CN105428679A - Solid oxide fuel cell electrolyte membrane and preparation method thereof and solid oxide fuel cell - Google Patents
Solid oxide fuel cell electrolyte membrane and preparation method thereof and solid oxide fuel cell Download PDFInfo
- Publication number
- CN105428679A CN105428679A CN201510874668.3A CN201510874668A CN105428679A CN 105428679 A CN105428679 A CN 105428679A CN 201510874668 A CN201510874668 A CN 201510874668A CN 105428679 A CN105428679 A CN 105428679A
- Authority
- CN
- China
- Prior art keywords
- fuel cell
- solid oxide
- oxide fuel
- electrolyte
- electrolyte cells
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a solid oxide fuel cell electrolyte membrane and a preparation method thereof and a solid oxide fuel cell. The electrolyte membrane comprises a first electrolyte unit and a second electrolyte unit which are alternately arranged, wherein the first electrolyte unit is formed by an oxygen ion conductor; and the second electrolyte unit is formed by a proton conductor. The problem that the ionic conductivity of the electrolyte membrane is significantly reduced due to reduction of a working temperature of the cell can be effectively relieved by introducing a proton conduction channel into a traditional oxygen ion conductor electrolyte membrane; and achievement of middle or low temperature and practical use of the solid oxide fuel cell is facilitated, so that the ionic resistance of solid oxide fuel cell under the middle or low temperature working condition is effectively reduced.
Description
Technical field
The invention belongs to fuel cell field, relate to a kind of parts of fuel cell, be specifically related to a kind of solid oxide fuel cell electrolyte film and preparation method thereof and Solid Oxide Fuel Cell.
Background technology
Solid Oxide Fuel Cell as a kind of can be directly that the energy conversion device of electric energy is subject to people's extensive concern owing to having the advantages such as energy conversion efficiency is high, fuel is widely applicable concurrently by chemical energy.As Japanese TOTO Ltd. at application number be have developed one by a part of aluminium oxide that adulterates in the electrolyte in the patent of invention of 201280016340.2 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 the cost of up to the present Solid Oxide Fuel Cell generating is still higher, this mainly produces higher relevant with operating cost with existing Solid Oxide Fuel Cell.Existing Solid Oxide Fuel Cell still adopts traditional yttria-stabilized zirconia (YSZ) to be electrolyte mostly, and working temperature is at 750 DEG C-1000 DEG C.Work long hours the side reaction that can cause between cell components material at such high temperatures, and electrode microstructure such as to be damaged due to sintering at the problem.In addition, higher working temperature makes the optional material of each assembly of Solid Oxide Fuel Cell very limited, can not adopt sealing and the electrode material of relative inexpensiveness.
The working temperature reducing Solid Oxide Fuel Cell is expected to significantly alleviate the problems referred to above to 300-750 DEG C of temperature range, is generally considered and realizes its practical effective way.But, the problem that the reduction of Solid Oxide Fuel Cell working temperature also can cause its power output significantly to decay.Wherein traditional YSZ electrolyte oxygen ionic conductance activation energy is higher, along with the decline electrolyte ion conduction resistance of temperature significantly increases, has become one of key factor of low temperature in restriction Solid Oxide Fuel Cell.
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 electrolyte film of architecture advances and the novel preparation method simultaneously providing this solid oxide fuel cell electrolyte film.
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 electrolyte film, described dielectric film comprises the first electrolyte cells and the second electrolyte cells that are arranged alternately, described first electrolyte cells is made up of mutually oxygen ion conductor, and described second electrolyte cells is made up of mutually proton conductor.
Optimally, described first electrolyte cells and described second electrolyte cells have multiple respectively.
According to a concrete and preferred aspect of the present invention, described first electrolyte cells and described second electrolyte cells are strip, and its length bearing of trend is vertical with the thickness direction of described dielectric film.Further, the length of described first electrolyte cells equals the width on a limit of dielectric film, and the thickness of described first electrolyte cells and the thickness of described second electrolyte cells are equal to the thickness of dielectric film.
According to another concrete and preferred aspect of the present invention, described multiple first electrolyte cells and described multiple second electrolyte cells are alternately arranged along the length direction of described dielectric film place plane and Width.Further, the thickness of described first electrolyte cells and described second electrolyte cells equals the thickness of described dielectric film, the length of described first electrolyte cells and described second electrolyte cells and be widely respectively 1 ~ 30 micron.Preferably, the length of described first electrolyte cells and described second electrolyte cells and be widely respectively 2 ~ 20 microns, is more preferably 2 ~ 10 microns.
According to the present invention, the size of multiple described multiple first electrolyte cells, shape can be identical or different; The size of described multiple second electrolyte cells can be identical or different, and size, the shape of described first electrolyte cells and described second electrolyte cells can be identical or different.As preferably, described multiple first electrolyte cells, the size of the second electrolyte cells, shape are all identical.
Optimally, described dielectric film is printed by 3D printer and forms.
Optimally, described proton conductor is BaZr mutually
0.1ce
0.7y
0.2o
3-δ, described oxygen ion conductor is Gd mutually
0.1ce
0.9o
1.95(GDC10), Gd
0.2ce
0.8o
1.9(GDC20), Sm
0.1ce
0.9o
1.95and Sm (SDC10)
0.2ce
0.8o
1.9(SDC20) one or more in.
Another object of the present invention is the preparation method providing a kind of above-mentioned solid oxide fuel cell electrolyte film, and it comprises the following steps:
A (), according to the dielectric film that will prepare, is prepared corresponding oxygen ion conductor phase slurry and proton conductor phase slurry, and is formulated corresponding print routine;
B () utilizes 3D printer successively to print one deck oxygen ion conductor phase and proton conductor phase on substrate;
C () repeats step (b), until obtain the thickness needed, stop printing, take out, carry out sintering processes, obtain described dielectric film.
Further, described substrate is the one in GDC10-NiO, GDC20-NiO, SDC10-NiO and SDC20-NiO composite anode plate of sintering processes, and in described composite anode plate, the content of NiO is 50 ~ 70wt%.
Preferably, in step (b), when printing, the print temperature of 3D printer is set to 30 ~ 70 DEG C, and the interval between adjacent secondary prints is set to 10 ~ 60 minutes.
Further, step (a) is specially: oxygen ion conductor phase powder, proton conductor phase powder are mixed with binding agent to be placed in ball grinder respectively and carry out ball-milling treatment, the method of ball milling the following is: first ball milling 30 ~ 180 minutes under the speed of 250 ~ 350 revs/min, then rotating speed is promoted to 500 ~ 600 revs/min of lower ball millings 120 ~ 480 minutes, finally ball milling 30 ~ 180 minutes under the speed of 250 ~ 350 revs/min.
Preferably, described binding agent is the aqueous solution of polyvinyl alcohol, and its addition is 200% ~ 400% of oxygen ion conductor phase powder or proton conductor phase powder quality.More preferably, the number-average molecular weight of described polyvinyl alcohol is 10000 ~ 60000, and its content in the described aqueous solution is 1 ~ 5wt%.
According to the present invention, the viscosity by the slurry prepared by rate-determining steps (a) controls each thickness printed.Preferably, controlling each thickness printed is 0.5 ~ 1 micron.
Preferably, the primary particle diameter of described oxygen ion conductor phase powder and described proton conductor phase powder is less than 100 nanometers.
Preferably, in step (f), described sintering method is: be warming up to 400 ~ 600 DEG C with the speed of 0.5 ~ 1.5 DEG C/min and be incubated 60-240 minute, is then warming up to 1300 ~ 1500 DEG C with the speed of 1 ~ 2 DEG C/min and is incubated 120 ~ 480 minutes, being finally down to room temperature with the speed of 1 ~ 2 DEG C/min.
The present invention also provides a kind of Solid Oxide Fuel Cell further, and it contains above-mentioned solid oxide fuel cell electrolyte film.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
Solid oxide fuel cell electrolyte film of the present invention, comprise the first electrolyte cells and the second electrolyte cells that are arranged alternately, first electrolyte cells is made up of mutually oxygen ion conductor, second electrolyte cells is made up of mutually proton conductor, introduce in traditional oxygen ion conductor dielectric film proton conducting channel can effectively alleviate dielectric film because battery operating temperature reduces the problem that the ionic conductance that causes significantly declines, be conducive to realizing the middle low temperature of Solid Oxide Fuel Cell and practical, thus effectively reduce the ion resistance of Solid Oxide Fuel Cell under middle low-temperature working condition.
The preparation method of solid oxide fuel cell electrolyte film provided by the present invention, because the dielectric film adopting 3D printing technique to prepare has structural design flexibly and the feature of film thickness controllable precise, therefore can according to the battery actual demand flexible design proton-lattice structure of oxonium ion mixing conductance dielectric film and the thickness of dielectric film, reduce Solid Oxide Fuel Cell ion resistance under running conditions, be conducive to the middle low temperature realizing Solid Oxide Fuel Cell; And 3D printing technique has technique simply, the feature of easy large-scale production.
Accompanying drawing explanation
The plane graph of solid oxide fuel cell electrolyte film in Fig. 1 (a) embodiment 1, the partial enlarged drawing at A place in (b) a figure;
The cutaway view of solid oxide fuel cell electrolyte film in Fig. 2 (a) embodiment 1, the partial enlarged drawing at B place in (b) a figure;
Fig. 3 is the plane graph of solid oxide fuel cell electrolyte film in embodiment 2;
Wherein, 1, electrolyte body; 11, the first electrolyte cells; 12, the second electrolyte cells; 2, substrate.
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 electrolyte film, as shown in Fig. 2 (a) He Fig. 2 (b), it is formed on arbitrary surface of substrate 2, comprise multiple the first electrolyte cells 11 and the second electrolyte cells 12 be arranged alternately, first electrolyte cells 11 is made up of mutually oxygen ion conductor, and the second electrolyte cells 12 is made up of mutually proton conductor.Introduce in traditional oxygen ion conductor dielectric film like this proton conducting channel can effectively alleviate dielectric film because battery operating temperature reduces the problem that the ionic conductance that causes significantly declines, the middle low temperature (300 ~ 800 DEG C) being conducive to realizing Solid Oxide Fuel Cell is changed and practical.
In the present embodiment, first electrolyte cells 11 is the strip that size and dimension is identical with the second electrolyte cells 12, their length bearing of trend is vertical with the thickness direction of dielectric film, and length equals the width on a limit of dielectric film, their thickness equals the thickness of dielectric film, namely as shown in Figure 1 (a) and Fig 1 (b) shows.Proton-oxonium ion mixed conductor dielectric film is alternately arranged by multiple first electrolyte cells 11 and multiple second electrolyte cells 12 and forms.Second electrolyte cells 12 by first being printed by 3D printer by the first electrolyte cells 11 on substrate, and then is printed by this structure.
The width of the first electrolyte cells 11 and the second electrolyte cells 12 can carry out determining that (width of the first electrolyte cells 11 and the width of the second electrolyte cells 12 can be the same or different as required; The width of each first electrolyte cells 11 can be the same or different, and the width of each equally the second electrolyte cells 12 can be the same or different).
In this example, proton conductor is BaZr mutually
0.1ce
0.7y
0.2o
3-δ(BZCY), and oxygen ion conductor for being selected from Gd
0.1ce
0.9o
1.95(GDC10), Gd
0.2ce
0.8o
1.9(GDC20), Sm
0.1ce
0.9o
1.95and Sm (SDC10)
0.2ce
0.8o
1.9(SDC20) mixture of one or more compositions in.
Embodiment 2
The present embodiment provides a kind of solid oxide fuel cell electrolyte film, it is formed on arbitrary surface of substrate 2, also multiple the first electrolyte cells 11 and the second electrolyte cells 12 be arranged alternately is comprised, consistent with embodiment 1 of its material, be alternately arranged along the length of dielectric film and Width unlike: multiple first electrolyte cells 11 and multiple second electrolyte cells 12, as shown in Figure 3, adjacent two electrolyte cells in every a line or in each row are made to be different electrolyte cells.In the present embodiment, the thickness of the first electrolyte cells 11 and the second electrolyte cells 12 forms by them the thickness of dielectric film, and length and the width of the first electrolyte cells 11 and the second electrolyte cells 12 are 3 microns.
Embodiment 3
The present embodiment provides a kind of preparation method of solid oxide fuel cell electrolyte film, and it comprises the following steps:
A agate material ball milling pearl that 5g primary particle size is about the GDC10 nano-powder of 50nm, 15g adhesive and about 20ml by () puts into first agate jar of 50ml; Agate material ball milling pearl 5g primary particle size being about the BZCY nano-powder of 90nm, 12g adhesive and about 20ml puts into second agate jar of 50ml; Above-mentioned two agate jars are fixed in ball mill and carry out ball milling; Ball grinding method is: first ball milling 30 minutes under the rotating speed of 250 revs/min, is then promoted to 500 revs/min of ball millings 480 minutes by rotating speed, finally under 250 revs/min of rotating speeds ball milling 30 minutes to obtain electrolyte slurry; Wherein, adhesive is polyvinyl alcohol ([C
2h
4o]
n) the aqueous solution, the concentration of polyvinyl alcohol is 2wt%, and mean molecule quantity is about 50000, and the addition of adhesive is 200% of corresponding electrolyte powder weight.
Collect above-mentioned electrolyte slurry, and be placed in airtight receiving flask stand-by; Open 3D printer power supply, GDC10-NiO through surface cleaning process is printed substrate and (also claims substrate, it is the GDC10-NiO positive plate through 1000 DEG C/4h sintering processes, and wherein the content of NiO is 60wt%) be fixed on 3D stamp pad, and the temperature of stamp pad is set as 40 DEG C; First GDC10 electrolyte slurry is put into printer ink cartridge, and respective ink tanks is fixed on 3D ink-cases of printers position.
Print routine is inputed in 3D printer, and adjust print cartridge mode out of ink and top of form, start the electrolytical print job of GDC10 in ground floor; Wait for 35 minutes after to be printed, the moisture in printing slurry is fully volatilized, and printed material can be good at adhering on substrate; It is the printer ink cartridge filling BZCY electrolyte slurry by the replacing ink cartridge in printer, adjustment print cartridge mode out of ink and top of form, repeat above-mentioned steps, start the electrolytical print job of BZCY in ground floor, 35 minutes are waited for after to be printed equally, moisture in printing slurry is fully volatilized, and printed material can be good at adhering on substrate.
Repeat above-mentioned steps, continue the print job of subsequent layers, print 10 layers altogether.It takes out after printing by matter to be electrolysed from 3D printer, is placed in Muffle furnace and carries out sintering processes.Wherein said sintering schedule is be warming up to 400 DEG C with the speed of 0.5 DEG C/min and be incubated 60 minutes, then be warming up to 1400 DEG C with the speed of 1 DEG C/min and be incubated 120 minutes, finally being down to room temperature with the speed of 1 DEG C/min can obtain described solid oxide fuel cell electrolyte film (electrolyte gross thickness is 8 microns, and every layer thickness is 0.8 micron).
Embodiment 4
The present embodiment provides a kind of preparation method of solid oxide fuel cell electrolyte film, basically identical in its step and embodiment 3, unlike: 1, sintering parameter is different, be specially: be warming up to 400 DEG C with the speed of 0.5 DEG C/min and be incubated 240 minutes, then be warming up to 1400 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 electrolyte film; 2, ball milling parameter is different, is specially: first ball milling 180 minutes under the rotating speed of 350 revs/min, is then promoted to 600 revs/min of ball millings 120 minutes by rotating speed, finally under the rotating speed of 350 revs/min 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, basically identical in its step and embodiment 3, unlike: the material of the oxygen ion conductor phase of employing is SDC10; Electrolyte gross thickness is 10 microns, and every layer thickness is 0.5 micron, totally 20 layers; Sintering parameter is different, be specially: be warming up to 600 DEG C with the speed of 1.5 DEG C/min and be incubated 240 minutes, then be warming up to 1300 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 electrolyte film; Ball milling parameter is different, is specially: first ball milling 60 minutes under the speed of 300 revs/min, is then promoted to 550 revs/min of lower ball millings 200 minutes by rotating speed, finally under the speed of 300 revs/min ball milling 60 minutes to obtain corresponding slurry; The concentration of polyvinyl alcohol is 1wt%, and mean molecule quantity is about 60000, and the addition of adhesive is 400% of corresponding electrolyte powder weight; Print temperature is 30 DEG C, is spaced apart 60 minutes; 5, in positive plate, the content of NiO is 50wt%.
Embodiment 6
The present embodiment provides a kind of preparation method of solid oxide fuel cell electrolyte film, basically identical in its step and embodiment 3, unlike: the material of the oxygen ion conductor phase of employing is SDC20, and electrolyte gross thickness is 10 microns, every layer thickness is 1 micron, totally 10 layers; Sintering parameter is different, be specially: be warming up to 500 DEG C with the speed of 1 DEG C/min and be incubated 200 minutes, then be warming up to 1500 DEG C with the speed of 1.5 DEG C/min and be incubated 400 minutes, being finally down to room temperature with the speed of 1.5 DEG C/min and can obtaining described solid oxide fuel cell electrolyte film; The concentration of polyvinyl alcohol is 5wt%, and mean molecule quantity is about 10000, and the addition of adhesive is 300% of corresponding electrolyte powder weight; Print temperature is 70 DEG C, is spaced apart 10 minutes; In positive plate, the content of NiO is 70wt%.
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 (18)
1. a solid oxide fuel cell electrolyte film, it is characterized in that: described dielectric film comprises the first electrolyte cells and the second electrolyte cells that are arranged alternately, described first electrolyte cells is made up of mutually oxygen ion conductor, and described second electrolyte cells is made up of mutually proton conductor.
2. solid oxide fuel cell electrolyte film according to claim 1, is characterized in that: described first electrolyte cells and described second electrolyte cells have multiple respectively.
3. solid oxide fuel cell electrolyte film according to claim 1 and 2, is characterized in that: described first electrolyte cells and described second electrolyte cells are strip, and its length bearing of trend is vertical with the thickness direction of described dielectric film.
4. solid oxide fuel cell electrolyte film according to claim 3, it is characterized in that: the length of described first electrolyte cells equals the width on a limit of dielectric film, the thickness of described first electrolyte cells and the thickness of described second electrolyte cells are equal to the thickness of dielectric film.
5. solid oxide fuel cell electrolyte film according to claim 2, is characterized in that: described multiple first electrolyte cells and described multiple second electrolyte cells are alternately arranged along the length direction of described dielectric film place plane and Width.
6. solid oxide fuel cell electrolyte film according to claim 1 or 5, it is characterized in that: the thickness of described first electrolyte cells and described second electrolyte cells equals the thickness of described dielectric film, the length of described first electrolyte cells and described second electrolyte cells and be widely respectively 1 ~ 30 micron.
7. solid oxide fuel cell electrolyte film according to claim 2, is characterized in that: size, the shape of multiple described first electrolyte cells are identical or different; The size of multiple described second electrolyte cells is identical or different, and size, the shape of described first electrolyte cells and described second electrolyte cells are identical or different.
8. solid oxide fuel cell electrolyte film according to claim 1, is characterized in that: described dielectric film is printed by 3D printer and forms.
9. solid oxide fuel cell electrolyte film according to claim 1, is characterized in that: described proton conductor is BaZr mutually
0.1ce
0.7y
0.2o
3-δ, described oxygen ion conductor is Gd mutually
0.1ce
0.9o
1.95(GDC10), Gd
0.2ce
0.8o
1.9(GDC20), Sm
0.1ce
0.9o
1.95and Sm (SDC10)
0.2ce
0.8o
1.9(SDC20) one or more in.
10. the preparation method of arbitrary described solid oxide fuel cell electrolyte film in claim 1 to 9, it is characterized in that, it comprises the following steps:
A (), according to the dielectric film that will prepare, is prepared corresponding oxygen ion conductor phase slurry and proton conductor phase slurry, and is formulated corresponding print routine;
B () utilizes 3D printer successively to print one deck oxygen ion conductor phase and proton conductor phase on substrate;
C () repeats step (b), until obtain the thickness needed, stop printing, take out, carry out sintering processes, obtain described dielectric film.
The preparation method of 11. solid oxide fuel cell electrolyte films according to claim 10, it is characterized in that: described substrate is the one in GDC10-NiO, GDC20-NiO, SDC10-NiO and SDC20-NiO composite anode plate of sintering processes, and in described composite anode plate, the content of NiO is 50 ~ 70wt%.
The preparation method of 12. solid oxide fuel cell electrolyte films according to claim 10, it is characterized in that: in step (b), when printing, the print temperature of 3D printer is set to 30 ~ 70 DEG C, and the interval between adjacent secondary prints is set to 10 ~ 60 minutes.
The preparation method of 13. solid oxide fuel cell electrolyte films according to claim 10, it is characterized in that, step (a) is specially: oxygen ion conductor phase powder, proton conductor phase powder are mixed with binding agent to be placed in ball grinder respectively and carry out ball-milling treatment, the method of ball milling the following is: first ball milling 30 ~ 180 minutes under the speed of 250 ~ 350 revs/min, then rotating speed is promoted to 500 ~ 600 revs/min of lower ball millings 120 ~ 480 minutes, finally ball milling 30 ~ 180 minutes under the speed of 250 ~ 350 revs/min.
14. according to the preparation method of solid oxide fuel cell electrolyte film described in claim 13, and it is characterized in that: described binding agent is the aqueous solution of polyvinyl alcohol, its addition is 200% ~ 400% of oxygen ion conductor phase powder or proton conductor phase powder quality; The number-average molecular weight of described polyvinyl alcohol is 10000 ~ 60000, and its content in the described aqueous solution is 1 ~ 5wt%.
15. according to claim 13 or 14 preparation method of solid oxide fuel cell electrolyte film, it is characterized in that: controlling each thickness printed by the viscosity of the slurry prepared by rate-determining steps (a) is 0.5 ~ 1 micron.
16., according to the preparation method of solid oxide fuel cell electrolyte film described in claim 13, is characterized in that: the primary particle diameter of described oxygen ion conductor phase powder and described proton conductor phase powder is less than 100 nanometers.
The preparation method of 17. solid oxide fuel cell electrolyte films according to claim 10, it is characterized in that, in step (c), the method of described sintering processes is: be warming up to 400 ~ 600 DEG C with the speed of 0.5 ~ 1.5 DEG C/min and be incubated 60-240 minute, then be warming up to 1300 ~ 1500 DEG C with the speed of 1 ~ 2 DEG C/min and be incubated 120 ~ 480 minutes, being finally down to room temperature with the speed of 1 ~ 2 DEG C/min.
18. 1 kinds of Solid Oxide Fuel Cell, is characterized in that: containing, for example the solid oxide fuel cell electrolyte film described in claim any one of claim 1 to 9.
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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105428679A true CN105428679A (en) | 2016-03-23 |
| CN105428679B CN105428679B (en) | 2018-07-06 |
Family
ID=55506721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510874668.3A Active 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 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105428679B (en) |
| WO (1) | WO2017092086A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967689A (en) * | 2016-05-04 | 2016-09-28 | 内蒙古科技大学 | Preparation method of electrolyte thin film material |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020009628A1 (en) * | 2000-07-04 | 2002-01-24 | Nissan Motor Co., Ltd. | Solid oxide fuel cell having perovskite solid electrolytes |
| 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 |
| WO2014172752A1 (en) * | 2013-04-26 | 2014-10-30 | Curtin University Of Technology | Channeled articles and methods for their manufacture |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3733030B2 (en) * | 2000-02-14 | 2006-01-11 | 松下電器産業株式会社 | Ionic conductor |
| 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 |
-
2015
- 2015-12-03 CN CN201510874668.3A patent/CN105428679B/en active Active
- 2015-12-22 WO PCT/CN2015/098187 patent/WO2017092086A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020009628A1 (en) * | 2000-07-04 | 2002-01-24 | Nissan Motor Co., Ltd. | Solid oxide fuel cell having perovskite solid electrolytes |
| 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 |
| WO2014172752A1 (en) * | 2013-04-26 | 2014-10-30 | Curtin University Of Technology | Channeled articles and methods for their manufacture |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967689A (en) * | 2016-05-04 | 2016-09-28 | 内蒙古科技大学 | Preparation method of electrolyte thin film material |
| CN105967689B (en) * | 2016-05-04 | 2019-04-02 | 内蒙古科技大学 | A kind of preparation method of electrolyte film material |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017092086A1 (en) | 2017-06-08 |
| CN105428679B (en) | 2018-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Baharuddin et al. | Fabrication of high‐quality electrode films for solid oxide fuel cell by screen printing: A review on important processing parameters | |
| CN104916850B (en) | Cathode of solid oxide fuel cell material and have its composite cathode material and preparation method thereof and battery composite cathode preparation method | |
| CN103296286B (en) | Novel high-temperature CO2 and H2O co-electrolysis superlattice composite oxygen electrode and preparation method thereof | |
| JP2015167137A (en) | Solid oxide fuel cell or solid oxide fuel cell sub-component, and manufacturing method thereof | |
| US20090297923A1 (en) | Sol-gel derived high performance catalyst thin films for sensors, oxygen separation devices, and solid oxide fuel cells | |
| CN103746134B (en) | A kind of electrolyte for solid oxide fuel cell and preparation method thereof | |
| CN105470529B (en) | A kind of solid oxide fuel cell electrode and preparation method thereof and solid oxide fuel cell based on it | |
| Yu et al. | Preparation and electrochemical behavior of dense YSZ film for SOEC | |
| CN104409742A (en) | BaCoO3-delta base B-position Bi2O3-Nb2O5 co-doped cathode material of solid oxide fuel cell, preparation method and applications thereof | |
| KR20130047534A (en) | Solid oxide fuel cell and solid oxide electrolysis cell including ni-ysz fuel(hydrogen) electrode, and fabrication method thereof | |
| CN105428679A (en) | Solid oxide fuel cell electrolyte membrane and preparation method thereof and solid oxide fuel cell | |
| CN103985888B (en) | The preparation method of ceramic membrane fuel cells connecting material film and electrolytic thin-membrane | |
| WO2022152093A1 (en) | Method for preparing nio/apatite-type lanthanum silicate submicron-nano porous anode functional layer | |
| CN106876753A (en) | The preparation method of the fuel cell with orderly pore structure electrode | |
| CN108390071A (en) | A kind of cathode of solid oxide fuel cell surface modification method | |
| Chen et al. | Study of carbon-supported Au catalyst as the cathodic catalyst in a direct formic acid fuel cell prepared using a polyvinyl alcohol protection method | |
| CN114420943A (en) | Heterogeneous interface composite electrode material and preparation method and application thereof | |
| CN101222050A (en) | Anti-carbon deposition anode film material and method for producing the same | |
| CN104795579A (en) | Single SOFC (solid oxide fuel cell) provided with cathode current collection layer and manufacturing method of single SOFC | |
| KR20110096998A (en) | Manufacturing method of lscf powder and cell having the powder for solid oxide fuel cell | |
| CN104022303A (en) | Preparation method of 8YSZ electrolyte film of anode supporting intermediate temperature single SOFC (Solid Oxide Fuel Cell) | |
| Kong et al. | CuCo2O4-Er0. 4Bi1. 6O3-δ: An active hybrid cathode for intermediate temperature solid oxide fuel cells | |
| CN110423114A (en) | A kind of ceramic electrolyte material and preparation method thereof | |
| CN100363116C (en) | Process for preparing film slurry for rotary coating | |
| CN104064782B (en) | Preparation method for solid oxide fuel cell cathode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |