CN105470529A - Electrode of solid oxide fuel cell and preparation method of electrode, and solid oxide fuel cell based on electrode - Google Patents
Electrode of solid oxide fuel cell and preparation method of electrode, and solid oxide fuel cell based on electrode Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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- 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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to an electrode of a solid oxide fuel cell and a preparation method of the electrode and the solid oxide fuel cell based on the electrode. The electrode comprises an electrode body which is arranged on an electrolyte layer and has a porous structure; particularly, a plurality of gas channels are also formed in the electrode body with the porous structure; each gas channel comprises a first extension direction; opposite first end and second end are formed in the first extension direction; and the gas channels are communicated with the outside through at least one opening in the first end and the second end. Diffusion of a gas in the electrode can be regulated, controlled and optimized through these gas channels, so that the problems of universal uneven reaction position distribution of the solid oxide fuel cell in an actual working process, caused uneven temperature field distribution and the like are effectively relieved or avoided; and in addition, due to the arrangement of the gas channels, timely discharge of water generated at a positive electrode (an oxygen-ion conductor solid oxide fuel cell) or a negative electrode (a proton conductor solid oxide fuel cell) is also facilitated.
Description
Technical field
The present invention relates to field of solid oxide fuel, be specifically related to a kind of solid oxide fuel cell electrode, preparation method and the Solid Oxide Fuel Cell based on it.
Background technology
Day by day become the overall background of the key factor of restriction society and economic development at the energy and environmental problem under, Solid Oxide Fuel Cell as a kind of can be directly the energy conversion device of electric energy by chemical energy, high owing to having energy conversion efficiency concurrently, the widely applicable extensive concern waiting outstanding advantages to receive people of fuel.As Japanese TOTO Ltd. each provides one in the patent of invention of 201180046923.5 and 201280016340.2 can improve comprehensive energy efficiency, and the Solid Oxide Fuel Cell preventing excessive temperature from rising and can steady operation 90000 hours Solid Oxide Fuel Cell; LG fuel cell system company of the U.S. is optimized the system of fuel cell in the patent of invention of 201280045198.4 and 201280045187.6.
But Solid Oxide Fuel Cell still exist in its practical process some problems need solve.Solid oxide fuel cell electrode preparation as existing in (1) adopts the technique such as flow casting molding, silk screen printing mostly, and prepared porous electrode inside often exists the closed cell region of some.As shown in Figure 1, electrode body 2 ' is formed on the surface of electrolyte 1 '; But the electrochemical reaction of electrode mainly concentrates on electrode body 2 '/reacting gas two-phase interface, the existence of closed cell region by problem uneven for the minimizing and electrochemical reaction area distribution that cause the actual effective electrochemical reaction activating area of electrode interior, this decline and battery temperature problem pockety bringing electrode performance further.(2) its hole of electrode adopting traditional flow casting molding and silk-screen printing technique to prepare is random, often there is the problems such as the narrow and small and skewness in duct, be unfavorable for the diffusion of reacting gas in whole electrode interior and the timely discharge of product, this also will affect the performance of performance in electrode practical work process further.(3) in traditional electrode preparation method, the thickness of single-layer electrodes is often thicker, is unfavorable for that this is also unfavorable for the exploitation of high-performance electrode according to Solid Oxide Fuel Cell real work demand to the regulation and control of its different spatial electrode component.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art to provide a kind of solid oxide fuel cell electrode of architecture advances and the novel preparation method simultaneously providing this solid oxide fuel cell electrode.
The present invention also provides a kind of Solid Oxide Fuel Cell further.
For solving above technical problem, a kind of technical scheme that the present invention takes is as follows:
A kind of solid oxide fuel cell electrode, it comprises is located on dielectric substrate, has the electrode body of loose structure, particularly: on the described electrode body with loose structure, be also formed with multiple gas passage, this gas passage has the first bearing of trend, and relative first end and the second end is formed on this first bearing of trend, at least one opening in first end and the second end, to be in communication with the outside gas passage.
Preferably, described multiple gas passage is uniformly distributed on electrode body.
Preferably, described first bearing of trend is the thickness direction of electrode body, described first end away from dielectric substrate, described second end near dielectric substrate, first end opening, the second end opening or close.
According to a concrete and preferred aspect of the present invention, described gas passage also has second bearing of trend vertical with the first bearing of trend, and the second bearing of trend is formed the 3rd relative end and the 4th end, the 3rd end and the equal opening of the 4th end and be in communication with the outside.
Further preferably, described multiple gas passage side by side and equidistantly arrange, makes electrode body form strip lattice structure.
In a concrete execution mode, described electrode body is square, and the second bearing of trend is parallel with the bearing of trend on a limit of electrode body.
According to another concrete and preferred aspect of the present invention, the arrangement in column in a row of described multiple gas passage, makes electrode body form latticed lattice structure.
As a kind of preferred implementation of the present invention, described gas passage is constant or diminish gradually to the cross-sectional area of the second end from first end.
According to the present invention, the width of the cross section of gas passage on the first bearing of trend can between 0.1 ~ 100 micron, preferably between 1 ~ 10 micron.
According to the present invention
,the component at the different spatial place of described electrode body can be identical or different, can adjust according to battery applications actual demand.
Preferably, electrode body of the present invention, by first utilizing 3D printer to print electrode precursor, then carries out sintering and obtains.
According to the present invention, described electrode can be anode, also can be negative electrode, and its one or more electrode materials can commonly used by this area form, and are not particularly limited.
The another technical scheme that the present invention takes is: a kind of preparation method of above-mentioned solid oxide fuel cell electrode, and the method utilizes 3D printer to prepare electrode, specifically comprises the steps:
(1) according to the component of the battery electrode that will prepare, corresponding electrode slurry is prepared;
(2) formulate print routine according to the structure of the electrode that will prepare, and be input in 3D printer;
(3) parameter that 3D printer prints is set: comprise temperature, print the number of plies, time-write interval interval;
(4) according to print routine and the parameter of setting, to comprise the material of dielectric substrate as printing matrix, put into corresponding electrode slurry, carry out 3D printing, obtain electrode precursor;
(5) carrying out sintering processes by printing the electrode precursor obtained, obtaining described solid oxide fuel cell electrode.
Further, step (1) can be implemented as follows: electrode powder and pore creating material are placed in ball grinder, the terpineol solution adding ethyl cellulose carries out ball-milling treatment as adhesive and namely obtains electrode slurry, and wherein pore creating material can be generally 0.01% ~ 40% of electrode powder quality for one or more the combination in starch, corn flour, nano-carbon material, its interpolation quality; In the terpineol solution of ethyl cellulose, the mass content of ethyl cellulose is generally 3% ~ 10%, and the addition of the terpineol solution of ethyl cellulose is 0.5 ~ 3 times of electrode powder and pore creating material gross mass.Electrode powder is formulated according to the electrode material that will prepare, and when the electrode that will prepare is negative electrode, can be single phase cathode material such as La
0.5sr
0.5co
0.8fe
0.2o
3-δor composite cathode material such as LSCF-SDC(Sm (LSCF)
0.2ce
0.8o
1.9).When the different electrode of different spatial component will be prepared, multiple electrode slurry can be prepared, when printing different layers, put into 3D printer and printing.
Further, in step (1), the method of ball milling is as follows: first at 200-350 rev/min of lower ball milling 5-180 minute, material is mixed, then rotating speed is promoted to 500-900 rev/min of lower ball milling 10-720 minute to reduce the granularity of powder in ball grinder, last at 200-350 rev/min of lower ball milling 5-180 minute, obtain electrode slurry.
Further, the viscosity by the electrode slurry prepared by rate-determining steps (1) controls each thickness printed.Preferably, controlling each thickness printed is 0.5 ~ 1 micron.Arranging and printing the number of plies is 15 ~ 25 layers, and setting print temperature is 30 ~ 70 DEG C, and the setting time-write interval is spaced apart 10-60 minute.
Preferably, in step (4), described in comprise dielectric substrate the material support half-cell that is electrolyte sheet or is made up of dielectric substrate and the electrode layer contrary with electrode to be prepared.Such as, when the electrode that will prepare is negative electrode, electrolyte sheet or anode-supported half-cell (anode/electrolyte double-decker, during printing, dielectric substrate upwards) can be used; When the electrode that will prepare is anode, electrolyte sheet or cathode support half-cell (negative electrode/electrolyte bilayer, during printing, dielectric substrate upwards) can be used.
Further, in step (5), the sintering schedule of described sintering processes is as follows: be first warming up to 400 ~ 600 DEG C with the speed of 1 DEG C/min ~ 1.5 DEG C/min and be incubated 5 ~ 240 minutes, then be warming up to 900 ~ 1350 DEG C with the speed of 2 ~ 8 DEG C/min and be incubated 30 ~ 480 minutes, being finally down to room temperature with the speed of 2 ~ 8 DEG C/min.
The invention still further relates to a kind of Solid Oxide Fuel Cell, it comprises above-mentioned solid oxide fuel cell electrode.
Further, described battery electrode is negative electrode and/or anode.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
Solid oxide fuel cell provided by the present invention is except the hole that electrode body has, also there is multiple gas passage, by these gas passages can optimising and adjustment gas in the diffusion of electrode interior, and then the unequal problem of thermo parameters method effectively alleviated or avoid ubiquitous response location skewness in Solid Oxide Fuel Cell practical work process and cause thus; In addition, the setting of gas passage also helps the timely discharge that anode place (oxygen ion conductor solid oxide fuel cell) or negative electrode place (proton conductor Solid Oxide Fuel Cell) generate water.
The preparation method of solid oxide fuel cell provided by the present invention, adopt 3D to print and sinter the preparation technology combined, effectively can reduce the non-chemically active region that electrode interior causes due to closed pore, the shape of gas passage, size can be adjusted easily and adjust the component of different spatial place electrode material easily, thus electrode can be adjusted flexibly according to battery actual demand, be conducive to the raising of prepared electrode combination property.In addition, this technological operation is simple, and controllability is strong, is easy to large-scale production.
Accompanying drawing explanation
Fig. 1 is traditional electrode micro-structural schematic diagram;
Fig. 2 lattice-shaped porous electrode micro-structural schematic diagram;
Fig. 3 (a) strip lattice structure La
0.5sr
0.5co
0.8fe
0.2o
3-δ(LSCF) single phase cathode planar structure schematic diagram, the partial enlarged drawing at A place in (b) a figure;
Fig. 4 (a) strip lattice structure La
0.5sr
0.5co
0.8fe
0.2o
3-δ(LSCF) single phase cathode cutaway view, the partial enlarged drawing at B place in (b) a figure;
The planar structure schematic diagram that Fig. 5 (a) is the anode of solid oxide fuel cell of embodiment 3, the broken section enlarged drawing at C place in (b) a figure;
Fig. 6 (a) is the cross-sectional schematic of the anode of solid oxide fuel cell of embodiment 3, the partial enlarged drawing at D place in (b) a figure;
Wherein, 1 ', electrolyte; 2 ', electrode body; 21 ', gas passage; 1, dielectric substrate; 2, electrode body; 21, gas passage; 3, dielectric substrate; 4, electrode body; 41, gas passage.
Embodiment
Below will set forth the present invention further by specific embodiment, but be not limited to protection scope of the present invention.In following embodiment, 3D printer is purchased from Fuji Photo Film Co., Ltd. (FUJIFILM), and the operation of 3D printer is carried out according to mode recommended by the manufacturer.
embodiment 1
The present embodiment provides a kind of solid oxide fuel cell electrode, its microstructure as shown in Figure 2, comprise and be located on dielectric substrate 1, there is the electrode body 2 of loose structure, the electrode body 2 with loose structure is also formed with multiple gas passage 21, this gas passage 21 has the first bearing of trend, and on this first bearing of trend, forms relative first end and the second end, first end opening, second end also opening, makes gas passage be in communication with the outside.This electrode has strip lattice structure, effectively can reduce the non-chemically active region that electrode interior causes due to closed pore; In addition, this lattice structure effectively can promote that gas is in the diffusion of cathode internal, the unequal problem of thermo parameters method effectively alleviated or avoid ubiquitous response location skewness in Solid Oxide Fuel Cell practical work process and cause thus.
In the present embodiment, as shown in Figure 3 and Figure 4, this solid oxide fuel cell electrode is single phase cathode electrode, and above-mentioned multiple gas passages 21 are evenly distributed on electrode body 2, and they side by side and equidistantly arrange make electrode body 2 form strip lattice structure.And the first bearing of trend is the thickness direction of electrode body, first end is away from dielectric substrate, and the second end is near dielectric substrate, and gas passage 21 is constant to the cross-sectional area of the second end from first end, its width can be arranged according to actual needs, is preferably 1 ~ 10 micron.
Particularly, in this example, solid oxide fuel cell electrode is cathode electrode, and it is prepared by following steps:
(1) weighing 5gLSCF powder and 5g cellulose content is that the terpineol solution of the ethyl cellulose of 6wt.% puts into 50ml agate jar, and adds the ball milling preparation that agate ball milling pearl that cumulative volume is about 20ml carries out cathode slurry.Wherein ball-milling technology is first ball milling 60 minutes under 350 revs/min of rotating speeds, then rotating speed is promoted to 800 revs/min of ball millings 300 minutes, finally under 350 revs/min of rotating speeds ball milling 30 minutes to obtain electrode slurry.
(2) collect above-mentioned electrode slurry, and be placed in airtight receiving flask stand-by.
(3) 3D printer power supply is opened, by the fine and close Gd through surface cleaning process
0.1ce
0.9o
1.95(GDC) electrolyte sheet is fixed on 3D stamp pad as printing matrix, and the temperature of stamp pad is set as 40 DEG C, and time-write interval interval is set to 20 minutes.
(4) cathode slurry is put into printer ink cartridge, and respective ink tanks is fixed on 3D ink-cases of printers position.
(5) print routine is inputed in 3D printer, and adjust print cartridge mode out of ink and top of form ready-to-print.
(6) start ground floor print job, wait for 20 minutes after to be printed, the solvent in printing slurry is fully volatilized, and printed material can be good at adhering on substrate.
(7) print job of subsequent layers is carried out according to step (5) and (6).Wherein the thickness of every layer is about 0.8 micron, prints 20 layers altogether.
(8) treat that it takes out after printing by electrode from 3D printer, be placed in Muffle furnace and carry out sintering processes.Wherein said sintering schedule is be warming up to 600 DEG C with the speed of 1 DEG C/min and be incubated 30 minutes, then be warming up to 1050 DEG C with the speed of 5 DEG C/min and be incubated 240 minutes, being finally down to room temperature with the speed of 5 DEG C/min and can obtaining described solid oxide fuel cell electrode.
embodiment 2
The present embodiment provides a kind of compound cathode of solid oxide fuel battery electrode, substantially identical with embodiment 1 of its microstructure, unlike: have employed LSCF-SDC composite material.Its preparation method comprises the following steps:
(1) the different LSCF-Sm of 2gSDC content is weighed respectively
0.2ce
0.8o
1.9(SDC) mixed powder and 4g cellulose content are that the terpineol solution of the ethyl cellulose of 6wt.% puts into 50ml agate jar, and add the ball milling preparation that agate ball milling pearl that cumulative volume is about 20ml carries out cathode slurry.Wherein in LSCF-SDC composite material, the content of SDC is respectively 0wt.%, 10wt.%, 20wt.%, 30wt.%, 40wt.%, 50wt.%, 60wt.% and 70wt.%.Ball-milling technology is first ball milling 180 minutes under 200 revs/min of rotating speeds, then rotating speed is promoted to 500 revs/min of ball millings 600 minutes, finally under 200 revs/min of rotating speeds ball milling 60 minutes to obtain electrode slurry.
(2) collect above-mentioned electrode slurry, and be placed in airtight receiving flask stand-by.
(3) open 3D printer power supply, be fixed on 3D stamp pad as printing matrix by the fine and close SDC electrolyte sheet through surface cleaning process, and the temperature of stamp pad is set as 60 DEG C, the time-write interval is spaced apart 10 minutes.
(4) cathode slurry is put into printer ink cartridge, and respective ink tanks is fixed on 3D ink-cases of printers position.
(5) print routine is inputed in 3D printer, and adjust print cartridge mode out of ink and top of form ready-to-print.
(6) start ground floor print job, wait for 10 minutes after to be printed, the solvent in printing slurry is fully volatilized, and printed material can be good at adhering on substrate.
(7) change the component of electrode slurry in print cartridge according to actual needs, carry out the print job of subsequent layers according to step (5) and (6).Wherein the thickness of every layer is about 0.5 micron, prints 24 layers altogether, and from electrolyte/negative electrode cross section to cathode layer, surface SDC content reduces and often kind of component successive print 3 layers gradually.
(8) treat that it takes out after printing by electrode from 3D printer, be placed in Muffle furnace and carry out sintering processes.Wherein said sintering schedule is be warming up to 600 DEG C with the speed of 1 DEG C/min and be incubated 30 minutes, then be warming up to 900 DEG C with the speed of 3 DEG C/min and be incubated 480 minutes, being finally down to room temperature with the speed of 3 DEG C/min and can obtaining described solid oxide fuel cell electrode.
embodiment 3
The present embodiment provides a kind of compound anode of solid-oxide fuel battery electrode, as shown in Figure 5 and Figure 6, it comprises is located on dielectric substrate 3, has the electrode body 4 of loose structure, electrode body 4 is formed the gas passage 41 of multiple arrayed in columns of embarking on journey, makes electrode form latticed lattice structure.Gas passage 41 extends along the thickness direction of electrode body 4, its end away from dielectric substrate 3 (first end) opening, and close near the end (the second end) of dielectric substrate 3, gas passage 41 diminishes to the cross-sectional area of the second end gradually from first end.
The preparation method of this composite cathode electrode comprises the following steps:
(1) the different GDC-NiO composite granule of 2gGDC content is weighed respectively, appropriate amount of starch and the terpineol solution of ethyl cellulose identical with starch gross mass with composite granule (cellulose content is 6wt.%) put into 50ml agate jar, and add the ball milling preparation that agate ball milling pearl that cumulative volume is about 20ml carries out cathode slurry: wherein in GDC-NiO composite material, the content of GDC is respectively 60wt.%, 50wt.% and 40wt.%, corresponding content of starch is the 0wt.% of GDC-NiO quality, 30wt.% and 40wt.%, ball-milling technology is first ball milling 120 minutes under 250 revs/min of rotating speeds, then rotating speed is promoted to 600 revs/min of ball millings 900 minutes, last under 250 revs/min of rotating speeds ball milling 120 minutes to obtain electrode slurry, collect above-mentioned electrode slurry, and be placed in airtight receiving flask stand-by,
(2) collect above-mentioned electrode slurry, and be placed in airtight receiving flask stand-by.
(3) open 3D printer power supply, be fixed on 3D stamp pad as printing matrix by the fine and close SDC electrolyte sheet through surface cleaning process, and the temperature of stamp pad is set as 50 DEG C, the time-write interval is spaced apart 15 minutes.
(4) cathode slurry is put into printer ink cartridge, and respective ink tanks is fixed on 3D ink-cases of printers position.
(5) print routine is inputed in 3D printer, and adjust print cartridge mode out of ink and top of form ready-to-print.
(6) start ground floor print job, wait for 15 minutes after to be printed, the solvent in printing slurry is fully volatilized, and printed material can be good at adhering on substrate.
(7) change the component of electrode slurry in print cartridge according to actual needs, carry out the print job of subsequent layers according to step (5) and (6).Wherein the thickness of every layer is about 0.8 micron, prints 20 layers altogether, and from electrolyte/anodic interface to anode layer, surface GDC component is from 60wt.%(2 layer) be in succession reduced to 50wt.%(2 layer) and 40wt.%(16 layer).
(8) treat that it takes out after printing by electrode from 3D printer, be placed in Muffle furnace and carry out sintering processes.Wherein said sintering schedule is be warming up to 400 DEG C with the speed of 1 DEG C/min and be incubated 240 minutes, then be warming up to 1350 DEG C with the speed of 2 DEG C/min and be incubated 480 minutes, being finally down to room temperature with the speed of 2 DEG C/min and can obtaining described solid oxide fuel cell electrode.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (19)
1. a solid oxide fuel cell electrode, it comprises is located on dielectric substrate, has the electrode body of loose structure, it is characterized in that: on the described electrode body with loose structure, be also formed with multiple gas passage, described gas passage has the first bearing of trend, and on this first bearing of trend, form relative first end and the second end, at least one opening in described first end and the second end.
2. solid oxide fuel cell electrode according to claim 1, is characterized in that: described multiple gas passage is uniformly distributed on described electrode body.
3. solid oxide fuel cell electrode according to claim 1, it is characterized in that: described first bearing of trend is the thickness direction of electrode body, described first end is away from described dielectric substrate, described second end is near described dielectric substrate, described first end opening, the second described end opening or closed.
4. the solid oxide fuel cell electrode according to claim 1 or 2 or 3, it is characterized in that: described gas passage also has second bearing of trend vertical with described first bearing of trend, described second bearing of trend forms the 3rd relative end and the 4th end, described 3rd end and the equal opening of the 4th end and be in communication with the outside.
5. solid oxide fuel cell electrode according to claim 4, is characterized in that: described multiple gas passage side by side and equidistantly arrange, makes described electrode body form strip lattice structure.
6. solid oxide fuel cell electrode according to claim 4, is characterized in that: described electrode body is square, and described second bearing of trend is parallel with the bearing of trend on a limit of described electrode body.
7. solid oxide fuel cell electrode according to claim 3, is characterized in that: the arrangement in column in a row of described multiple gas passage, makes described electrode body form latticed lattice structure.
8. solid oxide fuel cell electrode according to claim 3, is characterized in that: described gas passage is constant or diminish gradually to the cross-sectional area of the second end from described first end.
9. the solid oxide fuel cell electrode according to claim 1 or 3 or 8, is characterized in that: the width of the cross section of described gas passage on described first bearing of trend is between 0.1 ~ 100 micron.
10. solid oxide fuel cell electrode according to claim 9, is characterized in that: the width of the cross section of described gas passage on described first bearing of trend is between 1 ~ 10 micron.
11. solid oxide fuel cell electrodes according to claim 1, is characterized in that: the component at the different spatial place of described electrode body is identical or different.
12. solid oxide fuel cell electrodes according to claim 1, is characterized in that: described electrode body, by first utilizing 3D printer to print electrode precursor, then carries out sintering and obtains.
The preparation method of 13. 1 kinds of solid oxide fuel cell electrodes any one of claim 1 to 11 as described in claim, is characterized in that: the method utilizes 3D printer to prepare described electrode, specifically comprises the steps:
(1) according to the component of the battery electrode that will prepare, corresponding electrode slurry is prepared;
(2) formulate print routine according to the structure of the electrode that will prepare, and be input in 3D printer;
(3) parameter that 3D printer prints is set: comprise temperature, print the number of plies, time-write interval interval;
(4) according to print routine and the parameter of setting, to comprise the material of dielectric substrate as printing matrix, put into corresponding electrode slurry, carry out 3D printing, obtain electrode precursor;
(5) carrying out sintering processes by printing the electrode precursor obtained, obtaining described solid oxide fuel cell electrode.
14. preparation methods according to claim 13, it is characterized in that: step (1) is implemented as follows: electrode powder and pore creating material are placed in ball grinder, the terpineol solution adding ethyl cellulose carries out ball-milling treatment as adhesive and namely obtains described electrode slurry, and described pore creating material is one or more combination in starch, corn flour, nano-carbon material, to add quality be 0.01% ~ 40% of electrode powder quality for it; In the terpineol solution of described ethyl cellulose, the mass content of ethyl cellulose is 3% ~ 10%, and the addition of the terpineol solution of described ethyl cellulose is 0.5 ~ 3 times of described electrode powder and pore creating material gross mass.
15. preparation methods according to claim 14, it is characterized in that: in step (1), the method of ball milling is as follows: first at 200-350 rev/min of lower ball milling 5-180 minute, material is mixed, then rotating speed is promoted to 500-900 rev/min of lower ball milling 10-720 minute to reduce the granularity of powder in ball grinder, last at 200-350 rev/min of lower ball milling 5-180 minute, obtain electrode slurry.
16. preparation methods according to claim 13, is characterized in that: control each thickness printed by the viscosity of the electrode slurry prepared by rate-determining steps (1), and the thickness controlling each printing is 0.5 ~ 1 micron; Arranging and printing the number of plies is 15 ~ 25 layers, and setting print temperature is 30 ~ 70 DEG C, and the setting time-write interval is spaced apart 10-60 minute.
17. preparation methods according to claim 13, is characterized in that: in step (4), described in comprise dielectric substrate the material support half-cell that is electrolyte sheet or is made up of dielectric substrate and the electrode layer contrary with described electrode to be prepared.
18. preparation methods according to claim 13, it is characterized in that: in step (5), the sintering schedule of described sintering processes is as follows: be first warming up to 400 ~ 600 DEG C with the speed of 1 DEG C/min ~ 1.5 DEG C/min and be incubated 5 ~ 240 minutes, then be warming up to 900 ~ 1350 DEG C with the speed of 2 ~ 8 DEG C/min and be incubated 30 ~ 480 minutes, being finally down to room temperature with the speed of 2 ~ 8 DEG C/min.
19. 1 kinds of Solid Oxide Fuel Cell, is characterized in that: comprise the solid oxide fuel cell electrode any one of claim 1 to 12 as described in claim.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510874862.1A CN105470529B (en) | 2015-12-03 | 2015-12-03 | A kind of solid oxide fuel cell electrode and preparation method thereof and solid oxide fuel cell based on it |
| PCT/CN2015/098173 WO2017092085A1 (en) | 2015-12-03 | 2015-12-22 | Electrode of solid oxide fuel cell, preparation method therefor and solid oxide fuel cell based on same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109192995A (en) * | 2018-09-06 | 2019-01-11 | 深圳大学 | A kind of method of ink-jet 3D printing manufacture solid oxide fuel cell electrode |
| CN109378488A (en) * | 2018-10-25 | 2019-02-22 | 深圳市致远动力科技有限公司 | A kind of tubular solid oxide fuel cells and preparation method thereof |
| CN112713294A (en) * | 2020-12-29 | 2021-04-27 | 深圳大学 | Dual-ion fuel cell and preparation method thereof |
| WO2022077729A1 (en) * | 2020-10-16 | 2022-04-21 | 广东省科学院新材料研究所 | Solid oxide fuel cell/electrolyzer cell prepared on the basis of additive manufacturing, and stack |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6755540B1 (en) * | 2018-12-18 | 2020-09-16 | 武藤工業株式会社 | Cell structure and its manufacturing method, fuel cell and secondary battery |
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| CN1501536A (en) * | 2002-10-28 | 2004-06-02 | 韩国电力公社 | Solid oxide fuel cells having gas channel |
| CN101515647A (en) * | 2009-03-10 | 2009-08-26 | 中国科学院上海硅酸盐研究所 | Direct hydrocarbon fuel solid oxide fuel cell anti-carbon deposition anode and a preparation method thereof |
| CN103199265A (en) * | 2013-03-14 | 2013-07-10 | 北京科技大学 | Composite cathode material of medium/low-temperature proton transport solid oxide fuel cell |
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| CN109378488A (en) * | 2018-10-25 | 2019-02-22 | 深圳市致远动力科技有限公司 | A kind of tubular solid oxide fuel cells and preparation method thereof |
| WO2022077729A1 (en) * | 2020-10-16 | 2022-04-21 | 广东省科学院新材料研究所 | Solid oxide fuel cell/electrolyzer cell prepared on the basis of additive manufacturing, and stack |
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| CN112713294A (en) * | 2020-12-29 | 2021-04-27 | 深圳大学 | Dual-ion fuel cell and preparation method thereof |
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| Publication number | Publication date |
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| CN105470529B (en) | 2018-12-14 |
| WO2017092085A1 (en) | 2017-06-08 |
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