CN100511788C - Solid-oxide fuel battery complex cathode and method for making same - Google Patents
Solid-oxide fuel battery complex cathode and method for making same Download PDFInfo
- Publication number
- CN100511788C CN100511788C CNB2007100247894A CN200710024789A CN100511788C CN 100511788 C CN100511788 C CN 100511788C CN B2007100247894 A CNB2007100247894 A CN B2007100247894A CN 200710024789 A CN200710024789 A CN 200710024789A CN 100511788 C CN100511788 C CN 100511788C
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- cathode material
- porous
- skeleton
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to the solid fuel battery technology area, specifically relates to a composit cathode of solid oxide compound fuel cell with high stable and its preparation method. The composit cathode includes the negative pole material thin film which is composed by nanometer level spheroidal particle whose diameter is the 50-100nm the and the electrolyte basis, electrolyte basis thickness is 0.7-1mm, the negative pole material thin film quality/( the quality of negative pole material thin film + the quality of porous electrolyte skeleton) =50%-55%. The preparation method is that first prepares electrolyte powder body by the metal nitrate forerunner body, and forms the basis and the pulp, prints the pulp on the basis drtying, heating to obtain the porous three dimensional electrolyte skeleton, soaks the negative pole material forerunner body solution to the skeleton, puts heat treatment 2-3 hours under the 700-900deg.C , soaks the heat treatment cycle operation many times. The composit cathode has the very good electrochemistry performance.
Description
Technical field
The present invention relates to the solid fuel cell technical field, be specifically related to a kind of high stability soild oxide fuel battery complex cathode and preparation method thereof.
Background technology
Fuel cell (FC) is the new secondary energy sources device of 21 century, is the new and high technology that solves the low and dual problem of environmental pollution of efficiency of energy utilization, keeps the effective means of human civilization sustainable development.Because Solid Oxide Fuel Cell (SOFC) is that energy utilization efficiency is the highest in all fuel cells, can reach 90%, generating efficiency also can be up to 70%, and therefore electric power system and the traffic and transportation system in a large amount of consumes energy has very big competitiveness, and its application potential is very big.That research is many at present is high temperature (800-1000 ℃) SOFC, but a series of problems that conventional high-temperature SOFC brought, sintering as electrode, surface chemistry diffusion between electrolyte and the electrode and the coupling between the materials having different thermal expansion coefficient etc. have seriously hindered the business-like process of SOFC.The method of dealing with problems is to reduce the operating temperature of battery, but along with the reduction of SOFC operating temperature, the interface resistance of negative electrode increases sharply, and becomes the main source of the internal resistance of cell.The high performance cathodes material such as the La that are suitable for middle temperature (600-800 ℃) operation
1-xSr
xCoO
3, Sm
1-xSr
xCoO
3Deng, because thermal coefficient of expansion is higher, cause easily not match with electrolyte and performance steady in a long-term is relatively poor, influenced commercial applications.The preparation composite cathode can reduce the thermal coefficient of expansion of negative electrode and the interface resistance of negative electrode to a certain extent.Promptly the second phase material (normally electrolyte phase material) that adds ionic conductivity material in the material of electronic conductance (or ion electronics mixing electricity is led) is made the compound electrode of two-phase, as LSM and YSZ are mixed into the LSM-YSZ negative electrode, mixed composite cathode is equivalent to the active sites of cathode reaction is expanded to negative electrode inside, increase the length of three-phase reaction interface (TPB), can improve cathode performance.But the preparation method of composite cathode of the prior art, as silk screen printing, the method for the composite cathode of collosol and gel preparation still can not reach anticathode high activity of commercial applications and requirement steady in a long-term fully.It mainly is not cause owing to matching between cathode layer and the dielectric substrate that long-term behaviour descends, and battery is moving under the high temperature for a long time, and two-layer can the disengaging cause the battery power output slowly to descend.If take to increase negative electrode and electrolytical sintering temperature, though can improve the switching performance between cathode layer and the dielectric substrate, the degree that comes off between them is descended, but so, the activity of cathode material will reduce, make anxious poly-decline of resistance of negative electrode, thereby cause battery to have only lower power output.
2005, people such as the Li Songli of Shanghai Silicate Inst., Chinese Academy of Sciences applied for patent " dip forming tubular solid oxide fuel cells ", and publication number is CN 1700494A.Reported a kind of method that relates to the dip forming tubular solid oxide fuel cells in this patent: successively flood anode support at outer surface of matrix, the dipping electrolyte slurry forms anode/composite membrane after co-sintered after demoulding, the pre-burning, at electrolyte outside impregnated cathode film, obtain tubular solid oxide fuel cell behind the double sintering again.This method can be simplified technology, but the impedance magnitude of battery and long-time stability are still not ideal enough, especially the interface impedance of negative electrode and thermal coefficient of expansion are still than higher, because this technology is that cathode material and electrolyte are mixed, and then and the electrolyte co-sintered, unresolved cathode material is because of the high decreased performance that causes of sintering temperature, and negative electrode and the unmatched problem of electrolyte heat.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of compound cathode of solid oxide fuel battery and preparation method thereof, to solve the problem of negative electrode high activity and negative electrode long-time stability difference, again can negative electrode steady in a long-term thereby obtain existing high activity.
Technical scheme of the present invention is as follows:
Compound cathode of solid oxide fuel battery of the present invention, it includes cathode material film and the electrolyte substrate thereof that transmits electric current, it is characterized in that, described cathode material film is to be that the nano-level sphere particle of 50-100nm constitutes by diameter, they are equably attached on the porous three-dimensional electrolyte skeleton that can transmit oxonium ion, this porous three-dimensional electrolyte skeleton is tightly linked whole by high temperature sintering and electrolyte substrate, wherein the thickness of electrolyte substrate is 0.7-1mm, the thickness of porous three-dimensional electrolyte skeleton is 50-100 μ m, the quality of cathode material film/(quality of the quality of cathode material film+porous electrolyte skeleton)=50%～55%.
The preparation method of compound cathode of solid oxide fuel battery of the present invention, comprise with electrolytical metal ion nitrate and prepare the electrolyte powder as presoma, and make electrolyte substrate and electrolyte slurry with the electrolyte powder, then this slurry is brushed in the electrolyte substrate with silk screen printing, it is characterized in that preparation process after this is:
(1) baking oven is put in the electrolyte substrate that will be printed with electrolyte slurry, being incubated 2-5 hours slurry bone dries up to printing below 100 ℃, obtains drying body;
(2) above-mentioned oven dry body is carried out high-temperature process: the speed with 1-1.5 ℃/min is warmed up to 550 ℃ from room temperature, be incubated 2 hours, be warmed up to 1350 ℃ with 2-3 ℃/min speed then, be incubated and cool to 800 ℃ with 2-3 ℃/min speed after 5 hours, naturally cooling obtains porous three-dimensional electrolyte skeleton in the electrolyte substrate then;
(3) preparation cathode material precursor solution: the nitrate of selecting the metal ion that contains in the cathode material is as the cathode material presoma, and carries out proportioning by the stoichiometry of cathode material chemical formula; The preparation alcohol solution promptly, makes ethanol (volume): water (volume)=1:1～3; Then the cathode material presoma is dissolved in the alcohol solution as the negative electrode precursor solution, the molar concentration that makes solution is 0.3～1mol/L; Add glycine again, and with magnetic stirrer 3-5 hour, make metal ion even by the glycine complexing, wherein the glycine use amount is: the total amount of substance (unit mole) of nitrate anion in the amount of substance of glycine=1/2 solution;
(4) impregnated cathode material presoma: above-mentioned cathode material precursor solution is impregnated on the electrolyte skeleton of porous by the method for dripping, dries naturally then, be immersed in fully in the porous electrolyte skeleton up to the cathode material presoma and go;
(5) heat treatment: the product of (4) is placed 700-900 ℃ of environment heat treatment 2-3 hour, and the cathode material presoma is converted into nano level cathode material, promptly obtains being attached with on the porous electrolyte skeleton composite cathode of nanoscale cathode material film;
(6) repeat the operation of (4), (5), make quality/(quality of the quality of cathode material film+porous electrolyte skeleton)=50%～55% of cathode material film.
In above-mentioned preparation process, described cathode material is La
0.6Sr
0.4CoO
3(LSC), La
0.2Sr
0.8MnO
3(LSM), Sm
0.5Sr
0.5CoO
3(SSC) or the like.
The mixture of the nitrate of the metal ion that described cathode material presoma is in the cathode material to be contained, for example cathode material is Sm
0.50Sr
0.50CoO
3, the nitrate of the metal ion that then contains is Sm (NO
3)
3, Sr (NO
3)
2, Co (NO
3)
3
Described impregnated cathode material presoma, be that the cathode material precursor solution that will prepare is impregnated in the electrolyte skeleton of porous by the method for dripping, for example the skeleton that the cathode material precursor solution drips to porous is got on glue head dropper, cathode material precursor solution by every square centimeter of 0.05～0.2ml drips up, naturally dry then, be immersed in fully in the porous electrolyte skeleton up to the cathode material presoma and go.
Described electrolyte is Sm
0.2Ce
0.8O
1.9(SDC), 8mol% Y
2O
3-ZrO
2(YSZ), Gd
0.1Ce
0.9O
1.95(GDC) etc.
Described electrolyte powder is to be prepared by glycine-nitrate combustion synthesis method, and wherein the addition of glycine (amount of substance) is 0.5 times of nitrate ion amount of substance total amount.
Described electrolyte substrate is to be prepared by following mode: with the electrolyte powder of glycine-nitrate combustion synthesis method preparation, put into high temperature furnace heat treatment 2 hours under 800-1000 ℃ of air atmosphere, again this powder is poured in the mould, under 300MPa pressure, be cold-pressed into sheet, and the thickness that makes sheet is in the 0.7-1mm scope.
The preparation of described electrolyte slurry is: earlier with the electrolyte powder of glycine-nitrate combustion synthesis method preparation and organic solvent, pore creating material, binding agent, dispersant; Again with this compound ball milling 3 hours (rotating speed is 300 rev/mins) in ball mill; At last the compound behind the ball milling is put in the vacuum desiccator, be evacuated to vacuum degree for-below the 0.1MPa, promptly obtain electrolyte slurry behind vacuum treatment 1-2min.Wherein, the quality of electrolyte powder: the quality of organic solvent: the quality of pore creating material: the quality of adhesive: the quality=1:3 of dispersant～5:0.2～0.4:0.2～0.3:0.1～0.2; Described organic solvent is terpinol (Terpinoel), pore creating material is soluble starch (Soluble starch) or graphite (Graphite), binding agent is ethyl cellulose (EC) or methylcellulose (MC), and dispersant is polyethylene glycol (PVG) or polyvinyl alcohol (PVA).
Described electrolyte slurry is brushed in the electrolyte substrate with silk screen printing, by control silk screen printing number of times, the thickness that can control three-dimensional porous electrolyte skeleton within the required range.
Described electrolyte slurry is brushed in the electrolyte substrate with silk screen printing, be evenly be coated on the electrolyte substrate sheet one-sided, to form one-sided porous three-dimensional electrolyte skeleton, or be coated on the bilateral of electrolyte substrate sheet simultaneously, to form symmetrical porous three-dimensional electrolyte skeleton, be used for the needs of assembled battery.
Composite cathode of the present invention, slurry with electrolyte is printed in the electrolyte substrate earlier, behind the common high temperature sintering, form the structure of " being sintered into one ", make and form one deck 3 D stereo network structure above the fine and close electrolyte, the characteristics of this structure are: though all be electrolyte, but its micro-structural changes: carry out the transition to porous to the cathode direction micro-structural from densification from electrolyte, and connect into integral body by high temperature sintering, the particle particle on the interface of compact texture layer and porous structure layer closely links together later at sintering.The mechanical strength that this 3 D stereo network structure is suitable because of high temperature sintering has is not easy the fracture fragmentation.This 3-D solid structure that is made of electrolyte provides continuous ionic conduction passage for composite cathode simultaneously, and its porousness provides a place that holds for cathode material, provides a carrier for negative electrode in other words conj.or perhaps.After cathode material forms, on the skeleton of cathode material particle attached to loose structure, form continuous rete, for composite cathode provides continuous electron conduction passage in loose structure; Electrolyte skeleton wherein has closely with electrolytical interface and is connected, and not only for oxonium ion provides unimpeded ionic conduction passage, has also increased the hot matching between SOFC negative electrode and the electrolyte.On the other hand, burning the cathode material of dip forming altogether, is nano level catalyst granules, thereby improves the hydrogen reduction activity of negative electrode, reduces polarization of electrode resistance, and battery can be moved in middle temperature (500～700 ℃).
Compared to existing technology, preparation method of the present invention also has following advantage:
1. according to the special preparation technology who burns dip forming SOFC composite cathode altogether, the material of taking on the effect of ionic conduction (being the electrolyte skeleton) and electron conduction (being the cathode material film) is independent preparation respectively, this particular structure makes the selectivity of the material of taking on ionic conduction and electron conduction effect very strong, especially the cathode material of electron conduction, can select the cathode material of various electron conduction phases according to actual needs, also can adjust the mass percentage content (being the dipping content of cathode material) of electron conduction phase cathode material in the composite cathode as required, to improve the performance of SOFC.
2. simple, the easy row of whole process of preparation, good reproducibility are easy to grasp.
Be described further below by embodiment and accompanying drawing.
Description of drawings
Fig. 1 is a kind of one-sided generalized section that porous three-dimensional electrolyte skeleton embodiment is arranged by the inventive method preparation.
Fig. 2 be preparation in the embodiment of the invention 1 convenient test be that the symmetrical battery of composite cathode carries out the curve that thermal oscillation and long term stability tests obtain with LSC-SDC under 600 ℃ of air atmospheres.Abscissa is the time (test once every day, so also be the number of times of test) to the operation of battery heat among the figure, and ordinate is the size of 600 ℃ of cathode interface impedances.
Fig. 3 is by the sem photograph of the cathode/electrolyte interface of composite cathode LSC-SDC symmetry battery after thermal shock and long-time stability experiment of the inventive method preparation among the embodiment 1.
Referring to Fig. 1, cathode material film 3 is attached on the porous electrolyte skeleton 2 that can transmit oxonium ion, and porous electrolyte skeleton 2 is tightly linked whole with a side of electrolyte substrate 1.
Embodiment
Embodiment 1: burn dipping preparation Solid Oxide Fuel Cell LSC-SDC composite cathode altogether
(1) prepares electrolyte SDC (Sm with glycine-nitrate firing method
0.2Ce
0.80
1.9) powder: demarcating good Ce in advance
2+, Sm
3+Nitrate solution mixes by stoichiometric proportion, and keeping the mol ratio of Ce and Sm is 4:1, forms nitrate presoma Sm
0.2Ce
0.8(NO
3)
x, adding a certain amount of glycine then, the mol ratio of glycine and nitrate ion is 1:2, dissolving was stirred 1 hour, after mixing, got the Sm of about 0.02mol at every turn
0.2Ce
0.8(NO
3)
xNitrate solution places the beaker of 1000mL, heats on the electric hot plate of 500W, boils off redundant moisture.At this moment solution becomes thickly, continues heating, and jelly begins fuel, and gushes out light yellow powder, collects as electrolyte SDC powder.These powder 800 ℃ of heat treatments 2 hours, have just been obtained required electrolyte SDC powder.
(2) preparation electrolyte substrate: take by weighing electrolyte SDC powder 0.5 gram, pour in the mould that diameter is 15mm, shake smooth.Single shaft is colded pressing and is the disk of Φ 15mm under 300MPa pressure, and the thickness of disk is 0.8mm.
(3) preparation electrolyte slurry: get SDC powder 1g and terpinol 4.7g, ethyl cellulose 0.3g, polyethylene glycol 0.2g, soluble starch 0.3g mix, and add 50 gram zirconium oxide balls, are placed on the planetary ball mill ball milling 3 hours.The taking-up slurry is put in the vacuum desiccator, be evacuated to vacuum degree to be-below the 0.1MPa, vacuum treatment 1-2min removes the air in the slurry.
(4) the three-dimensional porous electrolyte skeleton of preparation: the both sides that on screen process press, the slurry of handling evenly are coated on the electrolyte disk, every side each coated 5 times, place baking oven to be incubated 3-5 hour up to oven dry for 70 ℃, form the fine and close SDC|| porous SDC three-decker (symmetrical battery structure) of porous SDC||, then 1350 ℃ of sintering 5 hours in high temperature furnace.The thickness that obtains fine and close SDC layer is 0.75mm, is respectively 50 μ m at the porous SDC of dense electrolyte both sides layer thickness, and the quality of every side porous SDC layer is 0.02g, area 1.2cm
2High temperature sintering heats up and it should be noted that: 1 ℃/min is raised to 550 ℃, insulation 2h, and 2 ℃/min is raised to 1350 ℃ then, is incubated 5 hours, and 2 ℃/min cools to 800 ℃, lowers the temperature naturally then, obtains the three-dimensional porous electrolyte skeleton of bilateral.
(5) preparation cathode material precursor solution: with La (NO
3)
3, Sr (NO
3)
2And Co (NO
3)
2Solution is mixed into uniform presoma La by metering than the 0.6:0.4:1 composition
0.60Sr
0.40Co (NO
3)
xNitrate solution adds a certain amount of glycine (mol ratio of glycine and nitrate ion is 1:2), and (ethanol: water=1:1) regulator solution concentration is 0.3mol/L, pH value=6-7 to add an amount of alcohol solution.
(6) impregnated cathode material presoma: each 2 LSC presoma nitrate solution (each drip about 0.05ml) on the electrolyte skeleton of symmetrical structure respectively, dry naturally, be immersed in fully in the three-dimensional porous electrolyte SDC skeleton up to the LSC presoma and go.
(7) heat treatment: the back is in 800 ℃ of sintering 2 hours, and obtaining by average diameter is the cathode material LSC film that the spheric granules of 50nm constitutes.
(8) repeat the operation 2 times of (6), (7) again, make the mass percentage content (be the dipping content of LSC) of LSC in composite cathode LSC-SDC reach 50%.
Composite cathode to above-mentioned preparation carries out every electrode performance test:
Thermal shock experiment and long term stability tests.With platinum slurry and spun gold collected current, test atmosphere is air.With the ac impedance spectroscopy of ZAHNERIM6e electrochemical workstation test electrode sample at 550-750 ℃.
Fig. 2 has expressed embodiment 1 sample has been carried out thermal shock experiment and long term stability tests result of experiment, and test once every day.Preceding 20 days be that electrode is carried out thermal cycle in the battery operated temperature range, i.e. 500 ℃-800 ℃ thermal cycle, sample between 500 ℃ to 800 ℃ with 10 ℃/minute speed heating and cooling, and 500 ℃ of insulations up to test next time.The 21st day to the 30th day be that electrode is carried out battery room temperature RT-800 ℃ thermal cycle, sample between room temperature to 800 ℃ with 10 ℃/minute speed heating and cooling, and in the room temperature insulation up to test next time.The 31st day to the 102nd day is that electrode is stabilized in 600 ℃ of tests of carrying out the battery long-term behaviour of working temperature.As seen from the figure, the interface resistance of this sample electrode is very little, is stabilized in 0.290 ± 0.007 Ω cm
2Scope in the fluctuation, no matter be thermal shock or long period of operation, electrode resistance does not have significant change.That is to say that composite cathode has high electrochemical performance.
Fig. 3 is the sem photograph that carries out target/electrolyte interface after the above-mentioned experiment.As can be seen from Figure: through such thermal shock experiment, cathode/electrolyte interface still keeps good contact.This shows that this cathode sample has good thermal shock resistance.
(1) prepares electrolyte YSZ (8mol% Y with glycine-nitrate firing method
2O
3-ZrO
2) powder: demarcating good Y in advance
3+, Zr
4+Nitrate solution mixes by stoichiometric proportion, and keeping the mol ratio of Y and Zr is 0.16:0.92, forms nitrate presoma Y
0.16Zr
0.92(NO
3)
x, adding a certain amount of glycine then, the mol ratio of glycine and nitrate ion is 1:2, dissolving was stirred 1 hour, after mixing, got the Y of about 0.02mol at every turn
0.16Zr
0.92(NO
3)
xNitrate solution places the beaker of 1000mL, heats on the electric hot plate of 500W, boils off redundant moisture.At this moment solution becomes thickly, continues heating, and jelly begins fuel, and gushes out shallow white powder, collects as electrolyte YSZ powder.These powder 1000 ℃ of heat treatments 2 hours, have just been obtained required electrolyte YSZ powder.Powder preparing technology is identical with powder preparing technology in the case 1.
(2) preparation electrolyte substrate: take by weighing electrolyte YSZ powder 0.63 gram, pour in the mould that diameter is 15mm, shake smooth.Single shaft is colded pressing and is the disk of Φ 15mm under 300MPa pressure, and the thickness of disk is 1mm.
(3) preparation electrolyte slurry: get YSZ powder 1g and terpinol 4.7g, methylcellulose 0.3g, polyvinyl alcohol 0.2g, soluble starch 0.3g mix, and add 50 gram zirconium oxide balls, are placed on the planetary ball mill ball milling 3 hours.The taking-up slurry is put in the vacuum desiccator, be evacuated to vacuum degree to be-below the 0.1MPa, vacuum treatment 1-2min removes the air in the slurry.
(4) the three-dimensional porous electrolyte skeleton of preparation a: side that on screen process press, the slurry of handling evenly is coated on the electrolyte disk, coatedly be placed in the baking oven 70 ℃ of insulations 3-5 hour for 7 times up to oven dry, form three-dimensional porous YSZ|| compact YSZ double-decker, then 1350 ℃ of sintering 5 hours in high temperature furnace.The thickness that obtains the compact YSZ layer is that 0.94mm, porous YSZ layer thickness are that 70 μ m, porous YSZ layer quality are 0.015g,, area is 1.2cm
2One-sided porous electrolyte skeleton.Wherein, the detailed process of high temperature sintering is: 1 ℃/min is raised to 550 ℃, insulation 2h, and 2 ℃/min is raised to 1350 ℃ then, is incubated 5 hours, and 2 ℃/min cools to 800 ℃, then cooling naturally.
(5) preparation cathode material precursor solution: with La (NO
3)
3, Sr (NO
3)
2And Mn (NO
3)
2Solution is mixed into uniform presoma La by metering than the 0.85:0.15:1 composition
0.85Sr
0.15Mn (NO
3)
xNitrate solution adds a certain amount of glycine (mol ratio of glycine and nitrate ion is 1:2), and (ethanol: water=1:2) regulator solution concentration is 0.6mol/L, pH value=6-7 to add an amount of alcohol solution.
(6) impregnated cathode material presoma: on porous YSZ skeleton, drip 1 LSM presoma nitrate solution (about 0.05ml), dry naturally, be immersed in fully in the porous electrolyte YSZ skeleton up to the LSM presoma and go.
(7) heat treatment: the back was in 850 ℃ of sintering 2 hours.Obtaining by average diameter is the cathode material LSM film that the spheric granules of 60nm constitutes.
(8) repeat the operation 2 times of (6), (7) again, make the mass percentage content (be the dipping content of LSM) of LSM in composite cathode LSM-YSZ reach 51%.
Embodiment 3: burn dipping preparation Solid Oxide Fuel Cell GDC-SSC composite cathode altogether
(1) prepares electrolyte GDC (Gd with glycine-nitrate firing method
0.1Ce
0.9O
1.95) powder: demarcating good Ce in advance
2+, Gd
3+Nitrate solution mixes by stoichiometric proportion, and keeping the mol ratio of Ce and Gd is 9:1, forms nitrate presoma Gd
0.1Ce
0.9(NO
3)
x, adding a certain amount of glycine then, the mol ratio of glycine and nitrate ion is 1:2, dissolving was stirred 1 hour, after mixing, got the Gd of about 0.02mol at every turn
0.1Ce
0.9(NO
3)
xNitrate solution places the beaker of 1000mL, heats on the electric hot plate of 500W, boils off redundant moisture.At this moment solution becomes thickly, continues heating, and jelly begins fuel, and gushes out white powder, collects as electrolyte GDC powder.These powder 900 ℃ of heat treatments 2 hours, have just been obtained required electrolyte GDC powder.
(2) preparation electrolyte substrate: take by weighing electrolyte GDC powder 0.53 gram, pour in the mould that diameter is 15mm, shake smooth.Single shaft is colded pressing and is the disk of Φ 15mm under 300MPa pressure, and the thickness of disk is 0.85mm.
(3) preparation electrolyte slurry: get GDC powder 1g and terpinol 4.7g, methylcellulose 0.3g, polyethylene glycol 0.2g, graphite 0.3g mix, and add 50 gram zirconium oxide balls, are placed on the planetary ball mill ball milling 3 hours.The taking-up slurry is put in the vacuum desiccator, be evacuated to vacuum degree to be-below the 0.1MPa, vacuum treatment 1-2min removes the air in the slurry.
(4) the three-dimensional porous electrolyte skeleton of preparation: the both sides that on screen process press, the slurry of handling evenly are coated on the electrolyte disk, in disk one side coated 5 times, place baking oven to be incubated 3-5 hour up to oven dry for 70 ℃, form the fine and close GDC double-decker of three-dimensional porous GDC||, then 1350 ℃ of sintering 5 hours in high temperature furnace.The thickness that obtains fine and close GDC layer is 0.8mm, and the porous GDC layer thickness of dense electrolyte one side is 50 μ m, and porous GDC layer quality is 0.02g, area 1.2cm
2High temperature sintering heats up and it should be noted that: 1 ℃/min is raised to 550 ℃, insulation 2h, and 2 ℃/min is raised to 1350 ℃ then, be incubated 5 hours, 2 ℃/min cools to 800 ℃, cooling naturally then, and the thickness that obtains whole three-decker is the three-dimensional porous electrolyte skeleton of 0.85mm.
(5) preparation cathode material precursor solution: with Sm (NO
3)
3, Sr (NO
3)
2And Co (NO
3)
2Solution is mixed into uniform presoma Sm by metering than the 0.5:0.5:1 composition
0.50Sr
0.50Co (NO
3)
xNitrate solution adds a certain amount of glycine (mol ratio of glycine and nitrate ion is 1:2), and (ethanol: water=1:3) regulator solution concentration is 1mol/L, pH value=6-7 to add an amount of alcohol solution.
(6) impregnated cathode material presoma: on porous GDC skeleton, drip 1 SSC presoma nitrate solution (each drips about 0.05ml), dry naturally, be immersed in fully in the porous electrolyte GDC skeleton up to the SSC presoma and go.
(7) heat treatment: the back was in 900 ℃ of sintering 2 hours.Obtaining by average diameter is the cathode material SSC film that the spheric granules of 80nm constitutes.
(8) repeat the operation 1 time of (6), (7) again, make the mass percentage content (be the dipping content of SSC) of SSC in composite cathode SSC-GDC reach 53%.
Claims (4)
1. compound cathode of solid oxide fuel battery, it includes cathode material film and the electrolyte substrate thereof that transmits electric current, the thickness of electrolyte substrate is 0.7-1mm, it is characterized in that, described cathode material film is to be that the nano-level sphere particle of 50-100nm constitutes by diameter, they are equably attached on the porous three-dimensional electrolyte skeleton that can transmit oxonium ion, this porous three-dimensional electrolyte skeleton is tightly linked whole by high temperature sintering and electrolyte substrate, wherein the thickness of porous three-dimensional electrolyte skeleton is 50-100 μ m, the quality of cathode material film/(quality of the quality of cathode material film+porous electrolyte skeleton)=50%～55%.
2. the method for preparing the compound cathode of solid oxide fuel battery of claim 1, comprise with electrolytical metal ion nitrate and prepare the electrolyte powder as presoma, and make electrolyte substrate and electrolyte slurry with the electrolyte powder, then this slurry is brushed in the electrolyte substrate with silk screen printing, it is characterized in that preparation process after this is:
(1) baking oven is put in the electrolyte substrate that will be printed with electrolyte slurry, being incubated 2-5 hours slurry bone dries up to printing below 100 ℃, obtains drying body;
(2) above-mentioned oven dry body is carried out high-temperature process: the speed with 1-1.5 ℃/min is warmed up to 550 ℃ from room temperature, be incubated 2 hours, be warmed up to 1350 ℃ with 2-3 ℃/min speed then, be incubated and cool to 800 ℃ with 2-3 ℃/min speed after 5 hours, naturally cooling obtains porous three-dimensional electrolyte skeleton in the electrolyte substrate then;
(3) preparation cathode material precursor solution: the nitrate of selecting the metal ion that contains in the cathode material is as the cathode material presoma, and carries out proportioning by the stoichiometry of cathode material chemical formula; The preparation alcohol solution promptly, makes ethanol volume: water volume=1:1～3; Then the cathode material presoma is dissolved in the alcohol solution as the negative electrode precursor solution, the molar concentration that makes solution is 0.3～1mol/L; Add glycine again, and with magnetic stirrer 3-5 hour, make metal ion even by the glycine complexing, wherein the glycine use amount is: the total amount of substance of nitrate anion in the amount of substance of glycine=1/2 solution;
(4) impregnated cathode material presoma: above-mentioned cathode material precursor solution is impregnated on the electrolyte skeleton of porous by the method for dripping, dries naturally then, be immersed in fully in the porous electrolyte skeleton up to the cathode material presoma and go;
(5) heat treatment: the product of (4) is placed 700-900 ℃ of environment heat treatment 2-3 hour, and the cathode material presoma is converted into nano level cathode material, promptly obtains being attached with on the porous electrolyte skeleton composite cathode of nanoscale cathode material film;
(6) repeat the operation of (4), (5), make quality/(quality of the quality of cathode material film+porous electrolyte skeleton)=50%～55% of cathode material film.
3. preparation method as claimed in claim 2, it is characterized in that, described impregnated cathode material presoma, be that the cathode material precursor solution that will prepare is impregnated in the electrolyte skeleton of porous by the method for dripping, cathode material precursor solution by every square centimeter of 0.05～0.2ml drips up, naturally dry then, be immersed in fully in the porous electrolyte skeleton up to the cathode material presoma and go.
4. preparation method as claimed in claim 2 is characterized in that, described electrolyte slurry brushed in the electrolyte substrate with silk screen printing, and be coated on the electrolyte substrate sheet one-sided, form one-sided porous three-dimensional electrolyte skeleton; Or be coated on the bilateral of electrolyte substrate sheet simultaneously, form two porous three-dimensional electrolyte skeletons of symmetry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100247894A CN100511788C (en) | 2007-06-22 | 2007-06-22 | Solid-oxide fuel battery complex cathode and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100247894A CN100511788C (en) | 2007-06-22 | 2007-06-22 | Solid-oxide fuel battery complex cathode and method for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101083324A CN101083324A (en) | 2007-12-05 |
| CN100511788C true CN100511788C (en) | 2009-07-08 |
Family
ID=38912699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100247894A Expired - Fee Related CN100511788C (en) | 2007-06-22 | 2007-06-22 | Solid-oxide fuel battery complex cathode and method for making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100511788C (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683722A (en) * | 2012-05-25 | 2012-09-19 | 南京工业大学 | Solid oxide fuel cell composite cathode and preparation method thereof |
| CN103107342B (en) * | 2013-01-22 | 2014-11-19 | 哈尔滨工业大学 | Preparation method of one-dimensional nanofiber SSC based composite cathode |
| CN104064782B (en) * | 2014-06-21 | 2017-01-18 | 景德镇陶瓷大学 | Preparation method for solid oxide fuel cell cathode |
| CN105261765B (en) * | 2014-07-17 | 2017-11-28 | 中国科学院大连化学物理研究所 | A kind of method that high temperature phase separation prepares LSM YSZ nanometer combined electrodes |
| 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 |
| CN106876726A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation method of SOFC high-activity cathode steady in a long-term |
| CN108448118B (en) * | 2018-03-08 | 2019-04-09 | 湖南工学院 | The preparation method of solid oxide electrode material with orderly 3D microchannel structure |
| CN108963216B (en) * | 2018-07-04 | 2020-05-12 | 湖南工学院 | Nano porous material infiltration liquid and preparation method thereof |
| CN109888305A (en) * | 2019-03-11 | 2019-06-14 | 湖南科技大学 | Dipping solution is improved to the method for solid oxide fuel cell porous cathode skeleton wetability |
| CN110407577B (en) * | 2019-07-26 | 2022-05-17 | 深圳市富济新材料科技有限公司 | Ceramic film material, catalytic electrode, preparation method and application thereof |
| CN110676480A (en) * | 2019-09-29 | 2020-01-10 | 武汉华科福赛新能源有限责任公司 | Porous tubular support body and preparation method thereof, and preparation method of composite cathode support body |
| CN113363505A (en) * | 2021-05-28 | 2021-09-07 | 山东工业陶瓷研究设计院有限公司 | LSCF-GDC core-shell structure cathode and preparation method thereof |
| CN114086198B (en) * | 2021-12-15 | 2022-11-08 | 中国科学院大连化学物理研究所 | Preparation method of solid oxide electrolytic cell membrane electrode |
| CN117039076A (en) * | 2023-08-29 | 2023-11-10 | 华中科技大学 | Framework-supported SOFC (solid oxide Fuel cell) suitable for hydrocarbon fuel and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017647A (en) * | 1995-11-16 | 2000-01-25 | The Dow Chemical Company | Electrode structure for solid state electrochemical devices |
| WO2001028024A1 (en) * | 1999-10-08 | 2001-04-19 | Global Thermoelectric Inc. | Composite electrodes for solid state electrochemical devices |
| CN1402372A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Method for mfg. anode carried thin film medium-temp. solid oxide fuel cell |
| JP2005310607A (en) * | 2004-04-23 | 2005-11-04 | Toyota Motor Corp | Cathode for fuel cell and its manufacturing method |
| CN1700494A (en) * | 2005-05-30 | 2005-11-23 | 中国科学院上海硅酸盐研究所 | Method for dip moulding pipe type solid oxide fuel battery |
-
2007
- 2007-06-22 CN CNB2007100247894A patent/CN100511788C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017647A (en) * | 1995-11-16 | 2000-01-25 | The Dow Chemical Company | Electrode structure for solid state electrochemical devices |
| WO2001028024A1 (en) * | 1999-10-08 | 2001-04-19 | Global Thermoelectric Inc. | Composite electrodes for solid state electrochemical devices |
| CN1402372A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Method for mfg. anode carried thin film medium-temp. solid oxide fuel cell |
| JP2005310607A (en) * | 2004-04-23 | 2005-11-04 | Toyota Motor Corp | Cathode for fuel cell and its manufacturing method |
| CN1700494A (en) * | 2005-05-30 | 2005-11-23 | 中国科学院上海硅酸盐研究所 | Method for dip moulding pipe type solid oxide fuel battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101083324A (en) | 2007-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100511788C (en) | Solid-oxide fuel battery complex cathode and method for making same | |
| Wang et al. | A study of multilayer tape casting method for anode-supported planar type solid oxide fuel cells (SOFCs) | |
| Xie et al. | Electrochemical gas–electricity cogeneration through direct carbon solid oxide fuel cells | |
| CN111900449B (en) | Solid oxide fuel cell, method for producing same and use thereof | |
| Wang et al. | Sm0. 5Sr0. 5CoO3− δ-infiltrated cathodes for solid oxide fuel cells with improved oxygen reduction activity and stability | |
| CN101577340B (en) | Method for preparing cathode-supported tubular solid oxide fuel cells | |
| CN101359746B (en) | Large size tubular solid oxide fuel cell and preparation thereof | |
| JP3502012B2 (en) | Solid oxide fuel cell and method of manufacturing the same | |
| CN101399352B (en) | Producing method for a high strength ultra-thin anode supporting type solid oxide fuel cell | |
| CN106848358B (en) | Doped cerium oxide based solid oxide fuel cell and preparation method thereof | |
| US5281490A (en) | Process for producing solid oxide fuel cells | |
| CN109921079B (en) | Composite solid oxide fuel cell and preparation method thereof | |
| Liu et al. | Fabrication and characterization of micro-tubular cathode-supported SOFC for intermediate temperature operation | |
| KR20140085431A (en) | Composite anode for a solid oxide fuel cell with improved mechanical integrity and increased efficiency | |
| CN107785598B (en) | Half-cell symmetrical solid oxide fuel cell | |
| CN100448088C (en) | A making method for self-supported solid oxide fuel battery | |
| CN104409742A (en) | BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof | |
| CN101515646B (en) | Medium temperature solid oxide fuel cell composite cathode material and preparation method thereof | |
| Zhang et al. | High-performance low-temperature solid oxide fuel cells using thin proton-conducting electrolyte with novel cathode | |
| Ding et al. | Fabrication and characterization of low-temperature SOFC stack based on GDC electrolyte membrane | |
| CN113667998A (en) | Reversible solid oxide electrolytic cell and preparation method thereof | |
| JP2513920B2 (en) | Fuel electrode for solid electrolyte fuel cell and method for manufacturing the same | |
| Han et al. | Experimental and numerical study of micro-tubular direct carbon solid oxide fuel cell fueled by the oilseed rape straw-derived biochar | |
| Xin et al. | Solid oxide fuel cells with dense yttria-stabilized zirconia electrolyte membranes fabricated by a dry pressing process | |
| CN1641919A (en) | Method for preparing anode-support type yttrium oxide stable zirconium oxide electrolyte membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090708 Termination date: 20150622 |
|
| EXPY | Termination of patent right or utility model |