CN104979575B - The porous inert of both ends open supports tubular solid oxide fuel cells, pile and preparation method thereof - Google Patents
The porous inert of both ends open supports tubular solid oxide fuel cells, pile and preparation method thereof Download PDFInfo
- Publication number
- CN104979575B CN104979575B CN201410136701.8A CN201410136701A CN104979575B CN 104979575 B CN104979575 B CN 104979575B CN 201410136701 A CN201410136701 A CN 201410136701A CN 104979575 B CN104979575 B CN 104979575B
- Authority
- CN
- China
- Prior art keywords
- battery
- porous inert
- support tube
- section
- inert support
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention supports tubular solid oxide fuel cells, pile and preparation method thereof for a kind of porous inert of both ends open.The battery include both ends open, it is interior have an electronic conduction connect but airtight partition porous inert support tube, its outer wall scribbles difference in functionality section：Inlet gas distance piece, Stringing cells section, section, battery terminal connections head is thermally isolated.Gas barrier section is used for air-isolation and fuel.Stringing cells section is a battery being connected in series successively.Be thermally isolated section by battery being conductively connected and be placed in outside high-temperature region externally.Battery terminal connections head provides battery external electric connection terminal.Battery of the present invention constitutes battery by battery terminal connections head and arranged, and battery row passes through further composition battery pile connected in series or in parallel.The cost of SOFC can be greatly lowered in the present invention, it is to avoid influence of the thermal expansion to battery, pile, reduce influence of the high temperature to being conductively connected, be easy to series connection and parallel connection between different batteries, it is easy to the assembling of battery pile.
Description
Technical field
The present invention relates to SOFC and its preparation that a kind of porous inert of both ends open supports cast
Method.The SOFC can apply to micro power, distributed power station and power plant, can reduce and be manufactured into
This, improves generating efficiency.
Background technology
SOFC（SOFC）It is that one kind uses soild oxide as electrolyte membrance, passes through electrochemistry
The TRT that the chemical energy of fuel efficiently, is cleanly converted into electric energy is reacted, its generating efficiency is up to more than 60%, thermoelectricity
Alliance can be imitated higher than 80%, be to reduce the novel power generation device of CO2 emission.SOFC not only can be with
Using hydrogen fuel, aboundresources and cheap natural gas, liquefied petroleum gas, fuel oil, the boil-off gas of matchmaker, city can also be used
City's coal gas and biogas etc. are used as fuel.
Different, the solid oxidation according to core component-membrane electrode of SOFC or the configuration of monocell
Thing fuel cell can be divided into tubular cells, planar cells and monoblock type battery.According to membrane electrode or battery supporter not
Together, SOFC can be divided into electrolyte-supporting type, cathode support type and anode support type.Different battery configurations
Battery build battery pile it is different with the modular construction that electric power station system is used, the mode of structure is also different, battery pile and power station
Structure it is also different.In various types of batteries, electrolyte-supporting cell development is more early, with Siemens of the U.S.-Xi Wugong
The cathode support tubular solid oxide fuel cells technology of department and the battery technology comparative maturity of electrolyte-supported, the two battery
Operating temperature all more than 900 DEG C, battery prepare cost it is higher, the manufacturing cost of electricity generation system is also higher.And anode
Support battery technology is that the operating temperature of its battery is reduced to 650-800 both at home and abroad in the last few years in the battery technology of research and development
DEG C, the preparation cost of battery can be reduced, but the cell sealing technical requirements of the type are higher.Monoblock type battery is because using
The more ceramic materials of function, structure is complex, and technology of preparing requires higher.
Monoblock type battery is to be prepared into the ceramic materials such as the anode of battery, anode, electrolyte and connector together, and
There are fuel gas or air duct portions, there is the electronics conduction pathway for connecting different batteries.Monoblock type SOFC
There is block-shaped, also there is cast.Whether block-shaped or tubular cells, different monoblock type batteries are because will in face of different application
Ask, its structure, material selection and preparation process are all different.The block that the Mitsubishi Heavy Industries Ltd as disclosed in United States Patent (USP) US06296963 report
The integral battery door of build, each battery is a section, and different batteries are connected together by ceramic joining body, form battery pile.Three
Water chestnut heavy industry uses the stable calcium oxide zirconium oxide support tube of porous, inert both ends open, and series connection is prepared in support pipe surface
Battery is connected, cast monoblock type battery is formd, support tube both ends open is characterized in, intermediate connection, fuel gas is from intermediate flow
Logical, electric current is connected by the two ends of cell tube and drawn.But high temperature is in due to being conductively connected, is conductively connected relatively difficult, is also compared
It is more difficult to safeguard.And for example, United States Patent (USP) US7,892,691 disclose a kind of concatenation cast battery structure of Luo Er-Roy Si company,
Using magnesium aluminate spinel support flat plate cell, the battery being connected in series be in interlude, different cell tubes by two ends with it is other
Cell tube is connected.The cell tube can reduce the preparation cost of battery using cheap raw material, but conductive different batteries
The gas supply connection request of connection and battery is higher, it has not been convenient to build battery pile.Chinese patent CN03114562.0 is disclosed
A kind of structure of tubular high temperature solid oxide fuel cell monocell, tubular high temperature solid oxide fuel cell list electricity
Pond is closed for one end, one end open, using cermet support tube, and one layer of ceramic insulation is provided with above cermet support tube
The multiple monocells member being mutually in series is dispersed with layer, ceramic insulating layer, each monocell member is one another in series by connecting pole, electricity
The external connection of pond pipe is arranged on anodic gas exit.On the one hand there is insulating barrier than relatively thin, metallic element diffusion in the battery
Easily cause the electric leakage in parallel of series-connected cell；On the other hand the battery structure needs wire that electric current is drawn out into low temperature from high-temperature region
Area.
In solid oxide fuel cell power generating system, not only the electrochemical reaction of battery is carried out at high temperature, fuel
Reforming reaction and the catalyst combustion reaction of tail gas also all carry out at high temperature, particularly exhaust combustion reaction can cause office
Portion's high temperature, material and part to periphery produce very big thermal shock, may result in the rupture of ceramic component, it is also possible to cause
Metal parts deformation and oxidation etc..The temperature of SOFC is high, and fuel exhaust gas needs to burn to reclaim heat energy,
The hair of raising system electrically and thermally efficiency of supply.Outlet such as fuel exhaust gas is bordered by combustion chamber, and its temperature is than battery operating temperature also
It is many higher, even up to more than 1000 DEG C sometimes.Power taking is connected from the fuel outlet position of cell tube, it is easy to cause metal to connect
Connecing the heating and cooling such as the oxidation of material, and the repeated priming of battery system and also arriving causes connecting portion to loosen, and electric conductivity becomes
Difference.In foregoing battery structure, the connection of the electric current of cell tube can influence the reliability of battery and steady all in high-temperature region
It is qualitative.
The matter of utmost importance of restriction SOFC development is the problem of cost is high at present.Next to that battery can
By sex chromosome mosaicism.Therefore, the structure design of SOFC and preparation should reduce cost, again improve battery can
By property.
The content of the invention
Electrochemical reaction, fuel reforming and exhaust combustion of SOFC etc. are all to carry out at high temperature
, cause battery system manufacturing cost higher, and some irrational battery structures can also cause the presence of battery reliability to be asked
Topic etc., they are all in restriction SOFC commercial application.How to design and prepare and be a kind of more rational
Battery structure, it is to avoid or reduce using expensive alloy material, manufacturing cost is reduced, reliability is improved, is solid oxidation
The major issue of thing fuel cell research and development.This patent is directed to this requirement, it is proposed that a kind of porous inert pipe branch of both ends open
The SOFC of support, pile and preparation method thereof.
The porous inert support tubular solid oxide fuel cells of a kind of both ends open, with a both ends open, pipe
There is the porous inert support tube of conductive communication but airtight partition, its outer wall scribbles different functional layers, be divided into inlet gas isolation
Section, Stringing cells section, section, battery terminal connections head is thermally isolated.Gas barrier section has airtight film layer, and Stringing cells section is by anode
The battery connected successively that layer, cathode layer, electrolyte membrane layer and connector layer are constituted, it is inside and outside in support tube that section, which is thermally isolated,
Wall scribbles electronic conductive layer, and battery terminal connections head is the external connection position of whole battery, including anode connection end and negative electrode
Connection end, the difference in functionality section is prepared on porous inert support tube by slurry dip-coating or slurry spraying method.
Porous inert support tube be both ends open, the pipe of one channel, pipe inherence Stringing cells section and be thermally isolated between section
Having on the middle closure of a conductive but airtight support tube, one end tube wall has one-point or multi-point to have the connection of electronic conduction ceramic material
Inside and outside conduction, the oxide material for densified sintering product.The material of porous inert support tube is aluminum oxide, stabilized with yttrium oxide oxidation
At least one of zirconium, stable calcium oxide zirconium oxide, spinelle, violet cyanines stone, corundum-mullite etc..Electronic conduction ceramic material is
The one or more of cermet, conductive perovskite composite oxides material, the composite wood constituted with porous inert tube material
Material.Porous inert support tube is one channel pipe, and pipe external diameter is 3-30mm, and length of tube is 63-2650mm, the hole of porous tube wall
Rate is 25-50%.
Inlet gas distance piece is located on the porous inert support tube of cell gas inlet side, has on the surface of support tube
One layer of high temperature resistant, airtight oxide membranes layer.Inlet gas isolation segment length is 10-200mm.The material of oxide membranes layer
For at least one of yttrium stable zirconium oxide, perovskite structural material, aluminum oxide, membrane layer is preferably and the same material of electrolyte
Material, now, oxide membranous layer can together be prepared with dielectric film, simplify preparation process.Gas barrier section main function be
Gas backmixing in pile is prevented, is easy to isolation fuel and air to appropriate area hybrid reaction, it is to avoid the high temperature of combustion reaction is straight
Connect impact battery.
The Stringing cells section is that one be made up of anode layer, cathode layer, electrolyte membrane layer and connector layer connects successively
Battery.Wherein, 15-100 μm of anode layer thickness, electrolyte membrane layer thickness is 5-50 μm, and cathode electrode layer thickness is 15-100 μm, even
Bulk layer thickness is connect for 20-100 μm.Electrolyte material in dielectric substrate is oxygen ion conductor oxide, be cerium oxide base oxygen from
It is a kind of in sub- conductor, zirconium oxide based oxygen ion conductor, lanthanum gallium based perovskite type oxide, the preferred 8-10mol% yittrium oxide of electrolyte
Stabilizing zirconia.Anode in anode layer is that the raw material of metal in metal-electrolyte composite anode, anode is transition metal
Oxide, or be the transition metal oxide of doping vario-property, the weight content of raw metal is 40-60%；Anode is preferably aoxidized
The composite anode that nickel-yttrium stable zirconium oxide is constituted.Negative electrode in cathode layer is perovskite composite oxide and electrolyte
The composite cathode of composition, the weight content of perovskite composite oxide is 40-60%, preferably manganous acid strontium lanthanum or sub- manganese
The composite cathode that sour calcium lanthanum is constituted with yttrium stable zirconium oxide.If cathode layer is on the outside of pipe, on the electrochemical layer of negative electrode,
There can also be one layer of porous pure perovskite material layer, for electric current collection and conduction, strengthen the electrical connection between different batteries.Even
Junctor material is at least one of lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide, and connector is used to isolate fuel
Gas and oxidant and series connected battery.Difference in functionality layer is arranged on porous tubular support in a certain order, is formed one and is saved
The battery being connected in series is saved, the length per batteries is that the joint number on 4-50mm, each battery saves for 10-50, Stringing cells section
Length be 40-2500mm.Wherein, anode layer thickness is 15-100 μm, and cathode electrode layer thickness is 15-100 μm, dielectric substrate thickness
For 5-50 μm, connection bulk layer thickness is 20-100 μm.
In Stringing cells section, what is directly contacted with an electrode on porous tubular support can be anode or negative electrode,
Therefore there are two kinds of structure batteries, be referred to as α battery and BEC beta electric cell.The anode of α battery is directly loaded in the support of porous inert
Guan Shang, negative electrode is on the outside of pipe, its structure such as Fig. 1（A）It is shown.The negative electrode of BEC beta electric cell is directly loaded in the support of porous inert
Guan Shang, anode is on the outside of pipe, its structure such as Fig. 1（B）It is shown.It is fuel cavity in the pipe of α battery, it is air chamber that pipe is outer.β electricity
It is air chamber in the pipe in pond, it is fuel cavity that pipe is outer.Meanwhile, it is conductively connected the material of coating also difference for extending.α battery
Anode cavities in current conducting layer can preferred Ni-YSZ coatings, the cathode current conducting shell of exposure air uses perovskite knot
Structure material, such as selects lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide at least one.In the cathode cavity of BEC beta electric cell
At least one such as current conducting layer lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide.
It is that the join domain of battery and metal is extended into low-temperature region that section, which is thermally isolated, to improve the reliability of battery connection
And stability.It is conductively connected to extend, section is thermally isolated and scribbles electronic conductive layer on the inside and outside wall of porous inert support tube,
One end of electronic conductive layer connects the electrode of battery, the other end connection corresponding electrode connecting end head of battery.A section electronics is thermally isolated
Conducting shell material is at least one of lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide.The length that section is thermally isolated is
10-300mm。
Battery terminal connections head is the external connection position of whole battery, including anode connection end and cathode connection terminal head,
It is connected in series or in parallel between different cell tubes for being carried out by metalwork.One battery terminal connections head passes through porous inert branch
Electronic conductive layer on stay tube outer wall or inwall connects the corresponding electrode tip of whole battery, and another battery terminal connections head leads to
The electronic conductive layer crossed on inwall connects another electrode tip of whole battery.The length of battery terminal connections head section is 3-
50mm。
Fig. 2 gives two kinds of tubular cells structures described in this patent：α battery and BEC beta electric cell；The Stringing cells section of α battery
Anode be directly loaded on porous inert support tube, negative electrode is on the outside of the pipe；The negative electrode of the Stringing cells section of BEC beta electric cell is direct
It is supported on porous inert support tube, anode is on the outside of pipe.α battery or BEC beta electric cell Stringing cells section with section is thermally isolated
Between there is an inside to cut off but electrically connect closure.
Such as Fig. 2（A）And Fig. 2（B）Shown, although α battery is different with BEC beta electric cell structure, the coating for preparing each functional layer is suitable
Sequence is different, but the two preparation process is similar, specifically includes following steps：
（1）The preparation of the porous inert support tube of both ends open：
After support tube raw material, organic binder bond, pore creating material and deionized water are mixed, prepared by extrusion or slip casting method
The porous inert support tube green compact of both ends open.Wherein, during organic binder bond is polyvinyl alcohol, methylcellulose, polyvinyl alcohol
At least one, pore creating material is at least one of starch, activated carbon, cellulose acetate.Use conductive but can be with the oxygen of densified sintering product
Compound material correct position in support tube green compact carries out closure green tube, is then punched in the correct position of tube wall, filling is led
Electrically connect material.Green tube is finally calcined into certain time at high temperature, the porous inert support tube of both ends open is obtained.Calcining
Temperature is 1100-1450 DEG C, and calcination time is 2-50h.
（2）The preparation of each functional section on porous inert support tube：
The material for constituting each functional section is added into organic binder bond, organic solvent functional layer slurry is made, according to each work(
Can section composition and its in the position of porous inert support tube, by spraying or dip-coating method sequentially on porous inert support tube
The slurry of corresponding function section is applied, is then calcined at high temperature, corresponding function section is obtained, is coated by multiple slurry and calcining is walked
Suddenly, obtain being supported on all functional sections on support tube.The organic binder bond added in slurries can increase coating material in pipe
Bond strength and thickness on wall, organic binder bond are at least one of polyvinyl alcohol, methylcellulose, polyvinyl alcohol；Pore-creating
Agent is at least one of starch, activated carbon, cellulose acetate；Organic solvent is ethanol, ethylene glycol, glycerine, isobutanol, third
At least one of ketone, butanone.Coating functional layer slurry method for optimizing is dip coating on support tube.Slurry thickness can be by adjusting
Become the concentration of slurry to control to obtain each time to soak coating layer thickness, parietal layer can also be increased by multiple dip-coating-drying process
Thickness.Inlet gas distance piece, section, the thickness control of battery terminal connections head section is thermally isolated between 2-100 microns, preferably controls
System is at 6~50 microns, 15-100 μm of Stringing cells section Anodic thickness, and Electrolyte film thickness is 5-50 μm, and cathode thickness is 15-
100 μm, connector film thickness is 20-100 μm.
The pile that a kind of porous inert support tubular solid oxide fuel cells of both ends open are built, passes through the moon first
The solid oxide fuel electricity that pole common electrical bonding ribbon and anode common electrical bonding ribbon support the porous inert pipe
Pond is connected in parallel to form cell tube row, then uses and connects different pipe rows in parallel or series to constitute pile.Into in cell tube
Gas introduced by metal or ceramic distribution pipe, the outer gas of cell tube is fed on battery by battery ligament.Into α knots
Gas in the porous inert support tube of the pile of structure battery introduced by fuel rail, into the pile of beta structure battery
Gas is introduced by air distribution in porous inert support tube, and the gas outside porous inert support tube is supported by porous inert
Ligament is supplied.
The present invention is for conventional batteries in afflux, gas distribution, intercell connection, high-temperature material selection, electricity generation system system
The problems such as causing high, it is proposed that a kind of concatenation solid oxide cell of porous inert pipe support, pile and preparation method thereof, it is main
There is following feature：（1）Use cheap inert material for support tube material, significantly reduce battery material cost；
（2）Using supporting tube structure, battery strength is improved, battery reliability is improved；（3）Battery is connected in series on support tube
Together, the output voltage of single battery is improved, the electric current of single battery is reduced, advantageously reduces current loss；（4）In battery
Devised in pipe and section is thermally isolated, prepared using the surfaces externally and internally of nonconducting porous tubular support and be conductively connected coating, by cell tube
Connection is placed in low-temperature space, and the electrical connection between cell tube is placed in into temperature lower region, high-temperature region is avoided, is conducive to connecting between battery
The stabilization connect, improves the reliability being conductively connected；（5）The electric current lead division of cell tube is placed in the another of gas feed
End, facilitates electrical connection, improves the reliability of connection, it is easy to the structure of battery pile；（6）In the inertia support tube of both ends open
Centre, design prepares a conductive communication but airtight closure, realizes electrics connection, but not make gas from another port stream
Go out；（7）The gas barrier section positioned at air inlet is devised, can prevent cathode air from mixing direct burning, side with anode fuel
Pile build.
Brief description of the drawings
Fig. 1 (A), the α battery structure of the concatenation solid oxide cell of the porous inert pipe support of both ends open planing surface
Schematic diagram；
Fig. 1 (B), the BEC beta electric cell structure of the concatenation solid oxide cell of the porous inert pipe support of both ends open planing surface
Schematic diagram；
Fig. 2 (A), 60 sections of the concatenation solid oxide cell of the porous inert pipe support of both ends open α structure batteries
Structural representation；
Fig. 2 (B), 60 sections of the concatenation solid oxide cell of the porous inert pipe support of both ends open beta structure battery
Structural representation；
The electric pile structure of Fig. 3, α structure battery；
Fig. 4, beta structure battery electric pile structure；
Wherein, 1- cathode layers；2- dielectric substrates；3- anode layers；4- porous inert support tubes；5- connectors layer；61- anodes
The current conducting layer of intracavitary；Current conducting layer in 62- cathode cavities；71- fuel cavities；72- air chambers；8- cathode connection terminal heads；
9- anode connection ends；Closure in the middle of 10- support tubes；11- inlet gas distance pieces；12- Stringing cells section；13- is thermally isolated
Section；14- battery terminal connections heads；15- single batteries；Cut off inside 16- but electrically connect closure；The connection end of 17- negative electrodes；18-
The connection end of anode；191- fuel rails；192- air distributions；The tubular cells of 201- α structures；202- beta structures
Tubular cells；The common electrical bonding ribbon of 21- negative electrodes；The common electrical bonding ribbon of 22- anodes.
Embodiment
Make further detailed and specific elaboration to the present invention below by embodiment.
Embodiment 1
After magnesium aluminate spinel, polyvinyl alcohol, starch and deionized water are mixed, two ends are prepared by extrusion or slip casting method
The green compact of porous inert support tube 4 of opening, the correct position addition strontium titanate lanthanum closure life in the green compact of porous inert support tube 4
Base, then punches in the correct position of tube wall, fills NiO-YSZ（Nickel protoxide-strontium doping lanthanum manganite）Conductive connecting material,
Finally green compact are calcined at 1450 DEG C 5h obtain both ends open, pipe in have electronic conduction connection but airtight partition porous magnesium
Aluminate support tube.Pipe external diameter is that 15mm, the porosity of tube wall are 42%.
The powder body material of each functional section is added into methylcellulose, ethylene glycol corresponding slurry is made, according to each functional section
Composition and its in the position of porous inert support tube 4, the corresponding slurry of dip-coating on the correct position of porous inert support tube 4,
Then corresponding function layer is obtained by high-temperature calcination, by the coating of multiple slurry and calcining step, obtains being supported on support tube
All functional sections.Wherein, the length of inlet gas distance piece 11 is 150mm, and surface coating 8mol% yttria-stabilized zirconias are caused
Close film.Stringing cells 12 length of section are 1200mm, and pond length of often economizing on electricity is 20mm, and 60 batteries are prepared for altogether.Anode is NiO-
YSZ（Nickel protoxide-strontium doping lanthanum manganite）, thickness is 45 μm, and electrolyte is 8mol% yttria-stabilized zirconias, and thickness is
20 μm, connector is strontium titanate lanthanum, and thickness is 25 μm, and negative electrode is LSM-YSZ（Strontium doping lanthanum manganite-stabilized with yttrium oxide oxidation
Zirconium）, electrochemical cathode conversion zone is 32 μm, 50 μm of the afflux conductive layer thickness of negative electrode.Segment length is thermally isolated for 200mm, support
Pipe outer wall bottom applies strontium titanate lanthanum, the sour lanthanum of outer layer coating cobalt.The length of battery terminal connections head is 50mm, wherein cathode connection terminal
Long 20mm, anode connection end long 20mm, midfeather 10mm.
Above-mentioned cell tube is assembled into 60 section α batteries, outer tube blowing air 10L min-1, pipe in be passed through hydrogen 800ml min-1, the electricity output performance tested at its 800 DEG C.At ambient pressure, when the output voltage of cell tube is 51V, output current is 1.2A,
Power output is 61.2W.
Embodiment 2
80, which are prepared, according to the methods described of embodiment 1 saves α battery.Wherein, porous inert support tube 4 is porous aluminum oxide
Pipe, pipe external diameter is that 10mm, the porosity of tube wall are 35%.The length of inlet gas distance piece 11 is 100mm, surface coating 8mol%
Yttria-stabilized zirconia dense film.Stringing cells 12 length of section are 1200mm, and pond length of often economizing on electricity is 15mm.Anode is NiO-
YSZ（Nickel protoxide-strontium doping lanthanum manganite）, thickness is 45 μm, and electrolyte is 8mol% yttria-stabilized zirconias, and thickness is
20 μm, connector is strontium titanate lanthanum, and thickness is 25 μm, and negative electrode is LSM-YSZ（Strontium doping lanthanum manganite-stabilized with yttrium oxide oxidation
Zirconium）, electrochemical cathode conversion zone is 32 μm, 50 μm of the afflux conductive layer thickness of negative electrode.The length of section 13 is thermally isolated for 200mm, it is many
The outer wall bottom of hole inertia support tube 4 applies strontium titanate lanthanum, the sour lanthanum of outer layer coating cobalt.The length of battery terminal connections head is 50mm, its
The middle long 20mm of cathode connection terminal head, anode connection end long 20mm, midfeather 10mm.
During battery testing, outer tube blowing air 12L min-1, inner tube is passed through hydrogen 1000ml min-1, test at its 800 DEG C
Electricity output performance.At ambient pressure, when the output voltage of cell tube is 64V, output current is 1.1A, and power output is 70.4W.
Embodiment 3
80, which are prepared, according to the methods described of embodiment 1 saves BEC beta electric cell.Wherein, porous inert support tube 4 is magnesium aluminate spinel pipe,
Pipe diameter is that 15mm, the porosity of tube wall are 42%.The length of inlet gas distance piece 11 is 100mm, surface coating 8mol% oxidations
Yttrium stable zirconium oxide dense film.Stringing cells 12 length of section are 1200mm, and pond length of often economizing on electricity is 15mm.Anode is NiO-YSZ
（Nickel protoxide-strontium doping lanthanum manganite）, thickness is 45 μm, and electrolyte is 8mol% yttria-stabilized zirconias, and thickness is 20 μ
M, connector is strontium titanate lanthanum, and thickness is 25 μm, and negative electrode is LSM-YSZ（Strontium doping lanthanum manganite-yttria-stabilized zirconia）,
Electrochemical cathode conversion zone is 32 μm, 50 μm of the afflux conductive layer thickness of negative electrode.The length of section 13 is thermally isolated for 200mm, it is porous lazy
Property support tube 4 outer wall bottom coating strontium titanate lanthanum, the sour lanthanum of outer layer coating cobalt.The length of battery terminal connections head is 50mm, wherein cloudy
The long 20mm of pole connection end, anode connection end long 20mm, midfeather 10mm.
During battery testing, inner tube blowing air 10L min-1, pipe is outer to be passed through hydrogen 800ml min-1, test at its 800 DEG C
Electricity output performance.At ambient pressure, when the output voltage of cell tube is 64V, output current is 0.72A, and power output is
46.1W。
Embodiment 4
The 80 section α batteries prepared with the methods described of embodiment 2, pass through negative electrode common electrical bonding ribbon and anode common electrical
5 80 section α batteries are connected in parallel to form cell tube row by bonding ribbon, are then used and are connected in parallel 10 cell tube rows with structure
Into pile.Introduced into the gas in cell tube by fuel rail, the outer gas of cell tube is fed to by battery ligament
On battery.
When pile is tested, outer tube blowing air 500L min-1, inner tube is passed through hydrogen 40L min-1, test at its 800 DEG C
Electricity output performance.At ambient pressure, pile power output is 3000W.
Claims (10)
1. the porous inert support tubular solid oxide fuel cells of a kind of both ends open, it is characterised in that including one two
There is the porous inert support tube (4) of electronic conduction connection but airtight partition in end opening, pipe；It is supported on the porous inert support
Guan Shangyou different functional sections successively：Inlet gas distance piece (11), Stringing cells section (12), be thermally isolated section (13), battery connect
Termination (14) is connect, the difference in functionality section is prepared in porous inert support tube (4) by slurry dip-coating or slurry spraying method
On；Pipe inherence Stringing cells section (12) and being thermally isolated have between section (13) a conductive but airtight support tube in the middle of block, one
There are one-point or multi-point to have the connection of electronic conduction ceramic material inside and outside conductive on end pipe wall；Use conductive but can be with the oxygen of densified sintering product
Compound material correct position in support tube green compact carries out closure green tube, is then punched in the correct position of tube wall, filling is led
Electrically connect material.
2. battery as claimed in claim 1, it is characterised in that：
The porous inert support tube (4) is the pipe of both ends open, one channel, and the external diameter of porous inert support tube is 3-
30mm, length is 63-2650mm, and the porosity of tube wall is 25-50%；The raw material of porous inert support tube is aluminum oxide, oxidation
At least one of yttrium stable zirconium oxide, stable calcium oxide zirconium oxide, spinelle, violet cyanines stone, corundum-mullite；Electronic conduction
Ceramic material is cermet, the one or more of conductive perovskite composite oxides material, with porous inert tube material group
Into composite.
3. battery as claimed in claim 1, it is characterised in that：
There are the middle closure (10) of a conductive and airtight support tube, porous inert support tube in porous inert support tube (4)
In the middle of closure (10) be located at Stringing cells section and (12) and be thermally isolated between section (13), the material of centre closure is by sintering cause
Close oxide material.
4. battery as claimed in claim 1, it is characterised in that：
The inlet gas distance piece (11) is located on the porous inert support tube of cell gas inlet side, inlet gas isolation
Segment length is 10-200mm, and inlet gas distance piece has an airtight membrane layer, membrane layer material be yttria-stabilized zirconia,
At least one of perovskite structure oxide, aluminum oxide.
5. battery as claimed in claim 1, it is characterised in that：
The Stringing cells section (12) is made up of anode layer (3), cathode layer (1), dielectric substrate (2) and connector layer (5)
One battery connected successively, the length per batteries is that battery number saves for 10-50 on 4-50mm, porous inert support tube, string
The length for connecing cell section is 40-2500mm；
Wherein, the electrolyte material in dielectric substrate is cerium oxide base oxygen ion conductor, zirconium oxide based oxygen ion conductor, lanthanum gallium base
One kind in perofskite type oxide；
Anode in anode layer is that raw metal is transition metal oxide in the composite anode of metal-electrolyte, anode,
Or be the transition metal oxide of doping vario-property, the weight content of raw metal is 40-60%；
Negative electrode in cathode layer is the composite cathode of perovskite composite oxide and electrolyte used, and Ca-Ti ore type is combined
The weight content of oxide is 40-60%, and connector material is in lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide
At least one；
Wherein, anode layer thickness is 15-100 μm, and cathode electrode layer thickness is 15-100 μm, and dielectric substrate thickness is 5-50 μm, connection
Bulk layer thickness is 20-100 μm.
6. battery as claimed in claim 1, it is characterised in that：
The section (13) that is thermally isolated scribbles electronic conductive layer, electronic conductive layer one end on the inside and outside wall of porous inert support tube
The electrode of battery is connected, the other end connects corresponding battery terminal connections head, the length that section is thermally isolated is 10-300mm, electronics conduction
Layer material is at least one of lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide.
7. battery as claimed in claim 1, it is characterised in that：
The battery terminal connections head includes anode connection end (18) and cathode connection terminal head (17), and battery terminal connections head passes through many
Electronic conductive layer in hole inertia support pipe outer wall or inwall connects the corresponding termination electrode of whole battery, battery terminal connections head
The length of section is 3-50mm.
8. battery as claimed in claim 1, it is characterised in that：
The SOFC includes the battery of 2 kinds of structures：α battery and BEC beta electric cell；
The anode of the Stringing cells section (12) of α battery is directly loaded on porous inert support tube, and negative electrode is on the outside of pipe；
The negative electrode of the Stringing cells section (12) of BEC beta electric cell is directly loaded on porous inert support tube, and anode is on the outside of pipe.
9. a kind of porous inert support Tubular solid for preparing a kind of both ends open as described in above-mentioned any one of claim 1-8
The method of oxide fuel cell, it is characterised in that specific steps include：
(1) preparation of the porous inert support tube of both ends open：By support tube raw material, organic binder bond, 3 pore creating materials and deionization
After water mixing, the porous inert support tube green compact of both ends open are prepared by extrusion or slip casting method, are added in support tube green compact
Plus the middle closure (10) of support tube, then punched on tube wall, conductive connecting material is filled, finally by green compact in 1100-
Calcined at 1450 DEG C, obtain the porous inert support tube of both ends open；
(2) on porous inert support tube each functional section preparation：The material for constituting each functional section is added into organic binder bond, it is organic
Functional layer slurry is made in solvent, according to the composition of each functional section and its in the position of porous inert support tube, by spraying or
Dip-coating method sequentially applies the slurry of corresponding function section, then calcines at high temperature, corresponding function section is obtained, by multiple slurry
Coating and calcining step, obtain being supported on all functional sections on porous inert support tube；Wherein, organic binder bond is polyethylene
At least one of alcohol, methylcellulose, polyvinyl alcohol；Pore creating material is at least one of starch, activated carbon, cellulose acetate；Have
Machine solvent is at least one of ethanol, ethylene glycol, glycerine, isobutanol, acetone, butanone.
10. a kind of pile, it supports Tubular solid oxide by a kind of porous inert of both ends open as claimed in claim 1
Fuel cell is built, it is characterised in that：Pass through negative electrode common electrical bonding ribbon (21) and anode common electrical bonding ribbon
(22) SOFC for being connected in parallel the support of porous inert pipe constitutes cell tube row, then different pipes rows it is in parallel or
It is connected in series composition pile；
Introduced into the gas in the porous inert support tube of the pile of α structure batteries by fuel rail (191), into β
Gas is introduced by air distribution (192) in the porous inert support tube of the pile of structure battery, outside porous inert support tube
Gas pass through porous inert support ligament supply.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410136701.8A CN104979575B (en) | 2014-04-04 | 2014-04-04 | The porous inert of both ends open supports tubular solid oxide fuel cells, pile and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410136701.8A CN104979575B (en) | 2014-04-04 | 2014-04-04 | The porous inert of both ends open supports tubular solid oxide fuel cells, pile and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104979575A CN104979575A (en) | 2015-10-14 |
| CN104979575B true CN104979575B (en) | 2017-09-26 |
Family
ID=54275866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410136701.8A Active CN104979575B (en) | 2014-04-04 | 2014-04-04 | The porous inert of both ends open supports tubular solid oxide fuel cells, pile and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104979575B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747578B (en) * | 2016-11-28 | 2019-08-27 | 佛山索弗克氢能源有限公司 | The preparation method and preparation facilities of SOFC anode-supported ceramic tube |
| CN108091915B (en) * | 2017-11-22 | 2020-09-01 | 江苏科技大学 | Sectional series tubular solid oxide fuel cell and preparation method thereof |
| CN108023096A (en) * | 2017-12-07 | 2018-05-11 | 北京理工大学 | The preparation method of solid oxide fuel cell densification double-layer ceramic connector |
| CN113745618B (en) * | 2021-08-28 | 2023-06-16 | 山东工业陶瓷研究设计院有限公司 | SOFC (solid oxide Fuel cell) and preparation method thereof |
| CN114914507A (en) * | 2022-05-26 | 2022-08-16 | 西安交通大学 | Conductive flat tube support type solid oxide fuel cell/electrolytic cell, preparation method thereof and cell stack structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845371A (en) * | 2006-03-21 | 2006-10-11 | 西安交通大学 | Structure of tubular high temperature solid oxide fuel cell single tube battery pack |
| CN101034753A (en) * | 2006-03-12 | 2007-09-12 | 中国科学技术大学 | Flat pole supporting solid oxide fuel battery |
| CN102013508A (en) * | 2009-09-04 | 2011-04-13 | 三星Sdi株式会社 | Combined cell structure for solid oxide fuel cell |
| CN103165924A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院大连化学物理研究所 | Fuel distribution pipe with functions of fuel gas reformation and waste gas combustion, and application |
| CN103296298A (en) * | 2013-05-22 | 2013-09-11 | 东方电气集团东方汽轮机有限公司 | Power generating unit of tubular solid oxide fuel cell, cell stack and assembling method of power generating unit |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004319152A (en) * | 2003-04-14 | 2004-11-11 | Nissan Motor Co Ltd | Cell body for tubular fuel cell and its manufacturing method |
| US7566509B2 (en) * | 2003-11-18 | 2009-07-28 | National Institute Of Advanced Industrial Science And Technology | Tubular fuel cell and method of producing the same |
| KR20130016140A (en) * | 2012-11-21 | 2013-02-14 | 주식회사 포스비 | Tube type solid oxide fuel cell stacks and their manufacturing methods |
-
2014
- 2014-04-04 CN CN201410136701.8A patent/CN104979575B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101034753A (en) * | 2006-03-12 | 2007-09-12 | 中国科学技术大学 | Flat pole supporting solid oxide fuel battery |
| CN1845371A (en) * | 2006-03-21 | 2006-10-11 | 西安交通大学 | Structure of tubular high temperature solid oxide fuel cell single tube battery pack |
| CN102013508A (en) * | 2009-09-04 | 2011-04-13 | 三星Sdi株式会社 | Combined cell structure for solid oxide fuel cell |
| CN103165924A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院大连化学物理研究所 | Fuel distribution pipe with functions of fuel gas reformation and waste gas combustion, and application |
| CN103296298A (en) * | 2013-05-22 | 2013-09-11 | 东方电气集团东方汽轮机有限公司 | Power generating unit of tubular solid oxide fuel cell, cell stack and assembling method of power generating unit |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104979575A (en) | 2015-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4771261B2 (en) | Electrochemical reactor bundle, stack and electrochemical reaction system composed of them | |
| US20070224481A1 (en) | Manifold and stack of electrochemical reactor cells, and electrochemical reactor system composed of these components | |
| JP5498510B2 (en) | Thermal shock resistant solid oxide fuel cell stack | |
| US8642229B2 (en) | Electrochemical reactor units and modules and systems composed of them | |
| CN104979575B (en) | The porous inert of both ends open supports tubular solid oxide fuel cells, pile and preparation method thereof | |
| WO2007005767A1 (en) | Advanced solid oxide fuel cell stack design for power generation | |
| JP2002289249A (en) | Stack structural body for solid electrolytic fuel cell | |
| JP4686123B2 (en) | Solid oxide fuel cell submodule and solid oxide fuel cell module using the same | |
| JP5105392B2 (en) | Electrochemical reactor tube cell and electrochemical reaction system comprising them | |
| JP4111325B2 (en) | Solid oxide fuel cell | |
| JP5674035B2 (en) | Medium / low temperature high efficiency electrochemical cell and electrochemical reaction system composed of them | |
| JP5126704B2 (en) | Electrochemical reactor stack and electrochemical reaction system comprising the same | |
| KR101186537B1 (en) | Micro cylindrical solid oxide fuel cell stack and solid oxide fuel cell power generation system comprising the same | |
| JP5560511B2 (en) | Electrochemical reactor | |
| JP2011096617A (en) | Tube type electrochemical cell with added catalyst layer and electrochemical reaction system composed of the above | |
| JP5935220B2 (en) | Electrochemical reactor cell | |
| JP5483013B2 (en) | Flat tube electrochemical cell and electrochemical reaction system | |
| JP4817230B2 (en) | Electrochemical microcoil reactor and electrochemical reaction system comprising the same | |
| JPH10189024A (en) | Solid electrolyte fuel cell having honeycomb monolithic structure | |
| JPH11297342A (en) | Solid electrolyte type fuel cell of honeycomb integrated structure | |
| JP5916013B2 (en) | Multi-stage electrochemical reactor | |
| JP2013105721A (en) | Fuel passage resident electrochemical cell and electrochemical cell module and electrochemical reaction system using the same | |
| CN103155256B (en) | Solid oxide fuel cell | |
| JP5196216B2 (en) | Electrochemical reactor | |
| KR20150116562A (en) | Manufacturing method of a tubular metal supported solid oxide fuel cell |
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 |