CN105428679B - A kind of solid oxide fuel cell electrolyte film and preparation method thereof and solid oxide fuel cell - Google Patents
A kind of solid oxide fuel cell electrolyte film and preparation method thereof and solid oxide fuel cell Download PDFInfo
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- CN105428679B CN105428679B CN201510874668.3A CN201510874668A CN105428679B CN 105428679 B CN105428679 B CN 105428679B CN 201510874668 A CN201510874668 A CN 201510874668A CN 105428679 B CN105428679 B CN 105428679B
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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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- 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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
-
- 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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
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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
-
- 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 electrolyte film and preparation method thereof and solid oxide fuel cell, the dielectric film includes the first electrolyte cells and the second electrolyte cells that are arranged alternately, first electrolyte cells are mutually made of oxygen ion conductor, and second electrolyte cells are mutually made of proton conductor.Proton conducting channel is introduced in traditional oxygen ion conductor dielectric film can effectively alleviate the problem of ionic conductance is remarkably decreased caused by dielectric film is reduced due to battery operating temperature, middle low temperature and the functionization of solid oxide fuel cell are advantageously implemented, so as to effectively reduce ion resistance of the solid oxide fuel cell under the conditions of middle low-temperature working.
Description
Technical field
The invention belongs to fuel cell fields, are related to a kind of component of fuel cell, and in particular to a kind of soild oxide
Electrolyte film in fuel cell and preparation method thereof and solid oxide fuel cell.
Background technology
Solid oxide fuel cell as it is a kind of can directly by chemical energy be converted into the energy conversion device of electric energy by
In having both the advantages that energy conversion efficiency is high, fuel is widely applicable by people's extensive concern.As Japanese TOTO Ltd. exists
Application No. is have developed one kind by adulterating a part of aluminium oxide in the electrolyte in 201280016340.2 patent of invention
It being capable of 90000 hours solid oxide fuel cell of steady operation；LG fuel cell systems company of the U.S. application No. is
201280045198.4 the system of fuel cell is optimized in 201280045187.6 patent of invention.
However, up to the present solid oxide fuel cell power generation cost it is still higher, this mainly with existing solid
Oxide fuel cell produces and operating cost is higher related.Existing solid oxide fuel cell is mostly still using traditional
Yttria-stabilized zirconia (YSZ) is electrolyte, and operating temperature is at 750 DEG C -1000 DEG C.Long-time work at such high temperatures
Make to cause side reaction between cell components material, the problems such as electrode microstructure is due to sintering and by destroying.Except this it
Outside, higher operating temperature so that the optional material of each component of solid oxide fuel cell is very limited, it is impossible to using cost
The sealing of relative moderate and electrode material.
The operating temperature for reducing solid oxide fuel cell is expected to significantly alleviate above-mentioned ask to 300-750 DEG C of temperature range
Topic is generally considered the effective way for realizing that it is practical.However, the reduction of solid oxide fuel cell operating temperature
The problem of its output power can be caused significantly to decay.Wherein traditional YSZ electrolyte oxygen ionic conductance activation energy is higher, with temperature
The decline electrolyte ion conduction resistance of degree dramatically increases, it has also become restricts the key of low temperature in solid oxide fuel cell
One of factor.
Invention content
The technical problems to be solved by the invention are that overcome the deficiencies in the prior art provides a kind of improved solid oxygen of structure
Compound electrolyte film in fuel cell and the novel preparation method that the solid oxide fuel cell electrolyte film is provided simultaneously.
For solution more than technical problem, a kind of technical solution that the present invention takes is as follows：A kind of solid oxide fuel electricity
Pond dielectric film, the dielectric film include the first electrolyte cells and the second electrolyte cells that are arranged alternately, and described first
Electrolyte cells are mutually made of oxygen ion conductor, and second electrolyte cells are mutually made of proton conductor.
Optimally, first electrolyte cells and second electrolyte cells have multiple respectively.
One according to the present invention specific and preferred aspect, first electrolyte cells and second electrolyte cells
It is strip, and its length extending direction is vertical with the thickness direction of the dielectric film.Further, first electrolysis
The length of matter unit is equal to the width of a line of dielectric film, the thickness of first electrolyte cells and second electrolysis
The thickness of matter unit is equal to the thickness of dielectric film.
Another specific and preferred aspect according to the present invention, the multiple first electrolyte cells and the multiple second electricity
Solution matter unit is alternately arranged along the length direction of plane and width direction where the dielectric film.Further, it is described
The thickness of first electrolyte cells and second electrolyte cells is equal to the thickness of the dielectric film, first electrolyte
The length of unit and second electrolyte cells and it is wide be respectively 1~30 micron.Preferably, first electrolyte cells and institute
State the second electrolyte cells length and it is wide be respectively 2~20 microns, more preferably 2~10 microns.
According to the present invention, size, the shape of multiple the multiple first electrolyte cells can be identical or different；It is described more
The size of a second electrolyte cells can be identical or different, first electrolyte cells and second electrolyte cells
Size, shape can be identical or different.Preferably, the size of the multiple first electrolyte cells, the second electrolyte cells,
Shape all same.
Optimally, the dielectric film is printed by 3D printer.
Optimally, the proton conductor is mutually BaZr0.1Ce0.7Y0.2O3-δ, the oxygen ion conductor is mutually
Gd0.1Ce0.9O1.95(GDC10)、Gd0.2Ce0.8O1.9(GDC20)、Sm0.1Ce0.9O1.95(SDC10) and Sm0.2Ce0.8O1.9(SDC20)
In it is one or more.
Another object of the present invention is to provide a kind of preparation method of above-mentioned solid oxide fuel cell electrolyte film,
It includes the following steps：
(a) according to dielectric film to be prepared, corresponding oxygen ion conductor phase slurry and proton conductor phase slurry are prepared, with
And formulate corresponding print routine；
(b) one layer of oxygen ion conductor phase and proton conductor phase are successively printed on substrate using 3D printer；
(c) step (b) is repeated, until obtaining the thickness needed, stops printing, takes out, be sintered to get described
Dielectric film.
Further, the substrate for by sintering processes GDC10-NiO, GDC20-NiO, SDC10-NiO and
One kind in SDC20-NiO composite anode plates, and the content of NiO is 50~70wt% in the composite anode plate.
Preferably, in step (b), when being printed, the print temperature of 3D printer is set as 30~70 DEG C, adjacent secondary to beat
Interval between print is set as 10~60 minutes.
Further, step (a) is specially：By oxygen ion conductor phase powder, proton conductor phase powder respectively with binding agent
Mixing, which is placed in ball grinder, carries out ball-milling treatment, and the method for ball milling the following is：First under 250~350 revs/min of speed
Then rotating speed is promoted to 500~600 revs/min of lower ball millings 120~480 minutes by ball milling 30~180 minutes, finally 250~
Ball milling 30~180 minutes under 350 revs/min of speed.
Preferably, the binding agent is the aqueous solution of polyvinyl alcohol, and additive amount is oxygen ion conductor phase powder or proton
The 200%~400% of conductor phase powder quality.It is highly preferred that the number-average molecular weight of the polyvinyl alcohol is 10000~60000,
Its content in the aqueous solution is 1~5wt%.
According to the present invention, can the thickness that printed every time be controlled by the viscosity of the slurry prepared by rate-determining steps (a).
Preferably, the thickness that control prints every time is 0.5~1 micron.
Preferably, the primary particle diameter of the oxygen ion conductor phase powder and the proton conductor phase powder is less than 100
Nanometer.
Preferably, in step (f), the sintering method is：400~600 are warming up to 0.5~1.5 DEG C/min of speed
DEG C and keep the temperature 60-240 minutes, then with 1~2 DEG C/min of speed be warming up to 1300~1500 DEG C and keep the temperature 120~480 points
Clock is finally down to room temperature with 1~2 DEG C/min of speed.
The present invention furthermore provides a kind of solid oxide fuel cell, it contains above-mentioned solid oxide fuel electricity
Pond dielectric film.
Due to the implementation of above technical scheme, the present invention has the following advantages that compared with prior art：
Solid oxide fuel cell electrolyte film of the present invention, including the first electrolyte cells being arranged alternately and the second electricity
Matter unit is solved, the first electrolyte cells are mutually made of oxygen ion conductor, and the second electrolyte cells are mutually made of proton conductor, are being passed
Proton conducting channel is introduced in system oxygen ion conductor dielectric film can effectively alleviate dielectric film since battery operating temperature reduces
Caused by ionic conductance the problem of being remarkably decreased, be advantageously implemented middle low temperature and the practicality of solid oxide fuel cell
Change, so as to effectively reduce ion resistance of the solid oxide fuel cell under the conditions of middle low-temperature working.
The preparation method of solid oxide fuel cell electrolyte film provided by the present invention, due to using 3D printing technique
The dielectric film of preparation has the characteristics that structure design flexibly and film thickness controllable precise, therefore can be according to the practical need of battery
Flexible design proton-lattice structure of oxonium ion mixing conductance dielectric film and the thickness of dielectric film are asked, reduces solid oxidation
The ion resistance of object fuel cell under running conditions is advantageously implemented the middle low temperature of solid oxide fuel cell；And
3D printing technique has the characteristics of simple for process, easy large-scale production.
Description of the drawings
The plan view of solid oxide fuel cell electrolyte film in Fig. 1 (a) embodiments 1, the part in (b) a figures at A are put
Big figure；
The sectional view of solid oxide fuel cell electrolyte film in Fig. 2 (a) embodiments 1, the part in (b) a figures at B are put
Big figure；
Fig. 3 is the plan view of solid oxide fuel cell electrolyte film in embodiment 2；
Wherein, 1, electrolyte ontology；11st, the first electrolyte cells；12nd, the second electrolyte cells；2nd, substrate.
Specific embodiment
It below will by specific embodiment, the present invention is further explained, but the protection domain being not intended to restrict the invention.
In following embodiments, 3D printer is purchased from Fuji Photo Film Co., Ltd. (FUJIFILM), 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 electrolyte films, as shown in Fig. 2 (a) and Fig. 2 (b), its shape
Into on any surface in substrate 2, including multiple the first electrolyte cells 11 and the second electrolyte cells 12 being arranged alternately,
One electrolyte cells 11 are mutually made of oxygen ion conductor, and the second electrolyte cells 12 are mutually made of proton conductor.In this way in tradition
In oxygen ion conductor dielectric film introduce proton conducting channel can effectively alleviate dielectric film due to battery operating temperature reduce and
The problem of caused ionic conductance is remarkably decreased is advantageously implemented the middle low temperature (300~800 DEG C) of solid oxide fuel cell
Change and practical.
In the present embodiment, the first electrolyte cells 11 strip identical for size and shape with the second electrolyte cells 12
Shape, their length extending direction is vertical with the thickness direction of dielectric film, and length is equal to the width of a line of dielectric film
Degree, their thickness are equal to the thickness of dielectric film, i.e., as shown in Fig. 1 (a) and Fig. 1 (b).Proton-oxonium ion mixed conductor electricity
Solution plasma membrane is alternately arranged and is formed by multiple first electrolyte cells 11 and multiple second electrolyte cells 12.The structure can by
First the first electrolyte cells 11 by 3D printer are printed on substrate, then again print the second electrolyte cells 12
Come.
The width of first electrolyte cells 11 and the second electrolyte cells 12 can be determined (the first electrolysis as needed
The width of the width of matter unit 11 and the second electrolyte cells 12 can be the same or different；Each first electrolyte cells 11
Width can be the same or different, the width of similary each second electrolyte cells 12 can be the same or different).
In this example, proton conductor is mutually BaZr0.1Ce0.7Y0.2O3-δ(BZCY), and oxygen ion conductor mutually be selected from
Gd0.1Ce0.9O1.95(GDC10)、Gd0.2Ce0.8O1.9(GDC20)、Sm0.1Ce0.9O1.95(SDC10) and Sm0.2Ce0.8O1.9(SDC20)
One or more of composition mixture.
Embodiment 2
The present embodiment provides a kind of solid oxide fuel cell electrolyte films, it is formed on any surface of substrate 2,
Also include multiple the first electrolyte cells 11 and the second electrolyte cells 12 being arranged alternately, material and one in embodiment 1
It causes, unlike：Multiple first electrolyte cells 11 and multiple second electrolyte cells 12 along dielectric film length and width
Degree direction is alternately arranged, as shown in Figure 3 so that the two neighboring electrolyte cells in each row or in each row are different
Electrolyte cells.In the present embodiment, the thickness of the first electrolyte cells 11 and the second electrolyte cells 12 is formed by them
The length and width of the thickness of dielectric film, the first electrolyte cells 11 and the second electrolyte cells 12 is 3 microns.
Embodiment 3
The present embodiment provides a kind of preparation methods of solid oxide fuel cell electrolyte film, it includes the following steps：
(a) the agate material of GDC10 nano-powders, 15g adhesives and about 20ml for being about 50nm by 5g primary particle sizes
Matter ball milling pearl is put into the first agate jar of 50ml；By 5g primary particle sizes be about 90nm BZCY nano-powders, 12g
The agate material ball milling pearl of adhesive and about 20ml are put into the second agate jar of 50ml；By above-mentioned two agate jar
It is fixed in ball mill and carries out ball milling；Ball grinding method is：Then ball milling 30 minutes first under 250 revs/min of rotating speed will turn
Speed is promoted to 500 revs/min of ball millings 480 minutes, and finally ball milling is electrolysed chylema in 30 minutes to obtain under 250 revs/min of rotating speeds
Material；Wherein, adhesive is polyvinyl alcohol ([C2H4O]n) aqueous solution, a concentration of 2wt% of polyvinyl alcohol, average molecular weight is about
It is 50000, the additive amount of adhesive is the 200% of corresponding electrolyte powder weight.
Above-mentioned electrolyte slurry is collected, and is placed it in for use in closed receiving flask；3D printer power supply is opened, will be passed through
(also referred to as substrate, it is the GDC10-NiO by 1000 DEG C/4h sintering processes to the GDC10-NiO printings substrate of surface cleaning processing
The content of anode plate, wherein NiO is 60wt%) it is fixed on 3D printing platform, and the temperature of stamp pad is set as 40 DEG C；First will
GDC10 electrolyte slurries are put into printer ink cartridge, and respective ink tanks are fixed on 3D printer print cartridge position.
Print routine is input in 3D printer, and adjusts print cartridge mode out of ink and top of form, starts first
The print job of GDC10 electrolyte in layer；It is waited for 35 minutes after to be printed, the moisture in printing slurry is made fully to be waved
Hair, printed material can be good at being adhered on substrate；It is to fill BZCY electrolyte slurries by the replacing ink cartridge in printer
Printer ink cartridge, adjustment print cartridge mode out of ink and top of form, repeat the above steps, and start BZCY electrolyte in first layer
Print job, it is similary it is to be printed after wait for 35 minutes, the moisture in printing slurry is made fully to be volatilized, printed material energy
It is enough to be adhered on substrate well.
It repeats the above steps, continues the print job of subsequent layers, print 10 layers altogether.By it after matter printing to be electrolysed
It is taken out from 3D printer, is placed in Muffle furnace and is sintered.Wherein described sintering schedule is with 0.5 DEG C/min of speed
Degree is warming up to 400 DEG C and keeps the temperature 60 minutes, is then warming up to 1400 DEG C with 1 DEG C/min of speed and keeps the temperature 120 minutes, finally
Using 1 DEG C/min of speed be down to room temperature can obtain the solid oxide fuel cell electrolyte film (electrolyte overall thickness as
8 microns, be 0.8 micron per layer thickness).
Embodiment 4
The present embodiment provides a kind of preparation method of solid oxide fuel cell electrolyte film, step and embodiment 3
In it is basically identical, unlike：1st, sintering parameter is different, specially：400 DEG C are warming up to 0.5 DEG C/min of speed and are protected
Then temperature 240 minutes is warming up to 1400 DEG C with 2 DEG C/min of speed and keeps the temperature 480 minutes, finally with 2 DEG C/min of speed
It is down to room temperature and can obtain the solid oxide fuel cell electrolyte film；2nd, ball milling parameter is different, specially：First 350
Rev/min rotating speed under ball milling 180 minutes, rotating speed is then promoted to 600 revs/min of ball millings 120 minutes, finally 350 turns/
Minute rotating speed under ball milling 180 minutes to obtain electrolyte slurry.
Embodiment 5
The present embodiment provides a kind of preparation method of solid oxide fuel cell electrolyte film, step and embodiment 3
In it is basically identical, unlike：The material of oxygen ion conductor phase used is SDC10；Electrolyte overall thickness is 10 microns, often
Layer thickness is 0.5 micron, totally 20 layers；Sintering parameter is different, specially：600 DEG C are warming up to 1.5 DEG C/min of speed and are protected
Then temperature 240 minutes is warming up to 1300 DEG C with 2 DEG C/min of speed and keeps the temperature 480 minutes, finally with 2 DEG C/min of speed
It is down to room temperature and can obtain the solid oxide fuel cell electrolyte film；Ball milling parameter is different, specially：First 300 turns/
Minute speed under ball milling 60 minutes, rotating speed is then promoted to 550 revs/min of lower ball millings 200 minutes, finally at 300 revs/min
Ball milling 60 minutes is to obtain corresponding slurry under the speed of clock；A concentration of 1wt% of polyvinyl alcohol, average molecular weight are about
60000, the additive amount of adhesive is the 400% of corresponding electrolyte powder weight；Print temperature is 30 DEG C, is divided into 60 minutes；
5th, the content of NiO is 50wt% in anode plate.
Embodiment 6
The present embodiment provides a kind of preparation method of solid oxide fuel cell electrolyte film, step and embodiment 3
In it is basically identical, unlike：The material of oxygen ion conductor phase used is SDC20, and electrolyte overall thickness is 10 microns, often
Layer thickness is 1 micron, totally 10 layers；Sintering parameter is different, specially：500 DEG C and heat preservation 200 are warming up to 1 DEG C/min of speed
Minute, then 1500 DEG C are warming up to 1.5 DEG C/min of speed and keep the temperature 400 minutes, finally dropped with 1.5 DEG C/min of speed
The solid oxide fuel cell electrolyte film is can obtain to room temperature；A concentration of 5wt% of polyvinyl alcohol, average molecular weight
About 10000, the additive amount of adhesive is the 300% of corresponding electrolyte powder weight；Print temperature is 70 DEG C, is divided into 10 points
Clock；The content of NiO is 70wt% in anode plate.
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 can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (17)
1. a kind of solid oxide fuel cell electrolyte film, it is characterised in that：The dielectric film includes be arranged alternately the
One electrolyte cells and the second electrolyte cells, first electrolyte cells are mutually made of oxygen ion conductor, second electricity
Solution matter unit is mutually made of proton conductor；
The dielectric film is printed by 3D printer, specifically includes following steps：
（a）According to dielectric film to be prepared, corresponding oxygen ion conductor phase slurry and proton conductor phase slurry and system are prepared
Fixed corresponding print routine；
（b）One layer of oxygen ion conductor phase and proton conductor phase are successively printed on substrate using 3D printer；
（c）Repeat step（b）, until obtaining the thickness needed, stop printing, take out, be sintered to get the electrolysis
Plasma membrane；
Wherein,
Step（a）Specially：Oxygen ion conductor phase powder, proton conductor phase powder are mixed with binding agent be placed on ball milling respectively
Ball-milling treatment is carried out in tank, the method for ball milling the following is：Ball milling 30 ~ 180 minutes first under 250 ~ 350 revs/min of speed,
Then rotating speed is promoted to 500 ~ 600 revs/min of lower ball millings 120 ~ 480 minutes, finally under 250 ~ 350 revs/min of speed
Ball milling 30 ~ 180 minutes；
The binding agent is the aqueous solution of polyvinyl alcohol, and additive amount is oxygen ion conductor phase powder or proton conductor phase powder matter
The 200% ~ 400% of amount；The number-average molecular weight of the polyvinyl alcohol is 10000 ~ 60000, and the content in the aqueous solution is 1
~5 wt%；
Pass through rate-determining steps（a）The viscosity of prepared slurry is come to control the thickness that prints every time be 0.5 ~ 1 micron.
2. solid oxide fuel cell electrolyte film according to claim 1, it is characterised in that：First electrolyte
Unit and second electrolyte cells have multiple respectively.
3. solid oxide fuel cell electrolyte film according to claim 1 or 2, it is characterised in that：First electricity
It is strip that matter unit, which is solved, with second electrolyte cells, and the thickness side of its length extending direction and the dielectric film
To vertical.
4. the solid oxide fuel cell electrolyte film described in claim 3, it is characterised in that：First electrolyte cells
Length be equal to dielectric film a line width, the thickness of first electrolyte cells and second electrolyte cells
Thickness be equal to the thickness of dielectric film.
5. solid oxide fuel cell electrolyte film according to claim 2, it is characterised in that：The multiple first electricity
Matter unit and the multiple second electrolyte cells are solved along the length direction of plane and width side where the dielectric film
To being alternately arranged.
6. solid oxide fuel cell electrolyte film according to claim 1 or 5, it is characterised in that：First electricity
The thickness for solving matter unit and second electrolyte cells is equal to the thickness of the dielectric film, first electrolyte cells and
The length of second electrolyte cells and it is wide be respectively 1 ~ 30 micron.
7. solid oxide fuel cell electrolyte film according to claim 2, it is characterised in that：Multiple first electricity
Size, the shape for solving matter unit are identical or different；The size of multiple second electrolyte cells is identical or different, and described first
Size, the shape of electrolyte cells and second electrolyte cells are identical or different.
8. solid oxide fuel cell electrolyte film according to claim 1, it is characterised in that：The proton conductor phase
For BaZr0.1Ce0.7Y0.2O3-δ, the oxygen ion conductor is mutually Gd0.1Ce0.9O1.95（GDC10）、Gd0.2Ce0.8O1.9（GDC20）、
Sm0.1Ce0.9O1.95（SDC10）And Sm0.2Ce0.8O1.9（SDC20）In it is one or more.
9. the preparation method of any solid oxide fuel cell electrolyte film, feature exist in a kind of claim 1 to 8
In it includes the following steps：
（a）According to dielectric film to be prepared, corresponding oxygen ion conductor phase slurry and proton conductor phase slurry and system are prepared
Fixed corresponding print routine；
（b）One layer of oxygen ion conductor phase and proton conductor phase are successively printed on substrate using 3D printer；
（c）Repeat step（b）, until obtaining the thickness needed, stop printing, take out, be sintered to get the electrolysis
Plasma membrane.
10. the preparation method of solid oxide fuel cell electrolyte film according to claim 9, it is characterised in that：It is described
Substrate is one in GDC10-NiO, GDC20-NiO, SDC10-NiO and SDC20-NiO composite anode plate by sintering processes
Kind, and the content of NiO is 50 ~ 70 wt% in the composite anode plate.
11. the preparation method of solid oxide fuel cell electrolyte film according to claim 9, it is characterised in that：Step
（b）In, when being printed, the print temperature of 3D printer is set as 30 ~ 70 DEG C, and the interval between adjacent secondary printing is set as 10 ~
60 minutes.
12. the preparation method of solid oxide fuel cell electrolyte film according to claim 9, which is characterized in that step
（a）Specially：Oxygen ion conductor phase powder, proton conductor phase powder are mixed to be placed in ball grinder respectively with binding agent and be carried out
Ball-milling treatment, the method for ball milling the following is：Then ball milling 30 ~ 180 minutes first under 250 ~ 350 revs/min of speed will turn
Speed is promoted to 500 ~ 600 revs/min of lower ball millings 120 ~ 480 minutes, finally under 250 ~ 350 revs/min of speed ball milling 30 ~
180 minutes.
13. the preparation method of solid oxide fuel cell electrolyte film according to claim 12, it is characterised in that：It is described
Binding agent is the aqueous solution of polyvinyl alcohol, and additive amount is the 200% of oxygen ion conductor phase powder or proton conductor phase powder quality
~400%；The number-average molecular weight of the polyvinyl alcohol is 10000 ~ 60000, and the content in the aqueous solution is 1 ~ 5 wt%.
14. according to the preparation method of the solid oxide fuel cell electrolyte film of claim 12 or 13, it is characterised in that：
Pass through rate-determining steps（a）The viscosity of prepared slurry is come to control the thickness that prints every time be 0.5 ~ 1 micron.
15. the preparation method of solid oxide fuel cell electrolyte film according to claim 12, it is characterised in that：It is described
The primary particle diameter of oxygen ion conductor phase powder and the proton conductor phase powder is less than 100 nanometers.
16. the preparation method of solid oxide fuel cell electrolyte film according to claim 9, which is characterized in that step
（c）In, the method for the sintering processes is：400 ~ 600 DEG C are warming up to 0.5 ~ 1.5 DEG C/min of speed and keep the temperature 60-240
Minute, then 1300 ~ 1500 DEG C are warming up to 1 ~ 2 DEG C/min of speed and keep the temperature 120 ~ 480 minutes, finally with 1 ~ 2 DEG C/minute
The speed of clock is down to room temperature.
17. a kind of solid oxide fuel cell, it is characterised in that：Contain such as any one of claim 1 to 8 claim institute
The solid oxide fuel cell electrolyte film stated.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510874668.3A CN105428679B (en) | 2015-12-03 | 2015-12-03 | A kind of solid oxide fuel cell electrolyte film and preparation method thereof and solid oxide fuel cell |
| PCT/CN2015/098187 WO2017092086A1 (en) | 2015-12-03 | 2015-12-22 | Solid oxide fuel cell electrolyte membrane and preparation method therefor, and solid oxide fuel cell |
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| CN112886042A (en) * | 2021-01-29 | 2021-06-01 | 郑州大学 | Electrolyte structure and method for improving long-term stability of solid oxide fuel cell by using same |
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| CN101440499A (en) * | 2007-11-20 | 2009-05-27 | 株式会社丰田自动织机 | Electrochemical device and exhaust gas purification apparatus |
| CN101847731A (en) * | 2009-03-23 | 2010-09-29 | 住友金属矿山株式会社 | Ionic electrolytes film structure and manufacture method thereof and the Solid Oxide Fuel Cell of using the ionic electrolytes film structure |
| CN103811788A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method for middle-temperature and low-temperature solid oxide fuel battery |
| CN205231183U (en) * | 2015-12-03 | 2016-05-11 | 苏州攀特电陶科技股份有限公司 | Solid oxide fuel cell electrolyte membrane and solid oxide fuel cell |
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| JP3733030B2 (en) * | 2000-02-14 | 2006-01-11 | 松下電器産業株式会社 | Ionic conductor |
| JP3843766B2 (en) * | 2000-07-04 | 2006-11-08 | 日産自動車株式会社 | Solid oxide fuel cell |
| CN102024973A (en) * | 2010-11-16 | 2011-04-20 | 成都振中电气有限公司 | Solid oxide fuel cell |
| CN102683722A (en) * | 2012-05-25 | 2012-09-19 | 南京工业大学 | Solid oxide fuel cell composite cathode and preparation method thereof |
| JP2016522081A (en) * | 2013-04-26 | 2016-07-28 | カーティン ユニバーシティ オブ テクノロジーＣｕｒｔｉｎ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ | Channel body and manufacturing method thereof |
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| CN101440499A (en) * | 2007-11-20 | 2009-05-27 | 株式会社丰田自动织机 | Electrochemical device and exhaust gas purification apparatus |
| CN101847731A (en) * | 2009-03-23 | 2010-09-29 | 住友金属矿山株式会社 | Ionic electrolytes film structure and manufacture method thereof and the Solid Oxide Fuel Cell of using the ionic electrolytes film structure |
| CN103811788A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method for middle-temperature and low-temperature solid oxide fuel battery |
| CN205231183U (en) * | 2015-12-03 | 2016-05-11 | 苏州攀特电陶科技股份有限公司 | Solid oxide fuel cell electrolyte membrane and solid oxide fuel cell |
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