CN113381047A - High-temperature oxide ion conductor battery and preparation method thereof - Google Patents
High-temperature oxide ion conductor battery and preparation method thereof Download PDFInfo
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- CN113381047A CN113381047A CN202110572108.8A CN202110572108A CN113381047A CN 113381047 A CN113381047 A CN 113381047A CN 202110572108 A CN202110572108 A CN 202110572108A CN 113381047 A CN113381047 A CN 113381047A
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- oxide ion
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- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010416 ion conductor Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000010406 cathode material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000011819 refractory material Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 229910052788 barium Inorganic materials 0.000 claims description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 13
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
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- 229940116411 terpineol Drugs 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052782 aluminium Inorganic materials 0.000 claims description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- IZGBMMQZORUOAA-UHFFFAOYSA-N [Fe].[Co].[Y] Chemical compound [Fe].[Co].[Y] IZGBMMQZORUOAA-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000630 rising effect Effects 0.000 claims 1
- 239000000446 fuel Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- RVRKDGLTBFWQHH-UHFFFAOYSA-N yttrium zirconium Chemical compound [Y][Zr][Y] RVRKDGLTBFWQHH-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
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- 238000003746 solid phase reaction Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inert Electrodes (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a high-temperature oxide ion conductor battery and a preparation method thereof. The method comprises the following steps: (1) mixing and pugging anode powder, a binder and a solvent to prepare a blank, wrapping the blank with a film, standing, and extruding with a die to obtain an anode support body; mixing a first binder solution, a dispersant solution and an electrolyte to obtain electrolyte slurry; (2) pre-sintering the anode support body in the step (1), coating the electrolyte slurry in the step (1) on the surface of the pre-sintered anode support body, suspending the coated anode support body on a refractory material or flatly placing the coated anode support body on a flat plate type lining body prepared from the same oxide ion conductor material, heating in two stages, cooling to obtain a half cell, coating a cathode material and sintering a cathode coating to obtain the high-temperature oxide ion conductor cell. The preparation method provided by the invention can be used for preparing large-area tubular or flat high-temperature oxide ion conductor batteries.
Description
Technical Field
The invention belongs to the field of batteries, relates to a high-temperature oxide ion conductor battery and a preparation method thereof, and particularly relates to a flat plate type or tubular high-temperature oxide ion conductor battery and a preparation method thereof.
Background
At present, the plan of stopping and selling fuel vehicles in 2030 years is issued by vehicle enterprises in Europe, China and the like in succession. The development of new energy vehicle-mounted battery technology is imperative. At present, the vehicle-mounted new energy battery technology mainly comprises a power lithium battery and a low-temperature oxide ion membrane fuel battery. The former has advantages in technical maturity, but has the problems of long charging time, liquid electrolyte safety and unexpected bottleneck of endurance mileage.
The low-temperature (the working temperature is about 25-150 ℃) organic oxide ionic membrane fuel cell technology can directly utilize hydrogen to generate electricity, the product is water, the problems of charging time, safety and endurance mileage are effectively solved, however, due to the limitation of low-temperature thermodynamics and dynamics, the catalyst used by the technology mainly depends on precious metals such as platinum at present, meanwhile, the requirement on the purity of the hydrogen is extremely high (99.999%), and the platinum catalyst can be poisoned by a small amount of carbon monoxide impurities such as dozens to hundreds of ppm, so that the performance is attenuated.
High temperature (operating temperature of about 450-. Compared with the low-temperature organic oxide ion membrane fuel cell technology, the high-temperature oxide ion conductor cell has higher fuel flexibility and higher CO poisoning resistance. Without the use of noble metals. The reversible application of the high-temperature oxide ion conductor battery is a high-temperature oxide ion conductor electrolytic cell which can be used for electrolyzing water to prepare dry pure hydrogen.
Although the high-temperature oxide ion conductor battery and the reversible application have a plurality of advantages, the process for preparing the large-area high-temperature oxide ion conductor battery is difficult.
CN111416138A discloses an oxide ion conductor battery and a preparation method thereof, wherein the preparation method comprises the steps of utilizing the existing compound to add a sintering aid, a dispersing agent, a solvent, a plasticizer and a binder to prepare electrolyte slurry, adding a pore-forming agent into the electrolyte slurry to prepare electrode side slurry, then carrying out tape casting or tape casting-laminating molding to obtain a green body, then carrying out sintering, carrying out in-situ solid-phase reaction in the green body to generate BaZrxCe1-x-yMyO3-δAnd then preparing the anode layer by dipping and preparing the cathode layer by a dipping method or a slurry coating method.
CN111819721A discloses an oxide ion conductor battery and a method for manufacturing the same. The preparation method comprises the following steps:in the presence of BaZrxCe1-x-zYzO3(x is 0.1 to 0.8, z is 0.1 to 0.25, and x + z is not more than 1.0) and a cathode, and a thin film having a thickness in the range of 1 to 100nm is formed; the thin film is composed of an electron-conducting oxide. The thin film of the electron-conductive oxide is formed by a sputtering method or a sol-gel method.
However, the above methods are not suitable for large-area production.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a high temperature oxide ion conductor battery and a method for manufacturing the same. The preparation method provided by the invention is suitable for preparing large-area tubular or flat high-temperature oxide ion conductor batteries. The high-temperature oxide ion conductor battery is an oxide ion conductor battery with the working temperature of 450-850 ℃.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a high temperature oxide ion conductor battery, the method comprising the steps of:
(1) preparing anode powder into a blank, wrapping the blank with a film, standing, and extruding with a die to obtain an extruded anode support body; mixing a first binder solution, a dispersant solution and an electrolyte to obtain electrolyte slurry;
(2) pre-sintering the anode support body in the step (1), coating the electrolyte slurry in the step (1) on the surface of the pre-sintered anode support body, heating the coated anode support body in two stages, cooling to obtain a half cell, coating a cathode material and sintering a cathode coating to obtain the high-temperature oxide ion conductor cell.
In the preparation method provided by the invention, the extrusion method can continuously extrude longer embryo bodies, is not easy to deform, has relatively higher solid content, and is more efficient than other methods such as a cold isostatic pressing method, a grouting method and a phase transformation method, so that the preparation method is suitable for large-area industrial production.
In the invention, the function of wrapping the blank by the film and standing is to ensure that the moisture is uniformly dispersed into the mixed blank as much as possible and the binder is fully wetted and has better bonding strength with the solid-phase powder.
In the invention, the method for preparing the green body can be to mix the anode powder containing the pore-forming agent with the binder and the solvent to prepare pug and prepare the green body.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferable technical scheme of the invention, the anode powder in the step (1) comprises nickel oxide and an oxide ion conductor material.
Preferably, the oxide ion conductor material comprises any one of yttrium-doped barium cerate, yttrium-zirconium-doped barium cerate or yttrium-zirconium-ytterbium-doped barium cerate or a combination of at least two of the same.
Wherein, the yttrium-zirconium-ytterbium doped barium cerate can adopt direct mixing BaCO3，CeO2，ZrO2，Y2O3And Yb2O3And added to nickel oxide, or presintered at 1300 deg.C for 2 hr and then added to nickel oxide.
Preferably, the mass fraction of nickel oxide is 60-70%, such as 60%, 62%, 65%, 68%, or 70%, etc., and the mass fraction of oxide ion conductor material is 30-40%, such as 30%, 33%, 35%, 37%, or 40%, etc., based on 100% of the total mass of the nickel oxide and oxide ion conductor material.
Preferably, the anode powder in step (1) further includes a pore-forming agent and a second binder. In the invention, the pore-forming agent is used in the anode powder to increase the porosity and facilitate gas diffusion.
Preferably, the pore-forming agent comprises any one of corn starch, polymethyl methacrylate or graphite or a combination of at least two of the foregoing.
Preferably, the pore-forming agent is present in a mass fraction of 18 to 22%, such as 18%, 19%, 20%, 21%, 22%, or the like, based on 100% by mass of the total of the nickel oxide and the oxide ion conductor material.
Preferably, the second binder comprises water-soluble organic molecules.
Preferably, the water-soluble organic molecule comprises methylcellulose.
Preferably, the mass fraction of the second binder is 2 to 8%, such as 2%, 3%, 4%, 5%, or 8%, etc., based on 100% of the total mass of the NiO and the oxide ion conductor material.
As a preferred technical scheme of the present invention, the method for preparing the anode powder into the green body in step (1) comprises: adding a solvent into the anode powder, mixing, and preparing into a blank by using a pug mill.
Preferably, the solvent comprises water. The water in the present invention may be deionized water or distilled water.
Preferably, the membrane of step (1) comprises aluminum foil.
Preferably, the standing time in step (1) is 20-28h, such as 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h or 28 h.
As a preferable technical scheme of the invention, the mould in the step (1) is a circular tube type mould. In the present invention, the use of the circular tube type mold is advantageous in that the relative mechanical strength of the sintered body is increased and sealing is facilitated.
Preferably, step (1) further comprises drying the anode support.
Preferably, the drying method comprises placing the anode support outside the room and drying with a drying oven.
In a preferred embodiment of the present invention, the mass ratio of the first binder solution, the dispersant solution and the electrolyte in step (1) is 5 (0.8-1.2) to (1.5-2.5), for example, 5:0.5:1.5, 5:1:2, 5:1.2:2.5, 5:0.8:2.5 or 5:1.2: 1.5.
Preferably, the first binder comprises any one or a combination of at least two of ethyl cellulose, Hewlett packard V-006, or polyvinyl butyral, which is advantageous in improving the toughness of the coating during drying to prevent cracking.
Preferably, the solvent of the first binder solution comprises terpineol, and the mass fraction of the solute in the solution is 3-7%, such as 3%, 4%, 5%, 6%, 7%, etc.
Preferably, the dispersant comprises any one of, or a combination of at least two of, an active content polymeric dispersant (Solsperse 28000), polyethylene glycol or fish oil. The advantage of using such a dispersant is that it is necessary to disperse the solid particles into the slurry as much as possible.
Preferably, the solvent of the dispersant solution comprises terpineol, and the mass fraction of solute in the solution is 15-25%, such as 15%, 17%, 20%, 23%, 25%, or the like.
Preferably, the electrolyte comprises yttrium-zirconium-ytterbium doped barium cerate.
As a preferable technical solution of the present invention, in the step (2), the anode support is heated to remove the pore-forming agent before the pre-firing.
Preferably, the temperature for removing the pore-forming agent by heating is 400-500 ℃, such as 400 ℃, 420 ℃, 450 ℃, 480 ℃ or 500 ℃, and the like.
Preferably, the time for heating to remove the pore former is 1-5h, such as 1h, 2h, 2.5h, 3h, 3.5h, 4h, 5h, and the like.
Preferably, the temperature of the pre-sintering in the step (2) is 1000-.
Preferably, the pre-sintering time in step (2) is 1-5h, such as 1h, 2h, 2.5h, 3h, 3.5h, 4h or 5 h.
As a preferred technical scheme of the invention, the coating method in the step (2) is tubular printing or screen printing.
Preferably, the electrolyte slurry of step (2) is coated to a thickness of 3 to 30 μm, for example, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, etc. The thickness can be adjusted by controlling the amount and number of applications.
Preferably, before the two-stage heating in step (2), the coated anode support is suspended on the refractory material without touching the refractory material, or the coated anode support is placed on a flat plate type lining body made of the same oxide ion conductor material.
In the present invention, the purpose of suspending the anode support from the refractory is to avoid high temperature reaction of the oxide ion ceramic material with the furnace lining or the support.
In the invention, the purpose of flatly placing the anode support body and the flat plate type lining body prepared from the same oxide ion conductor material is to simplify the migration of non-electrolyte elements into an electrolyte material through high-temperature reaction.
Preferably, the coated anode support is suspended with an alumina rod or platinum wire.
Preferably, the cathode material of step (2) comprises an oxide ion conductor battery cathode material.
Preferably, the oxide ion conductor battery cathode material comprises cobalt-iron-yttrium doped barium zirconate.
As a preferred embodiment of the present invention, the first stage temperature of the two-stage heating in step (2) is 400-500 deg.C, such as 400 deg.C, 425 deg.C, 450 deg.C, 475 deg.C or 500 deg.C.
Preferably, the first stage time of the two-stage heating in step (2) is 1-5h, such as 1h, 2h, 3h, 4h or 5h, etc.
Preferably, the first-stage heating rate of the two-stage heating in step (2) is below 5 ℃/min, such as 5 ℃/min, 4 ℃/min, 3 ℃/min, 2 ℃/min, or the like.
Preferably, the second stage temperature of the two-stage heating in step (2) is 1400-1500 ℃, such as 1400 ℃, 1425 ℃, 1450 ℃, 1475 ℃ or 1500 ℃, etc.
In the invention, the two-stage heating sintering is used for removing the pore-forming agent and sintering the electrolyte layer to be compact respectively.
Preferably, the second stage time of the two-stage heating in step (2) is 2-20h, such as 2h, 5h, 10h, 15h or 20 h.
Preferably, the second-stage heating rate of the two-stage heating in the step (2) is below 5 ℃/min, such as 5 ℃/min, 4 ℃/min, 3 ℃/min or 2 ℃/min, and the like.
Preferably, the cooling rate of the cooling in the step (2) is below 5 ℃/min, such as 5 ℃/min, 4 ℃/min, 3 ℃/min or 2 ℃/min, and the like.
In the invention, the two-stage sintering and cooling in the step (2) use a slower temperature change rate, because if the temperature change rate is too fast, the cell cracks, and if the temperature change rate is too slow, the crystal grain growth of the electrode material and the energy consumption increase.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) adding water into the anode powder, mixing, preparing into a blank by using a pugging machine, wrapping the blank by using a film, standing for 20-28h, extruding by using a circular tube type die to obtain an extruded anode support body, placing the anode support body outdoors, and drying by using a drying oven to dry the extruded anode support body; mixing a first binder solution, a dispersant solution and an electrolyte to obtain electrolyte slurry;
(2) heating the anode support body in the step (1) at the temperature of 400-, and coating a cathode material and sintering the cathode coating to obtain the high-temperature oxide ion conductor battery.
In a second aspect, the present invention provides a high temperature oxide ion conductor cell prepared according to the method of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention can be used for preparing large-area tubular or flat platesHigh temperature oxide ion conductor batteries and other energy related devices such as oxygen ion or sodium ion conducting electrolyte tubes. The maximum output power of the high-temperature oxide ion conductor battery obtained by the preparation method exceeds 500mW/cm at 600 DEG C2。
Drawings
FIG. 1a is a sectional scanning electron microscope of the high temperature oxide ion conductor cell provided in example 1;
FIG. 1b is a sectional scanning electron micrograph of the high temperature oxide ion conductor cell provided in example 1;
FIG. 1c is a scanning electron micrograph of a cross section of the high temperature oxide ion conductor cell provided in example 1;
fig. 2 is a performance graph of the high temperature oxide ion conductor battery provided in example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares a high temperature oxide ion conductor battery as follows:
(1) NiO and an oxide ion conductor material (yttrium-zirconium-ytterbium doped barium cerate, delta is 0.8) are mixed according to the mass ratio of 65:35, 20 wt.% of corn starch serving as a pore forming agent and 3.5% of water-soluble binder (methyl cellulose) are added according to the total mass of the NiO and the oxide ion conductor material being 100%, and the mixture is uniformly mixed to obtain anode powder. And uniformly mixing the anode powder with deionized water, and preparing a blank by using a pug mill. Wrapping the green body with a film or an aluminum foil, and standing for 24 hours. And putting the prepared blank after being placed into a proper extruder, and extruding the anode support body by adopting a circular tube type die. And then the prepared anode support body with the moisture is placed outdoors for one day and dried in a constant-temperature drying oven, and after the moisture is dried, the dried anode support body is taken out.
A binder solution was prepared by dissolving Heraeus V-006 in 5% by mass in terpineol, and a dispersant solution was prepared by dissolving Solsperse 28000 in 20% by mass in terpineol. Electrolyte powder (yttrium-zirconium-ytterbium doped barium cerate) and a binder solution and a dispersant solution are mixed according to the following powder ratio: binder solution: the dispersant solution is mixed uniformly as electrolyte slurry for later use as 5:1: 2.
(2) And (2) firstly, preserving the temperature of 450 ℃ for 3h, oxidizing and removing the pore-forming agent, then heating to 1200 ℃ and presintering for 2h to ensure that the blank keeps certain strength. The prepared electrolyte slurry was applied to the surface of the pre-fired green body using a brush so that the electrolyte thickness was maintained at 15 μm. The anode support body coated with the electrolyte is suspended on a refractory material (alumina) by an alumina rod and is ensured not to touch the refractory material. Heating up at a heating rate of 4 ℃/min, keeping the temperature at 450 ℃ for 1.5h, heating up to 1450 ℃ at a heating rate of 4 ℃/min, and keeping the temperature for 10 h. And then cooling at the cooling rate of 4 ℃/min to obtain the half cell. And finally, printing a cathode material on the half cell and sintering the cathode coating for 5 hours at 900 ℃ to prepare a full cell, namely the high-temperature oxide ion conductor cell.
Fig. 1a, fig. 1b and fig. 1c are scanning electron microscope cross-sectional views of the high-temperature oxide ion conductor cell provided in this embodiment after hydrogen fuel test, and it can be seen from the above-mentioned images that the intermediate electrolyte layer is relatively dense, the anode is porous, and has a cathode with a nano-structure and a nano-active particle separated out.
FIG. 2 is a graph showing the performance of the high temperature oxide ion conductor cell provided in this example at 600 deg.C with hydrogen as fuel, air as oxidant and 3% water, from which it can be seen that the maximum output power of the cell at 600 deg.C exceeds 500mW/cm2. More than 200mW/cm more than that required for assembling the electric pile2And (4) power output.
Example 2
This example prepares a high temperature oxide ion conductor battery as follows:
(1) NiO and an oxide ion conductor material (yttria-stabilized zirconia) are mixed according to the mass ratio of 60:40, 15 wt.% of corn starch serving as a pore forming agent and 3% of water-soluble binder (methyl cellulose) are added into the NiO and oxide ion conductor material based on the total mass of 100%, and the mixture is uniformly mixed to obtain anode powder. And uniformly mixing the anode powder with deionized water, and preparing a blank by using a pug mill. Wrapping the green body with a film or an aluminum foil, and standing for 36 hours. And putting the prepared blank after being placed into a proper extruder, and extruding the anode support body by adopting a flat plate type die. And then the prepared anode support body with the moisture is placed outdoors for one day and dried in a constant-temperature drying oven, and after the moisture is dried, the dried anode support body is taken out.
A binder solution was prepared by dissolving Heraeus V-006 in 5% by mass in terpineol, and a dispersant solution was prepared by dissolving Solsperse 28000 in 20% by mass in terpineol. Electrolyte powder (yttrium-zirconium doped barium cerate) and a binder solution and a dispersant solution are mixed according to the following powder: binder solution: the dispersant solution is mixed uniformly as electrolyte slurry for later use in a ratio of 4:1: 3.
(2) And (2) coating the prepared electrolyte slurry on the surface of the pre-sintered green body by using the dried anode support body in the step (1) through printing so that the thickness of the electrolyte is kept at 10 mu m. The anode support coated with the electrolyte was placed flat on a liner sintered from yttrium-zirconium doped barium cerate. The temperature is kept at 400 ℃ for 5h, the pore-forming agent and the organic matter of the electrolyte layer are removed by oxidation, the temperature is raised to 1400 ℃ at the heating rate of 3 ℃/min, and the temperature is kept for 5 h. And then cooling at the cooling rate of 3 ℃/min to obtain the half cell. And finally, screen-printing a cathode material on the half cell and sintering the cathode coating for 2h at 1000 ℃ to prepare a full cell, namely the flat plate type high-temperature oxide ion conductor cell.
Compared with the embodiment 1, the embodiment 2 of the invention has the main difference that the oxide ion conductor material and the shape of the extrusion die are changed, the effect of the prepared oxide ion conductor battery is similar to that of the embodiment 1, and further, the invention can effectively prepare the large-area high-temperature oxide ion conductor battery.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing a high-temperature oxide ion conductor battery, which is characterized by comprising the following steps:
(1) preparing anode powder into a blank, wrapping the blank with a film, standing, and extruding with a die to obtain an extruded anode support body; mixing a first binder solution, a dispersant solution and an electrolyte to obtain electrolyte slurry;
(2) pre-sintering the anode support body in the step (1), coating the electrolyte slurry in the step (1) on the surface of the pre-sintered anode support body, heating the coated anode support body in two stages, cooling to obtain a half cell, coating a cathode material and sintering a cathode coating to obtain the high-temperature oxide ion conductor cell.
2. The preparation method according to claim 1, wherein the anode powder of step (1) comprises nickel oxide and an oxide ion conductor material;
preferably, the oxide ion conductor material comprises any one of yttrium-doped barium cerate, yttrium-zirconium-doped barium cerate or yttrium-zirconium-ytterbium-doped barium cerate or a combination of at least two of the two;
preferably, the mass fraction of the nickel oxide is 60-70% and the mass fraction of the oxide ion conductor material is 30-40% based on 100% of the total mass of the nickel oxide and the oxide ion conductor material;
preferably, the anode powder in the step (1) further comprises a pore-forming agent and a second binder;
preferably, the pore-forming agent comprises any one or a combination of at least two of corn starch, polymethyl methacrylate or graphite;
preferably, the mass fraction of the pore-forming agent is 0-30% and does not include 0, based on 100% of the total mass of the nickel oxide and the oxide ion conductor material;
preferably, the second binder comprises water-soluble organic molecules;
preferably, the water-soluble organic molecule comprises methylcellulose, polyvinyl alcohol;
preferably, the mass fraction of the second binder is 2 to 8% based on 100% of the total mass of the NiO and the oxide ion conductor material.
3. The preparation method according to claim 1 or 2, wherein the method for preparing the anode powder into the green body in the step (1) comprises the following steps: adding a solvent into the anode powder, mixing, and preparing into a blank by using a pugging machine;
preferably, the solvent comprises water;
preferably, the membrane of step (1) comprises aluminum foil;
preferably, the standing time of the step (1) is 20-28 h.
4. The production method according to any one of claims 1 to 3, wherein the mold of step (1) is a circular tube-type mold;
preferably, step (1) further comprises drying the anode support;
preferably, the drying method comprises placing the anode support outside the room and drying with a drying oven.
5. The production method according to any one of claims 1 to 4, wherein the mass ratio of the first binder solution, the dispersant solution and the electrolyte in step (1) is 5 (0.8-1.2): 1.5-2.5;
preferably, the first binder comprises any one or a combination of at least two of ethyl cellulose, Hewlett packard V-006, or polyvinyl butyral;
preferably, the solvent of the first binder solution comprises terpineol, and the mass fraction of the solute in the solution is 3-7%;
preferably, the dispersant comprises any one or a combination of at least two of active content polymer dispersant Solsperse 28000, polyethylene glycol or fish oil;
preferably, the solvent of the dispersant solution comprises terpineol, and the mass fraction of solute in the solution is 15-25%;
preferably, the electrolyte comprises yttrium-zirconium-ytterbium doped barium cerate.
6. The preparation method according to any one of claims 1 to 5, wherein in the step (2), the anode support is heated to remove the pore-forming agent before pre-sintering;
preferably, the temperature for heating and removing the pore-forming agent is 400-500 ℃;
preferably, the time for heating to remove the pore-forming agent is 1-5 h;
preferably, the temperature of the pre-sintering in the step (2) is 1000-1250 ℃;
preferably, the pre-sintering time in the step (2) is 1-5 h.
7. The production method according to any one of claims 1 to 6, wherein the coating in the step (2) is performed by tubular printing or screen printing;
preferably, the electrolyte slurry of step (2) is coated to a thickness of 3 to 30 μm;
preferably, before the two-stage heating in step (2), the coated anode support is suspended on the refractory material without touching the refractory material, or the coated anode support is horizontally placed on a flat plate type lining body prepared from the same oxide ion conductor material;
preferably, the coated anode support is suspended with an alumina rod or platinum wire;
preferably, the cathode material of step (2) comprises an oxide ion conductor battery cathode material;
preferably, the oxide ion conductor battery cathode material comprises cobalt-iron-yttrium doped barium zirconate.
8. The method as set forth in any one of claims 1 to 7, wherein the first-stage temperature of the two-stage heating in the step (2) is 400-500 ℃;
preferably, the first stage time of the two-stage heating in the step (2) is 1-5 h;
preferably, the first-stage heating rate of the two-stage heating in the step (2) is below 5 ℃/min;
preferably, the second-stage temperature of the two-stage heating in the step (2) is 1400-1500 ℃;
preferably, the second stage time of the two-stage heating in the step (2) is 2-20 h;
preferably, the temperature rising rate of the second stage of the two-stage heating in the step (2) is below 5 ℃/min;
preferably, the cooling rate of the cooling in the step (2) is below 5 ℃/min.
9. The method for preparing according to any one of claims 1 to 8, characterized in that it comprises the steps of:
(1) adding water into the anode powder, mixing, preparing into a blank by using a pugging machine, wrapping the blank by using a film, standing for 20-28h, extruding by using a circular tube type die to obtain an extruded anode support body, placing the anode support body outdoors, and drying by using a drying oven to dry the extruded anode support body; mixing a first binder solution, a dispersant solution and an electrolyte to obtain electrolyte slurry;
(2) heating the anode support body in the step (1) at the temperature of 400-, and coating a cathode material and sintering the cathode coating to obtain the high-temperature oxide ion conductor battery.
10. A high temperature oxide ion conductor cell prepared according to the method of any one of claims 1 to 9.
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| CN101847734A (en) * | 2010-05-22 | 2010-09-29 | 东方电气集团东方汽轮机有限公司 | Method for preparing tubular solid oxide fuel cell |
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