CN102760898A - Linear-carbon fuel cell device with porous ceramic material as support - Google Patents
Linear-carbon fuel cell device with porous ceramic material as support Download PDFInfo
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Abstract
The invention relates a linear-carbon fuel cell device with a porous ceramic material as a support. The linear-carbon fuel cell device comprises an anode gas outlet pipe, a gas pump, a cathode gas inlet pipe, a cylindrical container, a heat-conducting pad, an anode gas inlet pipe, a cathode gas outlet pipe, a single cell and a heating coil, wherein the single cell sequentially comprises a porous ceramic sheet, a cell cathode, a cathode electrolyte transition layer and an electrolyte layer from the top down, which are stuck and sealed with a carbon fuel bin through high-temperature sealing adhesive; carbon fuel is filled in the single cell and taken as an anode; and the single cell is connected with an external load through a cathode current collector wire and an anode current collector wire. The linear-carbon fuel cell device has the advantages as follows: by adopting a fuel cell structure that the porous ceramic material, instead of the anode, the electrolyte or the cathode as in the prior art, is taken as the support, the mechanical strength of the cell is improved, the electrodes and the electrolyte material are saved, the consumption of the impedance inside the cell is reduced; and according to the novel structure, a large-power linear-carbon fuel cell pile can be researched and developed.
Description
Technical field
The present invention relates to straight carbon consuming cell field, particularly a kind of is the straight carbon consuming cell device that supports with the porous ceramic film material.
Background technology
In recent years, owing to being the sustainable growth of the fossil energy prices of raw and semifnished materials of representative with the oil, national governments all heightened awareness are a kind of non-sustainability strategies to the height dependence to fossil energy, and these resources not only will be by exploitation totally, the CO that it acts as a fuel and produces
2More at the greenhouse effect that constantly aggravate global climate.For this reason, many countries drop into a large amount of research fundings, study the more efficient method of utilizing existing energy resources of novel regenerative resource or exploitation.With regard to the fundamental realities of the country of China, coal in China reserves rank third place in the world, it mainly is used in thermal power generation as primary energy.But owing to there is this process of coal burning, not only efficient is limited to cause this energy utilization patterns, and can produce a large amount of greenhouse gas CO
2Therefore, people are necessary to study the new way of coal generating.
Straight carbon consuming cell is a kind of electrochemical energy battery.It is raw material with carbon, and directly the chemical energy with carbon is converted into electric energy; Rather than use traditional technology: the burning through carbon is converted into heat energy with its chemical energy, through steam turbine heat energy is converted into mechanical energy again, and then drives generator generation electric energy.Because do not experience the conversion of heat energy, therefore there be not the constraint of Carnot cycle to the efficient upper limit.In theory, the generating efficiency of straight carbon consuming cell can reach 100%, and this efficient with existing thermal power generation about 30% is compared, and can be described as revolutionary raising.In addition, because coal is solid, oxidation product is CO
2Gas, straight carbon consuming cell be designed with separation and the CO that is beneficial to both
2The recovery of gas reduces discharging even zero discharge CO thereby reach
2The effect of greenhouse gas.
Got into since the new century, along with solar energy, biomass energy, novel energy such as wind energy and regenerative resource research popular, fuel cell also gets into people's the visual field.Along with going deep into of research; The kind of fuel cell is also extensive day by day, develops alkaline fuel cell (AFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC), Proton Exchange Membrane Fuel Cells (PEMFC), SOFC (SOFC), DMFC polytypes such as (DMFC).These fuel cells are many to be fuel with gas and liquid, utilizes solid carbon to compare for fuel with straight carbon consuming cell, and in the storage of fuel with carry and all has big inferior position, so directly carbon consuming cell becomes the focus of fuel cell studies.
Straight carbon consuming cell mainly is divided into by structure has plate and two kinds of tubular types.In order to reach the purpose of continuous operation, carbon fuel is placed within cell panel top or the battery socket, it is closely contacted with galvanic anode because of action of gravity all the time, realize that carbon fuel is converted into CO
2Electrochemical reaction is carried out continuously.This just makes anode, among these three layers on electrolyte and the negative electrode, has more thick and heavy processed in order to support of one deck at least.The existing plate or straight carbon consuming cell of tubular type all is to make the structure that supports by electrode layer or dielectric substrate.
On the other hand, from the consideration that reduces internal resistance consumption and save electrode material, the thickness of electrode and dielectric substrate but is the Bao Yuehao more of processing.This just has higher requirement to electrode and the electrolytical strength of materials and structural design.If do not solve, will hinder the development of straight carbon consuming cell technology.Therefore, under the prerequisite that guarantees battery machine intensity, how with its make the frivolous big technical barrier that becomes straight carbon consuming cell of structure.
Summary of the invention
The object of the invention is exactly the above-mentioned defective that exists to prior art, and providing a kind of is the straight carbon consuming cell device that supports with the porous ceramic film material.
Its technical scheme is: mainly be made up of anode escape pipe, air pump, cathode inlet conduit, cylindrical pressure vessel, heat conduction pad, anode air inlet pipe, negative electrode outtake tube, seal washer, battery cell, heating collar; The top of described cylindrical pressure vessel is provided with lid; The outside is provided with the heating collar parcel; The cylindrical pressure vessel inner bottom part has the heat conduction pad, and battery cell is placed on it, reserves the runner that cathode gas flows through; The duct that negative electrode gas is seen through on the pottery contacts with negative electrode, by seal washer cylindrical pressure vessel is separated into cathodic region and anode region; The cylindrical pressure vessel bottom is the cathodic region, the negative electrode conductance is gone into through the cathode inlet conduit by air pump, and cathode exhaust gas is derived by the negative electrode outtake tube; On cylindrical pressure vessel top is the anode region, and the anode carrier gas imports through the anode air inlet pipe, is derived by the anode escape pipe;
Above-mentioned battery cell is followed successively by porous ceramics piece from top to bottom, cell cathode, catholyte transition zone; Dielectric substrate; With high-temperature seal adhesive and carbon Bunker adhesion sealing, the carbon fuel of packing within it is anode; Each parts formation battery cell of combining closely is connected external loading through the cathode collector lead with the anode current collector lead.
Above-mentioned battery cell can be four layers to six layers structure: wherein, four-layer structure is meant it is porous ceramics piece from top to bottom successively, negative electrode, negative electrode-electrolyte transition zone and dielectric substrate; Five-layer structure then is on four layers of basis, on electrolyte, adds one deck fused mass or liquid anode again; Six layers of structure then are on the five-layer structure basis, in the middle of anode and electrolyte, add anode-electrolyte transition zone.
Above-mentioned porous ceramics piece is by being aluminium oxide, zirconia, and magnesia etc. or wherein a kind of, two kinds or two or more porcelain powder sinterings form; Its pore size is 1mm to 10nm, and the porous ceramics piece of its application can be plate, can be tubular type also, comprises two types of a both ends open and ports.
Above-mentioned dielectric substrate is by transition metal oxide; The composite electrolyte that rare earth oxide and carbonate are mixed and processed; Concrete the is cerium oxide that samarium oxide mixes, the zirconia and the aluminium oxide Al 2O3 of scandia stabilized; Lithium carbonate Li2CO3, potash K2CO3, sodium carbonate Na2CO3 two kinds or the two or more compound electrolyte material of pressing certain mass formation wherein than mixing.
Above-mentioned carbon Bunker is an earthenware, and described heat conduction pad is a potsherd, and described seal washer is the alumina fibre plate, and described cylindrical pressure vessel is the stainless steel still, and described heating collar is the ceramic heat circle.
Above-mentioned carbon fuel is amorphous carbon, carbon black, and coal, coke or other contain the fuel of carbon rich.
Above-mentioned anode gas is nitrogen, and described negative electrode gas is air, oxygen or both gaseous mixtures.
The invention has the beneficial effects as follows: this straight carbon consuming cell monomer is support with the porous ceramic sheet material; But not it is existing with anode; Electrolyte or negative electrode fuel cell structure for supporting; When improving battery machine intensity, practiced thrift electrode and electrolyte, and reduced the consumption of internal battery impedance.Simultaneously, can carry out the research and development of high-power straight carbon consuming cell heap according to this new construction.
Description of drawings
Fig. 1 is a structural representation of the present invention;
Fig. 2 is the structural representation of battery cell of the present invention;
Among the last figure: cathode collector lead 1, carbon fuel 2, dielectric substrate 3, cell cathode 4, anode current collector lead 5, carbon Bunker 6, catholyte transition zone 7, porous ceramics piece 8; Anode escape pipe 9, air pump 10, cathode inlet conduit 11, cylindrical pressure vessel 12, heat conduction pad 13, anode air inlet pipe 14, negative electrode outtake tube 15, seal washer 16, battery cell 17, heating collar 18.
Embodiment
What the present invention mentioned is that the straight carbon consuming cell device that supports mainly is made up of anode escape pipe 9, air pump 10, cathode inlet conduit 11, cylindrical pressure vessel 12, heat conduction pad 13, anode air inlet pipe 14, negative electrode outtake tube 15, seal washer 16, battery cell 17, heating collar 18 with the porous ceramic film material; The top of described cylindrical pressure vessel 12 is provided with lid; The outside is provided with heating collar 18 parcels; Cylindrical pressure vessel 12 inner bottom parts have heat conduction pad 13, and battery cell 17 is placed on it, reserve the runner that cathode gas flows through; The duct that negative electrode gas is seen through on the pottery contacts with negative electrode, by seal washer 16 cylindrical pressure vessel 12 is separated into cathodic region and anode region; Cylindrical pressure vessel 12 bottoms are the cathodic region, the negative electrode conductance are gone into through cathode inlet conduit 11 by air pump 10, and cathode exhaust gas is derived by negative electrode outtake tube 15; On cylindrical pressure vessel 12 tops is the anode region, and the anode carrier gas imports through anode air inlet pipe 14, is derived by anode escape pipe 9.
Wherein, battery cell 17 is followed successively by porous ceramics piece 8 from top to bottom, cell cathode 4; Catholyte transition zone 7, dielectric substrate 3 is with high-temperature seal adhesive and carbon Bunker 6 adhesions sealing; The carbon fuel 2 of packing within it; Be anode, each parts formation battery cell of combining closely is connected external loading through cathode collector lead 1 with anode current collector lead 5.
Need to prove: battery cell 17 can be four layers to six layers structure: wherein, four-layer structure is meant it is porous ceramics piece from top to bottom successively, negative electrode, negative electrode-electrolyte transition zone and dielectric substrate; Five-layer structure then is on four layers of basis, on electrolyte, adds one deck fused mass or liquid anode again; Six layers of structure then are on the five-layer structure basis, in the middle of anode and electrolyte, add anode-electrolyte transition zone.
Wherein, porous ceramics piece 8 is by being aluminium oxide, zirconia, and magnesia etc. or wherein a kind of, two kinds or two or more porcelain powder sinterings form, and proportioning is well known to those skilled in the art; Its pore size is 1mm to 10nm, and the porous ceramics piece of its application can be plate, can be tubular type also, comprises two types of a both ends open and ports.
Above-mentioned dielectric substrate 3 is by transition metal oxide; The composite electrolyte that rare earth oxide and carbonate are mixed and processed; Concrete the is cerium oxide that samarium oxide mixes, the zirconia and the aluminium oxide Al 2O3 of scandia stabilized, lithium carbonate Li2CO3, potash K2CO3; Sodium carbonate Na2CO3 two kinds or the two or more compound electrolyte material that certain mass forms than mixing, the prior art that this mass ratio is well known to those skilled in the art of pressing wherein.
Above-mentioned carbon Bunker 6 is an earthenware, and described heat conduction pad 13 is a potsherd, and described seal washer 16 is the alumina fibre plate, and described cylindrical pressure vessel 12 is the stainless steel still, and described heating collar 18 is the ceramic heat circle.
Above-mentioned carbon fuel 2 is amorphous carbon, carbon black, coal; Coke or other contain the fuel of carbon rich, and above-mentioned anode gas is nitrogen, and described negative electrode gas is air; Oxygen or both gaseous mixtures, above-mentioned is the straight carbon consuming cell device that supports with the porous ceramic film material, its operating temperature range is 500 to 1000 ℃; Above-mentioned straight carbon consuming cell device can be according to actual conditions, and the supply of carbon fuel can be adopted the intermittent feeding working method, can attempt the continuous feed mode and transform.
Adopt plate and the design tubular type type, different with traditional plate shaped battery, at anode; Electrolyte on the basis of negative electrode three layer function material structures, has added one deck porous ceramic plate as backing material; Making plate shaped battery needn't be the structure (like anode-supported, electrolyte-supported) of support making with certain one deck because of the consideration of mechanical strength, has saved electrode material; More reduce the internal resistance of battery, thereby reduced the in-fighting of battery.Utilize its intensity that significantly improves, can carry out the trial of high power battery heap exploitation.
The instance of the present invention's technology generating is following:
Embodiment 1
As carbon fuel, in the fuel cavity of straight carbon consuming cell monomer that with the porous ceramic is support, add glass putty and carbon fuel, the good seal cell apparatus successively with carbon black by mass ratio 10:3.At normal temperatures, anode feeds nitrogen, gets rid of the air in the anode cavities.Heater, when being warmed up to 500 ℃, to the cathode cavity bubbling air, air pressure is 0.5Mpa, the recording cell operating mode is enumerated the battery performance situation under 600 ℃ at present, sees attached list one.
Embodiment 2
As carbon fuel, in the fuel cavity of straight carbon consuming cell monomer that with the porous ceramic is support, add glass putty and carbon fuel, the good seal cell apparatus successively with carbon black by mass ratio 20:3.At normal temperatures, anode feeds nitrogen, gets rid of the air in the anode cavities.Heater, when being warmed up to 500 ℃, to the cathode cavity bubbling air, air pressure is 0.5Mpa, the recording cell operating mode is enumerated the battery performance situation under 700 ℃ at present, sees attached list one.
Embodiment 3
As carbon fuel, in the fuel cavity of straight carbon consuming cell monomer that with the porous ceramic is support, add glass putty and carbon fuel, the good seal cell apparatus successively with carbon black by mass ratio 5:2.At normal temperatures, anode feeds nitrogen, gets rid of the air in the anode cavities.Heater, when being warmed up to 500 ℃, to the cathode cavity bubbling air, air pressure is 0.5Mpa, the recording cell operating mode is enumerated the battery performance situation under 750 ℃ at present, sees attached list one.
Embodiment 4
As carbon fuel, in the fuel cavity of straight carbon consuming cell monomer that with the porous ceramic is support, add glass putty and carbon fuel, the good seal cell apparatus successively with carbon black by mass ratio 20:3.At normal temperatures, anode feeds nitrogen, gets rid of the air in the anode cavities.Heater, when being warmed up to 500 ℃, flow is to the cathode cavity bubbling air, and air pressure is 0.5Mpa, and the recording cell operating mode is enumerated the battery performance situation under 800 ℃ at present, sees attached list one.
Embodiment 5
As carbon fuel, in the fuel cavity of straight carbon consuming cell monomer that with the porous ceramic is support, add glass putty and carbon fuel, the good seal cell apparatus successively with carbon black by mass ratio 10:1.At normal temperatures, anode feeds nitrogen, gets rid of the air in the anode cavities.Heater, when being warmed up to 500 ℃, to the cathode cavity bubbling air, air pressure is 0.5Mpa, the recording cell operating mode is enumerated the battery performance situation under 850 ℃ at present, sees attached list one.
Subordinate list one is following:
| Embodiment | Tin: carbon (mass ratio) | Temperature | Maximum current density | Maximum power density | Average power density |
| 1 | 10:3 | 600 | 4.44mA/cm 2 | 2.57mW/cm 2 | 2.32mW/cm 2 |
| 2 | 20:3 | 700 | 4.01mA/cm 2 | 3.64mW/cm 2 | 3.08mW/cm 2 |
| 3 | 5:2 | 750 | 8.45mA/cm 2 | 10.00mW/cm 2 | 8.31mW/cm 2 |
| 4 | 20:3 | 800 | 9.93mA/cm 2 | 12.53mW/cm 2 | 11.43mW/cm 2 |
| 5 | 10:1 | 850 | 54.33mA/cm 2 | 42.79mW/cm 2 | 34.12mW/cm 2 |
Claims (8)
1. one kind is the straight carbon consuming cell device that supports with the porous ceramic film material; It is characterized in that: mainly form by anode escape pipe (9), air pump (10), cathode inlet conduit (11), cylindrical pressure vessel (12), heat conduction pad (13), anode air inlet pipe (14), negative electrode outtake tube (15), seal washer (16), battery cell (17), heating collar (18); The top of described cylindrical pressure vessel (12) is provided with lid; The outside is provided with heating collar (18) parcel; Cylindrical pressure vessel (12) inner bottom part has heat conduction pad (13), and battery cell (17) is placed on it, reserves the runner that cathode gas flows through; The duct that negative electrode gas is seen through on the pottery contacts with negative electrode, by seal washer (16) cylindrical pressure vessel (12) is separated into cathodic region and anode region; Cylindrical pressure vessel (12) bottom is the cathodic region, the negative electrode conductance is gone into through cathode inlet conduit (11) by air pump (10), and cathode exhaust gas is derived by negative electrode outtake tube (15); On cylindrical pressure vessel (12) top is the anode region, and the anode carrier gas imports through anode air inlet pipe (14), is derived by anode escape pipe (9);
Described battery cell (17) is followed successively by porous ceramics piece (8) from top to bottom, cell cathode (4), catholyte transition zone (7); Dielectric substrate (3); With high-temperature seal adhesive and carbon Bunker (6) adhesion sealing, the carbon fuel (2) of packing within it is anode; Each parts formation battery cell of combining closely is connected external loading through cathode collector lead (1) with anode current collector lead (5).
2. according to claim 1 is the straight carbon consuming cell device that supports with the porous ceramic film material; It is characterized in that: described battery cell (17) can be four layers to six layers structure: wherein; Four-layer structure is meant it is porous ceramics piece from top to bottom successively; Negative electrode, negative electrode-electrolyte transition zone and dielectric substrate; Five-layer structure then is on four layers of basis, on electrolyte, adds one deck fused mass or liquid anode again; Six layers of structure then are on the five-layer structure basis, in the middle of anode and electrolyte, add anode-electrolyte transition zone.
3. according to claim 1 is the straight carbon consuming cell device that supports with the porous ceramic film material; It is characterized in that: described porous ceramics piece (8) is by being aluminium oxide; Zirconia, magnesia etc. or wherein a kind of, two kinds or two or more porcelain powder sinterings form; Its pore size is 1mm to 10nm.
4. according to claim 1 is the straight carbon consuming cell device that supports with the porous ceramic film material, and it is characterized in that: described dielectric substrate (3) is by transition metal oxide, the composite electrolyte that rare earth oxide and carbonate are mixed and processed.
5. according to claim 1 is the straight carbon consuming cell device that supports with the porous ceramic film material; It is characterized in that: described carbon Bunker (6) is an earthenware; Described heat conduction pad (13) is a potsherd; Described seal washer (16) is the alumina fibre plate, and described cylindrical pressure vessel (12) is the stainless steel still, and described heating collar (18) is the ceramic heat circle.
6. according to claim 1 is the straight carbon consuming cell device that supports with the porous ceramic film material, and it is characterized in that: described carbon fuel (2) is amorphous carbon, carbon black, and coal, coke or other contain the fuel of carbon rich.
7. according to claim 1 is the straight carbon consuming cell device that supports with the porous ceramic film material, and it is characterized in that: described anode gas is nitrogen.
8. according to claim 1 is the straight carbon consuming cell device that supports with the porous ceramic film material, and it is characterized in that: described negative electrode gas is air or oxygen.
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| CN201210197627.1A CN102760898B (en) | 2012-06-15 | 2012-06-15 | Linear-carbon fuel cell device with porous ceramic material as support |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800326A (en) * | 2010-04-17 | 2010-08-11 | 上海交通大学 | Two-electrolyte direct carbon fuel cell and assembling method thereof |
| US20120088165A1 (en) * | 2003-05-15 | 2012-04-12 | Lawrence Livermore National Security, Llc | Carbon fuel particles used in direct carbon conversion fuel cells |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120088165A1 (en) * | 2003-05-15 | 2012-04-12 | Lawrence Livermore National Security, Llc | Carbon fuel particles used in direct carbon conversion fuel cells |
| CN101800326A (en) * | 2010-04-17 | 2010-08-11 | 上海交通大学 | Two-electrolyte direct carbon fuel cell and assembling method thereof |
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Effective date of registration: 20181016 Address after: 221600 Jiangsu Peixian Economic Development Zone Hanxing Road East Patentee after: Jiangsu Huachang Aluminum Factory Co., Ltd. Address before: 257091 298 Fu Fu Street, Dongying District, Dongying, Shandong. Patentee before: Dongying Jieda Chemical Technology Co.,Ltd. |
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