CN105470529B - A kind of solid oxide fuel cell electrode and preparation method thereof and solid oxide fuel cell based on it - Google Patents

A kind of solid oxide fuel cell electrode and preparation method thereof and solid oxide fuel cell based on it Download PDF

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Publication number
CN105470529B
CN105470529B CN201510874862.1A CN201510874862A CN105470529B CN 105470529 B CN105470529 B CN 105470529B CN 201510874862 A CN201510874862 A CN 201510874862A CN 105470529 B CN105470529 B CN 105470529B
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electrode
fuel cell
solid oxide
oxide fuel
minutes
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CN105470529A (en
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庞胜利
沈湘黔
潘铁政
范景波
赵程
冯玉华
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SUZHOU PANT PIEZOELECTRIC TECH Co Ltd
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SUZHOU PANT PIEZOELECTRIC TECH Co Ltd
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Priority to PCT/CN2015/098173 priority patent/WO2017092085A1/en
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Abstract

The present invention relates to a kind of solid oxide fuel cell electrode and preparation method thereof and based on its solid oxide fuel cell, it includes on electrolyte layer, the electrode body with porous structure, especially: being also formed with multiple gas passages on the electrode body with porous structure, the gas passage has the first extending direction, and opposite first end and second end is formed on first extending direction, at least one of first end and second end is open so that gas passage to be in communication with the outside.By these gas passages can with optimising and adjustment gas electrode interior diffusion, and then be effectively relieved or avoid response location generally existing in solid oxide fuel cell practical work process be unevenly distributed and thus caused by thermo parameters method it is uneven the problems such as；In addition, the setting of gas passage also helps at anode at (oxygen ion conductor solid oxide fuel cell) or cathode the timely discharge that (proton conductor solid oxide fuel cell) generates water.

Description

A kind of solid oxide fuel cell electrode and preparation method thereof and solid based on it Oxide fuel cell
Technical field
The present invention relates to field of solid oxide fuel, and in particular to a kind of solid oxide fuel cell electrode, Preparation method and solid oxide fuel cell based on it.
Background technique
Under the overall background that energy and environmental problem has become the key factor for restricting today's society and economic development, Gu Oxide body fuel cell can directly convert chemical energy to the energy conversion device of electric energy as one kind, due to having both energy Outstanding advantages of high conversion efficiency, fuel is widely applicable, receives the extensive concern of people.If Japanese TOTO Ltd. is in Shen Please number to each provide one kind in 201180046923.5 and 201280016340.2 patent of invention comprehensive energy efficiency can be improved, And the solid oxide fuel cell for preventing excessive temperature from rising and being capable of 90000 hours solid oxide fuels of steady operation Battery；LG fuel cell system company of the U.S. is application No. is the patents of invention of 201280045198.4 and 201280045187.6 In the system of fuel cell is optimized.
However there are still some problems during its functionization needs to solve for solid oxide fuel cell.As (1) is existing There is solid oxide fuel cell electrode to prepare and mostly use the techniques such as tape casting, silk-screen printing greatly, in prepared porous electrode Often there are a certain number of closed cell regions in portion.As shown in Figure 1, electrode body 2 ' is formed on the surface of electrolyte 1 '；However The electrochemical reaction of electrode is concentrated mainly on electrode body 2 '/reaction gas two-phase interface, and the presence of closed cell region will lead to electricity The reduction and the non-uniform problem of electrochemical reaction area distribution of extremely internal actually active electrochemical reaction activating area, this will The problem of further bringing the decline of electrode performance and battery temperature to be unevenly distributed.(2) using traditional tape casting and silk screen Its hole of electrode of printing technology preparation in random distribution, often to there is duct narrow and the problems such as be unevenly distributed, be unfavorable for anti- Answer gas in the diffusion of entire electrode interior and the timely discharge of reaction product, this also will further influence electrode real work The performance of performance in journey.(3) thickness of single-layer electrodes is often thicker in traditional electrode preparation method, is unfavorable for according to solid oxidation Regulation of the object fuel cell real work demand to its different spatial electrode component, this is also unfavorable for opening for high-performance electrode Hair.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art to provide a kind of improved solid oxygen of structure Compound fuel cell electrode simultaneously provides the novel preparation method of the solid oxide fuel cell electrode simultaneously.
The present invention furthermore provides a kind of solid oxide fuel cell.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is as follows:
A kind of solid oxide fuel cell electrode comprising the electrode sheet on electrolyte layer, with porous structure Body, especially: being also formed with multiple gas passages on the electrode body with porous structure, which has the One extending direction, and opposite first end and second end is formed on first extending direction, in first end and second end extremely A few opening, gas passage is in communication with the outside.
Preferably, the multiple gas passage is uniformly distributed on electrode body.
Preferably, first extending direction is the thickness direction of electrode body, and the first end is far from electrolyte layer, institute Second end is stated close to electrolyte layer, the first end opening, the second end opening or closing.
One according to the present invention specific and preferred aspect, the gas passage also have vertical with the first extending direction The second extending direction, opposite third end and the 4th end are formed on the second extending direction, third end and the 4th end are open And it is in communication with the outside.
It is further preferred that the multiple gas passage side by side and is equally spaced, electrode body is made to form strip grid Lattice structure.
In a specific embodiment, the electrode body is rectangular, the second extending direction and electrode body The extending direction of a line is parallel.
Another specific and preferred aspect, the multiple gas passage according to the present invention are in a row arranged in column, make electrode sheet Bodily form networking lattice grid structure.
As a kind of preferred embodiment of the invention, cross-sectional area of the gas passage from first end to second end is not Become or gradually becomes smaller.
According to the present invention, the width of cross section of the gas passage on the first extending direction can 0.1 ~ 100 micron it Between, preferably between 1 ~ 10 micron.
According to the present invention, the component at the different spatial of the electrode body can be identical or different, can be according to electricity Pond is adjusted using actual demand.
Preferably, then electrode body of the invention is sintered by printing electrode precursor first with 3D printer It obtains.
According to the present invention, the electrode can be anode, be also possible to cathode, can be by one kind commonly used in the art or more Kind electrode material composition, is not particularly limited.
The another technical solution that the present invention takes is: a kind of preparation side of above-mentioned solid oxide fuel cell electrode Method, this method prepare electrode using 3D printer, specifically comprise the following steps:
(1) according to the component of battery electrode to be prepared, to prepare corresponding electrode slurry；
(2) print routine is formulated according to the structure of electrode to be prepared, and be input in 3D printer；
(3) parameter that setting 3D printer prints: including temperature, the printing number of plies, print time interval；
(4) it according to the print routine of setting and parameter, using the material comprising electrolyte layer as printing substrate, is put into corresponding Electrode slurry, carry out 3D printing, obtain electrode precursor；
(5) electrode precursor that printing obtains is sintered to get the solid oxide fuel cell electrode.
Further, step (1) is implementable as follows: electrode powder and pore creating material being placed in ball grinder, it is fine that ethyl is added The terpineol solution for tieing up element carries out ball-milling treatment as adhesive up to electrode slurry, and wherein pore creating material can be starch, corn One of powder, nano-carbon material or a variety of combinations, its addition quality are generally the 0.01% ~ 40% of electrode powder quality；Second The mass content of ethyl cellulose is generally 3% ~ 10% in the terpineol solution of base cellulose, the terpineol solution of ethyl cellulose Additional amount be 0.5 ~ 3 times of electrode powder and pore creating material gross mass.Electrode powder is formulated according to electrode material to be prepared, It can be single phase cathode material such as La when electrode to be prepared is cathode0.5Sr0.5Co0.8Fe0.2O3-δ(LSCF) or it is compound Cathode material such as LSCF-SDC(Sm0.2Ce0.8O1.9).When the different electrode of different spatial component to be prepared, Ke Yipei A variety of electrode slurrys are made, when printing different layers, is put into 3D printer and is printed.
Further, in step (1), the method for ball milling is as follows: first ball milling 5-180 minutes lower at 200-350 revs/min Make material be uniformly mixed, then by revolving speed be promoted to 500-900 revs/min lower ball milling 10-720 minutes to reduce in ball grinder The granularity of powder, finally 200-350 revs/min lower ball milling 5-180 minutes to get electrode slurry.
Further, the thickness printed every time can be controlled by the viscosity of electrode slurry prepared by rate-determining steps (1) Degree.Preferably, control print every time with a thickness of 0.5 ~ 1 micron.Setting printing the number of plies be 15 ~ 25 layers, set print temperature as 30 ~ 70 DEG C, set the print time between be divided into 10-60 minutes.
Preferably, in step (4), the material comprising electrolyte layer be electrolyte sheet or by electrolyte layer and with to The support half-cell that the opposite electrode layer of the electrode of preparation is constituted.For example, electricity can be used when electrode to be prepared is cathode Solve matter piece or anode-supported half-cell (anode/electrolyte double-layer structure, electrolyte layer is upward when printing)；When electrode to be prepared When for anode, electrolyte sheet or cathode support half-cell (cathode/electrolyte bilayer, electrolyte layer when printing can be used Upwards).
Further, in step (5), the sintering schedule of the sintering processes is as follows: first with 1 DEG C/min ~ 1.5 DEG C/ The speed of minute is warming up to 400 ~ 600 DEG C and keeps the temperature 5 ~ 240 minutes, is then warming up to 900 ~ 1350 with 2 ~ 8 DEG C/min of speed DEG C and keep the temperature 30 ~ 480 minutes, room temperature is finally down to 2 ~ 8 DEG C/min of speed.
The invention further relates to a kind of solid oxide fuel cell comprising above-mentioned solid oxide fuel cell electricity Pole.
Further, the battery electrode is cathode and/or anode.
Due to the implementation of above technical scheme, the invention has the following advantages over the prior art:
Other than solid oxide fuel cell provided by the present invention hole possessed by the electrode body, also have multiple Gas passage and then can be effectively relieved or be avoided with optimising and adjustment gas in the diffusion of electrode interior by these gas passages In solid oxide fuel cell practical work process generally existing response location be unevenly distributed and thus caused by temperature field The problems such as being unevenly distributed；In addition, the setting of gas passage also helps at anode (oxygen ion conductor solid oxide fuel electricity Pond) or cathode at (proton conductor solid oxide fuel cell) generate water timely discharge.
The preparation method of solid oxide fuel cell provided by the present invention, the system combined using 3D printing and sintering Standby technique, can be effectively reduced electrode interior non-chemical active region as caused by closed pore, it may be convenient to it is logical to adjust gas Shape, size and the convenient component for adjusting electrode material at different spatial in road, so as to according to battery reality Electrode is adjusted flexibly in demand, is conducive to the raising of prepared electrode comprehensive performance.In addition, the technological operation is simple, controllability is strong, It is easy to large-scale production.
Detailed description of the invention
Fig. 1 is traditional electrode micro-structure schematic diagram；
Fig. 2 lattice-shaped porous electrode micro-structure schematic diagram；
Fig. 3 (a) strip lattice structure La0.5Sr0.5Co0.8Fe0.2O3-δ(LSCF) single phase cathode planar structure schematic diagram, (b) partial enlarged view in a figure at A；
Fig. 4 (a) strip lattice structure La0.5Sr0.5Co0.8Fe0.2O3-δ(LSCF) single phase cathode cross-sectional view, (b) in a figure Partial enlarged view at B；
Fig. 5 (a) is the planar structure schematic diagram of the anode of solid oxide fuel cell of embodiment 3, (b) in a figure at C Partial section enlarged view；
Fig. 6 (a) is the schematic cross-sectional view of the anode of solid oxide fuel cell of embodiment 3, (b) office in a figure at D Portion's enlarged drawing；
Wherein, 1 ', electrolyte；2 ', electrode body；21 ', gas passage；1, electrolyte layer；2, electrode body；21, gas Channel；3, electrolyte layer；4, electrode body；41, gas passage.
Specific embodiment
Below will by specific embodiment, the present invention is further explained, but the protection scope being not intended to restrict the invention. In following embodiments, 3D printer is purchased from Fuji Photo Film Co., Ltd. (FUJI FILM), and 3D printer operates according to the manufacturer's recommendations Mode carries out.
Embodiment 1
The present embodiment provides a kind of solid oxide fuel cell electrode, microstructure is as shown in Fig. 2, include being set to electricity It solves on matter layer 1, the electrode body 2 with porous structure, is also formed with multiple gases on the electrode body 2 with porous structure Channel 21, the gas passage 21 have the first extending direction, and form on first extending direction opposite first end and the Two ends, the first end opening, second end is also open, so that gas passage is in communication with the outside.The electrode has strip lattice structure, It can effectively reduce electrode interior non-chemical active region as caused by closed pore；In addition to this, this lattice structure can effectively promote Air inlet body is effectively relieved or avoids and is generally existing in solid oxide fuel cell practical work process in the diffusion of cathode internal Response location be unevenly distributed and thus caused by thermo parameters method it is uneven the problems such as.
In the present embodiment, as shown in Figure 3 and Figure 4, which is single phase cathode electrode, on The multiple gas passages 21 stated are evenly distributed on electrode body 2, and they side by side and are equally spaced, and make electrode body 2 Form strip lattice structure.And the first extending direction is the thickness direction of electrode body, and first end is far from electrolyte layer, and second It holds close to electrolyte layer, cross-sectional area of the gas passage 21 from first end to second end is constant, and width can be according to practical need It is configured, preferably 1 ~ 10 micron.
Specifically, solid oxide fuel cell electrode is cathode electrode in this example, can be prepared by following steps:
(1) 5g LSCF powder and 5g cellulose content are weighed as the terpineol solution of the ethyl cellulose of 6 wt.% It is put into 50ml agate jar, and the ball milling preparation that the agate ball milling pearl that total volume is about 20ml carries out cathode slurry is added. Wherein ball-milling technology is ball milling 60 minutes first under 350 revs/min of revolving speeds, and revolving speed is then promoted to 800 revs/min of balls Mill 300 minutes, finally under 350 revs/min of revolving speeds ball milling 30 minutes to obtain electrode slurry.
(2) above-mentioned electrode slurry is collected, and is placed it in stand-by in closed receiving flask.
(3) 3D printer power supply is opened, by the fine and close Gd by surface cleaning processing0.1Ce0.9O1.95(GDC) electrolyte sheet It is fixed on 3D printing platform as printing substrate, and the temperature of stamp pad is set as 40 DEG C, print time interval is set as 20 points Clock.
(4) cathode slurry is put into printer ink cartridge, and respective ink tanks is fixed on 3D printer print cartridge position.
(5) print routine is input in 3D printer, and adjust print cartridge mode out of ink and top of form preparation beat Print.
(6) start first layer print job, waited 20 minutes after to be printed, fill the solvent printed in slurry Divide volatilization, printed material can be good at being adhered on substrate.
(7) carry out the print job of subsequent layers according to step (5) and (6).Wherein every layer of thickness is about 0.8 micron, 20 layers are printed altogether.
(8) it is taken out from 3D printer after being printed to electrode, is placed in Muffle furnace and is sintered.Wherein The sintering schedule is to be warming up to 600 DEG C with 1 DEG C/min of speed and keep the temperature 30 minutes, then with 5 DEG C/min of speed liter Temperature is to 1050 DEG C and keeps the temperature 240 minutes, and being finally down to room temperature with 5 DEG C/min of speed can be obtained the soild oxide combustion Expect battery electrode.
Embodiment 2
The present embodiment provides a kind of compound cathode of solid oxide fuel battery electrode, in microstructure and embodiment 1 It is essentially identical, unlike: use LSCF-SDC composite material.Preparation method includes the following steps:
(1) the different LSCF-Sm of 2g SDC content is weighed respectively0.2Ce0.8O1.9(SDC) mixed powder and 4g ethyl are fine The terpineol solution for the ethyl cellulose that dimension cellulose content is 6 wt.% is put into 50ml agate jar, and total volume is added and is about The agate ball milling pearl of 20ml carries out the ball milling preparation of cathode slurry.Wherein the content of SDC is respectively 0 in LSCF-SDC composite material Wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.% and 70 wt.%.Ball-milling technology is first Then revolving speed is promoted to 500 revs/min of ball millings 600 minutes, finally existed by ball milling 180 minutes under 200 revs/min of revolving speeds Under 200 revs/min of revolving speeds ball milling 60 minutes to obtain electrode slurry.
(2) above-mentioned electrode slurry is collected, and is placed it in stand-by in closed receiving flask.
(3) 3D printer power supply is opened, is consolidated by the fine and close SDC electrolyte sheet of surface cleaning processing as printing substrate Due on 3D printing platform, and the temperature of stamp pad is set as 60 DEG C, is divided between the print time 10 minutes.
(4) cathode slurry is put into printer ink cartridge, and respective ink tanks is fixed on 3D printer print cartridge position.
(5) print routine is input in 3D printer, and adjust print cartridge mode out of ink and top of form preparation beat Print.
(6) start first layer print job, waited 10 minutes after to be printed, fill the solvent printed in slurry Divide volatilization, printed material can be good at being adhered on substrate.
(7) component for replacing electrode slurry in print cartridge according to actual needs carries out subsequent layers according to step (5) and (6) Print job.Wherein every layer of thickness is about 0.5 micron, 24 layers is printed altogether, from electrolyte/cathode section to cathode layer surface SDC content gradually decreases and every kind 3 layers of component successive print.
(8) it is taken out from 3D printer after being printed to electrode, is placed in Muffle furnace and is sintered.Wherein The sintering schedule is to be warming up to 600 DEG C with 1 DEG C/min of speed and keep the temperature 30 minutes, then with 3 DEG C/min of speed liter Temperature is to 900 DEG C and keeps the temperature 480 minutes, and being finally down to room temperature with 3 DEG C/min of speed can be obtained the solid oxide fuel Battery electrode.
Embodiment 3
The present embodiment provides a kind of compound anode of solid-oxide fuel battery electrodes, as shown in Figure 5 and Figure 6 comprising On electrolyte layer 3, the electrode body with porous structure 4, the gas of multiple arrayed in columns of embarking on journey is formed on electrode body 4 Body channel 41, so that electrode forms latticed lattice structure.Gas passage 41 extends along the thickness direction of electrode body 4, End (first end) far from electrolyte layer 3 is open, and closes close to the end (second end) of electrolyte layer 3, and gas passage 41 is certainly First end gradually becomes smaller to the cross-sectional area of second end.
The preparation method of the composite cathode electrode the following steps are included:
(1) weigh respectively the different GDC-NiO composite granule of 2g GDC content, appropriate amount of starch and with composite granule and shallow lake The identical terpineol solution of ethyl cellulose of powder gross mass (cellulose content is 6 wt.%) is put into 50ml agate jar In, and the ball milling preparation that the agate ball milling pearl that total volume is about 20ml carries out cathode slurry: wherein GDC-NiO composite material is added The content of middle GDC is respectively 60 wt.%, 50 wt.% and 40 wt.%, and corresponding content of starch is the 0 of GDC-NiO mass Wt.%, 30 wt.% and 40 wt.%, ball-milling technology is ball milling 120 minutes first under 250 revs/min of revolving speeds, then by revolving speed Be promoted to 600 revs/min of ball millings 900 minutes, finally under 250 revs/min of revolving speeds ball milling 120 minutes to obtain electrode slurry； Above-mentioned electrode slurry is collected, and is placed it in stand-by in closed receiving flask；
(2) above-mentioned electrode slurry is collected, and is placed it in stand-by in closed receiving flask.
(3) 3D printer power supply is opened, is consolidated by the fine and close SDC electrolyte sheet of surface cleaning processing as printing substrate Due on 3D printing platform, and the temperature of stamp pad is set as 50 DEG C, is divided between the print time 15 minutes.
(4) cathode slurry is put into printer ink cartridge, and respective ink tanks is fixed on 3D printer print cartridge position.
(5) print routine is input in 3D printer, and adjust print cartridge mode out of ink and top of form preparation beat Print.
(6) start first layer print job, waited 15 minutes after to be printed, fill the solvent printed in slurry Divide volatilization, printed material can be good at being adhered on substrate.
(7) component for replacing electrode slurry in print cartridge according to actual needs carries out subsequent layers according to step (5) and (6) Print job.Wherein every layer of thickness is about 0.8 micron, 20 layers is printed altogether, from electrolyte/anodic interface to anode layer surface GDC component is from 60 wt.%(2 layers) it is reduced to 50 wt.%(2 layers in succession) and 40 wt.%(16 layers).
(8) it is taken out from 3D printer after being printed to electrode, is placed in Muffle furnace and is sintered.Wherein The sintering schedule is to be warming up to 400 DEG C with 1 DEG C/min of speed and keep the temperature 240 minutes, then with 2 DEG C/min of speed liter Temperature is to 1350 DEG C and keeps the temperature 480 minutes, and being finally down to room temperature with 2 DEG C/min of speed can be obtained the soild oxide combustion Expect battery electrode.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (15)

1. a kind of solid oxide fuel cell electrode comprising the electrode body on electrolyte layer, with porous structure, It is characterized by: multiple gas passages are also formed on the electrode body with porous structure, the gas passage tool There is the first extending direction, and forms opposite first end and second end, the first end and second on first extending direction At least one of end opening；
The width of cross section of the gas passage on first extending direction is between 0.1 ~ 100 micron；
Then the electrode body is sintered to obtain by printing electrode precursor first with 3D printer；
The preparation of the electrode specifically comprises the following steps:
(1) according to the component of battery electrode to be prepared, to prepare corresponding electrode slurry；
(2) print routine is formulated according to the structure of electrode to be prepared, and be input in 3D printer；
(3) parameter that setting 3D printer prints: including temperature be 30 ~ 70 DEG C, the printing number of plies is 15 ~ 25 layers, between the print time It is divided into 10-60 minutes；
(4) according to the print routine of setting and parameter, using the material comprising electrolyte layer as printing substrate, it is put into corresponding electricity Pole slurry carries out 3D printing, obtains electrode precursor；
(5) electrode precursor that printing obtains is sintered to get the solid oxide fuel cell electrode；
Wherein step (1) is implemented as follows: electrode powder and pore creating material being placed in ball grinder, the terpinol of ethyl cellulose is added Solution carries out ball-milling treatment as adhesive up to the electrode slurry, and the pore creating material is starch, corn flour, nano-carbon material One of or a variety of combinations, its add quality be electrode powder quality 0.01% ~ 40%；The pine of the ethyl cellulose The mass content of ethyl cellulose is 3% ~ 6% in oleyl alcohol, and the additional amount of the terpineol solution of the ethyl cellulose is institute 0.5 ~ 3 times for stating electrode powder and pore creating material gross mass；
The method of the ball milling is as follows: being first uniformly mixed lower ball milling 5-180 minutes at 200-350 revs/min material, so Afterwards by revolving speed be promoted to 500-900 revs/min lower ball milling 10-720 minutes to reduce the granularity of powder in ball grinder, finally 200-350 revs/min lower ball milling 5-180 minutes to get electrode slurry；
The thickness printed every time is controlled by the viscosity of electrode slurry prepared by rate-determining steps (1), and control is beaten every time Print with a thickness of 0.5 ~ 1 micron.
2. solid oxide fuel cell electrode according to claim 1, it is characterised in that: the multiple gas passage exists It is uniformly distributed on the electrode body.
3. solid oxide fuel cell electrode according to claim 1, it is characterised in that: first extending direction is The thickness direction of electrode body, for the first end far from the electrolyte layer, the second end is described close to the electrolyte layer The first end opening, second end opening or closing.
4. solid oxide fuel cell electrode according to claim 1 or 2 or 3, it is characterised in that: the gas is logical Road also has second extending direction vertical with first extending direction, and opposite is formed on second extending direction Three ends and the 4th end, the third end and the 4th end are open and are in communication with the outside.
5. solid oxide fuel cell electrode according to claim 4, it is characterised in that: the multiple gas passage is simultaneously It arranges and is equally spaced, the electrode body is made to form strip lattice structure.
6. solid oxide fuel cell electrode according to claim 4, it is characterised in that: the electrode body is side Shape, second extending direction are parallel with the extending direction of a line of the electrode body.
7. solid oxide fuel cell electrode according to claim 3, it is characterised in that: the multiple gas passage at Arrangement arranged in columns makes the electrode body form latticed lattice structure.
8. solid oxide fuel cell electrode according to claim 3, it is characterised in that: the gas passage is from institute The cross-sectional area for stating first end to second end is constant or gradually becomes smaller.
9. solid oxide fuel cell electrode according to claim 1, it is characterised in that: the gas passage is described The width of cross section on first extending direction is between 1 ~ 10 micron.
10. solid oxide fuel cell electrode according to claim 1, it is characterised in that: the electrode body is not Component at isospace position is identical or different.
11. a kind of preparation of the solid oxide fuel cell electrode as described in any one of claims 1 to 10 claim Method, it is characterised in that: this method prepares the electrode using 3D printer, specifically comprises the following steps:
(1) according to the component of battery electrode to be prepared, to prepare corresponding electrode slurry；
(2) print routine is formulated according to the structure of electrode to be prepared, and be input in 3D printer；
(3) parameter that setting 3D printer prints: including temperature, the printing number of plies, print time interval；
(4) according to the print routine of setting and parameter, using the material comprising electrolyte layer as printing substrate, it is put into corresponding electricity Pole slurry carries out 3D printing, obtains electrode precursor；
(5) electrode precursor that printing obtains is sintered to get the solid oxide fuel cell electrode,
Wherein step (1) is implemented as follows: electrode powder and pore creating material being placed in ball grinder, the terpinol of ethyl cellulose is added Solution carries out ball-milling treatment as adhesive up to the electrode slurry,
The method of the ball milling is as follows: being first uniformly mixed lower ball milling 5-180 minutes at 200-350 revs/min material, so Afterwards by revolving speed be promoted to 500-900 revs/min lower ball milling 10-720 minutes to reduce the granularity of powder in ball grinder, finally 200-350 revs/min lower ball milling 5-180 minutes to get electrode slurry,
The thickness printed every time is controlled by the viscosity of electrode slurry prepared by rate-determining steps (1), and control is beaten every time Print with a thickness of 0.5 ~ 1 micron；The setting printing number of plies is 15 ~ 25 layers, sets print temperature as 30 ~ 70 DEG C, sets the print time Between be divided into 10-60 minutes.
12. preparation method according to claim 11, it is characterised in that: the pore creating material is starch, corn flour, nano-sized carbon One of material or a variety of combinations, its addition quality are the 0.01% ~ 40% of electrode powder quality；The ethyl cellulose Terpineol solution in ethyl cellulose mass content be 3% ~ 6%, the additional amount of the terpineol solution of the ethyl cellulose It is 0.5 ~ 3 times of the electrode powder and pore creating material gross mass.
13. preparation method according to claim 11, it is characterised in that: in step (4), the material comprising electrolyte layer Material is electrolyte sheet or the support half-cell being made of electrolyte layer and the electrode layer opposite with electrode to be prepared.
14. preparation method according to claim 11, it is characterised in that: in step (5), the sintering system of the sintering processes Spend as follows: being warming up to 400 ~ 600 DEG C and heat preservation 5 ~ 240 minutes first with 1 DEG C/min ~ 1.5 DEG C/min of speed, then with 2 ~ 8 DEG C/min of speed is warming up to 900 ~ 1350 DEG C and keeps the temperature 30 ~ 480 minutes, is finally down to room with 2 ~ 8 DEG C/min of speed Temperature.
15. a kind of solid oxide fuel cell, it is characterised in that: including such as any one of claims 1 to 10 claim The solid oxide fuel cell electrode.
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