CN105206862B - A kind of direct carbon solid oxide fuel cell stack system of antimony anode and preparation method - Google Patents
A kind of direct carbon solid oxide fuel cell stack system of antimony anode and preparation method Download PDFInfo
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- CN105206862B CN105206862B CN201510555801.9A CN201510555801A CN105206862B CN 105206862 B CN105206862 B CN 105206862B CN 201510555801 A CN201510555801 A CN 201510555801A CN 105206862 B CN105206862 B CN 105206862B
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- antimony
- pile
- fuel
- collecting pit
- fuel tank
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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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0693—Treatment of the electrolyte residue, e.g. reconcentrating
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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
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- 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
- H01M8/2465—Details of groupings of fuel cells
-
- 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
- H01M2008/1293—Fuel cells with solid oxide 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
Abstract
The invention discloses a kind of direct carbon solid oxide fuel cell stack system of liquid circulation antimony anode tubular type and preparation method thereof, belong to fuel cell field.Battery stack system includes battery pile, antimony oxide collecting pit, fuel tank, fuel loading device, the outlet of battery pile is provided with the top of battery pile, and bottom is provided with battery pile entrance；The antimony oxide collecting pit entrance being connected with the outlet of battery pile is set at the top of antimony oxide collecting pit, and its bottom is provided with the antimony oxide collecting pit outlet for antimony oxide outflow；Fuel loading device is provided with the top of fuel tank, the top is additionally provided with the fuel tank entrance being connected with the outlet of antimony oxide collecting pit simultaneously, and its bottom is provided with the fuel tank flowed out for being reduced the antimony obtained by fuel and exported, battery pile described in the outlet.The invention also discloses the preparation method of battery stack system.Battery stack system of the present invention is conveniently loaded directly into solid carbon fuel, and liquid antimony anode is not easy to be poisoned pollution.
Description
Technical field
The invention belongs to the fuel cell field of clean energy resource, more particularly, to a kind of liquid circulation antimony anode tubular type
Direct carbon solid oxide fuel cell pile and preparation method thereof.
Background technology
Today's society, energy crisis have become worldwide subject under discussion.Now widely used fossil energy is non-renewable
, and the fast development of society causes substantial amounts of energy resource consumption, makes such traditional energy increasingly deficient.The combustion of fossil energy simultaneously
Environmental pollution caused by burning brings serious harm to human lives.More advanced, the more efficient, source of mankind's urgent need is more
Extensive and use more easily energy technology.In this context, reliable, the environmentally friendly energy sources of exploitation, mitigate traditional
The pressure of the stone energy, and global common recognition is had become using the energy technology more cleaned.
SOFC is (referred to as：SOFC) as a kind of new energy conversion device, can tackle at present
The energy shortage problem run into, thus the concern of many countries of the world has been obtained, increasing scientific worker puts into
Substantial amounts of time and efforts is engaged in correlative study.SOFC is to be converted into the chemical energy in fossil fuel using chemical reaction
Electric energy.In energy conversion process, without combustion process, also without mechanical process, therefore SOFC has that noise is low, energy conversion
The characteristics of rate is high.Simultaneously because the product to react is water, discharged without gases such as sulfide, nitride, SOFC has height
The characteristics of effect, cleaning, it is effective TRT of reply energy crisis generally acknowledged at present.
Presently, the fuel of SOFC is mainly hydrogen and natural gas, but hydrogen is prepared into
This is higher, and storage safety cost is too high；And on the other hand, natural gas needs extra reformer apparatus to aid in, and avoids anode one
The carbon distribution of side occurs, and anode side carbon distribution or sulphur phostoxinization can cause galvanic anode (NiO/YSZ) that irreversible knot occurs
Structure destroys, and finally results in battery pile and fails.For fuel, nature has the high carbon containing solid fuel of many,
Such as coal, oil and biomass fuel.These fuel bring electric power and heat in a manner of burning to people's life mostly now
Amount, but in general, their fuel availability is relatively low, and discharges many greenhouse gases.More it is essential that fossil
The storage of fuel is limited.So it come the technology that high efficiency generates electricity can be people directly using solid carbon fuel to seek a kind of
The active demand of class society.
Direct carbon solid oxide fuel cell is a kind of clean energy technology for directly using solid carbon fuel.Oxygen exists
Cell cathode absorption is dissociated into oxonium ion and transmitted reaches anode and carbon atom generation electrochemical reaction by dielectric substrate, produces
Electric energy.But oxonium ion is existed only near tens microns of electrolyte anodic interface, so it should be evident that carbon atom and oxygen
Ion does not have good physical chemistry to contact, and causes the power of battery relatively low.Many researchers employ many methods and go to improve electricity
The electrochemical reaction in pond, wherein producing the side of carbon monoxide and hydrogen using carbon dioxide or steam gasification solid carbon fuel
Method occupies main flow.Secondly, connect by the use of eutectic fused carbonate as oxonium ion carrier increase solid carbon and carbanion
Contacting surface is accumulated so as to realize higher electrochemistry speed.
Recently, the direct carbon solid oxide fuel electricity of metal or alloy anode of liquid condition is presented at the working temperature
Pond have received larger concern.Low-melting-point metal such as bismuth, lead, indium, tin antimony, silver and its alloy are all used as anode, research
Person uses relatively thin electrolyte to achieve the higher power of battery as supporter.
But plate armature battery is faced with used by most of liquid metal or alloy anode researchers at present
The problem of many：(1) after planar cells integration stacks, solid fuel is loaded without cavity space；(2) liquid phase anode
In the presence of causing planar cells can not assemble, seal at all, loading fuel can not be continued；(3) antimony of traditional plate armature
There is processing fuel ashes, residue challenge in anode cell, and its antimony anode is easily poisoned pollution so as to influence battery
Performance even causes to fail.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of direct carbon solid oxidation of antimony anode
Thing fuel cell pile system and preparation method, it is intended that the encapsulation of tubulose antimony anode monocell is assembled into pile device,
And antimony oxide pond, fuel tank, antimony purification devices are set gradually, it should be able to mutually realize that fuel cell pile system is loaded directly into solid carbon
Fuel, and liquid antimony passes through the problem of purifying will not occur to be poisoned pollution, thus solves existing directly carbon solid oxide combustion
Material battery can not continue loading fuel and the technical problem that anode is easily poisoned pollution be present.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of direct carbon solid oxide of antimony anode
Fuel cell pile system, it includes battery pile, antimony oxide collecting pit, fuel tank, fuel loading device, wherein,
The battery pile includes liquid antimony anode, the outlet of battery pile is provided with the top of the battery pile, for battery
The antimony oxide outflow that liquid antimony generates in pile reaction, its bottom is provided with the battery pile entrance of feed flow state antimony inflow；
The antimony oxide collecting pit entrance being connected with battery pile outlet is set at the top of the antimony oxide collecting pit, and
Its bottom is provided with the antimony oxide collecting pit outlet for antimony oxide outflow；
Fuel loading device is provided with the top of the fuel tank, the top is additionally provided with and the antimony oxide collecting pit simultaneously
The fuel tank entrance being connected is exported, the fuel tank bottom is provided with the fuel tank flowed out for being reduced the antimony obtained by fuel and gone out
Mouthful, battery pile described in the outlet, the antimony obtained after antimony oxide is reduced carries out recycling.
Further, in addition to antimony purification devices, the antimony purification devices two bottom sides are respectively arranged with antimony purification devices
Entrance and the outlet of antimony purification devices, the antimony purification devices entrance connect the fuel tank outlet, will reduce and obtain through fuel
Antimony be introduced into the antimony purification devices and carry out purification process.
Further, in addition to antimony holder, the antimony holder are provided with antimony holder entrance and antimony holder simultaneously
Outlet, the antimony holder entrance connect the antimony purification devices outlet, and battery electricity described in the antimony holder outlet
Heap.Antimony holder stores enough antimony, with the antimony of replenishment system loss and can ensure in the continual pile to battery
Face inputs enough liquid antimony.
Further, antimony oxide collecting pit outlet is provided with the passage of directly connection battery pile, for will be from electricity
The liquid antimony for not participating in cell reaction flowed out in the pile of pond is imported into battery pile again.
Further, antimony oxide collecting pit outlet be provided with directly connect respectively the antimony oxide collecting pit entrance and
The passage of the fuel tank entrance, antimony oxide collecting pit or fuel are re-fed into the antimony oxide that will likely be flowed out from bottom
Pond.
Further, the battery pile is integrated in multiple parallel with one another in pile cavity including pile cavity and encapsulation
Monocell, wherein, in a tubular form, the inwall of the tubular cell is negative electrode to the monocell or is loaded with the cathode branch of negative electrode
Support body, the outer wall of the tubular cell is electrolyte or electrolyte-supported body, and the anode of the tubular cell is located at the electricity
Solve matter surface or electrolyte-supported body surface face；The inside of the pile cavity has cavity, for the accommodating liquid as anode
State antimony.
Further, the pile cavity outward appearance is rectangular, is provided with the two opposite side walls of the rectangle pile cavity
Gas reserved opening is protected, being passed through protection liquid antimony for the protection gas reserved opening through side exempts from oxidized gas and through another
The protection gas reserved opening discharge of side.
One complicated electricity generation system is divided into each independent several parts by the present invention, is respectively：Battery pile, oxidation
Antimony collecting pit, fuel tank, antimony purification devices, antimony holder.Be connected between each part by pipeline, and between have switch with
And alternate channel, when some section failure needs to change or repaired, can open alternate channel can still ensure just
Often generate electricity.
The present invention generates electricity the pile of liquid antimony anode SOFC pile electricity generation system with anode antimony also
Original recycles two cores and has carried out mechanism segmentation, simplifies the working method of system so that system integrally becomes letter
Single, applicability and reliability are higher.The reduction of anode antimony recycles mutually independent, the convenient fuel loading that generated electricity with the pile of fuel tank
With the remaining rubbish of cleaning.The antimony recycled passes through purification process, and battery pile is not easy to be poisoned pollution.
It is another aspect of this invention to provide that additionally provide a kind of side for preparing fuel cell pile system as described above
Method, it is characterised in that it comprises the following steps：
S1：Pile cavity is prepared, and anode current collector device and cathode collector device are set in reserved location, by multiple single electricity
Pond integration packaging obtains pile intermediate on pile cavity, and metallic antimony powder is added into pile intermediate；
S2：The liquid antimony circulatory system is set on pile intermediate, obtains battery stack system, the liquid antimony cyclic system
System includes the antimony oxide collecting pit being connected with pile intermediate, the fuel tank connected with antimony oxide collecting pit, fuel tank upper end
It is provided with fuel loading device.
Further, the liquid antimony circulatory system described in step S2 also includes antimony purification devices, the antimony purification devices
Entrance is connected with fuel tank, and the outlet of the antimony purification devices is used to the antimony for entering purification process being sent into antimony holder.
Further, described in step S2, the liquid antimony circulatory system also includes antimony holder, the antimony holder simultaneously with
Antimony purification devices are connected with pile cavity.
In general, by the contemplated above technical scheme of the present invention, following beneficial effect can be obtained：
The 1st, antimony oxide collecting pit is set to realize the separation of antimony oxide and antimony metal caused by pile work, merely with oxidation
Antimony is different with the density of metallic antimony and realizes and is automatically separated, and does not expend energy, is also provided with fuel tank, makes the reduction of antimony oxide
Carried out in a single fuel chambers, compared to fuel tank, antimony oxide pond and liquid antimony in same chamber indoor design, we
Invention effectively prevent the operation of the overall pile of other adverse factors influence such as ashes, impurity of fuel.Also, the combustion of fuel chambers
Material loading can use timing load mode, without the continuous loading of continuation, greatly simplify the mode of fuel loading, improve effect
Rate.
2nd, set antimony purification devices to purify the antimony being reduced, the remaining ash of fuel in the reaction of pile can be prevented
Cinder, impurity or there are some metallic elements to be reduced into metallic state and enter in liquid antimony, prevent later stage antimony from recycling
During the adverse effect brought to battery pile.
Brief description of the drawings
Fig. 1 is tubular type single-cell structure schematic diagram in the embodiment of the present invention；
Fig. 2 is the diagrammatic cross-section that the set of tubular type monocell is sealed into pile trailing flank in the embodiment of the present invention；
Fig. 3 is that the set of tubular type monocell is sealed into positive diagrammatic cross-section after pile in the embodiment of the present invention；
Fig. 4 is that the set of tubular type monocell loads antimony after being sealed into pile in the embodiment of the present invention and the side profile of fuel shows
It is intended to；
Fig. 5 is that Chinese style monocell set of the embodiment of the present invention is sealed into the front cross-sectional of loading antimony and fuel signal after pile
Figure；
Fig. 6 is pile, antimony oxide collecting pit, fuel tank, antimony purification devices, antimony in the embodiment of the present invention in stack system
The flowing flow graph of holder and antimony loop control dress device in real work；
Fig. 7 is antimony and the substantially distribution situation of antimony oxide throughout in the embodiment of the present invention in the stack system course of work.
In all of the figs, identical reference is used for representing identical element or structure, wherein：
1- cathode support layers either negative electrode 2- electrolyte or electrolyte-supported layer
3- pile cavity 4- encapsulants
5- protects gas reserved opening 6- antimony powder load reservation mouths
7- carbon fuel 8- metallic antimonies
9- cathode collector line 10- anode current collector lines
Switch between the units of K- two, K1, K2, K3, K4, K5 represent respectively first switch, second switch, third switch,
4th switch and the 5th switch；
The standby antimony channel switch of S-, S1 switch for battery pile opening, and S2 switchs for antimony oxide collecting pit opening, and S3 is pipe
Road separates switch.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
The direct carbon solid oxide fuel cell stack system of a kind of antimony anode in the present invention, including battery pile, oxygen
Change antimony collecting pit, fuel tank, fuel loading device, the anode of battery pile is liquid antimony, and electricity is provided with the top of the battery pile
The outlet of pond pile, its bottom are provided with the battery pile entrance of feed flow state antimony inflow, set at the top of antimony oxide collecting pit with it is described
The antimony oxide collecting pit entrance that the outlet of battery pile is connected, and its bottom is provided with the antimony oxide collecting pit for antimony oxide outflow
Outlet, fuel tank top are provided with fuel loading device, and the top is additionally provided with simultaneously and the antimony oxide collecting pit exports phase
The fuel tank entrance of connection, fuel tank bottom are provided with the fuel tank flowed out for being reduced the antimony obtained by fuel and exported, the outlet
Connect the battery pile.
The battery pile of the battery stack system of the present invention is integrated in more in pile cavity including pile cavity 3 and encapsulation
Individual monocell parallel with one another, in a tubular form, the inwall of tubular cell is negative electrode or the cathode support for being loaded with negative electrode to monocell
Body 1, the outer wall of tubular cell is that electrolyte or the electrolyte-supported body 2 for being loaded with electrolyte, the anode of tubular cell are located at
Bath surface or the electrolyte-supported body surface face for being loaded with electrolyte；The inside of pile cavity has cavity, for housing
Liquid antimony as anode.
In the present invention, the operation principle of battery is：
Electrochemical cathode reacts：O2+4e-→2O2-
Anode electrochemical reacts：4/3Sb+2O2-→2/3Sb2O3+4e-
Overall reaction：4/3Sb+O2→2/3Sb2O3
Oxygen adsorbs on cathode material to be received electronics and is dissociated into oxonium ion, oxonium ion diffuse through electrolyte to electrolysis and
The interface of anode, electrochemical reaction generation antimony oxide occurs with metal antimony atoms and discharges electronics.The chemical property of battery
Determined by the electrochemical reaction of negative electrode and anode, and the long-term behaviour of battery then by battery material stability and antimony oxide also
The continuation and promptness of original reaction determine.
The reduction reaction of antimony oxide：2/3Sb2O3+C→4/3Sb+CO2
When higher than more than 700 DEG C, the side reaction for having generation CO occurs, while Bounduard Reaction for this reaction
(gasification reaction) can also occur, and generate CO.When the antimony oxide of anode electrochemical reaction generation is more than 656 DEG C, liquid state is presented
State.Due to having less density relative to liquid antimony, convection current can occur for antimony oxide and liquid antimony under gravity, float to liquid
The surface of state antimony, the antimony oxide to rise to the surface just have an opportunity and solid carbon fuel reaction, are reduced into antimony again.
Fig. 1 is tubular type single-cell structure schematic diagram in the embodiment of the present invention, and Fig. 2 is tubular type monocell in the embodiment of the present invention
Set is sealed into the diagrammatic cross-section of pile trailing flank, and Fig. 3 is that the set of tubular type monocell is sealed into pile in the embodiment of the present invention
Positive diagrammatic cross-section afterwards, as seen from the figure, the monocell intermediate arrangement that sealing is integrated in pile cavity are regular, have six
File and six horizontally-arranged, each tubulose monocell is mutually arranged in parallel, arranges 36 tubulose monocell intermediates altogether,
But the present invention is limited without specific the quantity of the monocell of the arrangement in pile.
The outward appearance of pile cavity 3 is rectangular, and protection gas reserved opening is provided with the two opposite side walls of the rectangle pile cavity
5, it is passed through for the protection gas reserved opening 5 through side and protects liquid antimony to exempt from oxidized gas and the guarantor through opposite side
Shield gas reserved opening 5 is discharged.The top of pile cavity 3 is also provided with antimony powder load reservation mouth 6, and antimony powder load reservation mouth 6 is not must
Must, the antimony powder load reservation mouth can also be not provided with, adding for original antimony powder can be carried out by the antimony powder load reservation mouth
Enter.
Fig. 4 is that the set of tubular type monocell loads antimony after being sealed into pile in the embodiment of the present invention and the side profile of fuel shows
It is intended to, Fig. 5 is that Chinese style monocell set of the embodiment of the present invention is sealed into the front cross-sectional schematic diagram of loading antimony and fuel after pile,
In above figure, 8 be metallic antimony, and it is anode, and 9 be cathode collector line, and 10 be anode current collector line.The antimony powder for carrying out most original adds
Afterwards, pile makes antimony powder melt referred to as liquid completely, it is necessary to perform heating to pile before being operated, and infiltrates in tubular type list electricity
The surface in pond, perform the function of anode.
Fig. 6 is battery pile, antimony oxide collecting pit, fuel tank, antimony purifying dress in the embodiment of the present invention in stack system
Put, flowing flow graph of the antimony holder in real work.As seen from the figure, battery stack system of the invention also includes antimony purifying
Device and antimony holder, antimony purification devices two bottom sides are respectively arranged with antimony purification devices entrance and the outlet of antimony purification devices, antimony
Purification devices entrance connects the fuel tank outlet.Antimony holder is provided with antimony holder entrance and the outlet of antimony holder simultaneously,
The outlet of antimony holder entrance connection antimony purification devices, and battery pile described in antimony holder outlet.Antimony oxide collecting pit goes out
Mouth is provided with the passage of directly connection battery pile.Antimony oxide collecting pit outlet is additionally provided with directly connects the oxidation respectively
The passage of antimony collecting pit entrance and the fuel tank entrance.
In a preferred embodiment of the invention, it is provided with first on the passage between battery pile and antimony oxide collecting pit
K1 is switched, second switch K2, antimony oxide collecting pit and antimony holder are set on the passage between antimony oxide collecting pit and fuel tank
Between be provided with the 3rd switch K3, have the 4th switch K4 between fuel tank outlet and antimony purification devices, antimony purification devices and antimony store up
The 5th switch K5 is provided between storage.
The first to the 5th on-off action is specifically described with reference to the battery stack system course of work：
Process one：In the course of work, K1 is kept it turned on, and K2 is closed, and K3 is opened, and K4 and K5 are closed, and antimony circulation is opened.Process
Two：After antimony oxide collecting pit collects full antimony oxide, close K3 and open K2 simultaneously, antimony oxide is passed through fuel tank, now antimony follows
Ring does not interrupt, and the antimony in antimony holder still keeps being passed through to inside battery pile, and in engineering practice, this process is quickly
Complete, afterwards, close K2 and open K3, system normal operation.Process three：After process two is carried out several times, will have in fuel big
The antimony oxide of amount, fuel loading device is now opened, antimony oxide is reduced, after reduction is over, opened K4, antimony is led to
Enter into antimony purification devices and purified, after completion, open K5, antimony enters in antimony holder, and is recycled in battery pile.
Process four：After process three has carried out certain number, impurity cleaning can be carried out to fuel tank, this is for this high impurity of coal
Fuel utilization it is very crucial.This Four processes is not to carry out simultaneously, the lasting progress of process one, but process two,
Three and four fundamental rules be interruption carry out.Above efforts can embody the independence of modular advantage, fuel tank and antimony purification devices
Operation greatly optimizes electricity generation system so that more independent between system components, operation is more stable.
The battery stack system of the present invention is equipped with Sb circulation alternate channels, specially battery pile opening switch S1, oxygen
Change antimony collecting pit opening switch S2, S1 and S2 to be typically turned off, also pipeline separates switch S3 in addition, and S3, which is generally, closes shape
State, for split it is standby by and regular channels.Specific use is：When antimony oxide collecting pit breaks down, then need to close
K1 is closed, opens switch S1, S2 and second switch K2 on alternate channel, and closes K3, allows antimony oxide to be directly entered fuel
Pond.When antimony oxide collecting pit and fuel tank simultaneous faults, K1 and K2 is closed, S1 and S2 is opened, allows antimony oxide temporarily with antimony
Circulated together in pipeline.
Fig. 7 is antimony and the substantially distribution situation of antimony oxide throughout in the embodiment of the present invention in the stack system course of work,
Further, illustrate that the course of work of battery system of the present invention is as follows with reference to the figure：
Operating temperature is warming up to, the certain Sb of flow velocity flows into from pile bottom, is recycled from pile top and carrys out and take out of electricity
Antimony oxide caused by the work of pond, is entered in antimony oxide collecting pit；Antimony oxide collecting pit is used for the antimony oxide of aggregation formation, relies on
Density contrast allows Sb and Sb2O3Sb can be exported and is recycled into battery by AUTOMATIC ZONING, bottom of pond end；Work as Sb2O3Collecting pit gathers
During a certain amount of antimony oxide, antimony oxide is rejected in fuel tank from bottom of pond end；Fuel tank possesses feed arrangement, and timing loads combustion
Material, Sb is reduced and generates metallic antimony；Through after a period of time, due to the remaining ashes of fuel, impurity can be gathered in fuel
Chi Zhong, and be layered according to density in fuel tank；There are some metallic elements to be reduced into metallic state and enter in Sb alloys；
The fuel ashes residue in fuel tank is handled, and purifies Sb, is put back into.
The method for preparing fuel cell pile system of the present invention, comprises the following steps：
S1：Pile cavity is prepared, and anode current collector device and cathode collector device are set in reserved location, by multiple single electricity
Pond integration packaging obtains pile intermediate on pile cavity, and metallic antimony powder is added into pile intermediate；
S2：The liquid antimony circulatory system is set on pile intermediate, obtains battery stack system, the liquid antimony cyclic system
System includes the antimony oxide collecting pit being connected with pile intermediate, the fuel tank connected with antimony oxide collecting pit, fuel tank upper end
It is provided with fuel loading device.
In a preferred embodiment of the present invention, the process for preparing the fuel cell pile system of the present invention is as follows：
(1) tubular type is prepared without anode monocell, and the zirconium oxide using the Yttrium oxide doping of 8% molal weight is used as electrolyte
(8YSZ), cathode collector device is distributed on monocell.In the step, monocell can be cathode support can also be electrolysis
Matter support, during the use of the monocell of tubular structure afterwards, without Volume Changes caused by redox, structure one
Cause property is good, it is not easy to damages.
(2) prepare the pile cavity of 8YSZ materials and complete anode and cathode collector device in reserved location.Its Anodic
Using conductive anode antimony afflux, using rhenium line extracted current, negative electrode smears the silver paste of uniform thickness as current collecting material, uses
LCN powders or oxidation resistant platinum line derived current.
Pile cavity solid content has certain thickness, by force more than 98%, and without larger defects such as through hole crackles
Degree.When preparing pile cavity, the base substrate of pile cavity is first prepared, the manufacture of base substrate uses traditional ceramic technique, made
Sintering is completed after base substrate, degreasing.Base substrate can reserve recycling-guard gas inlet and outlet.Using the electrolyte with monocell intermediate
Identical material prepares pile cavity, and homogeneous material prepares pile cavity, and the thermal expansion between pile cell has preferable
Match somebody with somebody, thermal stress is smaller, and the reliability of pile is greatly improved.
(3) the multiple monocells for being distributed cathode collector device are sealed on the pile cavity of 8YSZ materials, monocell
Arranged in pile cavity regular, cathode collector system uses traditional SOFC current collection mode, monocell
Between take parallel-connection structure, global failure caused by part easily occurs for the conventional cascaded structure of flat plate cell.The list of 8YSZ materials
Gap needs to seal between battery tube wall and 8YSZ pile cavitys, and sealing uses refractory ceramics fluid sealant, refractory ceramics fluid sealant
Heat to hold in both hands coefficient close with 8YSZ.
(4) metallic antimony powder is added into pile cavity by antimony powder load reservation mouth, the specific quality for adding antimony powder can
Volume is estimated according to pile cavity size and battery size, quality is calculated in conjunction with density.
(5) the liquid Sb circulatory systems are set, and what the circulatory system included being connected with battery pile end is used to collect electricity
The collecting pit of the antimony oxide generated in the course of reaction of pond, the fuel tank connected with antimony oxide collecting pit, fuel tank upper end are provided with
Fuel loading device, for loading fuel into fuel tank, fuel tank is for for the antimony oxide from antimony oxide collecting pit and admittedly
State carbon fuel occurs also to react, and is reduced into antimony oxide for metallic antimony, liquid Sb and Sb2O3The circulatory system also includes and combustion
The antimony purification devices that material pond is connected, for being purified to the liquid antimony reduced through solid carbon fuel, and purify and fill with antimony
The antimony memory being connected is put, the antimony memory is connected with the bottom of battery pile.Antimony oxide collecting pit upper end is provided with oxidation
Antimony import, and its bottom is provided with outlet, sets exit opening to be in bottom in order to by responseless Sb export and and then again
It is new to import in battery pile, while avoid antimony from occupying the space of antimony oxide collecting pit.
In the present invention, standby Sb circulating paths, the damage of some link or replacing of the liquid Sb circulatory systems can be set
During maintenance, flowpath redundancies can be enabled, the reaction of battery pile will not be interrupted.
In the present invention, the fuel of actual use is mostly fossil fuel, and they are after processing, still some oxygen of remaining
The impurity such as compound, sulfide, after the carbon of fuel is finished, has ashes and residue is retained.More seriously, Partial Elements
For example Fe, Ni, Cu etc. can be reduced into metallic state by fuel and enter in Sb, so as to cause Sb impure.These metallic elements due to
There is higher activity compared with Sb, and its oxide has higher fusing point, thus solid-state can be generated by oxonium ion preferential oxidation
Oxide, oxide concentration cause larger resistance in the interface of electrolyte and Sb, cause battery to decay rapidly.So and
When treatment of battery inside ashes residue, and it is particularly significant and necessary to purify Sb.When the reaction of pile passes through one section
Between after, remaining ashes, the impurity of fuel can be gathered in fuel tank, and are layered according to density in fuel tank, or also have
Some metallic elements can be reduced into metallic state and enter in liquid Sb, be unfavorable for recycling for later stage, so setting antimony
Purification devices purify to antimony.
In the present invention, the separation of antimony oxide and antimony metal caused by pile work is realized there is provided antimony oxide collecting pit,
Different only with the density of antimony oxide and metallic antimony and realize and be automatically separated, separate mode is very easily gravity effect
Should, without additional energy.Also, after antimony oxide reduction, the metallic antimony of formation is different from antimony oxide density, utilizes gravitational effect
Also can AUTOMATIC ZONING.
In the present invention, there is provided fuel tank, the reduction of antimony oxide is carried out in a single fuel chambers, compared to combustion
The design of material pond, antimony oxide pond and liquid antimony in same chamber, we's invention effectively prevent ashes, the impurity of fuel
The operation of overall pile is influenceed Deng other adverse factors.
In the present invention, the loading of the fuel of fuel chambers can use timing load mode, without the continuous loading of continuation, significantly
Simplify the mode of fuel loading, improve efficiency, it is even more important that the requirement for protective atmosphere is greatly reduced.
Furthermore, it is possible to reduction-oxidation antimony at a lower temperature, is even reduced in solid-state.The charging of fuel tank is uniform, can be with
Avoid once loading multi fuel, the violent heat release of meeting, it is contemplated that for the sake of safety, charging should be at the uniform velocity.
In the present invention, the Sb cyclic processes of pile can only be oxidized antimony collecting pit and directly affect, fuel tank, antimony purification devices
Efficiency can't directly affect the service behaviour of pile, fuel tank and antimony purification devices are to recycle antimony for reducing.
Antimony holder is then the direct guarantee of antimony needed for antimony circulation in battery pile.
In the present invention, compare due to the reduction process of no anode, while in view of the thermal coefficient of expansion of overall pile
Match somebody with somebody, so the thermal stress of pile is smaller.So the SOFC supported relative to traditional NiO/YSZ, pile
From room temperature to operating temperature and run time can be substantially reduced.
In the present invention, antimony oxide collecting pit is used for assembling antimony oxide, prepares the materials'use and list of the antimony oxide collecting pit
The identical material of cell electrolyte makes, and the size of collecting pit is changeable according to needing, and module can be used according to being actually needed
Mode handle, several collecting pits can be used simultaneously.
Present system has good thermal shock resistance, can be worked within the scope of wider temperature, between each module
Allow the temperature difference of certain limit, antimony oxide reduction process and antimony purification devices can be different from stack temperature in fuel tank
Carried out at a temperature of one, most desirable temperature can be selected according to industrial technology.
In the present invention, stack system is equipped with Sb circulation alternate channels, and when some device breaks down, at this moment Sb is standby
Passage can play good effect.
In the present invention, antimony oxide collecting pit, fuel tank, antimony purification devices, antimony holder are all separate, are each had
There is independent sensing and controlling system, when the conditions are met, will be fed back according to respective state and be worked accordingly,
It is convenient for changing expansion simultaneously.
Present system has a modularization advantage of height, and module has a selectivity of height, an independent module it is excellent
Change has no effect on effectiveness of the invention.Antimony oxide collecting pit and fuel tank can be single modules, possess independent temperature
Control and module management system.The purification process of residue and ashes processing method and Sb has no effect on the present invention in fuel tank
Application and validity.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (8)
1. a kind of direct carbon solid oxide fuel cell stack system of antimony anode, it is characterised in that it includes battery pile, oxygen
Change antimony collecting pit, fuel tank, fuel loading device, the battery pile, antimony oxide collecting pit, fuel tank, fuel loading device
Respective independence is simultaneously connected by pipeline, wherein,
The battery pile includes liquid antimony anode, the outlet of battery pile is provided with the top of the battery pile, for battery pile
The antimony oxide outflow that liquid antimony generates in reaction, its bottom is provided with the battery pile entrance of feed flow state antimony inflow；
The antimony oxide collecting pit entrance being connected with battery pile outlet, and its are provided with the top of the antimony oxide collecting pit
Bottom is provided with the antimony oxide collecting pit outlet for antimony oxide outflow；
Fuel loading device is provided with the top of the fuel tank, the top is additionally provided with simultaneously to be exported with the antimony oxide collecting pit
The fuel tank entrance being connected, the fuel tank bottom are provided with the fuel tank flowed out for being reduced the antimony obtained by fuel and exported,
Battery pile described in the outlet, the antimony obtained after antimony oxide is reduced carry out recycling,
Also include antimony purification devices, the antimony purification devices two bottom sides are respectively arranged with antimony purification devices entrance and antimony purifying dress
Outlet is put, the antimony purification devices entrance connects the fuel tank outlet, will reduce the antimony obtained the introducing antimony through fuel
Purification process is carried out in purification devices,
Also include antimony holder, the antimony holder is provided with antimony holder entrance and the outlet of antimony holder, the antimony storage simultaneously
Storage entrance connects the antimony purification devices outlet, and battery pile described in the antimony holder outlet,
First switch K1 is provided with passage between battery pile and antimony oxide collecting pit, between antimony oxide collecting pit and fuel tank
Passage on set second switch K2, be provided between antimony oxide collecting pit and antimony holder the 3rd switch K3, fuel tank outlet
There is the 4th switch K4 between antimony purification devices, the 5th switch K5 be provided between antimony purification devices and antimony holder,
Battery stack system is equipped with Sb circulation alternate channels, specifically, battery pile opening switchs S1, antimony oxide collecting pit
Opening switch S2, pipeline separate switch S3,
During use：When antimony oxide collecting pit breaks down, K1 is closed, opens switch S1, S2 and second on alternate channel
K2 is switched, and closes K3, allows antimony oxide to be directly entered fuel tank,
When antimony oxide collecting pit and fuel tank simultaneous faults, K1 and K2 is closed, S1 and S2 is opened, allows antimony oxide temporarily with antimony
Circulated together in pipeline.
A kind of 2. direct carbon solid oxide fuel cell stack system of antimony anode as claimed in claim 1, it is characterised in that
The antimony oxide collecting pit outlet is provided with the passage of directly connection battery pile, for not joining what is flowed out from battery pile
It is imported into again in battery pile with the liquid antimony of cell reaction.
A kind of 3. direct carbon solid oxide fuel cell stack system of antimony anode as claimed in claim 2, it is characterised in that
The antimony oxide collecting pit outlet is provided with the passage for directly connecting the fuel tank entrance, with the oxygen that will likely be flowed out from bottom
Change antimony and be fed again into fuel tank.
4. the direct carbon solid oxide fuel cell stack system of a kind of antimony anode as described in one of claim 1,2 or 3, its
It is characterised by, the battery pile includes pile cavity (3) and encapsulation is integrated in the list of multiple interconnections in pile cavity
Battery, wherein,
In a tubular form, the inwall of the tubular cell is negative electrode to the monocell or is integrated with the cathode support body (1) of negative electrode, institute
The outer wall for stating tubular cell is electrolyte-supported body or electrolyte (2), and the anode of the tubular cell is located at the electrolyte
Supporting body surface or bath surface；The inside of the pile cavity has cavity, for the accommodating liquid antimony as anode.
A kind of 5. direct carbon solid oxide fuel cell stack system of antimony anode as claimed in claim 4, it is characterised in that
Pile cavity (3) outward appearance is rectangular, and protection gas reserved opening is provided with the two opposite side walls of the rectangle pile cavity
(5), it is passed through for the protection gas reserved opening (5) through side and protects liquid antimony to exempt from oxidized gas and the institute through opposite side
State protection gas reserved opening (5) discharge.
A kind of 6. method for preparing the fuel cell pile system as described in one of claim 1-5, it is characterised in that it includes
Following steps：
S1：Pile cavity is prepared, and anode current collector device and cathode collector device are set in reserved location, by multiple monocells
Integration packaging obtains pile intermediate on pile cavity, and metallic antimony powder is added into pile intermediate；
S2：The liquid antimony circulatory system is set on pile intermediate, obtains battery stack system, the liquid antimony circulatory system bag
The antimony oxide collecting pit being connected with pile intermediate, the fuel tank connected with antimony oxide collecting pit are included, fuel tank upper end is set
There is fuel loading device.
7. the method as claimed in claim 6 for preparing fuel cell pile system, it is characterised in that liquid described in step S2
The antimony circulatory system also includes antimony purification devices, and the entrance of the antimony purification devices is connected with fuel tank, the antimony purification devices
Outlet be used for by Jing Guo purification process antimony feeding antimony holder.
8. the method as claimed in claim 7 for preparing fuel cell pile system, it is characterised in that described in step S2, liquid
The state antimony circulatory system also includes antimony holder, and the antimony holder is connected with antimony purification devices and pile cavity simultaneously.
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| CN201510555801.9A CN105206862B (en) | 2015-09-01 | 2015-09-01 | A kind of direct carbon solid oxide fuel cell stack system of antimony anode and preparation method |
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| CN201510555801.9A CN105206862B (en) | 2015-09-01 | 2015-09-01 | A kind of direct carbon solid oxide fuel cell stack system of antimony anode and preparation method |
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| CN105206862B true CN105206862B (en) | 2017-11-17 |
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| 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 |
| CN102723516B (en) * | 2012-06-15 | 2014-05-14 | 东营杰达化工科技有限公司 | Direct carbon fuel cell device with liquid metal tin serving as anode |
| CN103972526B (en) * | 2014-05-12 | 2016-04-06 | 清华大学 | Based on the electrification energy storage integrated apparatus of liquid metal anode Direct Carbon Fuel Cells |
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