CN113753854A - Hydrogen storage fuel with straight hole structure and preparation method thereof - Google Patents
Hydrogen storage fuel with straight hole structure and preparation method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 141
- 239000001257 hydrogen Substances 0.000 title claims abstract description 141
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000003860 storage Methods 0.000 title claims abstract description 120
- 239000000446 fuel Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims description 84
- 239000011230 binding agent Substances 0.000 claims description 31
- 239000002270 dispersing agent Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 239000004695 Polyether sulfone Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 16
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- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
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- 238000010345 tape casting Methods 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000005189 flocculation Methods 0.000 claims description 11
- 230000016615 flocculation Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 238000006479 redox reaction Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910002274 La1–xSrxMnO3+δ Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 3
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 241000764238 Isis Species 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000008358 core component Substances 0.000 description 1
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- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 238000009849 vacuum degassing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
-
- 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
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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 provides a hydrogen storage fuel with a straight-hole structure and a preparation method thereof. The hydrogen storage fuel can promote the material transmission of hydrogen and water vapor through an open straight-hole structure, and effectively accelerate the oxidation-reduction reaction of the hydrogen storage fuel. Meanwhile, the hydrogen storage fuel also comprises a catalyst and an oxide, and is beneficial to the oxidation-reduction reaction of the hydrogen fuel.
Description
Technical Field
The invention relates to a secondary solid oxide fuel cell, belonging to the field of electrochemistry.
Background
A high-temperature Solid Oxide Fuel Cell (SOFC) is a power generation device based on a high-temperature electrochemical reaction, and can only generate power and cannot store electric energy. Patent CN102652379B proposes a SOFC capable of reversible charge and discharge, i.e. a secondary SOFC. On the basis of the SOFC, a sealed hydrogen storage component is arranged on one side of an anode, and reversible storage and release of hydrogen are carried out by utilizing the reaction of hydrogen storage fuel in the hydrogen storage component and water vapor, so that the secondary operation of the SOFC is realized. Hydrogen storage fuels can use a variety of metals or alloys thereof, with iron being a typical hydrogen storage fuel. In the discharging process, iron reacts with water vapor to generate hydrogen and ferroferric oxide, and the hydrogen further reacts with oxygen through electrochemical reaction to generate electricity and generate water vapor. In the charging process, the secondary SOFC firstly generates hydrogen through water vapor electrolysis, and the hydrogen further reacts with ferroferric oxide to generate iron and water vapor so as to realize the storage of the hydrogen.
The hydrogen storage fuel is used as the core component of the secondary SOFC, and the structure of the hydrogen storage fuel has great influence on the electrochemical performance of the cell. The redox reaction rate of the hydrogen storage fuel is closely related to the gas transport rate, which is limited by the pore structure. Most of the existing hydrogen storage fuel are small holes which are randomly distributed, so that a gas transmission channel is tortuous and has high transmission resistance. Meanwhile, the hydrogen storage fuel can be sintered at high temperature, so that the surface area of the hydrogen storage fuel is reduced, and a gas transmission channel can be blocked. Because, in order to ensure the hydrogen storage fuel reaction to proceed smoothly, a good gas transmission path is necessary.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a hydrogen storage fuel with a straight hole structure and a preparation method thereof so as to solve the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows: a hydrogen storage fuel having a straight-hole structure and a method for producing the same, the hydrogen storage fuel comprising a hydrogen storage metal, an oxide and a catalyst, the hydrogen storage fuel having or partially having an open straight-hole structure.
Preferably, the diameter of the straight hole of the hydrogen storage fuel is 10-200 μm.
Preferably, the thickness of the hydrogen storage fuel is 100-5000 μm.
The hydrogen storage metal performs storage and release of hydrogen gas by reaction with water vapor, including but not limited to magnesium, calcium, aluminum, zinc, iron, manganese, lead, tin, nickel, molybdenum, tungsten, titanium, or alloys thereof. Preferably, the hydrogen storage metal is iron.
The oxide is used for relieving the sintering of the hydrogen storage metal at high temperature, has chemical inertness, and does not react with the hydrogen storage metal, hydrogen and water vapor at the working temperature of the secondary SOFC. The melting point of the oxide is above 800 ℃, preferably above 1000 ℃ to ensure that the oxide does not undergo a melting process. Preferably, the oxide isIs Al2O3、SiO2、ZrO2Yttria Stabilized Zirconia (YSZ), or mixtures thereof. The particle size of the oxide is between 100nm and 5 mu m. Preferably, the particle size is between 100nm and 500 nm.
The amount of the oxide is proper, so that the sintering process of the hydrogen storage metal at high temperature can be relieved, and the integral hydrogen storage amount of the hydrogen storage fuel cannot be greatly influenced, so that the amount of the oxide is limited. The dosage of the oxide is 1 wt% -20 wt% of the mass of the hydrogen storage metal. Preferably, it is 3 to 10 wt%.
The catalyst is used for promoting the oxidation-reduction reaction of the hydrogen storage metal, thereby accelerating the hydrogen storage and production rate. Preferably, the catalyst is Pd, Pt or CeO2And the like. The particle size of the catalyst should be as small as possible to fully perform its catalytic function. The particle size of the hydrogen storage fuel is 5 nm-500 nm. Preferably, it is 5nm to 100 nm. The dosage of the catalyst is 0.5 wt% -10 wt% of the total mass of the hydrogen storage metal. Preferably, it is 0.5 wt% to 5 wt%. The source of the catalyst is not limited, the catalyst can be directly used as a catalyst, and can also be used as a precursor of the catalyst, and the catalyst is generated through air calcination or high-temperature reduction.
The invention also provides a preparation method of the hydrogen storage fuel with the straight hole structure, which comprises the following steps:
(1) uniformly mixing sacrificial material powder, a binder, a dispersant and an organic solvent to obtain sacrificial material slurry;
(2) uniformly mixing hydrogen storage metal oxide, catalyst, binder, dispersant and organic solvent to obtain oxide slurry;
(3) carrying out tape casting on a bottom plate, sequentially arranging a first sacrificial material slurry layer, an oxide slurry layer and a second sacrificial material slurry layer on the bottom plate to obtain a wet blank, and carrying out flocculation treatment on the wet blank;
(4) and sequentially drying, air high-temperature calcining and high-temperature reducing treatment are carried out on the obtained wet blank.
Preferably, before casting, vacuum degassing is performed on the oxide slurry and the sacrificial material slurry.
The binder is mainly used for connecting powder particles in the slurry, so that the stability and plasticity of the slurry are improved, the appearance of a blank is kept in the subsequent drying process, and the phenomena of cracking, pulverization and the like are avoided. The dispersing agent can uniformly mix and distribute different powder in the slurry, thereby improving the stability of the slurry.
Preferably, in the process of obtaining the oxide slurry and the sacrificial material slurry, the binder includes but is not limited to polyethersulfone, the dispersant includes but is not limited to polyvinylpyrrolidone, and the organic solvent includes but is not limited to N-methyl-1-pyrrolidone.
In the slurry, the solid content of the oxide powder or the sacrificial material powder directly affects the viscosity of the slurry, and the viscosity of the slurry affects the structural distribution of the pores, so that the solid content of the slurry is limited to obtain a better straight pore structure.
Preferably, in the oxide slurry, the content of the binder is 4 wt% to 10 wt%, the content of the dispersant is 1 wt% to 2 wt%, the content of the organic solvent is 20 wt% to 38 wt%, and the total content of the hydrogen storage fuel and the oxide is 50 wt% to 75 wt%.
Preferably, in the sacrificial slurry, the content of the binder is 5 wt% -12 wt%, the content of the dispersant is 1 wt% -2 wt%, the content of the organic solvent is 35 wt% -50 wt%, and the content of the sacrificial material powder is 30 wt% -60 wt%.
Preferably, the sacrificial material powder is graphite or starch.
Preferably, the hydrogen storage metal is prepared into an oxide slurry using a corresponding hydrogen storage metal oxide as a raw material.
Preferably, the flocculating agent for flocculation treatment is one or two of water and ethanol. The specific operation of the flocculation treatment is to place the cast blank into a flocculating agent pool or a coagulating bath, and to stand and solidify for 2 to 72 hours at room temperature.
The drying condition is preferably room temperature or drying in a drying oven at 50-90 ℃, and the drying time is preferably 12-36 h.
The air high-temperature calcination process is to remove organic matter and sacrificial material layers to obtain a porous material containing hydrogen storage metal oxides, oxides and catalysts. The air high-temperature calcination temperature is preferably 600-850 ℃, more preferably 700-850 ℃, and the calcination time is 2-10 h, preferably 4-8 h.
The high temperature reduction treatment is to reduce the hydrogen storage metal oxide to metal while keeping the oxide unreduced. The temperature in the high-temperature reduction process is 600-900 ℃, the preferable temperature is 650-750 ℃, and the preferable reduction time is 2-20 h, and the preferable time is 2-8 h. The reducing atmosphere is hydrogen or a mixed gas of hydrogen and argon.
The thickness of the first sacrificial material slurry layer controls the thickness of the bottom layer to be removed in the phase-change green body, thereby obtaining an open pore of the bottom layer. The casting thickness of the first sacrificial material slurry layer is 0.1 to 10 μm, preferably 0.1 to 5 μm.
The thickness of the oxide slurry layer directly affects the thickness of the final hydrogen storage fuel, and is 5 μm to 5000 μm, preferably 500 μm to 1500 μm.
The thickness of the second slurry layer of sacrificial material controls the thickness of the upper layer to be removed in the phase-converted body, resulting in open pores of the upper layer. The casting thickness of the second sacrificial material slurry is 0.1 to 10 μm, preferably 0.1 to 5 μm.
The invention provides a preparation method of hydrogen storage fuel with a straight hole structure, which comprises the following steps: firstly preparing oxide slurry and sacrificial material slurry, then carrying out multilayer tape casting on a bottom plate, sequentially arranging a first sacrificial material slurry layer, an oxide slurry layer and a second sacrificial material slurry layer on the bottom plate to obtain a wet blank, and carrying out flocculation treatment on the wet blank to carry out phase inversion so as to exchange an organic solvent in the wet blank with a flocculating agent, thereby forming a relatively compact bottom layer, a straight-hole structured middle layer and a relatively compact upper layer. And then drying and calcining the flocculated wet blank to discharge the sacrificial materials of the bottom layer and the upper layer in the wet blank under the high-temperature air calcination condition, and leaving the middle layer with open straight holes to obtain the porous material of the oxide. Finally, high-temperature reduction is carried out to obtain the hydrogen storage fuel with the hydrogen storage metal, the oxide and the catalyst.
Compared with the background art, the invention has the advantages that:
(1) the hydrogen storage fuel provided by the invention has an open straight pore structure, and compared with the hydrogen storage fuel only containing pores distributed randomly, the open straight pore structure can effectively promote the transmission of hydrogen and water vapor, thereby being beneficial to the oxidation-reduction reaction of the hydrogen storage fuel;
(2) the hydrogen storage fuel module provided by the invention also has small holes which are randomly distributed, and the small holes are derived from the volume change of the hydrogen storage metal oxide when the hydrogen storage metal oxide is reduced into the hydrogen storage metal, the volatilization of a solvent in the oxide slurry, and the high-temperature air calcination process of a binder and a dispersing agent, so that the transmission of water vapor and hydrogen from the straight hole channel to the hydrogen storage fuel interface can be promoted for carrying out chemical reaction;
(3) the hydrogen storage fuel provided by the invention contains the catalyst, so that the dynamic process of the redox reaction of the hydrogen storage fuel can be accelerated;
(4) the hydrogen storage fuel provided by the invention contains oxide, so that the sintering of the hydrogen storage fuel at high temperature can be effectively inhibited, and the stability of the hydrogen storage fuel is improved.
The invention provides the hydrogen storage fuel with the straight hole structure and the preparation method thereof, which can effectively promote the transportation of gas in the hydrogen storage fuel, thereby promoting the oxidation-reduction reaction of the hydrogen storage fuel. Meanwhile, the hydrogen storage fuel module also contains a catalyst and an oxide, so that the dynamics of the oxidation-reduction reaction of the hydrogen storage fuel can be effectively improved, and the sintering of the hydrogen storage fuel at high temperature is relieved. The hydrogen storage fuel with the straight hole structure and the preparation method thereof provided by the invention can effectively solve the problems in the background art.
Drawings
FIG. 1 is a schematic diagram of the operation principle of a secondary SOFC;
FIG. 2 is a schematic flow diagram of a process for preparing a hydrogen storage fuel having a straight pore structure according to the present invention;
FIG. 3 is a schematic cross-sectional view of a hydrogen storage fuel having a straight pore structure;
FIG. 4 is the nitrogen permeability of examples 1, 2 and comparative examples;
fig. 1 is a schematic view of the operation principle of a secondary SOFC related to the present invention. Taking iron as an example of the hydrogen storage metal, during the discharging process, iron reacts with water vapor to generate hydrogen and ferroferric oxide, and the hydrogen further reacts with oxygen through an electrochemical reaction to generate electricity and generate water vapor. In the charging process, the secondary SOFC firstly generates hydrogen through water vapor electrolysis, and the hydrogen further reacts with ferroferric oxide to generate iron and water vapor so as to realize the storage of the hydrogen. The chemical reaction of the hydrogen storage fuel is closely related to the diffusion rate of hydrogen and water vapor in the hydrogen storage fuel. Fig. 2 is a schematic process flow diagram of the present invention for preparing a hydrogen storage fuel module having an open cell structure, and fig. 3 is a schematic cross-sectional view of a hydrogen storage fuel having a cell structure.
Detailed description of the preferred embodiments
Example 1
The graphite slurry and the oxide slurry both use polyether sulfone as a binder, polyvinylpyrrolidone as a dispersing agent and N-methyl-1-pyrrolidone as an organic solvent. 58g of graphite powder (with the average particle size of 1 mu m), 2g of polyvinylpyrrolidone, 5g of polyether sulfone and 35g N-methyl-1-pyrrolidone, and performing mixing and ball milling for 48 hours to obtain graphite slurry; 106g of ferroferric oxide powder (with the average particle size of 500nm), 14g of alumina (with the average particle size of 100nm), 10g of polyether sulfone, 66g N-methyl-1-pyrrolidone and 4g of polyvinylpyrrolidone are mixed and ball-milled for 48 hours to obtain oxide slurry.
The two slurries were vacuum degassed for 20 min.
Carrying out multilayer tape casting on a polyurethane film carrier tape, wherein the bottom layer is graphite slurry, and the tape casting thickness is 3 mu m; the second layer is oxide slurry with the casting thickness of 100 mu m; the top layer is graphite slurry, and the casting thickness is 3 mu m.
And (3) placing the film belt obtained in the last step into a coagulating bath, and standing and curing for 48 hours at 25 ℃.
Taking out the solidified body and drying the body in air at 80 ℃ for 24 hours.
And calcining the dried green body in a muffle furnace at 800 ℃ for 4h, and removing residual solvent, dispersant and binder.
The green body after air calcination was at 5 wt% H2Calcining for 10 hours at 700 ℃ in an Ar atmosphere to reduce ferroferric oxide into iron.
The resulting hydrogen storage fuel module was subjected to performance testing in a secondary SOFC. The anode of the secondary SOFC is La1-xSrxMnO3+δ(LSM), Yttria Stabilized Zirconia (YSZ) as electrolyte and Ni-YSZ as negative electrode. The test temperature was 700 ℃ and the current densities were 0.1C, 0.2C and 0.5C (calculated as hydrogen storage metal capacity).
Example 2
Example 2 differs from example 1 in the oxide slurry.
The graphite slurry and the oxide slurry both use polyether sulfone as a binder, polyvinylpyrrolidone as a dispersing agent and N-methyl-1-pyrrolidone as an organic solvent. 58g of graphite powder (with the average particle size of 1 mu m), 2g of polyvinylpyrrolidone, 5g of polyether sulfone and 35g N-methyl-1-pyrrolidone, and performing mixing and ball milling for 48 hours to obtain graphite slurry; 110g of molybdenum oxide powder (average particle diameter of 500nm), 10g of zirconium oxide (average particle diameter of 100nm), 9g of polyethersulfone, 60g N-methyl-1-pyrrolidone and 3g of polyvinylpyrrolidone were mixed and ball-milled for 48 hours to obtain an oxide slurry.
The two slurries were vacuum degassed for 20 min.
Carrying out multilayer tape casting on a polyurethane film carrier tape, wherein the bottom layer is graphite slurry, and the tape casting thickness is 3 mu m; the second layer is oxide slurry with the casting thickness of 100 mu m; the top layer is graphite slurry, and the casting thickness is 3 mu m.
And (3) placing the film belt obtained in the last step into a coagulating bath, and standing and curing for 48 hours at 25 ℃.
Taking out the solidified body and drying the body in air at 80 ℃ for 24 hours.
And calcining the dried green body in a muffle furnace at 800 ℃ for 4h, and removing residual solvent, dispersant and binder.
The green body after air calcination was at 5 wt% H2Calcining for 10 hours at 700 ℃ in an Ar atmosphere to reduce ferroferric oxide into iron.
The obtained hydrogen storage fuel was subjected to performance testing in a secondary SOFC. IIThe anode of the SOFC is La1-xSrxMnO3+δ(LSM), Yttria Stabilized Zirconia (YSZ) as electrolyte and Ni-YSZ as negative electrode. The test temperature was 700 ℃ and the current densities were 0.1C, 0.2C and 0.5C (calculated as hydrogen storage metal capacity).
Comparative example
The comparative example differs from example 1 in that the hydrogen storage fuel prepared in the comparative example does not have a straight-hole structure without being subjected to flocculation treatment.
The graphite slurry and the oxide slurry both use polyether sulfone as a binder, polyvinylpyrrolidone as a dispersing agent and N-methyl-1-pyrrolidone as an organic solvent. 58g of graphite powder (with the average particle size of 1 mu m), 2g of polyvinylpyrrolidone, 5g of polyether sulfone and 35g N-methyl-1-pyrrolidone, and performing mixing and ball milling for 48 hours to obtain graphite slurry; 106g of ferroferric oxide powder (with the average particle size of 500nm), 14g of alumina (with the average particle size of 100nm), 10g of polyether sulfone, 66g N-methyl-1-pyrrolidone and 4g of polyvinylpyrrolidone are mixed and ball-milled for 48 hours to obtain oxide slurry.
The two slurries were vacuum degassed for 20 min.
Carrying out multilayer tape casting on a polyurethane film carrier tape, wherein the bottom layer is graphite slurry, and the tape casting thickness is 3 mu m; the second layer is oxide slurry with the casting thickness of 100 mu m; the top layer is graphite slurry, and the casting thickness is 3 mu m.
And (3) drying the film tape obtained in the last step in air at 80 ℃ for 24 hours.
And calcining the dried green body in a muffle furnace at 800 ℃ for 4h, and removing residual solvent, dispersant and binder.
The green body after air calcination was at 5 wt% H2Calcining for 10 hours at 700 ℃ in an Ar atmosphere to reduce ferroferric oxide into iron.
The obtained hydrogen storage fuel was subjected to performance testing in a secondary SOFC. The anode of the secondary SOFC is La1-xSrxMnO3+δ(LSM), Yttria Stabilized Zirconia (YSZ) as electrolyte and Ni-YSZ as negative electrode. The test temperature was 700 ℃ and the current densities were 0.1C, 0.2C and 0.5C (calculated as hydrogen storage metal capacity).
As can be seen from the results of comparison with FIG. 4, the flocculation treatment was effectiveThe nitrogen permeability of the hydrogen storage fuel module is increased. It was found by calculation that the nitrogen permeability of example 1 was 61.1 x 105L.m-2.bar-1Example 2 is 57.8 x 105L.m-2.bar-1While the comparative example only has 6 x 105L.m-2.bar-1. After the flocculation treatment is carried out to form an open straight-hole structure, the air permeability of the nitrogen is improved by nearly 10 times, which shows that the open straight-hole structure can effectively promote gas transmission. Electrochemical performance tests were performed on the hydrogen storage fuel prepared above, and the performance results are shown in table one. The differences in cell capacity retention are derived from the hydrogen storage fuel, all as is the case with other test conditions. From the results, it is understood that as the current density is increased from 0.1C to 0.2C and 0.5C, the capacity retention ratio of example 1 can reach 98% and 90%, respectively, and the capacity retention ratio of example 2 is also higher, 95% and 87%, respectively. While the comparative examples were only 85% and 62%. The results show that the hydrogen storage fuel with open straight pore structure can significantly improve the rate capability of the secondary SOFC.
Table 1 shows capacity retention rates of example 1, example 2 and comparative example at different current densities in a secondary SOFC.
TABLE 1
| 0.1C | 0.2C | 0.5C | |
| Example 1 | 100％ | 98％ | 90％ |
| Example 2 | 100％ | 95％ | 87％ |
| Comparative example | 100％ | 85％ | 62％ |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (11)
1. A hydrogen storage fuel having a mesoporous structure, said hydrogen storage fuel comprising a hydrogen storage metal, an oxide and a catalyst, characterised in that the hydrogen storage fuel has, or partly has, an open mesoporous structure.
2. A hydrogen storage fuel having a mesoporous structure according to claim 1, wherein said hydrogen storage fuel has a mesoporous size of 10 μm to 200 μm.
3. A hydrogen storage fuel having a straight pore structure as claimed in claim 1, characterized in that said hydrogen storage metal comprises magnesium, calcium, aluminum, zinc, iron, manganese, lead, tin, nickel, molybdenum, tungsten, titanium or alloys thereof.
4. A hydrogen storage fuel having a straight pore structure as claimed in claim 1, wherein said oxide is Al2O3、SiO2、ZrO2Yttria stabilized zirconia(YSZ) or a mixture thereof, the particle size is between 100nm and 5 mu m, and the content is 1 to 20 weight percent of the mass of the hydrogen storage metal.
5. A hydrogen storage fuel having a straight pore structure as claimed in claim 1, characterized in that the catalyst comprises Pd, Pt, CeO2The grain diameter is 5 nm-500 nm, and the content is 0.5 wt% -10 wt% of the mass of the hydrogen storage metal.
6. A method of producing a hydrogen storage fuel having a straight pore structure according to claim 1, characterized in that the production method comprises the steps of:
(1) uniformly mixing sacrificial material powder, a binder, a dispersant and an organic solvent to obtain sacrificial material slurry;
the sacrificial material powder is graphite or starch, the binder comprises polyether sulfone, the dispersant comprises polyvinylpyrrolidone, and the organic solvent comprises N-methyl-1-pyrrolidone; in the sacrificial slurry, the content of the binder is 5 wt% -12 wt%, the content of the dispersant is 1 wt% -2 wt%, the content of the organic solvent is 35 wt% -50 wt%, and the content of the sacrificial material powder is 30 wt% -60 wt%;
(2) uniformly mixing hydrogen storage metal oxide, catalyst, binder, dispersant and organic solvent to obtain oxide slurry;
wherein, the hydrogen storage metal oxide is an oxide corresponding to the hydrogen storage metal; the oxide comprises Al2O3、SiO2、ZrO2One or a mixture thereof, Yttria Stabilized Zirconia (YSZ), the binder comprising polyethersulfone, the dispersant comprising polyvinylpyrrolidone, the organic solvent comprising but not N-methyl-1-pyrrolidone; in the oxide slurry, the content of the binder is 4 wt% -10 wt%, the content of the dispersant is 1 wt% -2 wt%, the content of the organic solvent is 20 wt% -38 wt%, and the total content of the hydrogen storage metal oxide and the oxide is 50 wt% -75 wt%;
(3) carrying out tape casting on a bottom plate, sequentially arranging a first sacrificial material slurry layer, an oxide slurry layer and a second sacrificial material slurry layer on the bottom plate to obtain a wet blank, and carrying out flocculation treatment on the wet blank;
wherein the casting thickness of the first sacrificial material slurry layer is 0.1-10 μm, the thickness of the oxide slurry layer is 5-5000 μm, and the casting thickness of the second sacrificial material slurry layer is 0.1-10 μm; the flocculating agent for flocculation treatment is one or two of water and ethanol;
the specific operation of the flocculation treatment is that the blank body formed by tape casting is put into a flocculating agent pool or a coagulating bath, and is kept stand and solidified for 2 to 72 hours at room temperature;
(4) and drying, calcining in air at high temperature and reducing at high temperature in sequence.
7. The method for producing a hydrogen storage fuel having a straight pore structure according to claim 6, wherein the step (4) is specifically: the drying condition is drying at room temperature or drying in a drying oven at 50-90 ℃, and the drying time is 12-36 h. The air high-temperature calcination temperature is preferably 600-850 ℃, and the calcination time is 2-10 h; the temperature of the high-temperature reduction treatment is 600-900 ℃, the reduction time is 2-20 h, and the reduction atmosphere is hydrogen or a mixed gas of hydrogen and argon.
8. A method of producing a hydrogen storage fuel having a straight pore structure according to claim 1, characterized in that the production method comprises the steps of:
(1) uniformly mixing sacrificial material powder, a binder, a dispersant and an organic solvent to obtain sacrificial material slurry;
the sacrificial material powder is graphite or starch, the binder comprises polyether sulfone, the dispersant comprises polyvinylpyrrolidone, and the organic solvent comprises N-methyl-1-pyrrolidone; in the sacrificial slurry, the content of the binder is 5 wt% -12 wt%, the content of the dispersant is 1 wt% -2 wt%, the content of the organic solvent is 35 wt% -50 wt%, and the content of the sacrificial material powder is 30 wt% -60 wt%;
(2) uniformly mixing hydrogen storage metal oxide, catalyst, binder, dispersant and organic solvent to obtain oxide slurry;
wherein, the hydrogen storage metal oxide is an oxide corresponding to the hydrogen storage metal; the oxide comprises Al2O3、SiO2、ZrO2One or a mixture thereof, Yttria Stabilized Zirconia (YSZ), the binder comprising polyethersulfone, the dispersant comprising polyvinylpyrrolidone, the organic solvent comprising but not N-methyl-1-pyrrolidone; in the oxide slurry, the content of the binder is 4 wt% -10 wt%, the content of the dispersant is 1 wt% -2 wt%, the content of the organic solvent is 20 wt% -38 wt%, and the total content of the hydrogen storage metal oxide and the oxide is 50 wt% -75 wt%;
(3) carrying out tape casting on the bottom plate, so that a first sacrificial material slurry layer, an oxide slurry layer and a second sacrificial material slurry layer are sequentially arranged on the bottom plate to obtain a wet blank;
wherein the casting thickness of the first sacrificial material slurry layer is 0.1-10 μm, the thickness of the oxide slurry layer is 5-5000 μm, and the casting thickness of the second sacrificial material slurry layer is 0.1-10 μm; the flocculating agent for flocculation treatment is one or two of water and ethanol;
placing the blank body subjected to tape casting into a water or ethanol medium pool, and standing for 2-72 h at room temperature;
(4) and drying, calcining in air at high temperature and reducing at high temperature in sequence.
9. The method for producing a hydrogen storage fuel having a straight pore structure according to claim 8, wherein the step (4) is specifically: the drying condition is drying at room temperature or drying in a drying oven at 50-90 ℃, and the drying time is 12-36 h. The air high-temperature calcination temperature is preferably 600-850 ℃, and the calcination time is 2-10 h; the temperature of the high-temperature reduction treatment is 600-900 ℃, the reduction time is 2-20 h, and the reduction atmosphere is hydrogen or a mixed gas of hydrogen and argon.
10. A method of producing a hydrogen storage fuel having a straight pore structure according to claim 1, characterized in that the production method comprises the steps of:
(1) uniformly mixing sacrificial material powder, a binder, a dispersant and an organic solvent to obtain sacrificial material slurry;
the sacrificial material powder is graphite or starch, the binder comprises polyether sulfone, the dispersant comprises polyvinylpyrrolidone, and the organic solvent comprises N-methyl-1-pyrrolidone; in the sacrificial slurry, the content of the binder is 5 wt% -12 wt%, the content of the dispersant is 1 wt% -2 wt%, the content of the organic solvent is 35 wt% -50 wt%, and the content of the sacrificial material powder is 30 wt% -60 wt%;
(2) uniformly mixing hydrogen storage metal oxide, catalyst, binder, dispersant and organic solvent to obtain oxide slurry;
wherein, the hydrogen storage metal oxide is an oxide corresponding to the hydrogen storage metal; the oxide comprises Al2O3、SiO2、ZrO2One or a mixture thereof, Yttria Stabilized Zirconia (YSZ), the binder comprising polyethersulfone, the dispersant comprising polyvinylpyrrolidone, the organic solvent comprising but not N-methyl-1-pyrrolidone; in the oxide slurry, the content of the binder is 4 wt% -10 wt%, the content of the dispersant is 1 wt% -2 wt%, the content of the organic solvent is 20 wt% -38 wt%, and the total content of the hydrogen storage metal oxide and the oxide is 50 wt% -75 wt%;
(3) carrying out tape casting on the bottom plate, and sequentially arranging a first sacrificial material slurry layer and an oxide slurry layer on the bottom plate to obtain a wet blank;
wherein the casting thickness of the first sacrificial material slurry layer is 0.1-10 μm, and the thickness of the oxide slurry layer is 5-5000 μm;
(4) and drying, calcining in air at high temperature and reducing at high temperature in sequence.
11. The method for producing a hydrogen storage fuel having a straight pore structure according to claim 10, wherein the step (4) is specifically: the drying condition is drying at room temperature or drying in a drying oven at 50-90 ℃, and the drying time is 12-36 h. The air high-temperature calcination temperature is preferably 600-850 ℃, and the calcination time is 2-10 h; the temperature of the high-temperature reduction treatment is 600-900 ℃, the reduction time is 2-20 h, and the reduction atmosphere is hydrogen or a mixed gas of hydrogen and argon.
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