CN108039506A - Cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell - Google Patents
Cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell Download PDFInfo
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- CN108039506A CN108039506A CN201711281432.4A CN201711281432A CN108039506A CN 108039506 A CN108039506 A CN 108039506A CN 201711281432 A CN201711281432 A CN 201711281432A CN 108039506 A CN108039506 A CN 108039506A
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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
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
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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
Abstract
The invention belongs to electrolytic tank of solid oxide technical field, and in particular to a kind of cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell.This method include prepare polymer solution, prepare ceramics polymer casting solution, prepare cross section be petal-shaped doughnut supporter idiosome, prepare cross section be petal-shaped doughnut supporter, prepare cross section be petal-shaped hollow fiber solid oxide fuel cell.The support external surface of the hollow fiber solid oxide fuel cell of the present invention is no longer smooth circular arc, but the curved surface that uniformly height rises and falls.This Novel hollow fibre electrolyte film support increases the area of hollow fiber solid oxide fuel cell to a certain extent, improves output power, promotes surface reaction, has saved cost.
Description
Technical field
The invention belongs to electrolytic tank of solid oxide technical field, and in particular to a kind of cross section is petal-shaped hollow fibre
Tie up the preparation method of solid oxide fuel cell.
Background technology
Solid oxide fuel cell is a kind of high temperature energy conversion device that chemical energy is converted into electric energy, by device
Shape is flat, tubular type, micro-tubular, is divided into anode support type, cathode support type and electrolyte-supporting type by supporter type.
Micro-tubular solid oxide fuel cell have the characteristics that easily sealing, high length-diameter ratio, while its preparation method be extrusion moulding,
Inversion of phases spin processes, greatly improve the surface area of solid oxide fuel cell.
Chinese patent CN201608235U discloses a kind of micro-tubular ceramic membrane fuel monocell stack, including several micro-pipe shapes
Metal arrangements of electric connection between ceramic membrane individual fuel cell and each battery, but the device fixes single electricity with center conductive rod
Pond, reduces mass-transfer efficiency, and then reduces cell output；Chinese patent CN103349918A, which is disclosed, prepares honeycomb type
The method of inoranic membrane, if being made fuel cell supporter, resistance to mass tranfer is of a relatively high, but the effective area of film drops on the contrary
It is low；Chinese patent CN101733048A discloses a kind of hollow fiber membrane reactor for gas phase oxidation and its preparation and should
With the relative surface area of the hollow fiber membrane reactor is relatively low；Chinese patent CN106316359A discloses a kind of dirty using water purification
The clay standby method of ceramic film support and the ceramic film support of preparation, the ceramic film support which obtains be difficult to for
Do solid oxide fuel cell；It is anti-that Chinese patent CN1676198A discloses a kind of ceramic hollow fibrous membrane for making oxygen by air separation
Device and its preparation method and application are answered, higher resistance to mass tranfer makes it be difficult to be used as male or female supporter in the patent.Pottery
The technical research of porcelain membrane reactor has become at present one of direction of material, chemical field primary study both at home and abroad.
The chip or plate type ceramic film used at present in laboratory research in production application there are film surface product with
The problem of volume ratio is too small, film thickness is relatively thick, thus cause surface react exchange area it is relatively low, separative efficiency compared with
It is low.In contrast, the hollow fiber ceramic membrane that prepared by inversion of phases-sintering technology of people's exploitation, can be in identical intensity
Requirement condition is issued to reduction film thickness, the advantages of increasing membrane area；Meanwhile it is less than conventional tubular ceramic membrane materials, compare table
Area bigger；With very high membrane area/volume ratio, to reduce ceramic membrane cost, realize that industrialization provides new direction.Such as
X.Tan,et al,Preparation of LSCF ceramic hollow fibre membranes for oxygen
production by a phase-inversion/sintering technique,Ind.Eng.Chem.Res.,2005,
44,61；S.Liu,et al,Oxygen selective ceramic hollow fibre membranes,
J.Member.Sci.,2005,246,103。
The standby support body thickness of above-mentioned patent system is big, external surface area is small, and efficiency is low.Therefore, there is an urgent need for research and develop a kind of outer surface
Product is big, the preparation method of efficient hollow fiber solid oxide fuel cell.
The content of the invention
The object of the present invention is to provide the system that a kind of cross section is petal-shaped hollow fiber solid oxide fuel cell
Preparation Method, the hollow fiber solid oxide fuel cell cost that is prepared is low, external surface area is big, efficient.
Cross section of the present invention is the preparation method of petal-shaped hollow fiber solid oxide fuel cell, including
Following steps：
(1) polymer solution is prepared
By organic polymer, additive A, additive B dissolving in organic solvent, polymer solution is obtained；
(2) ceramic-polymer casting solution is prepared
Ceramic powder is added in the polymer solution that step (1) obtains, stirred evenly, form ceramic-polymer casting
Film liquid；
(3) it is petal-shaped doughnut anode support idiosome or cathode support body idiosome to prepare cross section
The ceramic-polymer casting solution that step (2) obtains is vacuumized, is subsequently placed in spinning equipment tank, passes through spinneret
Head, which is spun into outer condensation water, to be soaked, and under the collective effect of interior condensation water and outer condensation water, cures to obtain cross section through inversion of phases
For petal-shaped doughnut anode support idiosome or cathode support body idiosome；
(4) it is petal-shaped doughnut anode support or cathode support body to prepare cross section
The cross section that step (3) is obtained is petal-shaped doughnut anode support idiosome or cathode support body idiosome
Stretch and dry, sinter, it is petal-shaped doughnut anode support or cathode support body to obtain cross section；
(5) it is petal-shaped hollow fiber solid oxide fuel cell to prepare cross section
It is to sink successively on petal-shaped doughnut cathode support body in the cross section that step (4) obtains using infusion process
Product dielectric substrate, anode layer, it is petal-shaped hollow fiber solid oxide fuel cell to form cross section；
It is to sink successively on petal-shaped doughnut anode support in the cross section that step (4) obtains using infusion process
Product dielectric substrate, cathode layer, it is petal-shaped hollow fiber solid oxide fuel cell to form cross section.
Wherein：
In step (1), organic polymer, additive A, additive B, the mass ratio of organic solvent are 12.5-25:0.1-5:
0.5-25:50-100, preferably 12.5:0.1-3:0.5-10:50；
The additive A is polyacrylamide (PAM, Mr≈ 150000), additive A is added in the form of mixed solution
Enter, additive A, water, the mass ratio of alcohol are 0.1-10 in mixed solution:0.1-50:0.1-100, preferably 0.1-3:0.1-15:5-
40；The alcohol is ethylene glycol or glycerine.
In step (1), the organic polymer is polysulfones (Mr≈ 22000), polyether sulfone, polyacrylonitrile, makrolon,
Poly- ethyleneimine (Mr≈ 10000), polyetherimide (melt index：9g/min) or cellulose acetate (Mr≈ 50000) in one kind
It is or a variety of.
In step (1), the additive B is polyvinylpyrrolidone (PVP, Mr≈ 360000), polyvinyl alcohol contracting fourth
Aldehyde (PVB, viscosity (10% ethanol solution)>580MPas), ammonium polymethacrylate, polyacrylate, gamma-butyrolacton, poly- first
One or more in base methyl acrylate or phosphate.
In step (1), the organic solvent is 1-methyl-2-pyrrolidinone (NMP), n,N-Dimethylformamide-d7、N,
N- dimethylacetylamides-d9Or dimethyl sulfoxide (DMSO)-d6In one or more.
The present invention have chosen that number-average molecular weight in polymer homolog is higher, melt index in the selection of organic polymer
Relatively low polymer；Additive A, additive B and organic solvent also choose molal weight is larger, viscosity is larger material to carry
High casting solution viscosity.
In step (2), the ceramic powder is cathodic ceramic powder, anode ceramic powder；
The cathodic ceramic powder is La0.6Sr0.4Co0.2Fe0.8O3-δ、La0.6Sr0.4CoO3-δ、
Ba0.5Sr0.5Co0.8Fe0.2O3-δOr Ba0.5Sr0.5CoO3-δ；
The anode ceramic powder is Ni0.8Fe0.2Ox、Ni0.8Cu0.2OxOr Ni0.5Cu0.5Ox；
The mass ratio of ceramic powder and polymer solution is 6-12:5,0.05-10 μm of the particle mean size of ceramic powder, pottery
The viscosity 25000-55000MPas of porcelain-polymeric casting film liquid.
In step (3), evacuated pressure 0.01-0.1MPa, pumpdown time 1-2h, spinning pressure 0-
0.25MPa；The soaking temperature is 20-80 DEG C, soaking time 12-48h.
In step (3), the interior condensation water is n,N-Dimethylformamide-d7, DMAC N,N' dimethyl acetamide-d9, diformazan
Base sulfoxide-d6, water, ethanol, the one or more in propyl alcohol or ethylene glycol；The outer condensation water is water or ethanol.
In step (4), the sintering：600-800 DEG C first is warming up to the programming rate of 2-5 DEG C/min, roasts 1-8h；
1000-1600 DEG C is warming up to the programming rate of 1-2 DEG C/min again, sinters 1-10h；Then cooled down with the speed of 1-2 DEG C/min
To 750-850 DEG C, room temperature is finally cooled to.
In step (5), the cathode layer, anode layer material respectively with cathodic ceramic powder, anode ceramic powder phase
Together；The material of the dielectric substrate is Gd0.1Ce0.9O2Or Y0.08Zr0.92O2-δ；The cathode layer, the thickness of anode layer are equal
For 5-20 μm；The thickness of the dielectric substrate is 1-20 μm.
Viscosity is that one kind of fluid viscosity is measured, and is expression of the fluid flow forces to its internal friction phenomenon, and viscosity is got over
It is big to represent that internal friction is bigger.In essence, viscosity is a kind of property that fluid resists flowing, is mutually inhaled between fluid molecule
The intermolecular relative motion ability of obstruction drawn and produced is measured, i.e. the internal drag of fluid flowing.Viscosity and shearing force and cut
Cut rate relational expression：Viscosity=shearing force/shearing rate.Casting solution viscosity is higher, its shearing force is bigger, and the strength used is also bigger,
Mobility is poor；Conversely, casting solution viscosity is lower, its shearing force is smaller, and the strength used is also smaller, and mobility is preferable.
With ceramic powder in casting solution the increase of content or to a certain extent reduce ceramic powder particles radius, compare table
Area is opposite to be increased, and the component of polymer of its outer surface is opposite to be increased, and casting solution viscosity rises.When viscosity is higher, casting solution system
The pressure that standby hollow-fibre membrane idiosome spinning process needs is higher, and frictional force acts in spinning process so that the hollow fibre of preparation
It is fine and close to tie up ceramic membrane, loses body phase pore structure.When viscosity is excessive, cause casting solution mobility very poor, during spinning moulding
Even if hollow-fibre membrane idiosome can not be formed by applying larger pressure.But by improving the viscosity of casting solution, it could prepare
Go out the big hollow fiber ceramic membrane of external surface area, therefore, there is an urgent need for prepare good fluidity, the high casting solution of viscosity.
Beneficial effects of the present invention are as follows：
In the present invention, when PAM is added, the viscosity of system greatly improves.Since PAM is dispersed among in water, formed
Stable system, is then dispersed in ethylene glycol or glycerine, ultimately joins and the homogeneous of " Water-In-Oil " is formed in organic solvent
Stable PAM- organic solvent systems, the system of this solid-liquid mixed phase greatly improve casting solution viscosity.PAM is had itself
Some drop resistance effects can ensure the good fluidity of casting film liquid system.Compared with existing adjusting casting solution viscosity method, this hair
It is bright PAM and additive B synergistic effect under, it is petal-shaped doughnut full-bodied casting solution is successfully spun out cross section
Solid oxide fuel cell, it is ensured that the loose structure of hollow fiber solid oxide fuel cell.
The present invention adjusts viscosity with additive B, realizes in successfully being spun out under high viscosity jointly under the premise of PAM is introduced
Hollow fiber solid oxide fuel cell.PAM is water-soluble, and trace P AM can reduce the friction of 50-80% in water solution system
Resistance.PAM can be partially dissolved in ethylene glycol or glycerine, insoluble in n,N-Dimethylformamide-d7, N, N- dimethylacetamides
Amine-d9Or dimethyl sulfoxide (DMSO)-d6.PAM is dispersed in water by the present invention first, is then added in ethylene glycol or glycerine, is formed equal
One mixed solution stablized, then adds the mixed solution to organic solvent system, is formed " by hydrone/alcohol parcel
Particle ", and be dispersed in organic solvent system, this solid-liquid mixed system considerably increases casting solution viscosity.
The support external surface of the hollow fiber solid oxide fuel cell of the present invention is no longer smooth circular arc, but
The curved surface that uniformly height rises and falls.This support body increases hollow fiber solid oxide fuel cell to a certain extent
Area, substantially increase output power, promote surface reaction, saved cost.
Brief description of the drawings
Fig. 1 is the structure diagram that cross section of the present invention is petal-shaped doughnut supporter；
Wherein 1：Doughnut supporter tube wall, 2：Doughnut supports intracoelomic cavity；
Fig. 2 is the hiccough figure that cross section of the present invention is petal-shaped doughnut supporter；
Fig. 3 is the scanning electron microscope (SEM) photograph that cross section of the present invention is petal-shaped doughnut supporter.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell, including following step
Suddenly：
(1) polymer solution is prepared
12.5g polyether sulfones, 0.1g polyacrylamides, 1g polyvinylpyrrolidones are dissolved in 50g N, N- dimethyl formyls
Amine-d7In, obtain polymer solution；Wherein polyacrylamide is added in the form of mixed solution：0.1g polyacrylamides is molten
In 3g water, then it is added into 10g ethylene glycol, forms mixed solution.
(2) ceramic-polymer casting solution is prepared
By 150g La0.6Sr0.4Co0.2Fe0.8O3-δCathodic ceramic powder is added to the polymer that 75.6g steps (1) obtain
In solution, 24h is sufficiently stirred, makes it completely homogeneously disperse in a polymer solution, to form ceramic-polymer casting solution, its
Viscosity is 26500MPas；Wherein the particle mean size of ceramic powder is 1 μm.
(3) it is petal-shaped doughnut cathode support body idiosome to prepare cross section
The ceramic-polymer casting solution that step (2) obtains is placed under the conditions of 0.08MPa and vacuumizes 1.5h, is subsequently placed in
In spinning equipment tank, under the conditions of spinning pressure is 0.15MPa, it is spun into by spinning head in 25 DEG C of condensation water and soaks 15h,
Under the collective effect of interior condensation water and outer condensation water, it is petal-shaped doughnut cathode branch to cure to obtain cross section through inversion of phases
Support body idiosome；Its China and foreign countries' condensation water is water, and interior condensation water is water and n,N-Dimethylformamide-d7Mixture, both quality
Than for 1:4；
(4) it is petal-shaped doughnut cathode support body to prepare cross section
The cross section that step (3) is obtained is to stretch to dry in the air under petal-shaped doughnut cathode support body idiosome room temperature environment
Dry 36h, then puts it into electric furnace by program sintering processes, is increased to 800 in atmosphere with the programming rate of 5 DEG C/min
4h, burn off wherein organic matter are roasted at DEG C；1450 DEG C are increased to the programming rate of 2 DEG C/min again, sinters 8h；Then with 2 DEG C/
The speed of min cools to 800 DEG C, finally freely cools to room temperature, and it is petal-shaped doughnut cathode support to obtain cross section
Body.
(5) it is petal-shaped hollow fiber solid oxide fuel cell to prepare cross section
It is to be sequentially depositing Gd on petal-shaped doughnut cathode support body in the cross section that step (4) obtains0.1Ce0.9O2
Dielectric substrate, Ni0.5Cu0.5OxAnode layer, acquisition cross section are petal-shaped hollow fiber solid oxide fuel cell, electrolysis
The thickness of matter layer is 10 μm, and the thickness of anode layer is 10 μm.
Embodiment 2
The cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell, including following step
Suddenly：
(1) polymer solution is prepared
12.5g polyether sulfones, 0.5g polyacrylamides, 2g polyvinyl butyral resins are dissolved in 50g N, N- dimethyl formyls
Amine-d7In, obtain polymer solution；Wherein polyacrylamide is added in the form of mixed solution：0.5g polyacrylamides is molten
In 5g water, then it is added into 20g ethylene glycol, forms mixed solution.
(2) ceramic-polymer casting solution is prepared
By 145.5g La0.6Sr0.4CoO3-δCathodic ceramic powder is added in the polymer solution that 79g steps (1) obtain,
30h is sufficiently stirred, makes it completely homogeneously disperse in a polymer solution, to form ceramic-polymer casting solution, its viscosity is
28400MPa·s；Wherein the particle mean size of ceramic powder is 4 μm.
(3) it is petal-shaped doughnut cathode support body idiosome to prepare cross section
The ceramic-polymer casting solution that step (2) obtains is placed under the conditions of 0.05MPa and vacuumizes 1.5h, is subsequently placed in
In spinning equipment tank, under the conditions of spinning pressure is 0.15MPa, it is spun into by spinning head in 24 DEG C of condensation water and soaks 15h,
Under the collective effect of interior condensation water and outer condensation water, it is petal-shaped doughnut cathode branch to cure to obtain cross section through inversion of phases
Support body idiosome；Its China and foreign countries' condensation water is water, and interior condensation water is water and dimethyl sulfoxide (DMSO)-d6Mixture, both mass ratioes be 1:
5；
(4) it is petal-shaped doughnut cathode support body to prepare cross section
The cross section that step (3) is obtained is to stretch to dry in the air under petal-shaped doughnut cathode support body idiosome room temperature environment
Dry 30h, then puts it into electric furnace by program sintering processes, is increased to 800 in atmosphere with the programming rate of 5 DEG C/min
4h, burn off wherein organic matter are roasted at DEG C；1400 DEG C are increased to the programming rate of 2 DEG C/min again, sinters 8h；Then with 2 DEG C/
The speed of min cools to 800 DEG C, finally freely cools to room temperature, and it is petal-shaped doughnut cathode support to obtain cross section
Body.
(5) it is petal-shaped hollow fiber solid oxide fuel cell to prepare cross section
It is to be sequentially depositing Gd on petal-shaped doughnut cathode support body in the cross section that step (4) obtains0.1Ce0.9O2
Dielectric substrate, Ni0.8Cu0.2OxAnode layer, acquisition cross section are petal-shaped hollow fiber solid oxide fuel cell, electrolysis
The thickness of matter layer is 10 μm, and the thickness of anode layer is 15 μm.
Embodiment 3
The cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell, including following step
Suddenly：
(1) polymer solution is prepared
12.5g polysulfones, 0.5g polyacrylamides, 4g ammonium polymethacrylates are dissolved in 50g N, N- dimethyl formyls
Amine-d7In, obtain polymer solution；Wherein polyacrylamide is added in the form of mixed solution：0.5g polyacrylamides is molten
In 5g water, then it is added into 25g ethylene glycol, forms mixed solution.
(2) ceramic-polymer casting solution is prepared
By 175g Ni0.8Fe0.2OxAnode ceramic powder is added in the polymer solution that 95g steps (1) obtain, fully
30h is stirred, makes it completely homogeneously disperse in a polymer solution, to form ceramic-polymer casting solution, its viscosity is
28500MPa·s；Wherein the particle mean size of ceramic powder is 5 μm.
(3) it is petal-shaped doughnut anode support idiosome to prepare cross section
The ceramic-polymer casting solution that step (2) obtains is placed under the conditions of 0.07MPa and vacuumizes 1.5h, is subsequently placed in
In spinning equipment tank, under the conditions of spinning pressure is 0.2MPa, it is spun into by spinning head in 25 DEG C of condensation water and soaks 20h,
Under the collective effect of interior condensation water and outer condensation water, it is petal-shaped doughnut anode branch to cure to obtain cross section through inversion of phases
Support body idiosome；Its China and foreign countries' condensation water is water, and interior condensation water is water and dimethyl sulfoxide (DMSO)-d6Mixture, both mass ratioes be 1:
4；
(4) it is petal-shaped doughnut anode support to prepare cross section
The cross section that step (3) is obtained is to stretch to dry in the air under petal-shaped doughnut anode support idiosome room temperature environment
Dry 30h, then puts it into electric furnace by program sintering processes, is increased to 800 in atmosphere with the programming rate of 5 DEG C/min
4h, burn off wherein organic matter are roasted at DEG C；1300 DEG C are increased to the programming rate of 2 DEG C/min again, sinters 8h；Then with 2 DEG C/
The speed of min cools to 800 DEG C, finally freely cools to room temperature, and it is petal-shaped doughnut anode-supported to obtain cross section
Body.
(5) it is petal-shaped hollow fiber solid oxide fuel cell to prepare cross section
It is to be sequentially depositing Gd on petal-shaped doughnut anode support in the cross section that step (4) obtains0.1Ce0.9O2
Dielectric substrate, Ba0.5Sr0.5Co0.8Fe0.2O3-δCathode layer, acquisition cross section are petal-shaped doughnut solid oxide fuel
Battery, the thickness of dielectric substrate is 15 μm, and the thickness of cathode layer is 10 μm.
Embodiment 4
The cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell, including following step
Suddenly：
(1) polymer solution is prepared
The poly- ethyleneimines of 12.5g, 1g polyacrylamides, 2.5g polyvinylpyrrolidones, 2.5g polyvinyl butyral resins is molten
Solution is in 50gN, dinethylformamide-d7In, obtain polymer solution；Wherein polyacrylamide is added in the form of mixed solution
Enter：1g polyacrylamides are dissolved in 10g water, then are added into 20g ethylene glycol, form mixed solution.
(2) ceramic-polymer casting solution is prepared
155g Ni0.8Cu0.2OxAnode ceramic powder is added in the polymer solution that 98.5g steps (1) obtain, fully
24h is stirred, makes it completely homogeneously disperse in a polymer solution, to form ceramic-polymer casting solution, its viscosity is
30000MPa·s；Wherein the particle mean size of ceramic powder is 8 μm.
(3) it is petal-shaped doughnut anode support idiosome to prepare cross section
The ceramic-polymer casting solution that step (2) obtains is placed under the conditions of 0.02MPa and vacuumizes 2h, is subsequently placed in spinning
In silk equipment tank, under the conditions of spinning pressure is 0.25MPa, it is spun into by spinning head in 22 DEG C of condensation water and soaks 20h, inside
Under the collective effect of condensation water and outer condensation water, it is petal-shaped doughnut anode-supported to cure to obtain cross section through inversion of phases
Body embryo body；Its China and foreign countries' condensation water is water, and interior condensation water is water and n,N-Dimethylformamide-d7Mixture, both mass ratioes
For 1:5；
(4) it is petal-shaped doughnut anode support to prepare cross section
The cross section that step (3) is obtained is to stretch to dry in the air under petal-shaped doughnut anode support idiosome room temperature environment
Dry 30h, then puts it into electric furnace by program sintering processes, is increased to 800 in atmosphere with the programming rate of 5 DEG C/min
4h, burn off wherein organic matter are roasted at DEG C；1400 DEG C are increased to the programming rate of 2 DEG C/min again, sinters 8h；Then with 2 DEG C/
The speed of min cools to 800 DEG C, finally freely cools to room temperature, and it is petal-shaped doughnut anode-supported to obtain cross section
Body.
(5) it is petal-shaped hollow fiber solid oxide fuel cell to prepare cross section
It is to be sequentially depositing Gd on petal-shaped doughnut anode support in the cross section that step (4) obtains0.1Ce0.9O2
Dielectric substrate, Ba0.5Sr0.5CoO3-δCathode layer, acquisition cross section are petal-shaped hollow fiber solid oxide fuel cell,
The thickness of dielectric substrate is 20 μm, and the thickness of cathode layer is 20 μm.
Cross section produced by the present invention is the structure of petal-shaped doughnut supporter as shown in Figure 1, centre is hollow
The inner cavity of fiber support, is the tube wall of doughnut supporter around inner cavity, petal-shaped top to the inner cavity of tube wall away from
From for 300-350 μm；
Fig. 2 is the hiccough figure that cross section is petal-shaped doughnut supporter；
From Fig. 3 it can be found that doughnut supports external surface recess equivalent to doughnut supporter whole cross section
The 30%-35% of thickness.
Embodiment 5
It is molten by different additive, water, ethylene glycol, 12.5g polysulfones, the obtained polymer of 50g 1-methyl-2-pyrrolidinones (NMP)
Liquid, further prepares the viscosity of casting solution, test polymer solution viscosity and casting solution, such as table 1.
1 test data table of table
Note：Test 7-9 to test for two-component, the additive A in experiment 7 is PVP, additive B PVB, remaining is with reference to real
The step of applying example 1 carries out；The process of experiment 8 is carried out with reference to the step of embodiment 1；Additive B in experiment 9 is PVB, remaining ginseng
Carried out according to the step of embodiment 1.
Appearance is carried out for petal-shaped hollow fiber solid oxide fuel cell to the cross section obtained in embodiment 1-4
Area estimation, measurement result such as table 2.
2 Timeing Detection Table of table
| Embodiment | 1 | 2 | 3 | 4 |
| External surface area (cm2/cm) | 0.35 | 0.34 | 0.38 | 0.38 |
It is petal-shaped hollow fiber solid oxide fuel cell and document 1- to the cross section obtained in embodiment 1-4
Fuel cell in 2 carries out output test, measurement result such as table 3.
3 Timeing Detection Table of table
| Material | Test temperature (DEG C) | Output power (mWcm-2) |
| 1 hollow fiber solid oxide fuel cell of embodiment | 500 | 480 |
| 2 hollow fiber solid oxide fuel cell of embodiment | 500 | 475 |
| 3 hollow fiber solid oxide fuel cell of embodiment | 800 | 750 |
| 4 hollow fiber solid oxide fuel cell of embodiment | 800 | 700 |
| Fuel cell in document 1 | 800 | 411 |
| Fuel cell in document 2 | 500 | 366 |
Document：
1.Meng,X.；Liu,Y.；Yang,N.；Tan,X.；Liu,J.；Diniz da Costa,J.C.；Liu,S.,
Highly compact and robust hollow fiber solid oxide cells for flexible power
generation and gas production.Applied Energy 2017,205,741-748.
2.Guo,Y.；Shi,H.；Ran,R.；Shao,Z.,Performance of SrSc0.2Co0.8O3-δ+
Sm0.5Sr0.5CoO3-δmixed-conducting composite electrodes for oxygen reduction at
intermediate temperatures.International journal of hydrogen energy 2009,34
(23),9496-9504.
Claims (10)
1. a kind of cross section is the preparation method of petal-shaped hollow fiber solid oxide fuel cell, it is characterised in that including
Following steps：
(1) polymer solution is prepared
By organic polymer, additive A, additive B dissolving in organic solvent, polymer solution is obtained；
(2) ceramic-polymer casting solution is prepared
Ceramic powder is added in the polymer solution that step (1) obtains, stirred evenly, form ceramic-polymer casting solution；
(3) it is petal-shaped doughnut anode support idiosome or cathode support body idiosome to prepare cross section
The ceramic-polymer casting solution that step (2) obtains is vacuumized, is subsequently placed in spinning equipment tank, is spun by spinning head
Enter and soaked in outer condensation water, under the collective effect of interior condensation water and outer condensation water, cure to obtain cross section through inversion of phases as flower
The doughnut anode support idiosome or cathode support body idiosome of valve type；
(4) it is petal-shaped doughnut anode support or cathode support body to prepare cross section
The cross section that step (3) is obtained stretches for petal-shaped doughnut anode support idiosome or cathode support body idiosome
Dry, sinter, it is petal-shaped doughnut anode support or cathode support body to obtain cross section；
(5) it is petal-shaped hollow fiber solid oxide fuel cell to prepare cross section
It is to be sequentially depositing electricity on petal-shaped doughnut cathode support body in the cross section that step (4) obtains using infusion process
Matter layer, anode layer are solved, it is petal-shaped hollow fiber solid oxide fuel cell to form cross section；
It is to be sequentially depositing electricity on petal-shaped doughnut anode support in the cross section that step (4) obtains using infusion process
Matter layer, cathode layer are solved, it is petal-shaped hollow fiber solid oxide fuel cell to form cross section.
2. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (1), organic polymer, additive A, additive B, the mass ratio of organic solvent are 12.5-25:
0.1-5:0.5-25:50-100；The additive A is polyacrylamide, and additive A is added in the form of mixed solution, is mixed
It is 0.1-10 to close additive A, water, the mass ratio of alcohol in solution:0.1-50:0.1-100；The alcohol is ethylene glycol or the third three
Alcohol.
3. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (1), the organic polymer is polysulfones, polyether sulfone, polyacrylonitrile, makrolon, poly- second
One or more in imines, polyetherimide or cellulose acetate.
4. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (1), the additive B is polyvinylpyrrolidone, polyvinyl butyral resin, poly- methyl-prop
One or more in olefin(e) acid ammonium, polyacrylate, gamma-butyrolacton, polymethyl methacrylate or phosphate.
5. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (1), the organic solvent is 1-methyl-2-pyrrolidinone, n,N-Dimethylformamide-d7、N,
N- dimethylacetylamides-d9Or dimethyl sulfoxide (DMSO)-d6In one or more.
6. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (2), the ceramic powder is cathodic ceramic powder, anode ceramic powder；
The cathodic ceramic powder is La0.6Sr0.4Co0.2Fe0.8O3-δ、La0.6Sr0.4CoO3-δ、Ba0.5Sr0.5Co0.8Fe0.2O3-δ
Or Ba0.5Sr0.5CoO3-δ；
The anode ceramic powder is Ni0.8Fe0.2Ox、Ni0.8Cu0.2OxOr Ni0.5Cu0.5Ox；
The mass ratio of ceramic powder and polymer solution is 6-12:5,0.05-10 μm of the particle mean size of ceramic powder, ceramics-poly-
The viscosity 25000-55000MPas of compound casting solution.
7. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (3), evacuated pressure 0.01-0.1MPa, pumpdown time 1-2h, spinning pressure 0-
0.25MPa, soaking temperature are 20-80 DEG C, soaking time 12-48h.
8. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (3), the interior condensation water is n,N-Dimethylformamide-d7, DMAC N,N' dimethyl acetamide-
d9, dimethyl sulfoxide (DMSO)-d6, water, ethanol, the one or more in propyl alcohol or ethylene glycol；The outer condensation water is water or ethanol.
9. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (4), the sintering：600-800 DEG C first is warming up to the programming rate of 2-5 DEG C/min, roasting
Burn 1-8h；1000-1600 DEG C is warming up to the programming rate of 1-2 DEG C/min again, sinters 1-10h；Then with the speed of 1-2 DEG C/min
Degree is cooled to 750-850 DEG C, is finally cooled to room temperature.
10. cross section according to claim 1 is the preparation side of petal-shaped hollow fiber solid oxide fuel cell
Method, it is characterised in that：In step (5), the cathode layer, the material of anode layer are ceramic with cathodic ceramic powder, anode respectively
Powder is identical；The material of the dielectric substrate is Gd0.1Ce0.9O2Or Y0.08Zr0.92O2-δ；The cathode layer, anode layer
Thickness is 5-20 μm；The thickness of the dielectric substrate is 1-20 μm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200374A (en) * | 2007-10-24 | 2008-06-18 | 山东理工大学 | Method for preparing composite structural ceramic hollow fiber membrane |
| CN101252199A (en) * | 2008-04-01 | 2008-08-27 | 南京工业大学 | Method for preparing hollow fiber-type solid-oxide fuel battery |
| CN101733048A (en) * | 2009-12-25 | 2010-06-16 | 中国科学技术大学 | Hollow fiber membrane reactor for gaseous oxidation reaction, preparation and application thereof |
| CN102332592A (en) * | 2011-08-09 | 2012-01-25 | 华南理工大学 | Preparation method for asymmetric hollow fiber type solid oxide fuel cell |
| CN105289319A (en) * | 2015-11-20 | 2016-02-03 | 湖南澳维环保科技有限公司 | Preparation method of polymer hollow fiber membrane |
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2017
- 2017-12-07 CN CN201711281432.4A patent/CN108039506B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200374A (en) * | 2007-10-24 | 2008-06-18 | 山东理工大学 | Method for preparing composite structural ceramic hollow fiber membrane |
| CN101252199A (en) * | 2008-04-01 | 2008-08-27 | 南京工业大学 | Method for preparing hollow fiber-type solid-oxide fuel battery |
| CN101733048A (en) * | 2009-12-25 | 2010-06-16 | 中国科学技术大学 | Hollow fiber membrane reactor for gaseous oxidation reaction, preparation and application thereof |
| CN102332592A (en) * | 2011-08-09 | 2012-01-25 | 华南理工大学 | Preparation method for asymmetric hollow fiber type solid oxide fuel cell |
| CN105289319A (en) * | 2015-11-20 | 2016-02-03 | 湖南澳维环保科技有限公司 | Preparation method of polymer hollow fiber membrane |
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Inventor after: Meng Bo Inventor after: Han Ning Inventor after: Wang Xiaobin Inventor after: Zhang Jinjin Inventor after: Zhang Shuguang Inventor before: Meng Bo Inventor before: Han Ning Inventor before: Liu Shaomin Inventor before: Wang Xiaobin Inventor before: Zhang Jinjin Inventor before: Zhang Shuguang |