CN107579268A - The directly SOFC using propane fuel and its application - Google Patents
The directly SOFC using propane fuel and its application Download PDFInfo
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- CN107579268A CN107579268A CN201710694590.6A CN201710694590A CN107579268A CN 107579268 A CN107579268 A CN 107579268A CN 201710694590 A CN201710694590 A CN 201710694590A CN 107579268 A CN107579268 A CN 107579268A
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Abstract
The invention discloses SOFC and its application for directly using propane fuel.The SOFC includes dense electrolyte, porous cathode, porous anode, porous catalyst and tubular cells conduit；Tubular cells tube at one end is connected with dense electrolyte openend, and junction is provided with encapsulant, and the other end is provided with plug；Gas conduit is stretched into tubular cells conduit and the porous catalyst for promoting carbon distribution reaction of dense electrolyte from plug；Porous catalyst iron, cobalt or nickel, or the porous catalyst are the oxide powder of any one in iron, cobalt and nickel.The method that the high temperature pyrolysis of propane and direct carbon solid oxide fuel cell are combined by the present invention, while SOFC is directly discharged using propane as fuel, using the catalyst for promoting carbon distribution reaction (cracking reaction), make propane by rear Carbon deposition on a catalyst secondary use to reach the purpose of effective use propane.
Description
Technical field
The present invention relates to a kind of fuel cell, more particularly to a kind of solid oxide fuel of effective use propane fuel
Battery (SOFC), belongs to cell art.
Background technology
Propane is the main component of liquefied petroleum gas, have be at normal temperatures and pressures gaseous state and after applying certain pressure
The characteristics of just turning into liquid.The boiling point of propane is -42 DEG C, and this causes LPG can rapid gas after being discharged from high-pressure bottle
Change.Therefore, the simple designs of a similar metering nozzle can enormously simplify device structure to realize the supply of propane.Together
When, LPG has high theoretical volumetric energy density, reachable~7Whml‐1.Therefore, propane is that one kind is very suitable for
The fuel of portable equipment, available for camp, unmanned plane, individual soldier's equipment, small-sized airplane power source etc..
SOFC (SOFC) is the fuel cell using soild oxide as electrolyte.It is mainly by sun
Pole, dielectric film, negative electrode are formed.Different from other fuel cells, SOFC operating temperature it is higher (>500 DEG C), this causes its tool
Dynamic process is fast, without noble metal catalyst, overall efficiency is high, is easy to that modularized design, fuel be applied widely, work
The not high advantage of environmental requirement.
There are some researches show, propane may be used as SOFC fuel, but output performance to be present inadequate by existing propane SOFC
The high, problem such as stability is poor, fuel availability is low.To find out its cause, mainly have：(1) when using traditional Ni-based anode material, third
Alkane produces a large amount of carbon distributions on anode, destroys anode construction, so that the performance of battery decays until being stopped rapidly；
(2) electro-chemical activity of most of non-Ni-based anodes is not high enough；(3) the kinetics process of propane fuel is slow, while in height
Temperature is lower to produce carbon distribution, makes the utilization rate of fuel low.
To solve the problems, such as above-mentioned propane in galvanic anode carbon distribution, Many researchers are proposed using reformation or partial oxidation
Method propane is changed into mainly to contain H2, the small molecule such as CO gas, these micro-molecular gas are then transported to galvanic anode
Generation cell reaction.But if being reformed (outer reform) or partial oxidation to propane in the outside of battery, increase and be
The complexity of system；And if realizing reformation or partial oxidation in the inside of battery, due to fuel concentration step-down, electricity will be had a strong impact on
The output voltage in pond, and then influence the power output of battery.Either reformation or partial oxidation, all it is that electrification occurs in fuel
Before learning oxidation reaction, substantial amounts of vapor, carbon dioxide or oxygen are added into fuel, so as to severely impact the electricity of fuel
Transformation efficiency.If propane fuel is directly carried out into high temperature pyrolysis, although can be obtained on the premise of oxidizing gas is not added with
Micro-molecular gas, but this will produce substantial amounts of carbon distribution, also result in the loss of propane fuel energy, and irregular carbon distribution also can be right
The supply of fuel produces with consumption further to be influenceed.
However, carbon in itself also can be as SOFC fuel.N.Nakagawa and M.Ishida reports direct carbon and consolidated earliest
Oxide body fuel cell (DC-SOFC) (Performance of an internal direct-oxidation carbon
fuel cell and its evaluation by graphic exergy analysis,Industrial&
Engineering Chemistry Research, 27 (7) (1988) 1181-1185), isolated using sheet YSZ electrolyte
Air chamber (cathode chamber) and fuel chambers (anode chamber), electrolyte two sides are coated with platinum slurry and are used as negative electrode and anode respectively, and will be pure
Coke fuel is placed in away from anode 5mm.They also proposed the operation principle of the battery：The electrochemical reaction occurred on anode is
CO and oxonium ion reaction generation CO2And electronics, and the CO generated2Be diffused at carbon fuel with C react generation CO (Bouduard is anti-
Should), so move in circles, the purpose for realizing the mass transfer of solid carbon fuel and then generating electricity.
2009, DC-SOFC power output was brought up to 9mW cm by inventor seminar‐2；Then, inventor seminar
Activated carbon fuel is used again, DC-SOFC has continuously been worked 37 hours.Then, further to improve battery performance, in activated carbon
Fe is supported on fuel as Boudouard catalysts, power output is reached 45mW cm‐2.On this basis, using biography
The SOFC of the Ni-based anode-supported of system, has obtained 465mW cm‐2Power density, and run one three section series connection DC-
SOFC battery packs, obtain 2.4W power output and 710mW cm‐3Power density.As can be seen here, carbon serves not only as
SOFC fuel, and be a kind of efficient, convenient SOFC fuel.
To sum up, carbon is a kind of important fuel source for SOFC.Meanwhile the solid oxide fuel using propane as fuel
The processing of carbon distribution and raising battery performance, the most important thing of fuel availability in battery.However, propane fuel splits in anode chamber
Carbon caused by solution, not only can be also not high to the influence of commercial Ni-based damaging property of anode, itself reactivity, it is difficult to straight
Connect utilization.
The content of the invention
The object of the present invention is to overcome the problems of the prior art, there is provided a kind of output for improving propane SOFC
Can, stability and fuel availability, and can solve the problems, such as using propane as the SOFC of fuel in carbon distribution height
Effect uses the SOFC (SOFC) of propane.
The catalyst for promoting carbon distribution has been filled in the anode chamber of direct propane SOFC by the present invention.
During battery operation, SOFC first is run using propane gas, stops the offer of propane gas after a period of time, then use is deposited on
Carbon on catalyst is fuel, and after carbon distribution is approached and is exhausted, discharge voltage is close to after 0V, then is passed through propane；So repeatedly,
Realize SOFC Effec-tive Function.The time using propane gas operation is unlimited, and shorter interval duration of ventilation can obtain
Higher fuel availability.The present invention makees anode using the silver-based material of anti-carbon, meanwhile, creative added in anode chamber promotees
Enter the catalyst of carbon distribution reaction, and using being run by the way of alternately running.Promote the addition of the porous catalyst of carbon distribution reaction,
Not only increase the cracking of propane, reduce being expelled directly out for unreacted propane fuel and caused by energy loss；It is simultaneously also right
The Bouduard reactions of carbon have catalytic action so that carbon distribution caused by cracking can have phase with carbon fuel used in laboratory research
The output performance to match in excellence or beauty.
The purpose of the present invention is realized especially by following technical scheme：
A kind of SOFC using propane, including it is dense electrolyte, porous cathode, porous anode, more
Pore catalyst and tubular cells conduit；Dense electrolyte is the cone tubular structure of one end closing, and the inside pipe wall of dense electrolyte is set
There is porous anode, outer wall is provided with porous cathode；Tubular cells tube at one end is connected with dense electrolyte openend, and junction is provided with
Encapsulant, the other end are provided with plug；Gas conduit stretches into tubular cells conduit and the promotion carbon distribution of dense electrolyte from plug
In the porous catalyst of reaction；Tail gas escape pipe is stretched into battery conduit from plug；Propane inlet and offgas outlet are respectively provided at
Gas conduit and tail gas escape pipe entrance point and the port of export；Porous catalyst iron, cobalt or the nickel, or the porous catalytic
Agent is the oxide powder of any one in iron, cobalt and nickel.
Further to realize the object of the invention, it is preferable that described porous cathode and porous anode all use silver powder and gadolinium
Or the composite of Sm doped CeO_2 is made；Wherein, silver powder accounts for the 45%~70% of mixed powder quality；Using brush or
Slurry prepared by composite is coated in the inner and outer wall of electrolytic tube supporter by spraying process, the air at 600-880 DEG C
Middle sintering 2-4h is formed.
Preferably, the material of described dense electrolyte is the zirconium oxide of stabillzed with yttrium；Using slip casting or dipping
Conical tube type green compact prepared by method, sintering 3-4h is formed in air at 1400-1600 DEG C.
Preferably, the oxide powder of any one corresponds to nitrate mixing by iron, cobalt and nickel in described iron, cobalt and nickel
Glycine, dissolving are heated with stirring to spontaneous combustion, obtained by combustion method.
Preferably, described seal is DAD-87 silver conductive adhesives.
Preferably, described battery conduit, gas conduit and tail gas escape pipe are all made by fire-resistant oxidation resistant material
Pipe.
Preferably, described battery conduit, gas conduit and tail gas escape pipe are all quartz ampoule or earthenware.
Preferably, openend 3mm more than of the described porous cathode apart from electrolytic tube supporter tubulose.
Using the method using propane fuel of the SOFC：First from propane inlet through gas conduit
Propane fuel is passed through to galvanic anode room, after propane reaches anode chamber, is tentatively urged via the porous catalyst of carbon distribution reaction is promoted
Change forms anode reaction gas, and electrochemical oxidation occurs in porous anode, with from porous cathode occur the former reaction of oxidation and via
The oxonium ion that dense electrolyte passes over combines；Meanwhile electrochemical reaction product and the propane that does not react are promoting to accumulate
The porous catalyst surface of carbon reaction occurs carbon distribution and reacts to form carbon distribution；Anodic product gas passes through from tubular cells conduit, warp
By tail gas escape pipe, discharged from offgas outlet；After continuing 1-10min, stop ventilation；Battery is to promote the product on carbon deposition catalyst
Carbon is fuel, and into DC-SOFC mode of operations, Bouduard reactions occur in the case where promoting the catalysis of carbon distribution catalysts for carbon distribution
CO is generated, CO is combined with the former oxonium ion for reacting and being passed over via dense electrolyte of oxidation occurs from porous cathode, generated
CO2And sustained release goes out electric energy, CO is generated2Tail gas has not contained energy, is discharged via tail gas escape pipe from offgas outlet；When
Carbon distribution repeats above-mentioned journey, realizes direct, the efficient utilization of propane fuel close to when ruing out of
Propane of the present invention is commercially available 99.99% propane gas.
The present invention uses the soild oxide YSZ with oxygen conduction as electrolyte, and is made into branch
The cone tubular structure of one end closing of support effect, anode and negative electrode are prepared using brushing method in the medial and lateral of electrolyte, afterwards will
Battery sealing-in will promote carbon deposition catalyst powder to be placed in anode chamber, airway tube imported in the catalyst of anode chamber on conduit
Centre.
Propane fuel from air inlet input battery when, first pass through the catalyst preliminary catalytic for promoting carbon distribution, it is anti-that cracking occur
Part carbon distribution and micro-molecular gas, such as H should be produced2、CH4Deng
C3H8=3C+4H2 (1)
C3H8=C+2CH4 (2)
Then, the propane of cracking reaction does not occur and these micro-molecular gas reach anode and electrochemical oxidation reactions occur simultaneously
Generate electricity, generate H2O、CO2Deng
H2+O2‐=H2O+2e‐ (3)
CH4+4O2‐=CO2+2H2O+8e‐ (4)
C3H8+10O2‐=3CO2+4H2O+20e‐ (5)
Because the electro-chemical activity of small molecule caused by Deposition During Propane Pyrolysis is higher, the fuel after preliminary catalytic is advantageous to carry
The performance of high battery.
In principle, occur also to contain H in the reacted gas of anode electrochemical2、CO、CH4And C3H8, due to H2Reaction live
Property is very high, therefore H in reacted gas2Content is very low；CO is the partial oxidation products of carbon；And CH4And C3H8Mean
Them also not contributed cell power generation.Then, these reaction after gas again by promote carbon distribution catalysts,
Such as Fe, Ni, Co etc., C therein will be by " retentions ".After battery works a period of time in the state of logical propane fuel, cut
Disconnected propane supply, battery start to consume the C wherein " retained " automatically, with DC-SOFC mode operation, i.e.,：Oxygen is in battery
Negative electrode obtains electronics and is reduced into oxonium ion O2‐, O2‐By conducting O2‐Electrolyte transport to anode, react generation CO with CO2
And electronics is discharged, realize CO electrochemical oxidation reactions.
CO+O2-=CO2+2e- (6)
The CO of generation2The surface of deposition carbon is diffused into, Bouduard reaction generations CO occurs with carbon
C+CO2=2CO (7)
CO is diffused into anode as fuel again and electrochemical oxidation reactions (6) occurs, and passes through the reality that intercouples of (6) and (7)
Existing SOFC generates electricity.Treat that carbon distribution close to ruing out of and then passing to propane, such iterative cycles, realizes that the Effec-tive Function of battery is sent out
Electricity.
The porous catalyst for promoting carbon distribution reaction is also the catalyst of Bouduard reactions simultaneously, can be in battery with DC-
The reaction rate of Bouduard reactions is effectively improved when SOFC mode operation, ensure that the mass transfer of solid carbon smoothly enters
OK, the steady operation of battery is ensured that.
It can be seen that by the design of new propane SOFC battery structures, propane fuel, especially third can be ensured to greatest extent
The efficient utilization of carbon in alkane, so that propane SOFC fuel availability greatly improves.Also, such structure design is also right
There is highly important directive significance in SOFC application using remaining high-carbon organic matter.
Propane fuel SOFC involved in the present invention, its operation logic are gaseous fuel SOFC and DC-SOFC alternate runs,
And fuel is provided in a manner of propane, that is, solves the storage of gaseous fuel SOFC small moleculars gas such as hydrogen, carbon monoxide
Deposit and carrying problem, solve the problem without interruption of carbon fuel in DC-SOFC again, meanwhile, also solve and directly use propane
Operating fuel SOFC carbon distribution problem.
The method that the high temperature pyrolysis of propane and direct carbon solid oxide fuel cell are combined by the present invention, using rush
Enter carbon distribution reaction (cracking reaction) catalyst, make propane by rear Carbon deposition on a catalyst；Battery is passing to propane luck
After row a period of time, stop the supply of propane, battery starts to bring into operation with DC-SOFC pattern；Treat that carbon distribution is close to run out of
Bi Shi, then pass to propane, such iterative cycles, reach the purpose of effective use propane.
Relative to prior art, the present invention has following features：
(1) directly using propane as fuel, without reformer, SOFC work system is simplified.
(2) propane fuel is contained before reaching anode and being electrochemically reacted by promoting the catalyst that carbon distribution reacts to produce
There is the small molecule of hydrogen and methane, be advantageous to the raising of battery performance.
(3) efficiently utilize battery with propane make during operating fuel it is inevitable caused by carbon distribution, and by its turn
Turn to electric energy.
(4) by being recycled to the orientation of carbon distribution, the utilization rate of propane fuel is substantially increased.
(5) promote the use of carbon deposition catalyst, not only promote the orientated deposition of carbon distribution, and can be in DC-SOFC works
Play a part of promoting Bouduard reactions as the stage so that SOFC is stabilized work in the stuffiness stage.
Brief description of the drawings
Fig. 1 is the structural representation of the solid oxide fuel cell device of effective use propane fuel of the present invention.
Shown in figure：Dense electrolyte 1, porous cathode 2, porous anode 3, the porous catalyst 4, close for promoting carbon distribution reaction
Closure material 5, battery conduit 6, gas conduit 7, tail gas escape pipe 8, propane inlet 9, anode reaction gas 10, anodic product gas
11st, offgas outlet 12, plug 13
Fig. 2 be the silver proposed by the present invention of embodiment 1-Ceramic Composite electrode when using propane as fuel 800 DEG C output it is special
Linearity curve.
Output performance curve when Fig. 3 is a length of 1min when propane is ventilated under the conditions of 800 DEG C in embodiment 2.
Output performance curve when Fig. 4 is a length of 2min when propane is ventilated under the conditions of 800 DEG C in embodiment 3.
Output performance curve when Fig. 5 is a length of 5min when propane is ventilated under the conditions of 800 DEG C in embodiment 4.
Output performance curve when Fig. 6 is a length of 10min when propane is ventilated under the conditions of 800 DEG C in embodiment 5.
Embodiment
The present invention is further described with reference to embodiment and accompanying drawing, but the scope of protection of present invention is not
It is confined to the scope of embodiment expression.
As shown in figure 1, a kind of SOFC of effective use propane fuel, including：Dense electrolyte 1,
Porous cathode 2, porous anode 3, the porous catalyst 4 for promoting carbon distribution reaction, tubular cells conduit 6, gas conduit 7, tail gas go out
Tracheae 8 and plug 13.Dense electrolyte 1 be used as electrolytic tube supporter, be one end closing cone tubular structure, electrolytic tube branch
The inside pipe wall of support body is provided with porous anode 3, and outer wall is provided with porous cathode 2；Porous cathode is apart from electrolytic tube supporter tubulose
More than openend 3mm, negative electrode and anode short circuit during avoiding sealing-in；The one end of tubular cells conduit 6 and the openend of dense electrolyte 1
Connection, junction are provided with encapsulant 5, and the other end is provided with plug 13；Gas conduit 7 stretches into battery conduit 6 from plug 13 and caused
In the porous catalyst 4 for promoting carbon distribution reaction of close electrolyte 1；Tail gas escape pipe 8 is stretched into battery conduit 6 from plug 13；Third
Alkane entrance 9 and offgas outlet 12 are respectively provided at gas conduit 7 and the entrance point of tail gas escape pipe 8 and the port of export.Propane is entered by propane
After mouth 9 enters anode chamber, the initial reaction of porous catalyst 4 with promoting carbon distribution reaction, anode reaction gas 10 is generated, porous
Electrochemical oxidation occurs for anode 3, while is promoting the surface of porous catalyst 4 of carbon distribution reaction to crack to form carbon distribution；Generate sun
Pole product gas 11 flows through tubular cells conduit 6, is discharged by tail gas escape pipe 8 by offgas outlet 12.
The material of dense electrolyte 1 is the zirconium oxide (YSZ) of stabillzed with yttrium, is prepared using slip casting or infusion process
Conical tube type green compact, sintering 3-4h is formed in air at 1400-1600 DEG C；Porous cathode 2 and porous anode 3 all using silver powder with
The composite of gadolinium or Sm doped CeO_2；Wherein, silver powder accounts for the 45%~70% of mixed powder quality；Using brushing or spray
Slurry prepared by composite is coated in the inner and outer wall of electrolytic tube supporter by coating, and silver electrode composite is in 600-880
2-4h is sintered at DEG C in air to be formed.The present invention uses the soild oxide YSZ with oxygen conduction as electrolyte, and
The cone tubular structure of one end closing with supporting role is made into, it is more in the preparation of the medial and lateral of electrolyte using brushing method
Hole anode and porous cathode.
The catalyst 4 for promoting carbon distribution to react is iron, cobalt or nickel, due to metal oxide catalyst meeting in course of reaction
It is reduced, therefore can also is the oxide powder of iron, cobalt or nickel.The material can both use commercial chemicals raw material,
Nitrate can be corresponded to and mix a certain amount of glycine, dissolving is heated with stirring to spontaneous combustion, its oxidation is obtained by combustion method
Powder, to obtain bigger specific surface area, improve catalytic effect；
Seal 5 is DAD-87 (Shanghai synthetic resin research institute) silver conductive adhesive.This silver conductive adhesive is mainly by silver powder and ring
Oxygen resinoid bond forms.It is filled with the gap of the openend of dense electrolyte 1, after dry heat, in this silver conductive adhesive
Organic additive (epoxy resin etc.) volatilization, Argent grain is sintered densification, reaches the effect of sealing, meanwhile, this encapsulant
Also act as the effect for drawing anode electric charge.
Battery conduit 6, gas conduit 7 and tail gas escape pipe 8, it is the pipe made by fire-resistant oxidation resistant material；Described
Fire-resistant oxidation resistant material is quartz or ceramics.
Direct effective use propane fuel, is realized especially by following manner：First from propane inlet 8 through gas conduit 7 to
Galvanic anode room is passed through propane fuel, after propane reaches anode chamber, via the preliminary catalytic of porous catalyst 4 for promoting carbon distribution reaction
Anode reaction gas 10 is formed, electrochemical oxidation is instead given birth in porous anode 3, with reacting and passing through from the generation oxidation original of porous cathode 2
The oxonium ion passed over by dense electrolyte 1 combines；Meanwhile electrochemical reaction product and the propane that does not react are promoting
The surface of porous catalyst 4 of carbon distribution reaction occurs carbon distribution and reacts to form carbon distribution.Then, anodic product gas 11 is from battery conduit 6
Pass through, via tail gas escape pipe 8, discharged from offgas outlet 12.Carbon distribution reaction is promoted to urge because anodic product gas 11 has been subjected to
The content of the catalysis of agent 4, wherein carbon substantially reduces, and forms carbon distribution mostly and is deposited on the surface for promoting carbon distribution reaction 4.Continue 1-
After 10min, stop ventilation.Now battery can be to promote the carbon distribution on carbon deposition catalyst 4 as fuel, into DC-SOFC Working moulds
Bouduard reaction generation CO occur in the case where promoting the catalysis of carbon distribution catalysts 4 for formula, carbon distribution, and CO from porous cathode 2 with sending out
The former oxonium ion for reacting and being passed over via dense electrolyte 1 of raw oxidation combines, and generates CO2And sustained release goes out electric energy, institute
Generate CO2Tail gas has not contained energy, is discharged via tail gas escape pipe 8 from offgas outlet 12.When carbon distribution is close to be run out of, weight
Multiple above-mentioned venting process continues to ventilate, and circulation said process work, direct, the efficient utilization of propane fuel is reached with this.
Embodiment 1
25gYSZ (Japanese Tosoh) is weighed, adds 38g alcohol, 2g polyvinyl butyral resins (PVB), 0.8g O-phthalics
Dioctyl phthalate (DOP), 0.8g polyethylene glycol (PEG), 0.8g triethanolamines (TEA), ball milling 2h obtain dispersed slurry, adopted
YSZ electrolytic tube green compact are prepared with infusion process.Obtained green compact are positioned in the crucible equipped with YSZ female powders, are put into Muffle furnace
It is interior, 4h is sintered at 1450 DEG C, obtains the good YSZ electrolytic tubes of the mechanical strength of densification.This pipe range about 2cm, external diameter 1cm,
Wall thickness 0.3mm.
Mass ratio is weighed respectively as 1:9 PVB and terpinol, is placed in beaker, and 24h conducts are dissolved in 60 DEG C of baking oven
Binding agent is stand-by.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 4.38g silver pastes, and (DAD-87, Shanghai City are closed
80%) and 1.5g GDC (after ball milling) resin research institute, amount containing Ag is, then weighs the binding agent that quality is 5g, adds agate
4h is ground in Nao mortars, obtains dispersed Ag-GDC combination electrode slurries.With pigment tools pen by Ag-GDC electrode slurrys
It is uniform to brush the whole inwall in electrolytic tube as anode, dry in 140 DEG C of high temperature oven, so repeat 3 times.Again
The slurry of a long 0.9cm of circle is applied as negative electrode in electrolytic tube outer wall, is dried in 140 DEG C of high temperature oven, so repeatedly 3
Time.It is then placed in Muffle furnace, the lower 880 DEG C of burnings 2h of air atmosphere, obtains the electrode that thickness is about 20 μm.The effective area of battery
(in terms of less negative electrode) is 2.8cm2。
Openend is fixed on diameter 10mm corundum battery conduit by obtained monocell with silver paste.It is another to take two pairs
Hole alundum tube, a silver wire is respectively imported in each hole.Two silver wires of a piece diplopore alundum tube are connected to monocell with silver paste
Negative electrode on, two silver wires of another diplopore alundum tube be connected in the sealing-in silver paste at monocell beginning end with silver paste (i.e. with
Anode connects).Propane airway tube is passed directly into anode chamber, blend compounds plug seals the other end of alundum tube, while exports one
Pipe is truncated as tail gas escape pipe.
During test, the heated constant temperature area that the battery assembled is put into electric tube furnace rises to 800 DEG C, and propane flow is adjusted to
5mL/min, the output characteristics of battery is tested with IM6 electrochemical workstations (ZAHNER).
Accompanying drawing 2 is shown when making fuel using the SOFC of Ag-GDC anodes with propane, the output performance at 800 DEG C, its
Open-circuit voltage is 0.9V, maximum power density 80mW/cm2。
In theory, using flow velocity as 5ml min‐1If electrochemical oxidation reactions (5) all occur for the propane for inputting SOFC, quite
In generation electric current:(5 × 20 × 96500)/(22400 × 60)=7.2A, if the time for being passed through propane is t (min), pass through
The theoretical capacity of battery is 7.2t A min.And in fact, battery with 0.5A electric current operation t ' (min), passes through the reality of battery
Border electricity is 0.5t ' A min.The utilization rate of fuel is represented by (0.5/7.2) (t '/t) ≈ 0.07 (t '/t).
For being continuously passed through the battery of propane, it is equal with the time t of actual motion to be passed through the time t of propane, that is, fires
The utilization rate of material is 0.07 (1/1)=7%.
The main purpose of the present embodiment is checking when using Ag-GDC as anode, SOFC can using direct propane as
Fuel, it is passed directly into without reforming process in the case that anode chamber discharges and realizes continuous, stable work.Meanwhile this implementation
Example also serves as the contrast with lower embodiment 2-5, to prove efficient utilization of the method for the invention to propane fuel.
The present invention uses silver-based electrode as the anode material using propane as the SOFC of fuel, due to
Carbon distribution will not cause structural influence and destruction to silver electrode, and the carbon distribution effect for avoiding propane fuel is Ni-based to commercial SOFC
The influence of anode.During using Ag-GDC as anode, SOFC can using direct propane as fuel, it is straight without reforming process
Continuous, stable work is realized in the case of connecting anode chamber's electric discharge, without any obvious decay；The feature is to realizing
Commercialized propane SOFC has great significance.
Embodiment 2
25gYSZ is weighed, addition 38g alcohol, 2g PVB, 0.8g DOP, 0.8g PEG, 0.8g TEA, ball milling 2h are obtained
Even scattered slurry, YSZ electrolytic tube green compact are prepared using infusion process.Obtained green compact are positioned over the earthenware equipped with YSZ female powders
In crucible, it is put into Muffle furnace, 4h is sintered at 1450 DEG C, obtains the good YSZ electrolytic tubes of the mechanical strength of densification.This pipe range
About 2cm, external diameter 1cm, wall thickness 0.3mm.
Mass ratio is weighed respectively as 1:9 PVB and terpinol, is placed in beaker, and 24h conducts are dissolved in 60 DEG C of baking oven
Binding agent is stand-by.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 4.38g silver pastes, and (DAD-87, Shanghai City are closed
80%) and 1.5g GDC (after ball milling) resin research institute, amount containing Ag is, then weighs the binding agent that quality is 5g, adds agate
4h is ground in Nao mortars, obtains dispersed Ag-GDC combination electrode slurries.With pigment tools pen by Ag-GDC electrode slurrys
It is uniform to brush the whole inwall in electrolytic tube as anode, dry in 140 DEG C of high temperature oven, so repeat 3 times.Again
The slurry of a long 0.9cm of circle is applied as negative electrode in electrolytic tube outer wall, is dried in 140 DEG C of high temperature oven, so repeatedly 3
Time.It is then placed in Muffle furnace, the lower 880 DEG C of burnings 2h of air atmosphere, obtains the electrode that thickness is about 20 μm.The effective area of battery
(in terms of less negative electrode) is 2.8cm2。
Openend is fixed on diameter 10mm alundum tube by obtained monocell with silver paste.Separately take two diplopore corundum
Manage, a silver wire is respectively imported in each hole.Two silver wires of a piece diplopore alundum tube are connected to the negative electrode of monocell with silver paste
On, two silver wires of another diplopore alundum tube are connected in the sealing-in silver paste at monocell beginning end with silver paste (to be connected with anode
It is logical).
Fe(NO3)39H2O 20.20g is weighed, glycine 7.31g, is together dissolved in 100mL distilled water, magnetic agitation
30min, it is subsequently heated until spontaneous combustion.The precursor powder of generation is collected into crucible, burns 2h at 900 DEG C, obtains the promotion
Carbon deposition catalyst iron oxide.According to position shown in Fig. 1,0.5g iron oxide is taken to be positioned in anode chamber, and propane gas is led
Pipe is passed directly into anode chamber.The other end of alundum tube is sealed with plug afterwards, while exports one and truncates pipe as tail gas outlet
Pipe.
During test, the heated constant temperature area that the battery assembled is put into electric tube furnace rises to 800 DEG C.With IM6 electrochemistry works
Stand (ZAHNER) battery is tested, battery 0.5A constant-current discharges are set, and intermittence with 5mL/min flow is passed through third
Alkane, ventilate duration 1min every time.When stopping ventilation, battery is with DC-SOFC mode operation.When discharge voltage is down to 0V, depending on
Make deposition carbon electric discharge to complete, continuation is ventilated next time.Accompanying drawing 3 is battery under conditions of 800 DEG C, interval duration of ventilation 1min
Discharge curve.As seen from Figure 3, battery still has one section of about 3min stable discharging platform after the supply of propane is stopped, with
Voltage is just begun to decline afterwards.The appearance of discharge platform, is the direct performance of DC-SOFC mode of operations, i.e. battery leads at this stage
Carbon distribution caused by consumption Deposition During Propane Pyrolysis is crossed to be operated.
In theory, using flow velocity as 5ml min‐1If electrochemical oxidation reactions (5) all occur for the propane for inputting SOFC, quite
In generation electric current:(5 × 20 × 96500)/(22400 × 60)=7.2A, if the time for being passed through propane is t (min), pass through
The theoretical capacity of battery is 7.2t A min.And in fact, battery with 0.5A electric current operation t ' (min), passes through the reality of battery
Border electricity is 0.5t ' A min.The utilization rate of fuel is represented by (0.5/7.2) (t '/t) ≈ 0.07 (t '/t).
Run within 1 minute for above-mentioned logical propane, t=1min, t '=1min, the utilization rate of fuel is 0.07 (1/1) ≈
7%.And stop after inputting propane fuel into battery, battery again to lead to propane when deposition carbon on a catalyst as fuel stabilization
Run 3 minutes, 4 minutes, i.e. t '=4min, therefore the total fuel effectively to discharge have been run with 0.5A electric current equivalent to battery
Utilization rate is 0.07 (4/1)=28%.
The major measure of the present invention is that the catalyst for promoting carbon distribution reaction is added in anode chamber so that propane gas is in anode
After the preliminary electric discharge of room, the Carbon deposition in remaining propane is on a catalyst.After stopping ventilation, deposit the carbon to get off and be re-used as fuel confession
Discharged to SOFC, so as to which the utilization rate of propane fuel greatly improved.Using such as upper type, by specifically adjusting between ventilation
Every, SOFC can be caused directly to make fuel with propane and efficiently discharged, and simple in construction, without the device of additional complexity,
This is to realizing that propane SOFC commercial applications have great significance.
Embodiment 3
25gYSZ is weighed, addition 38g alcohol, 2g PVB, 0.8g DOP, 0.8g PEG, 0.8g TEA, ball milling 2h are obtained
Even scattered slurry, YSZ electrolytic tube green compact are prepared using infusion process.Obtained green compact are positioned over the earthenware equipped with YSZ female powders
In crucible, it is put into Muffle furnace, 4h is sintered at 1450 DEG C, obtains the good YSZ electrolytic tubes of the mechanical strength of densification.This pipe range
About 2cm, external diameter 1cm, wall thickness 0.3mm.
Mass ratio is weighed respectively as 1:9 PVB and terpinol, is placed in beaker, and 24h conducts are dissolved in 60 DEG C of baking oven
Binding agent is stand-by.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 4.38g silver pastes, and (DAD-87, Shanghai City are closed
80%) and 1.5g GDC (after ball milling) resin research institute, amount containing Ag is, then weighs the binding agent that quality is 5g, adds agate
4h is ground in Nao mortars, obtains dispersed Ag-GDC combination electrode slurries.With pigment tools pen by Ag-GDC electrode slurrys
It is uniform to brush the whole inwall in electrolytic tube as anode, dry in 140 DEG C of high temperature oven, so repeat 3 times.Again
The slurry of a long 0.9cm of circle is applied as negative electrode in electrolytic tube outer wall, is dried in 140 DEG C of high temperature oven, so repeatedly 3
Time.It is then placed in Muffle furnace, the lower 880 DEG C of burnings 2h of air atmosphere, obtains the electrode that thickness is about 20 μm.The effective area of battery
(in terms of less negative electrode) is 2.8cm2。
Openend is fixed on diameter 10mm alundum tube by obtained monocell with silver paste.Separately take two diplopore corundum
Manage, a silver wire is respectively imported in each hole.Two silver wires of a piece diplopore alundum tube are connected to the negative electrode of monocell with silver paste
On, two silver wires of another diplopore alundum tube are connected in the sealing-in silver paste at monocell beginning end with silver paste (to be connected with anode
It is logical).
Fe(NO3)39H2O 20.20g is weighed, glycine 7.31g, is together dissolved in 100mL distilled water, magnetic agitation
30min, it is subsequently heated until spontaneous combustion.The precursor powder of generation is collected into crucible, burns 2h at 900 DEG C, obtains the promotion
Carbon deposition catalyst iron oxide.According to position shown in Fig. 1,0.5g iron oxide is taken to be positioned in anode chamber, and propane gas is led
Pipe is passed directly into anode chamber.The other end of alundum tube is sealed with plug afterwards, while exports one and truncates pipe as tail gas outlet
Pipe.
During test, the heated constant temperature area that the battery assembled is put into electric tube furnace rises to 800 DEG C.With IM6 electrochemistry works
Stand (ZAHNER) battery is tested, battery 0.5A constant-current discharges are set, and intermittence with 5mL/min flow is passed through third
Alkane, ventilate duration 2min every time.When stopping ventilation, battery is with DC-SOFC mode operation.When discharge voltage is down to 0V, depending on
Make deposition carbon electric discharge to complete, continuation is ventilated next time.Accompanying drawing 4 is battery under conditions of 800 DEG C, interval duration of ventilation 2min
Discharge curve.As seen from Figure 4, battery still has one section of about 5min stable discharging platform after the supply of propane is stopped, with
Voltage is just begun to decline afterwards.The appearance of discharge platform, is the direct performance of DC-SOFC mode of operations, i.e. battery leads at this stage
Carbon distribution caused by consumption Deposition During Propane Pyrolysis is crossed to be operated.
In theory, using flow velocity as 5ml min‐1If electrochemical oxidation reactions (5) all occur for the propane for inputting SOFC, quite
In generation electric current:(5 × 20 × 96500)/(22400 × 60)=7.2A, if the time for being passed through propane is t (min), pass through
The theoretical capacity of battery is 7.2t A min.And in fact, battery with 0.5A electric current operation t ' (min), passes through the reality of battery
Border electricity is 0.5t ' A min.The utilization rate of fuel is represented by (0.5/7.2) (t '/t) ≈ 0.07 (t '/t).
Run within 2 minutes for above-mentioned logical propane, t=2min, t '=2min, the utilization rate of fuel is 0.07 (2/2) ≈
7%.And stop after inputting propane fuel into battery, battery again to lead to propane when deposition carbon on a catalyst as fuel stabilization
Run 5 minutes, 7 minutes, i.e. t '=7min, therefore the total fuel effectively to discharge have been run with 0.5A electric current equivalent to battery
Utilization rate is 0.07 (7/2) ≈ 25%.
The major measure of the present invention is that the catalyst for promoting carbon distribution reaction is added in anode chamber so that propane gas is in anode
After the preliminary electric discharge of room, the Carbon deposition in remaining propane is on a catalyst.After stopping ventilation, deposit the carbon to get off and be re-used as fuel confession
Discharged to SOFC, so as to which the utilization rate of propane fuel greatly improved.Using such as upper type, by specifically adjusting between ventilation
Every, SOFC can be caused directly to make fuel with propane and efficiently discharged, and it is simple in construction, without the device of additional complexity.
This is to realizing that propane SOFC commercial applications have great significance.
Embodiment 4
25gYSZ is weighed, addition 38g alcohol, 2g PVB, 0.8g DOP, 0.8g PEG, 0.8g TEA, ball milling 2h are obtained
Even scattered slurry, YSZ electrolytic tube green compact are prepared using infusion process.Obtained green compact are positioned over the earthenware equipped with YSZ female powders
In crucible, it is put into Muffle furnace, 4h is sintered at 1450 DEG C, obtains the good YSZ electrolytic tubes of the mechanical strength of densification.This pipe range
About 2cm, external diameter 1cm, wall thickness 0.3mm.
Mass ratio is weighed respectively as 1:9 PVB and terpinol, is placed in beaker, and 24h conducts are dissolved in 60 DEG C of baking oven
Binding agent is stand-by.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 4.38g silver pastes, and (DAD-87, Shanghai City are closed
80%) and 1.5g GDC (after ball milling) resin research institute, amount containing Ag is, then weighs the binding agent that quality is 5g, adds agate
4h is ground in Nao mortars, obtains dispersed Ag-GDC combination electrode slurries.With pigment tools pen by Ag-GDC electrode slurrys
It is uniform to brush the whole inwall in electrolytic tube as anode, dry in 140 DEG C of high temperature oven, so repeat 3 times.Again
The slurry of a long 0.9cm of circle is applied as negative electrode in electrolytic tube outer wall, is dried in 140 DEG C of high temperature oven, so repeatedly 3
Time.It is then placed in Muffle furnace, the lower 880 DEG C of burnings 2h of air atmosphere, obtains the electrode that thickness is about 20 μm.The effective area of battery
(in terms of less negative electrode) is 2.8cm2。
Openend is fixed on diameter 10mm alundum tube by obtained monocell with silver paste.Separately take two diplopore corundum
Manage, a silver wire is respectively imported in each hole.Two silver wires of a piece diplopore alundum tube are connected to the negative electrode of monocell with silver paste
On, two silver wires of another diplopore alundum tube are connected in the sealing-in silver paste at monocell beginning end with silver paste (to be connected with anode
It is logical).
Fe(NO3)39H2O 20.20g is weighed, glycine 7.31g, is together dissolved in 100mL distilled water, magnetic agitation
30min, it is subsequently heated until spontaneous combustion.The precursor powder of generation is collected into crucible, burns 2h at 900 DEG C, obtains the promotion
Carbon deposition catalyst iron oxide.According to position shown in Fig. 1,0.5g iron oxide is taken to be positioned in anode chamber, and propane gas is led
Pipe is passed directly into anode chamber.The other end of alundum tube is sealed with plug afterwards, while exports one and truncates pipe as tail gas outlet
Pipe.
During test, the heated constant temperature area that the battery assembled is put into electric tube furnace rises to 800 DEG C.With IM6 electrochemistry works
Stand (ZAHNER) battery is tested, battery 0.5A constant-current discharges are set, and intermittence with 5mL/min flow is passed through third
Alkane, ventilate duration 5min every time.When stopping ventilation, battery is with DC-SOFC mode operation.When discharge voltage is down to 0V, depending on
Make deposition carbon electric discharge to complete, continuation is ventilated next time.Accompanying drawing 5 is battery under conditions of 800 DEG C, interval duration of ventilation 5min
Discharge curve.As seen from Figure 5, battery still has one section of about 9min stable discharging platform after the supply of propane is stopped, with
Voltage is just begun to decline afterwards.The appearance of discharge platform, is the direct performance of DC-SOFC mode of operations, i.e. battery leads at this stage
Carbon distribution caused by consumption Deposition During Propane Pyrolysis is crossed to be operated.
In theory, using flow velocity as 5ml min‐1If electrochemical oxidation reactions (5) all occur for the propane for inputting SOFC, quite
In generation electric current:(5 × 20 × 96500)/(22400 × 60)=7.2A, if the time for being passed through propane is t (min), pass through
The theoretical capacity of battery is 7.2t A min.And in fact, battery with 0.5A electric current operation t ' (min), passes through the reality of battery
Border electricity is 0.5t ' A min.The utilization rate of fuel is represented by (0.5/7.2) (t '/t) ≈ 0.07 (t '/t).
Run within 5 minutes for above-mentioned logical propane, t=5min, t '=5min, the utilization rate of fuel is 0.07 (5/5) ≈
7%.And stop after inputting propane fuel into battery, battery again to lead to propane when deposition carbon on a catalyst as fuel stabilization
Run 9 minutes, 14 minutes, i.e. t '=14min, therefore the total combustion effectively discharged have been run with 0.5A electric current equivalent to battery
Material utilization rate is 0.07 (14/5) ≈ 20%.
The major measure of the present invention is that the catalyst for promoting carbon distribution reaction is added in anode chamber so that propane gas is in anode
After the preliminary electric discharge of room, the Carbon deposition in remaining propane is on a catalyst.After stopping ventilation, deposit the carbon to get off and be re-used as fuel confession
Discharged to SOFC, so as to which the utilization rate of propane fuel greatly improved.Using such as upper type, by specifically adjusting between ventilation
Every, SOFC can be caused directly to make fuel with propane and efficiently discharged, and it is simple in construction, without the device of additional complexity.
This is to realizing that propane SOFC commercial applications have great significance.
Embodiment 5
25gYSZ is weighed, addition 38g alcohol, 2g PVB, 0.8g DOP, 0.8g PEG, 0.8g TEA, ball milling 2h are obtained
Even scattered slurry, YSZ electrolytic tube green compact are prepared using infusion process.Obtained green compact are positioned over the earthenware equipped with YSZ female powders
In crucible, it is put into Muffle furnace, 4h is sintered at 1450 DEG C, obtains the good YSZ electrolytic tubes of the mechanical strength of densification.This pipe range
About 2cm, external diameter 1cm, wall thickness 0.3mm.
Mass ratio is weighed respectively as 1:9 PVB and terpinol, is placed in beaker, and 24h conducts are dissolved in 60 DEG C of baking oven
Binding agent is stand-by.According to Ag and GDC (Ce0.8Gd0.2O1.9) mass ratio be 7:3 weigh 4.38g silver pastes, and (DAD-87, Shanghai City are closed
80%) and 1.5g GDC (after ball milling) resin research institute, amount containing Ag is, then weighs the binding agent that quality is 5g, adds agate
4h is ground in Nao mortars, obtains dispersed Ag-GDC combination electrode slurries.With pigment tools pen by Ag-GDC electrode slurrys
It is uniform to brush the whole inwall in electrolytic tube as anode, dry in 140 DEG C of high temperature oven, so repeat 3 times.Again
The slurry of a long 0.9cm of circle is applied as negative electrode in electrolytic tube outer wall, is dried in 140 DEG C of high temperature oven, so repeatedly 3
Time.It is then placed in Muffle furnace, the lower 880 DEG C of burnings 2h of air atmosphere, obtains the electrode that thickness is about 20 μm.The effective area of battery
(in terms of less negative electrode) is 2.8cm2。
Openend is fixed on diameter 10mm alundum tube by obtained monocell with silver paste.Separately take two diplopore corundum
Manage, a silver wire is respectively imported in each hole.Two silver wires of a piece diplopore alundum tube are connected to the negative electrode of monocell with silver paste
On, two silver wires of another diplopore alundum tube are connected in the sealing-in silver paste at monocell beginning end with silver paste (to be connected with anode
It is logical).
Fe(NO3)39H2O 20.20g is weighed, glycine 7.31g, is together dissolved in 100mL distilled water, magnetic agitation
30min, it is subsequently heated until spontaneous combustion.The precursor powder of generation is collected into crucible, burns 2h at 900 DEG C, obtains the promotion
Carbon deposition catalyst iron oxide.According to position shown in Fig. 1,0.5g iron oxide is taken to be positioned in anode chamber, and propane gas is led
Pipe is passed directly into anode chamber.The other end of alundum tube is sealed with plug afterwards, while exports one and truncates pipe as tail gas outlet
Pipe.
During test, the heated constant temperature area that the battery assembled is put into electric tube furnace rises to 800 DEG C.With IM6 electrochemistry works
Stand (ZAHNER) battery is tested, battery 0.5A constant-current discharges are set, and intermittence with 5mL/min flow is passed through third
Alkane, ventilate duration 2min every time.When stopping ventilation, battery is with DC-SOFC mode operation.When discharge voltage is down to 0V, depending on
Make deposition carbon electric discharge to complete, continuation is ventilated next time.Accompanying drawing 6 is battery under conditions of 800 DEG C, interval duration of ventilation 10min
Discharge curve.As seen from Figure 6, battery after the supply of propane is stopped, putting down by the stable discharging for still having one section of about 15min
Platform, subsequent voltage are just begun to decline.The appearance of discharge platform, it is the direct performance of DC-SOFC mode of operations, i.e., battery is in the rank
Section is operated by consuming carbon distribution caused by Deposition During Propane Pyrolysis.
In theory, using flow velocity as 5ml min‐1If electrochemical oxidation reactions (5) all occur for the propane for inputting SOFC, quite
In generation electric current:(5 × 20 × 96500)/(22400 × 60)=7.2A, if the time for being passed through propane is t (min), pass through
The theoretical capacity of battery is 7.2t A min.And in fact, battery with 0.5A electric current operation t ' (min), passes through the reality of battery
Border electricity is 0.5t ' A min.The utilization rate of fuel is represented by (0.5/7.2) (t '/t) ≈ 0.07 (t '/t).
Run within 10 minutes for above-mentioned logical propane, t=10min, t '=10min, the utilization rate of fuel is 0.07 (10/10)
≈ 7%.And stop after inputting propane fuel into battery, carbon of the battery again using deposition during logical propane on a catalyst is steady as fuel
Run 15 minutes, run 25 minutes, i.e. t '=7min with 0.5A electric current equivalent to battery, therefore it is total effectively to discharge calmly
Fuel availability is 0.07 (25/10) ≈ 18%.
The major measure of the present invention is that the catalyst for promoting carbon distribution reaction is added in anode chamber so that propane gas is in anode
After the preliminary electric discharge of room, the Carbon deposition in remaining propane is on a catalyst.After stopping ventilation, deposit the carbon to get off and be re-used as fuel confession
Discharged to SOFC, so as to which the utilization rate of propane fuel greatly improved.Using such as upper type, by specifically adjusting between ventilation
Every, SOFC can be caused directly to make fuel with propane and efficiently discharged, and it is simple in construction, without the device of additional complexity.
This is to realizing that propane SOFC commercial applications have great significance.
From the point of view of fuel availability, the contrast of embodiment 2-5 and embodiment 1 can embody the advantage of the present invention：Based on this hair
It is bright that the catalyst for promoting carbon distribution reaction is added in anode chamber, and using being run by the way of alternately running, successfully by propane
Fuel availability (7%) improves 1.5~3 times (18%~28%), for realizing that propane SOFC commercial applications have emphatically
Big meaning.
Claims (9)
- A kind of 1. SOFC using propane, it is characterised in that：Including dense electrolyte, porous cathode, more Hole anode, porous catalyst and tubular cells conduit；Dense electrolyte is the cone tubular structure of one end closing, dense electrolyte Inside pipe wall is provided with porous anode, and outer wall is provided with porous cathode；Tubular cells tube at one end is connected with dense electrolyte openend, even Meet place and be provided with encapsulant, the other end is provided with plug；Gas conduit stretches into tubular cells conduit and dense electrolyte from plug In the porous catalyst for promoting carbon distribution reaction；Tail gas escape pipe is stretched into battery conduit from plug；Propane inlet and offgas outlet It is respectively provided at gas conduit and tail gas escape pipe entrance point and the port of export；Porous catalyst iron, cobalt or the nickel, or it is described Porous catalyst is the oxide powder of any one in iron, cobalt and nickel.
- 2. the SOFC according to claim 1 using propane, it is characterised in that：Described porous the moon Pole and porous anode are all made of the composite of silver powder and gadolinium or Sm doped CeO_2；Wherein, silver powder accounts for mixed powder The 45%~70% of quality；The slurry prepared by composite is coated in electrolytic tube supporter using brushing or spraying process Wall and outer wall, sintering 2-4h is formed in air at 600-880 DEG C.
- 3. the SOFC according to claim 1 using propane, it is characterised in that：Described densification electricity The material for solving matter is the zirconium oxide of stabillzed with yttrium；The conical tube type green compact prepared using slip casting or infusion process, in 1400- 3-4h is sintered at 1600 DEG C in air to be formed.
- 4. the SOFC according to claim 1 using propane, it is characterised in that：Described iron, cobalt Nitrate mixing glycine is corresponded to by iron, cobalt and nickel with the oxide powder of any one in nickel, dissolving is heated with stirring to spontaneous combustion, Obtained by combustion method.
- 5. the SOFC according to claim 1 using propane, it is characterised in that：Described seal For DAD-87 silver conductive adhesives.
- 6. the SOFC according to claim 1 using propane, it is characterised in that：Described battery is led The pipe of pipe, gas conduit and tail gas escape pipe all made by fire-resistant oxidation resistant material.
- 7. the SOFC according to claim 6 using propane, it is characterised in that：Described battery is led Pipe, gas conduit and tail gas escape pipe are all quartz ampoule or earthenware.
- 8. the SOFC according to claim 1 using propane, it is characterised in that：Described porous the moon Openend 3mm more than of the pole span from electrolytic tube supporter tubulose.
- 9. the method using propane fuel of any one of the application claim 1-8 SOFC, its feature It is, first propane fuel is passed through to galvanic anode room from propane inlet through gas conduit, after propane reaches anode chamber, via promotion The porous catalyst preliminary catalytic of carbon distribution reaction forms anode reaction gas, and electrochemical oxidation occurs in porous anode, and from more The oxonium ion that hole negative electrode occurs the former reaction of oxidation and passed over via dense electrolyte combines；Meanwhile electrochemical reaction product And the propane not reacted is promoting the porous catalyst surface generation carbon distribution of carbon distribution reaction to react to form carbon distribution；Anodic product Gas passes through from tubular cells conduit, via tail gas escape pipe, is discharged from offgas outlet；After continuing 1-10min, stop ventilation； Battery is to promote the carbon distribution on carbon deposition catalyst as fuel, and into DC-SOFC mode of operations, carbon distribution is promoting carbon distribution catalytic reaction Bouduard reaction generation CO, CO occurs under the catalysis of agent with the former reaction of oxidation occurring and via dense electrolyte from porous cathode The oxonium ion that matter passes over combines, and generates CO2And sustained release goes out electric energy, CO is generated2Tail gas has not contained energy, via Tail gas escape pipe is discharged from offgas outlet；When carbon distribution is close to be run out of, above-mentioned journey is repeated, realizes the direct, high of propane fuel Effect utilizes.
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| CN109755611A (en) * | 2019-01-25 | 2019-05-14 | 广东工业大学 | The solid oxide fuel cell stack of direct propane partial oxidation steam reforming |
| CN110752399A (en) * | 2019-08-14 | 2020-02-04 | 华南理工大学 | Tube type direct carbon solid oxide fuel battery pack with reusable row structure |
| CN114280495A (en) * | 2021-12-17 | 2022-04-05 | 中国地质大学（武汉） | Device for testing single solid oxide battery |
| CN115275242A (en) * | 2022-08-17 | 2022-11-01 | 华南理工大学 | Device for continuously providing fuel for direct carbon solid oxide fuel cell |
| CN116137341A (en) * | 2023-04-19 | 2023-05-19 | 安徽华曙科技有限公司 | Power generation device using plants as raw materials and power generation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109755611A (en) * | 2019-01-25 | 2019-05-14 | 广东工业大学 | The solid oxide fuel cell stack of direct propane partial oxidation steam reforming |
| CN110752399A (en) * | 2019-08-14 | 2020-02-04 | 华南理工大学 | Tube type direct carbon solid oxide fuel battery pack with reusable row structure |
| CN110752399B (en) * | 2019-08-14 | 2020-12-22 | 华南理工大学 | Tube type direct carbon solid oxide fuel battery pack with reusable row structure |
| CN114280495A (en) * | 2021-12-17 | 2022-04-05 | 中国地质大学（武汉） | Device for testing single solid oxide battery |
| CN115275242A (en) * | 2022-08-17 | 2022-11-01 | 华南理工大学 | Device for continuously providing fuel for direct carbon solid oxide fuel cell |
| CN115275242B (en) * | 2022-08-17 | 2024-06-07 | 华南理工大学 | Device for continuously supplying fuel for direct carbon solid oxide fuel cell |
| CN116137341A (en) * | 2023-04-19 | 2023-05-19 | 安徽华曙科技有限公司 | Power generation device using plants as raw materials and power generation method thereof |
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| CN107579268B (en) | 2020-05-22 |
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