 中国科学技术大学 | Preparation of solid oxide fuel cell |
| CN102130354A (en) * | 2011-01-14 | 2011-07-20 | 华南理工大学 | A direct carbon solid oxide fuel cell power system |
| CN101320814B (en) * | 2008-06-25 | 2012-08-29 | 施秀英 | Electrolyte material of low temperature oxide fuel battery and preparation method thereof |
| CN104868145A (en) * | 2015-04-02 | 2015-08-26 | 昆山艾可芬能源科技有限公司 | Preparation device and technology of solid oxide fuel cell coating |
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