CN107180978A - A kind of tubular solid oxide fuel cell anode support and preparation method thereof - Google Patents
A kind of tubular solid oxide fuel cell anode support and preparation method thereof Download PDFInfo
- Publication number
- CN107180978A CN107180978A CN201710254609.5A CN201710254609A CN107180978A CN 107180978 A CN107180978 A CN 107180978A CN 201710254609 A CN201710254609 A CN 201710254609A CN 107180978 A CN107180978 A CN 107180978A
- Authority
- CN
- China
- Prior art keywords
- anode
- fuel cell
- preparation
- powder
- tubular
- 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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (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)
- Inert Electrodes (AREA)
Abstract
The present invention relates to a kind of tubular solid oxide fuel cell anode support and preparation method thereof, the preparation method comprises the following steps：Prepare the dispersed slurry for having an anode powder；Gained slurry is subjected to mist projection granulating, modified anode powder is obtained；By in modified anode powder injection tubing die, the stripping forming after isostatic pressed obtains formed body；Gained formed body is sintered, soild oxide tubular type anode of fuel cell supporter is obtained.The present invention obtains soild oxide tubular type anode of fuel cell supporter by mist projection granulating, isostatic pressing, sintering, simple production process, strong operability, with good technology stability, obtained soild oxide tubular type anode of fuel cell supporter electric current collection is simple and convenient, power attenuation is small, receiving electric material and straight anode reaction region has good physics binding face, increases substantially the collection efficiency of electronics.
Description
Technical field
The invention belongs to SOFC manufacturing technology field, more particularly to a kind of pipe type solid oxide combustion
Expect galvanic anode supporter and preparation method thereof.
Background technology
SOFC (SOFC) is the solid-state energy conversion based on ceramic material, passes through high-temperature electric
Chemical energy in fuel is converted into electric energy by chemical reaction, and its clean, efficient energy-provision way is to solve China's city energy
Source and the active demand of environmental problem.Distributed energy resource system based on SOFC technologies can realize that the heat supply of high-efficiency cleaning is supplied
Electricity, it will replace traditional urban energy supply mode, leads supply, the production and consumption mode revolution of the energy.SOFC has height
The outstanding advantages such as efficiency, low stain, low noise, modularization, small volume, reliability be high and fuel tolerance is wide, are widely used in
In terms of large-scale distributed power station, household cogeneration systems and military compact power, while being also to realize coal, stone
One of important technology that the fossil energy high-efficiency cleaning such as oil, natural gas is utilized.
SOFC has all solid state component characteristic, and its research direction is concentrated mainly on two kinds of structure classes
Type：Tubular type and flat.Flat solid oxide fuel cell has higher volumetric power density, commonly used to as big
Type distribution power station.Tubular solid oxide fuel cell has startup time fast and good thermal shock resistance etc. due to it
Advantage, is the ideal structure developed as compact power.
At present, the patent of invention for the Application No. 200510101487.3 announced discloses a kind of vertebra tubular anode branch
SOFC monocell is supportted, anode support prepared by this method is the Taper Pipe shape that one end is big, one end is small so that
Sealing is easier to realize when being connected in series, but tubular cells anode current prepared by this method collects relatively difficult；Patent
Number disclose a kind of method that use gypsum mould grouting method prepares electrolyte thin wall tube, this method for 99108725.9 patent of invention
The uniformity and suspension of slurry are very big on the influence of the quality of slip casting product in casting process, batch prepare uniformity compared with
Difference；Publication number CN 2547010Y patent of invention discloses a kind of anode support tube type solid oxide fuel battery, using crowded
It is molded go out in have a seven special-shaped tubular anode supports by all means, polymorphic structure increase effective affecting acreage and to improve power close
Degree, but labyrinth requires harshness to mold design and extrusion process, it is impossible to ensure success rate while being also unfavorable for industry
Metaplasia is produced；Publication No. CN 1700494A patent of invention discloses the side of dip moulding pipe type solid oxide fuel battery
Method, describe it is a kind of by dispensing, ball milling, vacuumize, impregnate, be stripped, pre-burning, sintering, the process such as pretreatment, by impregnating
The control of number of times, adjusts the thickness of difference in functionality structure sheaf, the method preparation time is longer and can not meet industrial want
Ask.
The content of the invention
The purpose of the present invention is to be directed to tubular solid oxide fuel cell (SOFC) preparation technology in existing technology of preparing
Unstable, yield rate is low, anode receives the stubborn problems such as electricity is difficult, industrialization difficulty is big, it is proposed that a kind of pipe type solid oxidation
Tubular solid oxide fuel cell of thing anode of fuel cell supporter including the anode support and preparation method thereof.
On the one hand, the present invention provides a kind of preparation method of tubular solid oxide fuel cell anode support, and it is wrapped
Include following steps：
Prepare the dispersed slurry for having an anode powder；
Gained slurry is subjected to mist projection granulating, modified anode powder is obtained；
By in modified anode powder injection tubing die, the stripping forming after isostatic pressed obtains formed body；
Gained formed body is sintered, soild oxide tubular type anode of fuel cell supporter is obtained.
The present invention obtains soild oxide tubular type anode of fuel cell by mist projection granulating, isostatic pressing, sintering and supported
Body, simple production process, strong operability, with good technology stability, obtained soild oxide tubular type fuel cell sun
Pole supporter electric current collection is simple and convenient, and power attenuation is small, and receiving electric material and straight anode reaction region has good thing
Binding face is managed, the collection efficiency of electronics is increased substantially；With good chemical property；It is with low cost, farthest carry
High anode supports the utilization rate of powder, reduces the cost of raw material.Specifically：After process aspect, slip casting, dip forming
Need to dry while to control after the humiture of environment, mist projection granulating the direct isostatic pressing of solid particle than slip casting, impregnate into
Type technique is simple and efficient；In terms of product, material strength is low after slip casting, dip forming, it is yielding, corrugation, isostatic pressed into
Intensity is high after type, while the rigid plug in mould makes tubular type base substrate inner surface have good circularity and linearity, with anode
Receive electric layer laminating more preferably and prepare more convenient；In terms of cost, through ball milling, mistake when slip casting, the slurry of dipping or pug preparation
The processes such as filter, deaeration inevitably produce material loss, and mist projection granulating preparation technology loss is relatively small, and cost is lower.
It is preferred that the slurry includes：Anode powder, bonding agent, dispersant and pore creating material, its proportioning are as follows：
Anode powder：100 mass parts；
Pore creating material：0~20 mass parts；
Bonding agent：1~10 mass parts；
Dispersant：1~5 mass parts.
It is preferred that the solvent of the slurry is water, the solid content of the slurry is 50%~60wt%.
It is preferred that the anode powder is mixed powder or the NiO oxidations stable with scandium of the NiO zirconium oxides stable with yttrium
The mixed powder of zirconium；
The pore creating material is wheat flour or graphite powder；
The binding agent is polyvinyl alcohol；
The dispersant is triethanolamine.
It is preferred that the temperature of mist projection granulating is 0~250 DEG C, more preferably preferably 100~250 DEG C, 120~180 DEG C.
It is preferred that working media used in the isostatic pressed is hydraulic oil, pressure is 160~200MPa, dwell time
For 15~60 minutes.
It is preferred that the temperature of the sintering is 800~1000 DEG C, soaking time is 1~3 hour.
It is preferred that the tubing die includes：
The flexible sleeve of one end open other end closing；
It is arranged inside the flexible sleeve and is formed between the flexible sleeve in the coaxial form of the flexible sleeve
The rigid plug of material feeding cavity；And
Have on the material feeding component for being arranged at the openend of the flexible sleeve and fixing the rigid plug, the material feeding component
There is the material hole for the material feeding into the material feeding cavity.
According to above-mentioned tubing die, material hole can be used for injecting powder into material feeding cavity.Flexible sleeve is after isostatic pressed
It can be automatically separated with base substrate outer surface so that be convenient in demoulding quick.Rigid plug in mould has tubular type base substrate inner surface
Good circularity and linearity, fit more preferably and prepare more convenient with anode receipts electric layer.
It is preferred that the blind end of the flexible sleeve is hemisphere face end socket, the close flexible boot of the rigid plug
The top end of the blind end of pipe is hemispherical.So, the tubular type supporter that one end is hemisphere face closure can be prepared.
It is preferred that the flexible sleeve is made up of soft rubber or silastic material.Soft rubber or silastic material have good
Good elastic memory performance, is automatically separated more conducively after isostatic pressed with base substrate outer surface so that the demoulding is more convenient.
It is preferred that the thickness of the flexible sleeve is 5~10mm.It can keep good with the certain thickness flexible sleeve
Good release property, while ensureing the linearity and circularity of base substrate.
It is preferred that the rigid plug is made up of zirconia material.So, forming process can be caused not cause pollution.
It is preferred that the rigid plug is the rigid plug by polishing.Good release property can so be kept simultaneously
Ensure that anode support inwall keeps straight.
It is preferred that the material feeding component is formed as ring-type, the material hole is multiple, and in the material feeding component of ring-type
On be uniformly distributed.In this manner it is ensured that the apparent density of powder keeps uniform in injection pot, outer surface equally has after isostatic pressed
There is preferable circularity, good basis is provided for the follow-up thin layer of electrolyte for preparing densification.
It is preferred that the number of the material hole is 3~5.So, can keep the apparent density of powder in injection pot
Uniformly.
Second aspect, the present invention provides a kind of preparation method of tubular solid oxide fuel cell, and it includes following step
Suddenly：
Soild oxide tubular type anode of fuel cell supporter is prepared according to above-mentioned preparation method；
The anode support of gained is impregnated into electrolyte slurry, sintering obtains soild oxide tubular type fuel half-cell after drying；
By the half-cell impregnated cathode material of gained, sintering obtains soild oxide tubular type fuel cell after drying.
The third aspect, the present invention provides a kind of tubular solid oxide fuel cell sun prepared according to above-mentioned preparation method
Pole supporter.
Fourth aspect, the present invention provides a kind of tubular solid oxide fuel cell, and it includes successively from inside to outside：It is above-mentioned
Tubular solid oxide fuel cell anode support, dielectric substrate and cathode layer.
Brief description of the drawings
Fig. 1 prepares the structure sectional view that tubular type anode of fuel cell supports forming die for the present invention, wherein：
1 flexible sleeve (outer die casing), 2 plugs, 3 material feeding cavitys, 4 material feeding rings, 5 material holes；
Fig. 2 is the tubular type anode of fuel cell supporter for preparing of the present invention, wherein (a) be pictorial diagram, to scheme (b) be that structure section view is shown
It is intended to；
The tubular type fuel cell structure schematic diagram that Fig. 3 is prepared for the present invention；
The anode support tube type fuel cell pictorial diagram that Fig. 4 is prepared for the present invention；
Fig. 5 is the micro-structural scanning electron microscope (SEM) photograph of above-mentioned anode support tube type battery；
Fig. 6 is test pictorial diagram in the stove of above-mentioned anode support tube type battery；
Fig. 7 is the I-V-P curves of above-mentioned tubular cells at different temperatures；
Fig. 8 is the EIS curves of above-mentioned tubular cells at different temperatures；
Fig. 9 is the V-t curves of above-mentioned tubular cells constant current discharge
Figure 10 is the performance comparison that different moulding process prepare anode support；
Figure 11 is the impedance spectrum contrast that different moulding process prepare anode support；
Figure 12 is the I-V-P curves of battery testing under the different Content of Pore-forming Agents of anode powder；
Figure 13 is the EIS curves of battery testing under the different Content of Pore-forming Agents of anode powder.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
The present invention is merely to illustrate, is not intended to limit the present invention.
The present invention obtains soild oxide tubular type anode of fuel cell by mist projection granulating, isostatic pressing, sintering and supported
Body.Hereinafter, as an example, illustrating the preparation method of the present invention.
First, the dispersed slurry (anode powdery pulp) for having an anode powder is prepared.In the present invention, anode powder can be
Any anode material powder suitable for tubular solid oxide fuel cell, for example, can be that nickel oxide (NiO) and yttrium are stable
Zirconium oxide (YSZ) (mole doping of yttrium is 3%~10%) mixing, or be nickel oxide (NiO) and the stable zirconium oxide of scandium
(ScSZ or SSZ) (mole doping of scandium is 0%~15%) mixing.The weight/mass percentage composition of general nickel oxide (NiO) can be
30%~70%.
Pore creating material can also be contained in the slurry.Described pore creating material is, for example, wheat flour or graphite powder.The matter of pore creating material
Amount number is generally within 20%.In the range of within 20%, the content of pore creating material is The more the better.Pore creating material is in sintering process
In produce hole after burning completely, to increase the three-phase reaction interface area of anode functional layer, the diffusion velocity of lift gas and
Electrochemical reaction speed.
Binding agent, such as polyvinyl alcohol (PVA) can also be contained in the slurry.The mass fraction of binding agent is generally 1%
~10%.Binding agent in forming process be used for resist intermolecular drag be easier to shaping, while so that shaping after base substrate
Keep spatial geometric shape.
Dispersant, such as triethanolamine can also be contained in the slurry.The mass fraction of dispersant is generally 1%~5%.
Dispersant by mixed powder during the aqueous solution is prepared into, the uniformity for keeping the aqueous solution good.
The solvent of the slurry can be water or alcohol, can so avoid the use of organic solvent, not only prepare environment and be good for
Kang Huanbao, and it is with low cost.The solid content general control of the slurry so both can guarantee that slurry had good 50%~60%
Good mobility, it is to avoid Spray Grain-make Drier spray gun is blocked, while being also easy to granulating and forming.
In one example, the slurry is prepared by the following method：By mixed powder (the anode powder of anode of fuel cell
Body), pore forming material (pore creating material), binding agent, dispersant proportionally uniformly mix (for example uniformly being mixed with mortar), obtain sun
Pole mixed powder material, and it is configured to the aqueous solution with pure water.The proportioning of anode mixture powder is as follows：
The mass parts of anode powder 100
The mass parts of pore creating material 0~20 (not preferably being 0)
The mass parts of bonding agent 1~10
The mass parts of dispersant 1~5.
Then, mist projection granulating is carried out to anode powdery pulp using high-temperature spray comminutor, obtains modified anode and mix
Close powder.The operating temperature interval of high-temperature spray comminutor can be 0~250 DEG C, preferably 100~250 DEG C, more preferably 120
~180 DEG C, such as 150 DEG C.Solvent can be allowed to evaporate vaporific slurry rapid shaping simultaneously rapidly in above-mentioned operating temperature interval.
The pulp spraying speed of sponging granulator can be 0~100ml/min (not preferably being 0), preferably 20~30ml/min.Made by spraying
Grain, can obtain the mixed powder of centralized particle diameter and good fluidity.In the present invention, the particle diameter of mixed powder can for 1~
100μm。
By in modified anode mixture powder injection tubing die, vibration is stripped into after being pressurizeed after filling through isostatic pressing machine
Type.
Fig. 1 shows the exemplary construction sectional view of tubing die.As shown in figure 1, the mould includes another end seal of one end open
The flexible sleeve 1 closed.Rigid plug 2 is arranged at the inside of flexible sleeve 1 and material feeding cavity 3 is formed between flexible sleeve 1.Rigidity
Plug 2 is coaxially disposed with flexible sleeve 1, and its top end is apart from the blind end certain distance of flexible sleeve 1.The base of rigid plug 2
End is close to the openend of flexible sleeve 1.Material feeding component is arranged at the openend of flexible sleeve 1 and consolidates the cardinal extremity of rigid plug 2
Fixed, the material feeding component can be formed as ring-type, the material feeding ring 4 as shown in Fig. 1.That is, mould is by flexible sleeve 1 and rigid plug
2 are assembled by material feeding ring 4.There is the material hole 5 for being used for the material feeding into the material feeding cavity on material feeding ring 4.
As shown in figure 1, flexible sleeve 1 can be cylindrical, and its blind end can be hemisphere face.Rigid plug 2 can be cylinder
Shape, and its top end also can be hemispherical.So, the Formation cross-section of material feeding cavity 3 can be made to be the shape of U-shaped, and then be may be such that into
The base substrate that type goes out is the cylindrical tube of one end hemisphere face closure and another end opening.The big I of material feeding cavity 3 is soft by adjusting
Property sleeve pipe 1 and the size of rigid plug 2 change, and then the size of the base substrate molded can be adjusted.
Flexible sleeve 1 can be elastomeric material, for example, soft rubber or silastic material, because it has good elastic memory
It is automatically separated after performance, isostatic pressed with base substrate outer surface so that be convenient in demoulding quick.The thickness of flexible sleeve 1 can for 5~
10mm。
Rigid plug 2 can use ceramic material, and preferably zirconia material so may be such that forming process does not cause dirt
Dye.In addition, rigid plug 2 preferably does polishing, good release property can be kept to ensure that anode support inwall is protected simultaneously
Hold straight.
Material feeding ring 4 can be metal material.Material feeding ring 4 is removable installed in the openend of flexible sleeve 1.Rigid plug 2
Cardinal extremity be securable on material feeding ring 4, can also be detachable between the two.For example, can be by material feeding ring 4 and rigid plug 2
The openend of cardinal extremity and flexible sleeve 1 is mutually clamped.The material hole 5 communicated with material feeding cavity 3 is provided with material feeding ring 4, with
This injects material to be formed, such as powder to material feeding cavity 3.Material hole 5 be preferably be uniformly distributed it is multiple, such as 3~5, more
Body such as 4, can so ensure that the apparent density of powder in injection pot keeps uniform, outer surface equally has after isostatic pressed
Preferable circularity, good basis is provided for the follow-up thin layer of electrolyte for preparing densification.The aperture of material hole 5 can be 2~5mm.
It using above-mentioned tubing die, can make that obtained anode support electric current collection is simple and convenient, power attenuation is small, receive electricity
Material has good physics binding face with straight anode reaction region, increases substantially the collection efficiency of electronics；With good
Good chemical property；It is with low cost, farthest improve anode-supported powder utilization rate, reduce raw material into
This；Simple production process, strong operability, with good technology stability.
After described mould anode batch mixing is filled and vibrates and tamp, after mould is vented with polybag wrapped multiple to prevent
Only hydraulic medium penetrates into.
The working media of isostatic pressing machine can be hydraulic oil.The operating pressure of isostatic pressing machine can be 160~200MPa, for example
200MPa, the pressure energy makes powder granule crush completely, and base substrate has good intensity after shaping.The work temperature of isostatic pressing machine
Degree can be 10~35 DEG C.Operating pressure, such as 10~15MPa/min can be loaded onto by ramp system.Can be in operating pressure
Lower pressurize 30~60 minutes, such as 30 minutes.Remove the demoulding after pressure and produce tubular solid oxide fuel cell anode-supported
Body base substrate.Fig. 2 shows photo and section view after the tubular solid oxide fuel cell anode support base substrate demoulding of the present invention
Schematic diagram, it can be seen that the supporter idiosome outward appearance is in cylinder, and one end is hemisphere face closure, another end opening.
Level is put into Muffle furnace (such as 1200 DEG C high temperature Muffle furnaces) in the lump after gained idiosome is supported with alumina tube,
Pre-burning 1~3 hour at 800~1000 DEG C, obtains being molded tubular type anode of solid oxide fuel cell supporter.
The tubular solid oxide fuel cell anode support of gained is that one end is closed and the tubular type knot of another end opening
Structure, the thickness of anode support tube is generally 200~2000 μm.The thickness is adjustable, by change flexible sleeve and rigid plug it
Between space control to be filled with the total amount of powder, i.e., various sizes of flexible outer die casing customized coordinates to adjust sun with rigid plug
The thickness of pole support tube.
On the basis of pipe type solid oxide anode support, dielectric substrate and cathode layer are prepared, you can prepare sun
Pole supports tubular solid oxide fuel cell.
For example, described tubular solid oxide fuel cell anode support can impregnate the stable zirconium oxide (YSZ) of yttrium
The electrolyte slurry such as (mole doping of yttrium is 3%~8%) or the stable zirconium oxide (ScSZ) of scandium, after drying 1350
2~4 hours (such as 4 hours) are incubated at~1450 DEG C, the tubular type fuel cell half-cell of surface-brightening is sintered into.
Described half-cell can impregnate porous cathode material lanthanum-strontium manganese (La0.75Sr0.25)0.95MnO3Or lanthanum-strontium gallium magnesium (LSM)
(LSGM) 2~3 hours (such as 2 hours), are incubated at 1150~1200 DEG C after drying, pipe type solid oxide combustion is sintered into
Expect cell single cells.
Fig. 3 shows tubular solid oxide fuel cell (monocell) structure chart of the present invention, the pipe type solid oxide
Fuel cell is followed successively by anode support, dielectric substrate and cathode layer from inside to outside.Fuel gas can be from the opening of anode support
End is passed through.Anode-supported external surface prepared by the present invention has preferable circularity, is conducive to preparing the electrolysis of densification thereon
Matter thin layer.
The tubular solid oxide fuel cell monocell of the present invention can be used to integrated tubular type battery pile or tubular type fuel electricity
Cell system.
The present invention uses isostatic pressing process, prepares the good powder of processability by mist projection granulating first, i.e.,
Good mobility and crushing performance, secondly by suitable mould, can guarantee that even density while being convenient in demoulding, finally
Excellent molding effect is realized by the technology controlling and process of isostatic pressed.Compared with prior art, the advantage of the invention is that：Electric current is received
Collect simple and convenient, power attenuation small, receiving electric material and straight anode reaction region has good physics binding face, significantly
Improve the collection efficiency of electronics；With good chemical property；It is with low cost, farthest improve anode-supported powder
Utilization rate, reduces the cost of raw material；Simple production process, strong operability, with good technology stability.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1：The preparation of anode support tube type solid oxide fuel cell and performance characterization
By the mixed powder (NiO and 8YSZ) of anode of fuel cell, PVA, triethanolamine, graphite composite powder according to mass ratio 100：
10：3：After 10 uniform mixing, pulp suspension is configured to pure water, its solid content is 60%；Utilize high-temperature spray comminutor pair
Anode powdery pulp carries out mist projection granulating, and spray dryer operating temperature is set to 180 DEG C, and pulp spraying speed is set to 20ml/min,
Modified anode mixture powder is obtained after granulation, its particle diameter distribution is tested at 1~10 μm through electronic scanner microscope；By anode
Pelletizing, which injects tubing die and filled, shakes rear isostatic pressing, and isostatic pressing machine is loaded onto with 10MPa/min compression rate
Pressurize 30 minutes after 200MPa, remove the pressure demoulding and produce tubular solid oxide fuel cell anode support base substrate；Base substrate
Muffle furnace is put into through 1000 DEG C of pre-burnings 2 hours, one end closing is obtained and the anode of solid oxide fuel cell of another end opening
Supporter, the thickness for measuring the anode support tube is 1200 μm.
Gained anode support coats one layer of ScSZ electrolyte slurry using dipping method, and Muffle furnace warp is put into after drying
1400 DEG C are incubated 3 hours, sinter the tubular type fuel cell half-cell of surface-brightening into；Then porous cathode material lanthanum-strontium manganese is impregnated
(La0.75Sr0.25)0.95MnO3(LSM), finally it is prepared into Tubular solid oxide fuel monocell.
Fig. 4 is the pictorial diagram of micro-tubular anode support tube type monocell manufactured in the present embodiment, it can be seen that party's legal system
Standby Microtubular cells have linearity good, and technology stability is good, are adapted to batch production；Fig. 5 is anode manufactured in the present embodiment
Support tubular type monocell section micro-structural scanning electron microscope (SEM) photograph, it can be seen that the sandwich construction on tubular cells through-thickness, from
Supporting anodes layer, dielectric substrate, cathode layer are followed successively by from left to right.
Electrochemical Characterization is carried out according to the general method of testing of tubular cells, the wherein receipts electric material of cathode side is silver
＆ platinum slurry is netted, anode-side is that test case is as shown in Figure 6 in NiO slurries and nickel felt, the stove of the anode support tube type battery；Test
Condition is 100sccm hydrogen and 200sccm air, is tested respectively under the conditions of 850 DEG C, 800 DEG C, 750 DEG C, chemical property is such as
Shown in Fig. 7, ac impedance spectroscopy is as shown in Figure 8；Then constant current mode is selected to investigate the stability of tubular cells at 750 DEG C,
Current density is set to 187mAcm-2, voltage changes with time as shown in Figure 9.
The test result of the present embodiment shows：Power output at 850,800,750 DEG C is respectively 225,200,
175mW·cm-2, ohmage is respectively 0.55,0.65,0.75 Ω cm2, the Ω cm of polarization impedance 3.50,3.65,2.752,
Good stability is remain under the conditions of long term constant current load, as a result illustrates the preparation work of the present embodiment anode support
Skill is effective.The tubular anode supporter stable preparation process and be easy to industrialization, the micro-pipe prepared using the inventive method
Formula battery can be used for portable power source system, and the large size tubular battery of preparation is applied to distributed generation system.
Embodiment 2：Extruding, dipping, isostatic pressing method prepare tubular anode support battery performance contrast by fuel electricity
The mixed powder (NiO and 8YSZ) of pond anode, PVA, triethanolamine, graphite composite powder are according to mass ratio 100：10：3：10 is uniform mixed
After conjunction, take etc. and to prepare tubular anode supporter in the way of extruding, dipping, isostatic pressed respectively after three parts of quality, that is, prepare
Extrusion forming after pug, prepares lifting impregnation drying after slurry and is molded, isostatic pressing (referring to embodiment 1) after mist projection granulating,
The size and thickness of anode-supported base substrate are adjusted by controlling extrusion die size, dipping time, isostatic tooling size, with
Make the size and consistency of thickness (three kinds of base substrates for taking size and consistency of thickness respectively) for the base substrate that three kinds of methods obtain, base substrate is put into
Muffle furnace obtained one end closing and the anode of solid oxide fuel cell of another end opening is supported through 1000 DEG C of pre-burnings 2 hours
Body, selection prepares the anode-supported base substrate that thickness is 800 μm or so and carries out subsequent contrast's experiment in aforementioned manners respectively.
One layer of ScSZ electrolyte slurry is respectively coated with dipping method for three kinds of anode supports of gained, and horse is put into after drying
Not stove is incubated 3 hours through 1400 DEG C, sinters the tubular type fuel cell half-cell of surface-brightening into；Then porous cathode is impregnated respectively
Material lanthanum-strontium manganese (La0.75Sr0.25)0.95MnO3(LSM), finally it is prepared into the tubular type fuel electricity of three kinds of different anode molding modes
Pond monocell.
Electrochemical Characterization, its Anodic are carried out to three kinds of tubular cells respectively according to tubular cells universal testing method
The receipts electric material of side is NiO slurries and nickel felt, and cathode side is silver net ＆ platinum slurries, and test condition is 100sccm hydrogen and 200sccm
Air, is tested under the conditions of 750 DEG C respectively, and chemical property contrast is as shown in Figure 10, and electrochemical alternate impedance spectrum is to such as scheming
Shown in 11.
Result of this example indicate that：Anode support tube type fuel prepared by isostatic pressed, extruding, impregnation technology molding mode
Battery, the power output at 750 DEG C is respectively 328,280,240mWcm-2, ohmage：0.55,0.70,0.8 Ω
cm2, tubular cells anode receive electricity be by insert the nickel foam in its pipe contacted with anode surface realize electric current conduction, ohm hinder
Resist and can be considered contact resistance after subtracting dielectric substrate Ohmic resistance, it is known that contact resistance is followed successively by from big to small：Dip forming,
Extrusion forming, mist projection granulating shaping.Because anode support shape retentivity prepared by dip forming is not good, prepared by extrusion forming
Anode support blank strength it is poor, and the bending strength of isostatic pressing base substrate prepared by the present invention is 0.3MPa or so,
The blank strength of dip forming and extrusion forming is poor, its intensity and at least poor magnitude of isostatic pressing blank strength, and
The good linearity of tubular cells and circularity prepared by the inventive method so that receiving electric nickel felt can be smoothly in insertion tube, it is ensured that
Nickel foam and the good contact of whole anode surface, contact is not good to cause larger contact resistance；Therefore, isostatic pressing compared with
Tubular type fuel cell prepared by extruding and dip forming technology receives electricity efficiently and chemical property is more excellent.
Embodiment 3：The performance comparison of anode support tube type solid oxide fuel cell will fire under different Content of Pore-forming Agents
Expect the mixed powder (NiO and 8YSZ) of galvanic anode, PVA, triethanolamine, graphite composite powder according to mass ratio 100：10：3：12 is equal
Even mixing, obtains anode mixture powder sample one, further according to mass ratio 100：10：3：8 uniform mixing, obtain anode mixture powder
Body sample two, is configured to the pulp suspension that solid content is 60% with pure water respectively；Using high-temperature spray comminutor respectively to sun
Pole powdery pulp carries out mist projection granulating, and spray dryer operating temperature is set to 180 DEG C, and pulp spraying speed is set to 25ml/min, point
Not Zao Li after obtain two kinds of modified anode mixture powders, testing its particle diameter through electronic scanner microscope is distributed in 1~10 μ
m；Anode pelletizing is injected separately into the tubing die of same size and filled and shakes rear isostatic pressing, isostatic pressing machine with
10MPa/min compression rate is loaded onto pressurize 30 minutes after 200MPa, removes the demoulding after pressure and produces pipe type solid oxide
Anode of fuel cell supporter base substrate；Two kinds of base substrate samples are put into Muffle furnace through 1000 DEG C of pre-burnings 2 hours, two kinds of solids are obtained
Anode of oxide fuel cell supporter, the thickness for testing its anode support tube is 1000 μm or so.
Gained anode support coats one layer of ScSZ electrolyte slurry with dipping method, and Muffle furnace warp is put into after drying
1400 DEG C are incubated 3 hours, sinter the tubular type fuel cell half-cell of surface-brightening into；Then porous cathode material lanthanum-strontium manganese is impregnated
(La0.75Sr0.25)0.95MnO3(LSM) two kinds of tubular solid oxide fuel cell monocells, are finally prepared into, i.e.,：Pore creating material
Mass ratio is 12% sample one, and pore creating material mass ratio is 8% sample two.
Electrochemical Characterization is carried out according to the general method of testing of tubular cells, two kinds of sample chemical properties are to such as
Shown in Figure 12, the contrast of ac impedance spectroscopy test result is as shown in figure 13.
Result of this example indicate that：Pore creating material mass ratio is 12% sample one and pore creating material mass ratio is 8% sample two
Power output be respectively 300 and 255mWcm-2, ohmage and polarization impedance are respectively：0.70,0.71 Ω cm2, Europe
Nurse resistance is substantially close to receiving that galvanic process is consistent is consistent with electrolyte preparation technology and test, polarization impedance is respectively：1.50,
1.70Ω·cm2, because pore creating material can produce hole after sintering process, increase Content of Pore-forming Agents is increase anode functional layer three-phase
Reaction interface area, the diffusion velocity and electrochemical reaction speed of lift gas, so higher Content of Pore-forming Agents is with smaller
Polarization impedance, have the beneficial effect that more preferable output performance, therefore the inventive method is the effective of tubular cells anode support
Forming method.
Claims (10)
1. a kind of preparation method of tubular solid oxide fuel cell anode support, it is characterised in that comprise the following steps：
Prepare the dispersed slurry for having an anode powder；
Gained slurry is subjected to mist projection granulating, modified anode powder is obtained；
By in modified anode powder injection tubing die, the stripping forming after isostatic pressed obtains formed body；
Gained formed body is sintered, soild oxide tubular type anode of fuel cell supporter is obtained.
2. preparation method according to claim 1, it is characterised in that the slurry includes：Anode powder, bonding agent, point
Powder and pore creating material, its proportioning are as follows：
Anode powder：100 mass parts；
Pore creating material：0~20 mass parts；
Bonding agent：1~10 mass parts；
Dispersant：1~5 mass parts.
3. preparation method according to claim 1 or 2, it is characterised in that the solvent of the slurry is water, the slurry
Solid content is 50%~60 wt%.
4. preparation method according to any one of claim 1 to 3, it is characterised in that the anode powder is NiO and yttrium
The mixed powder of the mixed powder or NiO of stable zirconium oxide and the zirconium oxide of scandium stabilization；
The pore creating material is wheat flour or graphite powder；
The binding agent is polyvinyl alcohol；
The dispersant is triethanolamine.
5. preparation method according to any one of claim 1 to 4, it is characterised in that the temperature of mist projection granulating is 0~
250 DEG C, preferably 120~180 DEG C.
6. preparation method according to any one of claim 1 to 5, it is characterised in that work used in the isostatic pressed
Make medium for hydraulic oil, pressure is 160~200MPa, the dwell time is 15~60 minutes.
7. preparation method according to any one of claim 1 to 6, it is characterised in that the temperature of the sintering is 800~
1000 DEG C, soaking time is 1~3 hour.
8. a kind of preparation method of tubular solid oxide fuel cell, it is characterised in that comprise the following steps：
Preparation method according to any one of claim 1 to 7 prepares the support of soild oxide tubular type anode of fuel cell
Body；
The anode support of gained is impregnated into electrolyte slurry, sintering obtains soild oxide tubular type fuel half-cell after drying；
By the half-cell impregnated cathode material of gained, sintering obtains soild oxide tubular type fuel cell after drying.
9. tubular solid oxide fuel cell prepared by a kind of preparation method according to any one of claim 1 to 7
Anode support.
10. a kind of tubular solid oxide fuel cell, it is characterised in that include successively from inside to outside：According to claim 9 institute
Tubular solid oxide fuel cell anode support, dielectric substrate and the cathode layer stated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710254609.5A CN107180978B (en) | 2017-04-18 | 2017-04-18 | Tubular solid oxide fuel cell anode support and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710254609.5A CN107180978B (en) | 2017-04-18 | 2017-04-18 | Tubular solid oxide fuel cell anode support and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107180978A true CN107180978A (en) | 2017-09-19 |
| CN107180978B CN107180978B (en) | 2020-05-19 |
Family
ID=59830894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710254609.5A Active CN107180978B (en) | 2017-04-18 | 2017-04-18 | Tubular solid oxide fuel cell anode support and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107180978B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655415A (en) * | 2018-06-28 | 2020-01-07 | 东莞信柏结构陶瓷股份有限公司 | Ceramic structural member and method for manufacturing same |
| CN112299841A (en) * | 2019-07-28 | 2021-02-02 | 苏州国绿新材料科技有限公司 | Electrode support body of energy conversion device and preparation method thereof |
| CN113270591A (en) * | 2021-05-13 | 2021-08-17 | 西安石油大学 | Preparation method of anode-supported SOFC electrolyte film |
| CN114204044A (en) * | 2020-09-17 | 2022-03-18 | 浙江氢邦科技有限公司 | Preparation method of supported anode in anode-supported solid oxide fuel cell with symmetrical structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101363560A (en) * | 2008-10-06 | 2009-02-11 | 山东华星环保集团有限公司 | Ceramic composite pipe for conveying flue gas desulfurization glue size in electric power plant and method for manufacturing same |
| CN101456741A (en) * | 2008-12-29 | 2009-06-17 | 陕西宝光陶瓷科技有限公司 | Process for preparing ceramic cartridge for super long type high voltage fuse |
| CN106207221A (en) * | 2016-08-11 | 2016-12-07 | 山西大学 | A kind of method preparing tubular solid oxide fuel cell |
-
2017
- 2017-04-18 CN CN201710254609.5A patent/CN107180978B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101363560A (en) * | 2008-10-06 | 2009-02-11 | 山东华星环保集团有限公司 | Ceramic composite pipe for conveying flue gas desulfurization glue size in electric power plant and method for manufacturing same |
| CN101456741A (en) * | 2008-12-29 | 2009-06-17 | 陕西宝光陶瓷科技有限公司 | Process for preparing ceramic cartridge for super long type high voltage fuse |
| CN106207221A (en) * | 2016-08-11 | 2016-12-07 | 山西大学 | A kind of method preparing tubular solid oxide fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| M. Á. LAGUNA-BERCERO等: "Long-Term Stability Studies of Anode-Supported Microtubular Solid Oxide Fuel Cells", 《FUEL CELLS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655415A (en) * | 2018-06-28 | 2020-01-07 | 东莞信柏结构陶瓷股份有限公司 | Ceramic structural member and method for manufacturing same |
| CN112299841A (en) * | 2019-07-28 | 2021-02-02 | 苏州国绿新材料科技有限公司 | Electrode support body of energy conversion device and preparation method thereof |
| CN114204044A (en) * | 2020-09-17 | 2022-03-18 | 浙江氢邦科技有限公司 | Preparation method of supported anode in anode-supported solid oxide fuel cell with symmetrical structure |
| CN113270591A (en) * | 2021-05-13 | 2021-08-17 | 西安石油大学 | Preparation method of anode-supported SOFC electrolyte film |
| CN113270591B (en) * | 2021-05-13 | 2022-05-06 | 西安石油大学 | Preparation method of anode-supported SOFC electrolyte film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107180978B (en) | 2020-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101306954B (en) | Method for preparing porous ceramic support | |
| CN107180978A (en) | A kind of tubular solid oxide fuel cell anode support and preparation method thereof | |
| CN1961443A (en) | Nickel foam and felt-based anode for solid oxide fuel cells | |
| CN103236548B (en) | Preparation method of multihole anode support of solid oxide fuel cell | |
| Panthi et al. | Tubular solid oxide fuel cells fabricated by a novel freeze casting method | |
| CN100448088C (en) | A making method for self-supported solid oxide fuel battery | |
| KR100622711B1 (en) | The anode of solid oxide fuel cell with networking structure and the preparing method of it | |
| CN103151548A (en) | Solid oxide fuel cell with Al2O3-YSZ electrolyte membrane and preparation method thereof | |
| JP5746309B2 (en) | Solid oxide fuel cell electrode paste, solid oxide fuel cell using the same, and method for producing the same | |
| EP2692003B1 (en) | Method for manufacture an electrode for a solid oxide fuel cell | |
| CN103319182B (en) | High-performance solid oxide electrolytic tank support | |
| CN116722189A (en) | Preparation method of anode-supported tubular proton conductor ceramic fuel cell | |
| CN101222050A (en) | Anti-carbon deposition anode film material and method for producing the same | |
| CN110137551A (en) | A kind of SOFC and preparation method thereof of three pole cofiring | |
| CN103493273A (en) | Method of preparing an electrochemical half-cell | |
| CN102503531A (en) | Method for preparing SOFC (Solid Oxide Fuel Cell) anode by adopting spherical and fibrous composite pore forming agent | |
| Pan et al. | Paper‐fibres used as a pore‐former for anode substrate of solid oxide fuel cell | |
| KR100660218B1 (en) | Fabrication method for anode of solid oxide fuel cell | |
| CN101847734B (en) | Method for preparing tubular solid oxide fuel cell | |
| CN101510612A (en) | Method for preparing stephanoporate anode support body using paper fabric a pore-forming agent | |
| CN103959525A (en) | Fuel electrode which also serves as supporting body of solid oxide fuel cell, and fuel electrode-supported solid oxide fuel cell | |
| CN100355137C (en) | Filtering coating preparing method of solid oxide electrolytic film | |
| CN206864552U (en) | For preparing the tubing die of tubular solid oxide fuel cell anode support | |
| CN102347493A (en) | Method for preparing panel SOFC (Solid Oxide Fuel Cell) anode by using natural fibre as pore-forming agent | |
| CN101420044B (en) | Method for preparing proton conductive film fuel cell by spin-coating process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |