CN110534781A - The direct carbon solid oxide fuel cell group of townhouse structure tubular type that can be recycled - Google Patents
The direct carbon solid oxide fuel cell group of townhouse structure tubular type that can be recycled Download PDFInfo
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- CN110534781A CN110534781A CN201910749430.6A CN201910749430A CN110534781A CN 110534781 A CN110534781 A CN 110534781A CN 201910749430 A CN201910749430 A CN 201910749430A CN 110534781 A CN110534781 A CN 110534781A
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- monocell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
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- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses the direct carbon solid oxide fuel cell groups of townhouse structure tubular type that can be recycled；The battery pack is serially connected by a series of tubular type monocells and is formed, and tubular type monocell is the electrolyte-supporting type of end opening closed at one end and another, and inner wall covers anode film, and carbon fuel is contained in tubular cells, and open end is sealed by a movable plug；The mode of multiple tubular type cells in series closed at one end is that two neighboring tubular type monocell is arranged side by side, and is connected by multiple connecting holes with conductive material；Cathode membrane part covers the external area of electrolytic tube, in electrolytic tube supporter open end periphery and connecting hole periphery not covered cathode film；Conductive material is arranged in connecting hole, the connecting hole on the anode film between connecting hole and on the outside of monocell and between the cathodic coating of adjacent tubular type monocell.Battery pack of the present invention have many advantages, such as structure it is simple, without sealant, can Reusability, high conversion efficiency, be particularly suitable for movement or backup power source application.
Description
Technical field
The present invention relates to fuel cells to be specifically related to one kind more particularly to a kind of solid oxide fuel cell stack
The direct carbon solid oxide fuel cell group recycled being serially connected in the form of townhouse by multiple tubular type monocells.
Background technique
As the improvement of people's living standards, the demand to the power supply of high-energy density is growing, and traditional energy storage
Battery cannot fully meet demand, and therefore, more and more research interests go to the fuel cell with high-energy density.
Fuel cell is the device that a kind of chemical energy by fuel is directly changed into electric energy by electrochemical reaction.Because whole
A process is not limited by Carnot cycle, with very high energy conversion efficiency.Its theoretical efficiency is the Ji Bu in fuel
This free energy ΔfChemical energy (enthalpy) Δ that G and fuel are containedfThe ratio between H.Because process is not necessarily to the combustion reaction of high temperature and pressure, and fire
Expect that gas and oxygen are separated by electrolyte at the two poles of the earth of battery always, the discharge amount of pollutant greatly reduces.Therefore, fuel cell
Technology is a kind of energy conversion technique of high-efficiency cleaning.
Compared to other fuel cells, solid oxide fuel cell has many advantages, such as, is considered to have most wide answer
With prospect: (1) the problems such as using structure of whole solid state, capable of effectively avoiding the burn into sealing-in of liquid or molten salt electrolyte；(2) In
Medium and high temperatureIt works, is not necessarily to noble metal catalyst, and current density with higher and power density.
(3) since the carrier in electrolyte is oxonium ion, so in addition to the hydrogen, synthesis gas and various hydro carbons, alcohol also can be used directly
The hydrocarbons such as class work as fuel, have extremely strong fuel tolerance；(4) the high quality waste heat generated when running
Cogeneration can be achieved, be conducive to improve fuel availability and integral energy transfer efficiency；(5) it is easy to modularized design, is applicable in
Range is wide, can be according to actual use demand flexible design, assembling.
And directly carbon solid oxide fuel cell (DC-SOFC) is the SOFC directly using solid carbon for fuel, reason
By generating efficiency ΔfG/ΔfH even slightly above 100% (Second Law Efficiency of Thermodynamics), carbon fuel have be easy to get extensively, energy
The advantages that density is high, safety is good, therefore the DC-SOFC of structure of whole solid state is expected to obtain in portable or distributed electrical source domain
It is widely applied.
In practical applications, often lead to obtain higher voltage or electric current output, solid oxide fuel cell monomer
The mode for crossing serial or parallel connection is assembled into battery pack.Currently, typical battery pack structure design includes flat and tubular type.Plate
Formula solid oxide fuel cell has relatively high energy density, flexible structure, preparation process simple, and assembles respectively, transports
The advantages of row quality is easy to control.Compared with flat solid oxide fuel cell, tubular cells have preferably mechanical
With thermal stability, simple sealing technique, quick start ability and good thermal-shock resistance and thermal cycling capability.
There are three types of the designs of common tubular solid oxide fuel cell group, including electrode supporting long tube type, based on more
The band-like series type of full membranization and casing series type of hole tubular type supporter.These three typical tubular solid oxide fuel cells
Group design, respectively there is advantage and disadvantage and the scope of application.The batteries monomer length of electrode supporting long tube type is very long, generally 0.5-
2.2m is suitable for large-scale power station.And the design of the complete band-like concatenation type of membranization and casing concatenation type battery pack, it applies in general to small-sized
Pile and mobile power source.For electrode supporting long tube type and the band-like concatenation type battery pack of full membranization, electrolyte must be film, by
It is higher in the sintering temperature of the SOFC electrolyte (such as yttria-stabilized zirconia, YSZ) generallyd use, and dielectric film must
Must be with porous supporting body co-sintering, this just seriously limits the selection of porous supporting body material, while excessively high sintering temperature
Also decline the performance of electrode support.And for casing concatenation type battery pack, since seal line compares between the battery that is related to
Long, battery pack quality is more difficult to control.Electrolyte-supporting type tubular type SOFC battery, which has, prepares easy, electrode material range of choice
The advantages that wide, battery performance is stablized, but for long tube type electrolyte-supporting type SOFC, there are no good series systems for making
The standby portable battery pack for meeting practical application.
Currently, Chinese invention patent CN200910192848.8 is the direct carbon solid oxide fuel cell (DC- of representative
SOFC) also in the laboratory research stage, prepared tubular cells open at one end need to use sealant by small-bore
Gas-guide tube sealing-in is smoothly discharged in the open end of cell tube, the gas for enabling cell reaction to generate, meanwhile, prevent air to electricity
It is spread in pond, but after the carbon fuel consumption in battery, new carbon fuel can not be added from the gas port of small-bore, because
This, this mode in practical applications, will be caused using DC-SOFC as using carbon and air as the one-shot battery of active material
The consequences such as the at high cost, wasting of resources.Meanwhile being unfavorable for the assembling of battery pack using gas-guide tube sealing-in, it is limited in portable electric
The application in source.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, proposes the opening of a kind of plug and electrolytic tube supporter
End is flexibly connected, and realizes the tubular type electrolyte-supporting type of the townhouse structure recycled for being refilled by and utilizing of carbon fuel
Direct carbon solid oxide fuel cell group.
The anode of one tubular type monocell is passed through the yin of connecting hole and another battery using connecting material by the present invention
Pole connects, and realizes the series connection of two batteries, connects multiple batteries in this way, obtains the concatenated battery of multiple batteries
Group；Size, electrode area and the monomer series-connected number of battery cell can flexible designs according to actual needs.
Cathodic coating cannot contact the conductive material on itself connecting hole and connecting hole, while can not contact electrolytic tube branch
The open end of support body, to avoid short circuit；Carbon fuel is placed in the inside of tubular type monocell；In the open end of tubular type monocell using resistance to
The plug of high temperature blocks carbon fuel, and plug causes certain vapour lock to the anode reaction of battery, makes to react efficient progress；
Due to direct carbon solid oxide fuel cell running when, anode cavities happens is that CO electrochemical oxidation reactions with
And the Boudouard reaction of carbon surface, reaction process is the process that pressure increases, and compared with the external world, anode cavities are in always
The environment of one positive pressure.DC-SOFC cannot be fully sealed, and the excessive gas that anode cavities generate need to constantly be discharged.In middle promulgated by the State Council
In the DC-SOFC research of bright patent CN200910192848.8, using sealant by the gas-guide tube sealing-in of cell tube and small-bore
Get up, the excessive gas that cell reaction can be made to generate is discharged from gas-guide tube, while preventing extraneous air from spreading into battery.If
Removable plug is designed in battery nozzle, anode cavities excessive gas can be discharged from the gap of plug and battery nozzle, while extraneous
Air can due to anode cavities always existing positive pressure environment and be difficult to enter anode cavities consumption carbon fuel, and the design of plug
Conducive to the replacement of carbon fuel, to realize recycling for DC-SOFC.
The purpose of the present invention is realized especially by following technical solution:
The townhouse concatenation direct carbon solid oxide fuel cell group of tubular type that can be recycled, by multiple pipes closed at one end
Formula cells in series composition；The tubular type monocell is electrolyte-supporting type monocell, and tubular type monocell includes electrolytic tube, sun
Pole film, cathodic coating, connecting hole, carbon fuel and plug；Electrolytic tube supporter is long tubular structure closed at one end, electrolytic tube
The tubular inner wall of supporter is equipped with anode film, and outer wall is equipped with cathodic coating；The anode film of battery all covers the inside of electrolytic tube
Area, cathode membrane part cover the external area of electrolytic tube, and carbon fuel is placed in the anode cavities of electrolytic tube supporter；In electricity
The open end of Xie Zhiguan supporter is equipped with plug；
The plug is flexibly connected with the open end of electrolytic tube supporter；The side wall of tubular type monocell is along pipe range direction
There is row's connecting hole；The mode of multiple tubular type cells in series closed at one end be two neighboring tubular type monocell side by side
Setting, is connected by multiple connecting holes with conductive material；Cathode membrane part covers the external area of electrolytic tube, in electrolytic tube
Supporter open end periphery and connecting hole periphery not covered cathode film；Conductive material is arranged in connecting hole, between connecting hole
Anode film on and monocell on the outside of connecting hole and adjacent tubular type monocell cathodic coating between.
To further realize the object of the invention, it is preferable that the diameter of the connecting hole is 0.1-2mm, between connecting hole
Away from for 2-10mm.
Preferably, the conductive material is DAD-87 silver conductive adhesive.
Preferably, the plug is made of fire-resistant oxidation resistant material.
Preferably, the fire-resistant oxidation resistant material is quartz or ceramic material.
Preferably, the material of the electrolytic tube supporter is the zirconium oxide of stabillzed with yttrium, using slip casting or
Infusion process preparation, In3-4h is sintered in lower air to be formed.
Preferably, the material of the anode film and cathodic coating is the composite material that gadolinium or samarium stabilize cerium oxide and silver powder,
Organic binder is added, is prepared into electrode slurry, wherein silver powder accounts for the 45%-60% of electrode slurry quality；The organic adhesive
Agent is made of polyvinyl butyral and terpinol mixing；Electrode slurry is brushed to the inner and outer wall in electrolytic tube respectively,
InIt is sintered 2-4h in lower air, electrode film is made.
Preferably, the carbon fuel includes solid carbon and Boudouard catalysts；The solid carbon is graphite
Powder, activated carbon, coke, carbon black or charcoal；The Boudouard catalysts are Fe, Co, Ni or Cu；Boudouard is anti-
Catalyst is answered to account for the 2%-20% of quality；When preparation, the oxide of Fe, Co, Ni or Cu and solid carbon are sufficiently mixed, added
The ethanol solution of polyvinyl butyral, which is fully ground, to be granulated, and obtains carbon powder and Boudouard catalytic reaction after dry
The mixture of agent.
Preferably, the difference of the internal diameter of the outer diameter of the plug and tubular cells open end is 0.01-
0.5mm。
Preferably, the number of the tubular type monocell is 3-20.
Preferably, the difference of the internal diameter of the outer diameter of the plug and tubular cells open end is 0.01-
0.5mm。
Anode film of the present invention all covers the internal area of electrolytic tube, and cathode membrane part covers the exterior face of electrolytic tube
Product, cathodic coating cannot contact the conductive material on itself connecting hole and connecting hole, while can not contact the opening of electrolytic tube
End, to avoid short circuit；Carbon fuel is placed in the inside of tubular type monocell；Plug resistant to high temperature is used in the open end of tubular type monocell
Carbon fuel is blocked, plug causes certain vapour lock to the anode reaction of battery, improves the output performance of battery.
Battery pack is to realize that multiple being serially connected for tubular type monocell obtain by connecting hole using conductive material, specifically
Experimental method is: conductive material being prepared into slurry, is carried out with slurry to connecting hole on anode film and on the outside of electrolytic tube
It brushes, slurry is seeped into connecting hole, meanwhile, slurry cannot contact the cathodic coating of the monocell, when slurry is not dry by single electricity
The connecting hole in pond is bonded together with the cathodic coating of another battery, the series connection of two batteries is achieved that after dry, in this way
Mode obtain the concatenated battery pack of multiple batteries.Conductive material seals connecting hole, while shortening long tube type battery electricity
Lotus transmission path realizes charge-trapping.The battery pack is heated in air, so that it may which power output needed for obtaining, carbon fuel disappear
After consumption, fresh carbon fuel is refilled in tubular cells, enables battery pack by the plug of openable tubular cells open end
It continues to run.
Compared with the existing technology, the present invention has a characteristic that
(1) present invention is ingenious is utilized in electrolytic tube anode cavities in battery pack operational process always in positive pressure ring
Border is blocked by designing moveable high temperature resistant plug, and avoids for plug being fixed on electrolytic tube open end, Ke Yi
Facilitate addition carbon fuel in, greatly solving prior art Chinese invention patent CN200910192848.8 can not increase newly
Carbon fuel, lead at high cost, the wasting of resources the technical problem, seem simple, but solve the long-standing problem prior art really
The problem of personnel, breakthrough, which carrys out such tubular cells, to have high practical value in the obstacle of the application of portable power,
It realizes that carbon fuel can be replaced at any time, realizes recycling for battery pack, greatly reduce cost.
(2) present invention designs row's connecting hole along pipe range direction by the side wall in electrolytic tube, realizes adjacent cell list
The electrical connection of body, can design series connection number according to actual needs, and key is that cathodic coating cannot contact itself connecting hole and connection
Conductive material on hole, while the open end of electrolytic tube can not be contacted, the townhouse structure tubular type that can be recycled is direct
The design of carbon solid oxide fuel cell group is simple, and preparation cost is low.
(3) size of electrolyte-supported pipe of the present invention, electrode area can flexible design according to actual needs, convenient for design
The direct carbon solid oxide fuel cell group of townhouse structure tubular type of different size recycled.
Detailed description of the invention
Fig. 1 is the side sectional view of present invention tubular type monocell closed at one end.
Fig. 2 is the left view of present invention tubular type monocell closed at one end.
Fig. 3 is the front view of present invention tubular type monocell closed at one end.
Fig. 4 is the rearview of present invention tubular type monocell closed at one end.
Fig. 5 be three tubular type single battery groups at the direct carbon solid oxide fuel of townhouse structure tubular type recycled
The side sectional view of battery pack.
Fig. 6 is the top view for the direct carbon solid oxide fuel cell group of townhouse structure tubular type that Fig. 5 can be recycled.
Fig. 7 is the single tubular solid oxide fuel cell of embodiment 1 using activated carbon as the output characteristics of fuel.
Fig. 8 is the direct carbon solid oxygen of townhouse structure tubular type recycled of 2 three tubular type cells in series of embodiment
Compound fuel cell unit is using activated carbon as the output characteristics of fuel.
Fig. 9 is the direct carbon solid oxygen of townhouse structure tubular type recycled of 3 six tubular type cells in series of embodiment
Compound fuel cell unit is using activated carbon as the output characteristics of fuel.
Figure 10 is that the single tubular solid oxide fuel cell of embodiment 4 carries out constant current twice by fuel of activated carbon and puts
The performance of electricity compares.
It is shown in figure: plug 1, electrolytic tube supporter 2, cathodic coating 3, anode film 4, connecting hole 5, carbon fuel 6, connection material
Material 7.
Specific embodiment
The present invention is further described below with reference to examples and drawings, but the scope of protection of present invention is not
It is confined to the range of embodiment expression.
As shown in figures 1 to 6, the direct carbon solid oxide fuel cell group of townhouse structure tubular type that can be recycled, by multiple
Tubular type cells in series composition closed at one end；Tubular type monocell is electrolyte-supporting type monocell, and tubular type monocell includes plug
Son 1, electrolytic tube supporter 2, cathodic coating 3, anode film 4, connecting hole 5, carbon fuel 6 and connecting material 7；Electrolytic tube supporter
2 be long tubular structure closed at one end, and the tubular inner wall of electrolytic tube supporter 2 is equipped with anode film 4, and outer wall is equipped with cathodic coating 3；
Anode film 4 and the mutual all standing of 2 inner wall of electrolytic tube supporter, 3 part of cathodic coating covers the outer wall of electrolytic tube 2, first is that such as
Shown in Fig. 5 and Fig. 6, it is not provided with cathodic coating 3 in the longitudinal direction of 2 right part of electrolytic tube supporter, especially setting connecting hole 5,
Either 5 periphery of connecting hole is not provided with cathodic coating 3；Second is that not set such as Fig. 1-5 in the periphery of 2 opening of electrolytic tube supporter
Set cathodic coating 3；Cathodic coating 3 cannot contact the conductive material 7 on itself connecting hole 5 and connecting hole 5, while can not contact electricity
The open end of Xie Zhiguan supporter 2, to avoid short circuit；Carbon fuel 6 is placed in the anode cavities of electrolytic tube supporter 2；It is being electrolysed
The open end of matter pipe supporter 2 is equipped with plug 1, and plug 1 is flexibly connected with the open end of electrolytic tube supporter 2；The pipe
The mode of formula cells in series is that two neighboring tubular type monocell is arranged side by side, and is connected by multiple connecting holes 5 and conductive material 7
It connects；Conductive material 7 is arranged in connecting hole 5, the connecting hole 5 on the anode film 4 between connecting hole 5 and on the outside of monocell with
Between the cathodic coating 3 of adjacent tubular type monocell；Conductive material 7 passes through electrolyte-supported body 2 for itself tubular type list by connecting hole 5
The anode film 4 of battery is connect with the cathodic coating 3 of adjacent tubular type monocell, to realize series connection；Preferred conductive material 7 is DAD-87
Silver conductive adhesive；It is preferred that the diameter of connecting hole 5 is 0.1-2mm, the spacing of connecting hole 5 is 2-10mm；It is preferred that the outer diameter of plug 1
And the difference of the internal diameter of tubular cells open end is 0.01-0.5mm.
Each tubular type monocell is complete battery unit, that is, possesses independent anode film 4, electrolytic tube supporter
2, cathodic coating 3, connecting hole 5, carbon fuel 6, the conductive material 7 between battery can pass through the connecting hole 5 on electrolytic tube supporter 2
The anode film 4 of tubular type monocell and the cathodic coating 3 of adjacent tubular type monocell are connected, fuel gas occurs on anode film 4
Electrochemical reaction loses electronics, and electronics is transmitted on the cathodic coating 3 of adjacent tubular type monocell by conductive material 7, and oxygen is at this
It obtains being electronically generated oxonium ion on cathodic coating 3, oxonium ion is then passed through electrolytic tube supporter 2, anode film 4 is reached, with fuel gas
In conjunction with so transmitting of realization electricity.
The plug 1 is made of fire-resistant oxidation resistant material, and fire-resistant oxidation resistant material is preferably quartz or ceramic material.
Carbon fuel 6 is blocked using plug 1 resistant to high temperature in the open end of electrolytic tube supporter 2, anode reaction of the plug 1 to battery
Certain vapour lock is caused, the output performance of battery is improved.After carbon fuel 6 consumes, the plug 1 of openable tubular cells open end,
Fresh carbon fuel 6 is refilled in tubular cells, battery pack is made to can continue to run.
The material of the electrolytic tube supporter 2 is the zirconium oxide of stabillzed with yttrium, using slip casting or dipping legal system
It is standby, In3-4h is sintered in lower air to be formed；
Preferably, the material of the anode film and cathodic coating is the composite material that gadolinium or samarium stabilize cerium oxide and silver powder,
Organic binder is added, is prepared into electrode slurry, wherein silver powder accounts for the 45%-60% of electrode slurry quality；The organic adhesive
Agent is made of polyvinyl butyral and terpinol mixing；Electrode slurry is brushed to the inner and outer wall in electrolytic tube respectively,
InIt is sintered 2-4h in lower air, electrode film is made.
Preferably, the carbon fuel includes solid carbon and Boudouard catalysts；The solid carbon is graphite
Powder, activated carbon, coke, carbon black or charcoal；The Boudouard catalysts are Fe, Co, Ni or Cu；Boudouard is anti-
Catalyst is answered to account for the 2%-20% of quality；When preparation, the oxide of Fe, Co, Ni or Cu and solid carbon are sufficiently mixed, added
The ethanol solution of polyvinyl butyral, which is fully ground, to be granulated, and obtains carbon powder and Boudouard catalytic reaction after dry
The mixture of agent.
Embodiment 1
The preparation of electrolytic tube is carried out using infusion process.Infusion process includes dipping, lifting, dry, demoulding four basic steps
Suddenly.Firstly, preparing the uniform and stable electrolyte slurry of YSZ by way of ball milling, raw material contains 25g YSZ powder, the poly- second of 2g
Enol butyral (PVB), 0.8g triethanolamine (TEA), 0.8g polyethylene glycol (PEG-600), 0.8g dioctyl phthalate
(DOP), 38g dehydrated alcohol.Ball grinder is put into planetary ball mill, with the revolving speed ball milling 3h of 500r/min, must be uniformly dispersed
Electrolyte slurry.Then, the test tube mold with uniform paraffin layer is placed in slurry and carries out duplicate Best-Effort request process,
To obtain the green compact of electrolytic tube supporter 2, the length of green compact is 13.5cm, in the side of the green compact of electrolytic tube supporter 2
Wall equally spacedly makes a call to a round along pipe range direction, and the number of connecting hole 5 is 8, diameter 1.5mm, spacing 1.5cm.Gained
The green compact of electrolytic tube supporter 2 are sintered 4h in air at 1450 DEG C, finally obtain the electrolytic tube branch with ceramic structure
Support body 2.The length of gained electrolytic tube supporter 2 is 9.5cm, diameter 1.1cm, with a thickness of 0.2mm, the connecting hole 5 of side wall
Quantity be 8, diameter 1mm, spacing 1cm.
Prepare electrode film.The PVB and terpinol that mass ratio is 1:9 are weighed, is placed in a beaker, is dissolved in 60 DEG C of baking ovens
It is stand-by as binder for 24 hours.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 7.25g silver paste (DAD-87,
80%) and 2.5g GDC (after ball milling) SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS, amount containing Ag are, then to weigh 9.75g PVB- terpinol
Binder is added in agate mortar and grinds 4h, obtains uniform, good fluidity Ag-GDC combination electrode slurry.As Fig. 1-6 institute
Show, Ag-GDC slurry is painted on to the inside and outside wall of the electrolytic tube supporter 2 of tubular type using brushing method.Anode film 4 and electrolyte
The mutual all standing of 2 inner wall of pipe supporter, 3 part of cathodic coating cover the outer wall of electrolytic tube 2, and cathodic coating 3 cannot contact itself and connect
Hole is connect, while the open end of electrolytic tube supporter 2 can not be contacted, to avoid short circuit.It is dried in 140 DEG C of high temperature ovens.
So repeat 4 times.It is then placed in Muffle furnace, is sintered 2h in air at 880 DEG C, obtain the electrode that thickness is about 20 μm.It is single
The effective area of battery is 21cm2。
Prepare carbon fuel.Active carbon particle is crushed by electric crusher, is sieved with 70 mesh sieve, obtains particle size
Activated carbon less than 200 μm.Activated carbon and iron (form of di-iron trioxide) are weighed according to the ratio of mass ratio 95:5, weighs 5g
Activated carbon and 0.36g di-iron trioxide are fitted into ball grinder, and 30g dehydrated alcohol is added, ball grinder is placed on planetary ball mill
With the revolving speed ball milling 2h of 500r/min, the PVB- ethanol solution (PVB concentration is 6%) for adding 4ml continues with same rotational speed ball
Grind 1h.Gained slurry is placed under infrared lamp and is dried, last ball milling 10min takes off pearl, can must support 5wt.%Fe and be catalyzed
The carbon fuel of agent.
Assembled battery.Connecting hole 5 is brushed in 2 outside of electrolytic tube supporter using connecting material 7, connecting hole
5 seal simultaneously connect, connecting material 7 cannot contact itself cathodic coating 3 and electrolytic tube supporter 2 open end, with
Avoid short circuit.Connecting hole 5 is connected with connecting material 7 on anode film 4.InIt is dried in high temperature oven.It will
3.3g activated carbon fuel is placed in electrolytic tube supporter 2.Nozzle use ceramic wool fixed carbon fuel 6, while using plug 1 into
Row blocking.The difference of the internal diameter of the outer diameter and tubular cells open end of plug 1 is 0.1mm.
Carry out electrochemical property test.When test, the operating temperature of battery is provided and controlled with electric tube furnace, uses Ivium
The output characteristics of electrochemical workstation test battery.
It is output performance of the fuel at 700 DEG C, 750 DEG C, 800 DEG C, In that monocell, which uses activated carbon, thus shown in attached drawing 7
At 800 DEG C, open-circuit voltage 0.96V, maximum power output 1.95W, conversion power density are 93mWcm-2。
Embodiment 2
The preparation of electrolytic tube is carried out using infusion process.Infusion process includes dipping, lifting, dry, demoulding four basic steps
Suddenly.Firstly, preparing the uniform and stable electrolyte slurry of YSZ by way of ball milling, raw material contains 25g YSZ powder, the poly- second of 2g
Enol butyral (PVB), 0.8g triethanolamine (TEA), 0.8g polyethylene glycol (PEG-600), 0.8g dioctyl phthalate
(DOP), 38g dehydrated alcohol.Ball grinder is put into planetary ball mill, with the revolving speed ball milling 3h of 500r/min, must be uniformly dispersed
Electrolyte slurry.Then, the test tube mold with uniform paraffin layer is placed in slurry and carries out duplicate Best-Effort request process,
To obtain the green compact of electrolytic tube supporter 2, the length of green compact is 13.5cm, in the side of the green compact of electrolytic tube supporter 2
Wall equally spacedly makes a call to a round along pipe range direction, and the number of connecting hole 5 is 8, diameter 1.5mm, spacing 1.5cm.Gained
The green compact of electrolytic tube supporter 2 are sintered 4h in air at 1450 DEG C, finally obtain the electrolytic tube branch with ceramic structure
Support body 2.The length of gained electrolytic tube supporter 2 is 9.5cm, diameter 1.1cm, with a thickness of 0.2mm, the connecting hole 5 of side wall
Quantity be 8, diameter 1mm, spacing 1cm.
Prepare electrode film.The PVB and terpinol that mass ratio is 1:9 are weighed, is placed in a beaker, is dissolved in 60 DEG C of baking ovens
It is stand-by as binder for 24 hours.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 7.25g silver paste (DAD-87,
80%) and 2.5g GDC (after ball milling) SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS, amount containing Ag are, then to weigh 9.75g PVB- terpinol
Binder is added in agate mortar and grinds 4h, obtains uniform, good fluidity Ag-GDC combination electrode slurry.As Fig. 1-6 institute
Show, Ag-GDC slurry is painted on to the inside and outside wall of the electrolytic tube supporter 2 of tubular type using brushing method.Anode film 4 and electrolyte
The mutual all standing of 2 inner wall of pipe supporter, 3 part of cathodic coating cover the outer wall of electrolytic tube 2, and cathodic coating 3 cannot contact itself and connect
Hole is connect, while the open end of electrolytic tube supporter 2 can not be contacted, to avoid short circuit.It is dried in 140 DEG C of high temperature ovens.
So repeat 4 times.It is then placed in Muffle furnace, is sintered 2h in air at 880 DEG C, obtain the electrode that thickness is about 20 μm.It is single
The effective area of battery is 21cm2。
Prepare carbon fuel.Active carbon particle is crushed by electric crusher, is sieved with 70 mesh sieve, obtains particle size
Activated carbon less than 200 μm.Activated carbon and iron (form of di-iron trioxide) are weighed according to the ratio of mass ratio 95:5, weighs 5g
Activated carbon and 0.36g di-iron trioxide are fitted into ball grinder, and 30g dehydrated alcohol is added, ball grinder is placed on planetary ball mill
With the revolving speed ball milling 2h of 500r/min, the PVB- ethanol solution (PVB concentration is 6%) for adding 4ml continues with same rotational speed ball
Grind 1h.Gained slurry is placed under infrared lamp and is dried, last ball milling 10min takes off pearl, can must support 5wt.%Fe and be catalyzed
The carbon fuel of agent.
Assembled battery group.Connecting hole 5 is connected on anode film 4 using connecting material 7, while in electrolytic tube branch
Connecting hole 5 is brushed in 2 outside of support body, and connecting material 7 cannot contact the cathodic coating 3 of itself, will when connecting material 7 is not dry
The connecting hole 5 of the monocell is bonded together with the cathodic coating 3 of another monocell.It dries, realizes in 140 DEG C of high temperature ovens
The series connection of two batteries obtains three concatenated battery packs of battery in the same way.In the electrolytic tube of each monocell
3.3g activated carbon fuel is placed in supporter 2.Nozzle uses ceramic wool fixed carbon fuel 6, while being blocked using plug 1.
The difference of the internal diameter of 1 outer diameter of plug and tubular cells open end is 0.1mm.
Carry out electrochemical property test.When test, the operating temperature of battery is provided and controlled with electric tube furnace, uses Ivium
The output characteristics of electrochemical workstation test battery.
Three section series-connected cell groups are defeated at 700 DEG C, 750 DEG C, 800 DEG C for fuel using activated carbon thus shown in attached drawing 8
Performance out, at 800 DEG C, open-circuit voltage 2.95V, maximum power output 5.8W, conversion power density are 92mWcm-2。
Embodiment 3
The preparation of electrolytic tube is carried out using infusion process.Infusion process includes dipping, lifting, dry, demoulding four basic steps
Suddenly.Firstly, preparing the uniform and stable electrolyte slurry of YSZ by way of ball milling, raw material contains 25g YSZ powder, the poly- second of 2g
Enol butyral (PVB), 0.8g triethanolamine (TEA), 0.8g polyethylene glycol (PEG-600), 0.8g dioctyl phthalate
(DOP), 38g dehydrated alcohol.Ball grinder is put into planetary ball mill, with the revolving speed ball milling 3h of 500r/min, must be uniformly dispersed
Electrolyte slurry.Then, the test tube mold with uniform paraffin layer is placed in slurry and carries out duplicate Best-Effort request process,
To obtain the green compact of electrolytic tube supporter 2, the length of green compact is 13.5cm, in the side of the green compact of electrolytic tube supporter 2
Wall equally spacedly makes a call to a round along pipe range direction, and the number of connecting hole 5 is 8, diameter 1.5mm, spacing 1.5cm.Gained
The green compact of electrolytic tube supporter 2 are sintered 4h in air at 1450 DEG C, finally obtain the electrolytic tube branch with ceramic structure
Support body 2.The length of gained electrolytic tube supporter 2 is 9.5cm, diameter 1.1cm, with a thickness of 0.2mm, the connecting hole 5 of side wall
Quantity be 8, diameter 1mm, spacing 1cm.
Prepare electrode film.The PVB and terpinol that mass ratio is 1:9 are weighed, is placed in a beaker, is dissolved in 60 DEG C of baking ovens
It is stand-by as binder for 24 hours.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 7.25g silver paste (DAD-87,
80%) and 2.5g GDC (after ball milling) SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS, amount containing Ag are, then to weigh 9.75g PVB- terpinol
Binder is added in agate mortar and grinds 4h, obtains uniform, good fluidity Ag-GDC combination electrode slurry.As Fig. 1-6 institute
Show, Ag-GDC slurry is painted on to the inside and outside wall of the electrolytic tube supporter 2 of tubular type using brushing method.Anode film 4 and electrolyte
The mutual all standing of 2 inner wall of pipe supporter, 3 part of cathodic coating cover the outer wall of electrolytic tube 2, and cathodic coating 3 cannot contact itself and connect
Hole is connect, while the open end of electrolytic tube supporter 2 can not be contacted, to avoid short circuit.It is dried in 140 DEG C of high temperature ovens.
So repeat 4 times.It is then placed in Muffle furnace, is sintered 2h in air at 880 DEG C, obtain the electrode that thickness is about 20 μm.It is single
The effective area of battery is 21cm2。
Prepare carbon fuel.Active carbon particle is crushed by electric crusher, is sieved with 70 mesh sieve, obtains particle size
Activated carbon less than 200 μm.Activated carbon and iron (form of di-iron trioxide) are weighed according to the ratio of mass ratio 95:5, weighs 5g
Activated carbon and 0.36g di-iron trioxide are fitted into ball grinder, and 30g dehydrated alcohol is added, ball grinder is placed on planetary ball mill
With the revolving speed ball milling 2h of 500r/min, the PVB- ethanol solution (PVB concentration is 6%) for adding 4ml continues with same rotational speed ball
Grind 1h.Gained slurry is placed under infrared lamp and is dried, last ball milling 10min takes off pearl, can must support 5wt.%Fe and be catalyzed
The carbon fuel of agent.
Assembled battery group.Connecting hole 5 is connected on anode film 4 using connecting material 7, while in electrolytic tube branch
Connecting hole 5 is brushed in 2 outside of support body, and connecting material 7 cannot contact the cathodic coating 3 of itself, will when connecting material 7 is not dry
The connecting hole 5 of the monocell is bonded together with the cathodic coating 3 of another monocell.It dries, realizes in 140 DEG C of high temperature ovens
The series connection of two batteries obtains six concatenated battery packs of battery in the same way.In the electrolytic tube of each monocell
3.3g activated carbon fuel is placed in supporter 2.Nozzle uses ceramic wool fixed carbon fuel 6, while being blocked using plug 1.
The difference of the internal diameter of 1 outer diameter of plug and tubular cells open end is 0.1mm.
Carry out electrochemical property test.When test, the operating temperature of battery is provided and controlled with electric tube furnace, uses Ivium
The output characteristics of electrochemical workstation test battery.
Six section series-connected cell groups are defeated at 700 DEG C, 750 DEG C, 800 DEG C for fuel using activated carbon thus shown in attached drawing 9
Performance out, at 800 DEG C, open-circuit voltage 5.58V, maximum power output 11.6W, conversion power density be
92mWcm-2。
Embodiment 4
The preparation of electrolytic tube is carried out using infusion process.Infusion process includes dipping, lifting, dry, demoulding four basic steps
Suddenly.Firstly, preparing the uniform and stable electrolyte slurry of YSZ by way of ball milling, raw material contains 25g YSZ powder, the poly- second of 2g
Enol butyral (PVB), 0.8g triethanolamine (TEA), 0.8g polyethylene glycol (PEG-600), 0.8g dioctyl phthalate
(DOP), 38g dehydrated alcohol.Ball grinder is put into planetary ball mill, with the revolving speed ball milling 3h of 500r/min, must be uniformly dispersed
Electrolyte slurry.Then, the test tube mold with uniform paraffin layer is placed in slurry and carries out duplicate Best-Effort request process,
To obtain the green compact of electrolytic tube supporter 2, the length of green compact is 13.5cm, in the side of the green compact of electrolytic tube supporter 2
Wall equally spacedly makes a call to a round along pipe range direction, and the number of connecting hole 5 is 8, diameter 1.5mm, spacing 1.5cm.Gained
The green compact of electrolytic tube supporter 2 are sintered 4h in air at 1450 DEG C, finally obtain the electrolytic tube branch with ceramic structure
Support body 2.The length of gained electrolytic tube supporter 2 is 9.5cm, diameter 1.1cm, with a thickness of 0.2mm, the connecting hole 5 of side wall
Quantity be 8, diameter 1mm, spacing 1cm.
Prepare electrode film.The PVB and terpinol that mass ratio is 1:9 are weighed, is placed in a beaker, is dissolved in 60 DEG C of baking ovens
It is stand-by as binder for 24 hours.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 7.25g silver paste (DAD-87,
80%) and 2.5g GDC (after ball milling) SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS, amount containing Ag are, then to weigh 9.75g PVB- terpinol
Binder is added in agate mortar and grinds 4h, obtains uniform, good fluidity Ag-GDC combination electrode slurry.As Fig. 1-6 institute
Show, Ag-GDC slurry is painted on to the inside and outside wall of the electrolytic tube supporter 2 of tubular type using brushing method.Anode film 4 and electrolyte
The mutual all standing of 2 inner wall of pipe supporter, 3 part of cathodic coating cover the outer wall of electrolytic tube 2, and cathodic coating 3 cannot contact itself and connect
Hole is connect, while the open end of electrolytic tube supporter 2 can not be contacted, to avoid short circuit.It is dried in 140 DEG C of high temperature ovens.
So repeat 4 times.It is then placed in Muffle furnace, is sintered 2h in air at 880 DEG C, obtain the electrode that thickness is about 20 μm.It is single
The effective area of battery is 21cm2。
Prepare carbon fuel.Active carbon particle is crushed by electric crusher, is sieved with 70 mesh sieve, obtains particle size
Activated carbon less than 200 μm.Activated carbon and iron (form of di-iron trioxide) are weighed according to the ratio of mass ratio 95:5, weighs 5g
Activated carbon and 0.36g di-iron trioxide are fitted into ball grinder, and 30g dehydrated alcohol is added, ball grinder is placed on planetary ball mill
With the revolving speed ball milling 2h of 500r/min, the PVB- ethanol solution (PVB concentration is 6%) for adding 4ml continues with same rotational speed ball
Grind 1h.Gained slurry is placed under infrared lamp and is dried, last ball milling 10min takes off pearl, can must support 5wt.%Fe and be catalyzed
The carbon fuel of agent.
Assembled battery.Connecting hole 5 is brushed in 2 outside of electrolytic tube supporter using connecting material 7, connecting hole
5 seal simultaneously connect, connecting material 7 cannot contact itself cathodic coating 3 and electrolytic tube supporter 2 open end, with
Avoid short circuit.Connecting hole 5 is connected with connecting material 7 on anode film 4.It is dried in 140 DEG C of high temperature ovens.By 3.3g
Activated carbon fuel is placed in electrolytic tube supporter 2.Nozzle uses ceramic wool fixed carbon fuel 6, while being blocked up using plug 1
Plug.The difference of the internal diameter of the outer diameter and tubular cells open end of plug 1 is 0.1mm.
Carry out electrochemical property test.When test, the operating temperature of battery is provided and controlled with electric tube furnace, uses Ivium
The output characteristics of electrochemical workstation test battery.
It is that fuel carries out constant current twice at 800 DEG C with the electric current of 0.5A that monocell, which uses activated carbon, thus shown in attached drawing 10
The performance comparison of electric discharge.Under first time constant current discharge, discharge platform 0.92V, when electric discharge a length of 20h, fuel utilization
Rate is 33.9%.Carbon fuel is replaced, carries out second of constant current discharge, discharge platform 0.88V, when electric discharge is a length of
19.5h, fuel availability 33.1%, although performance is variant, this is the experiment proves that activity designed in the present invention
Plug can realize being refilled by and utilizing for carbon fuel.
Multiple test results of above-described embodiment demonstrate, and the open end of tubular type monocell is using plug resistant to high temperature to carbon
Fuel is blocked, and plug causes certain vapour lock to inside battery reaction, makes to react efficient progress.The present invention can be straight simultaneously
It connects and anode cavities is utilized in electrolytic tube in battery pack operational process always in positive pressure environment, it is not necessary that plug is fixed on electricity
Matter tube opening end is solved, without designing gas-guide tube, addition carbon fuel can be facilitated in the application, greatly solve prior art China
Patent of invention CN200910192848.8 can not increase new carbon fuel, lead at high cost, the wasting of resources the technical problem, seem
Simply, but really long-standing problem existing technical staff is solved the problems, such as, breakthrough carrys out such tubular cells can not be in portable electric
The obstacle of the application in source has high practical value, realizes that carbon fuel can be replaced at any time, realizes the repeatedly sharp of battery pack
With greatly reducing cost.
Meanwhile the anode of a tubular type monocell is passed through connecting hole and another battery using connecting material by the present invention
Cathode connect, thus realize two batteries series connection；Multiple batteries are connected in this way, obtain multiple battery strings
The battery pack of connection solves the problems, such as that the connection of prior art battery pack is difficult.
Battery pack of the present invention have many advantages, such as structure it is simple, without sealant, can Reusability, high conversion efficiency, especially
It is suitble to movement or backup power source application.
It should be noted that the present invention is not constrained by above embodiment, it is other any without departing from spirit of the invention
Essence and made changes, modifications, substitutions, combinations, simplifications under principle, should be equivalent alternative, are included in this hair
Within bright protection scope.
Claims (10)
1. the townhouse concatenation direct carbon solid oxide fuel cell group of tubular type that can be recycled, by multiple tubular types closed at one end
Cells in series composition；The tubular type monocell is electrolyte-supporting type monocell, and tubular type monocell includes electrolytic tube, anode
Film, cathodic coating, connecting hole, carbon fuel and plug；Electrolytic tube supporter is long tubular structure closed at one end, electrolytic tube branch
The tubular inner wall of support body is equipped with anode film, and outer wall is equipped with cathodic coating；The anode film of battery all covers the inside face of electrolytic tube
Product, carbon fuel are placed in the anode cavities of electrolytic tube supporter；Plug is equipped in the open end of electrolytic tube supporter；
It is characterized by: the plug is flexibly connected with the open end of electrolytic tube supporter；The side wall edge of tubular type monocell
There is row's connecting hole in pipe range direction；The mode of multiple tubular type cells in series closed at one end is two neighboring tubular type list
Battery is arranged side by side, and is connected by multiple connecting holes with conductive material；Cathode membrane part covers the external area of electrolytic tube, In
Electrolytic tube supporter open end periphery and connecting hole periphery not covered cathode film；Conductive material is arranged in connecting hole, even
Between the cathodic coating for connecing the connecting hole and adjacent tubular type monocell on the anode film between hole and on the outside of monocell.
2. the tubular type direct carbon solid oxide fuel cell monocell according to claim 1 recycled, special
Sign is: the diameter of the connecting hole is 0.1-2mm, and the spacing of connecting hole is 2-10mm.
3. the tubular type direct carbon solid oxide fuel cell monocell according to claim 1 recycled, special
Sign is: the conductive material is DAD-87 silver conductive adhesive.
4. the tubular type direct carbon solid oxide fuel cell monocell according to claim 1 recycled, special
Sign is: the plug is made of fire-resistant oxidation resistant material.
5. the tubular type direct carbon solid oxide fuel cell monocell according to claim 4 recycled, special
Sign is: the fire-resistant oxidation resistant material is quartz or ceramic material.
6. the tubular type direct carbon solid oxide fuel cell monocell according to claim 1 recycled, special
Sign is: the material of the electrolytic tube supporter is the zirconium oxide of stabillzed with yttrium, using slip casting or dipping legal system
It is standby, In3-4h is sintered in lower air to be formed.
7. the tubular type direct carbon solid oxide fuel cell monocell according to claim 1 recycled, special
Sign is: the material of the anode film and cathodic coating is the composite material that gadolinium or samarium stabilize cerium oxide and silver powder, is added organic
Binder is prepared into electrode slurry, and wherein silver powder accounts for the 45%-60% of electrode slurry quality；The organic binder is by poly- second
Enol butyral and terpinol mixing composition；Electrode slurry is brushed to the inner and outer wall in electrolytic tube, In respectivelyIt is sintered 2-4h in lower air, electrode film is made.
8. the tubular type direct carbon solid oxide fuel cell monocell according to claim 1 recycled, special
Sign is: the carbon fuel includes solid carbon and Boudouard catalysts；The solid carbon is graphite powder, activity
Carbon, coke, carbon black or charcoal；The Boudouard catalysts are Fe, Co, Ni or Cu；Boudouard catalytic reaction
Agent accounts for the 2%-20% of quality；When preparation, the oxide of Fe, Co, Ni or Cu and solid carbon are sufficiently mixed, polyethylene is added
The ethanol solution of butyral, which is fully ground, to be granulated, and the mixed of carbon powder and Boudouard catalysts is obtained after dry
Close object.
9. the tubular type direct carbon solid oxide fuel cell monocell according to claim 8 recycled, special
Sign is: the difference of the internal diameter of the outer diameter and tubular cells open end of the plug is 0.01-0.5mm.
10. the tubular type direct carbon solid oxide fuel cell monocell according to claim 1 recycled, special
Sign is: the number of the tubular type monocell is 3-20.
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| CN201911127670.9A CN110752399B (en) | 2019-08-14 | 2019-11-18 | Tube type direct carbon solid oxide fuel battery pack with reusable row structure |
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| CN113381050A (en) * | 2021-06-09 | 2021-09-10 | 广东石油化工学院 | Electrode support type tubular SOFC (solid oxide Fuel cell) applied to surrounding chessboard cell stack with high electrochemical reaction area and manufacturing method |
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| US6824907B2 (en) * | 2002-01-16 | 2004-11-30 | Alberta Reasearch Council, Inc. | Tubular solid oxide fuel cell stack |
| CN1253959C (en) * | 2004-03-16 | 2006-04-26 | 哈尔滨工业大学 | Group battery composed of single air chamber solid oxide fuel cell |
| CN101540411A (en) * | 2009-04-15 | 2009-09-23 | 中国科学院上海硅酸盐研究所 | Solid electrolyte direct carbon fuel cell |
| CN101694883B (en) * | 2009-09-30 | 2011-12-28 | 华南理工大学 | Direct carbon solid oxide fuel cell |
| CN101800326B (en) * | 2010-04-17 | 2012-09-05 | 上海交通大学 | Two-electrolyte direct carbon fuel cell and assembling method thereof |
| CN102130354B (en) * | 2011-01-14 | 2013-09-25 | 华南理工大学 | Direct carbon solid oxide fuel cell power system |
| CN102544565A (en) * | 2012-03-19 | 2012-07-04 | 郭丰亮 | Tubular solid oxide fuel battery pack with three-ring combined structure |
| CN202474081U (en) * | 2012-03-19 | 2012-10-03 | 郭丰亮 | Tubular solid oxide fuel battery pack with high space utilization ratio |
| CN102832397B (en) * | 2012-09-04 | 2015-04-22 | 北京斯塔能源科技有限公司 | Battery unit of solid oxide fuel battery, battery pack, and reacting device |
| CN203871424U (en) * | 2014-04-10 | 2014-10-08 | 华南理工大学 | Solid oxide fuel battery pack based on monolithic electrolyte |
| CN203811573U (en) * | 2014-04-17 | 2014-09-03 | 武汉科技大学 | Device for testing electrochemical behaviors of electroactive oxides in fused electrolyte |
| CN105047969B (en) * | 2015-09-01 | 2017-09-12 | 华中科技大学 | A kind of direct carbon solid oxide fuel cell pile of antimony anode and preparation method thereof |
| CN107579268B (en) * | 2017-08-15 | 2020-05-22 | 华南理工大学 | Solid oxide fuel cell directly using propane fuel and application thereof |
| CN109193007A (en) * | 2018-09-25 | 2019-01-11 | 山东理工大学 | Portable direct carbon solid oxide fuel cell power generator |
| CN109599582B (en) * | 2018-11-15 | 2021-10-19 | 江苏科技大学 | Direct carbon solid oxide fuel cell stack and power generation device thereof |
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| CN113381050A (en) * | 2021-06-09 | 2021-09-10 | 广东石油化工学院 | Electrode support type tubular SOFC (solid oxide Fuel cell) applied to surrounding chessboard cell stack with high electrochemical reaction area and manufacturing method |
| CN113381050B (en) * | 2021-06-09 | 2022-06-07 | 广东石油化工学院 | Electrode support type columnar SOFC surrounding chessboard cell stack and manufacturing method |
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Application publication date: 20191203 |