CN114843569A - Preparation method of proton-oxygen ion mixed conductor electrolyte, product and battery - Google Patents
Preparation method of proton-oxygen ion mixed conductor electrolyte, product and battery Download PDFInfo
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a preparation method of a proton-oxygen ion mixed conductor electrolyte, a product and a battery, belonging to the field of solid oxide fuel batteries. The invention also provides the proton-oxygen ion mixed conductor electrolyte prepared by the method and a battery. The method can reduce the sintering temperature in the preparation process, can realize in-situ humidification of the anode, and can finally reduce the production and operation costs of the solid oxide battery.
Description
Technical Field
The invention belongs to the field of solid oxide batteries, and particularly relates to a preparation method of a proton-oxygen ion mixed conductor electrolyte, a product and a battery.
Background
In order to actively respond to national policy calls and scientific and technological layouts and achieve the aims of carbon peak reaching and carbon neutralization as early as possible, the research, development and popularization of a novel clean energy technology are very important. Among many new energy devices, Solid Oxide Fuel Cells (SOFC) have been widely paid attention and studied because of their advantages of high efficiency, stability, quietness, environmental protection, and the like. The SOFC can convert chemical energy into electric energy in one step, and fig. 1 shows the total cell reactions during a discharge reaction using hydrogen as fuel gas, where the total cell reactions are: h 2 +1/2O 2 →H 2 O, in particular, H as the reaction product thereof 2 O, thus being very friendly to the ecological environment.
The conventional SOFC is an oxygen ion conductor type, and the working temperature of the conventional SOFC is usually 600-850 ℃. Higher temperatures can achieve higher energy conversion efficiencies, but also present formidable challenges to the practical production, popularization, application, and maintenance of devices. Therefore, people strive to reduce the working temperature of the SOFC to a medium-low temperature range (500-600 ℃) so as to expand the selection range of key materials of the cell, prolong the service life of the cell and reduce the time and economic cost for maintaining the cell. Proton conductor SOFC (H-SOFC) comes from the beginning, fig. 2 shows the total cell reaction during the discharge reaction of the proton conductor SOFC using hydrogen as fuel gas, which has the following advantages: 1) in a low temperature range, the proton conductor electrolyte material has higher ionic conductivity and lower ohmic resistance, and has lower electrolyte potential loss and higher energy conversion efficiency in the H-SOFC operation; 2) in an H-SOFC system, water is used as a product and exists on a cathode side but not on an anode side, so that the oxidation/agglomeration of Ni particles caused by a large amount of water vapor in the anode can be avoided, and the long-term working stability of the anode is improved; 3) the water vapor on one side of the cathode can timely dilute the high-purity oxygen generated by the electrolytic reaction, so that the working safety of the device is improved.
However, the development of key materials for H-SOFCs is currently underway. Most of the cathodes for catalytic oxygen reduction still use the material system of the conventional oxygen ion conductor type SOFC, and on the basis of the material system, BaCoO with triple conduction characteristics (proton, oxygen ion and electron) is developed 3 Perovskite-based oxides, e.g. BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ Most of the cathode materials can meet the performance requirements of the low-temperature H-SOFC. The selection of the electrolyte and anode materials which can be selected is limited, and the material which is most widely applied in the proton conductor electrolyte is doped BaCeO 3 Perovskite-based oxide BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYb for short), the material has excellent proton conductivity, but the weak sintering activity of the material poses great challenges to the preparation of batteries. Research by O' Hayre et al shows that the electrolyte-anode half cell part of the H-SOFC needs to be formed by co-firing at a high temperature of more than 1600 ℃, and an excessively high sintering temperature is not favorable for the microstructure of the porous electrode, which is also a key problem in the preparation process and structural stability of the H-SOFC. The anode material of H-SOFC is generally a composite system of electrolyte-metal Ni, wherein the most widely used anode is bzcyb-Ni, as mentioned above, water is only present on the cathode side in H-SOFC as reaction product, the anode does not involve moisture in the cell reaction, however, the completely dry environment is not favorable for the reactivity of the anode, so that a lower degree of humidification (-3%) is usually performed in the gas path to the anode during the actual operation of H-SOFC, which will increase the complexity of the external gas path of the cell and the control system.
Therefore, it is necessary to develop a new electrode material to overcome the above-mentioned problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a proton-oxygen ion mixed conductor electrolyte preparation method, a product and a battery, wherein SDC is introduced into BZCYb and uniformly distributed to prepare proton-leading proton-oxygen ion mixed conductor electrolyte and an anode, the sintering temperature is reduced, a small amount of oxygen ions can be conducted to the anode and react to generate a certain amount of water vapor, the in-situ humidification of the anode is realized, and the production and operation cost can be finally reduced.
In order to achieve the purpose, the invention provides a proton-oxygen ion mixed conductor electrolyte preparation method, which comprises the steps of firstly preparing a proton-oxygen ion mixed conductor anode support body blank, then attaching electrolyte slurry to the proton-oxygen ion mixed conductor anode support body blank, and then sintering the proton-oxygen ion mixed conductor anode support body blank and the proton-oxygen ion mixed conductor support body blank to form the proton-oxygen ion mixed conductor electrolyte, wherein the proton-oxygen ion mixed conductor anode support body blank comprises NiO, BZCYb and SDC, and the electrolyte slurry comprises SDC and BZCYb.
Further, in the proton-oxygen ion mixed conductor anode support body blank, the mass fractions of NiO, BZCYb and SDC are 45 wt.% to 55 wt.%, 35 wt.% to 45 wt.%, and 0 wt.% to 10 wt.%, respectively, wherein the NiO is a standard type.
Further, when preparing the proton-oxygen ion mixed conductor anode support green body, firstly weighing NiO, BZCYb and SDC for mixing, then adding herring oil, ethanol, xylene and starch, carrying out ball milling on the obtained mixed powder, then adding PVB-98, PAG, BBP and cyclohexanone, continuing ball milling to enable the slurry to be mixed more uniformly, and finally carrying out defoaming on the ball-milled slurry under the vacuum degree of 0.8MPa to obtain the proton-oxygen ion mixed conductor anode support slurry.
Further, pouring the proton-oxygen ion mixed conductor anode support body slurry onto a casting machine, wherein the flow speed of the casting machine is 3mm s -1 ～5mm s -1 And fixing the height of a cutter head to be 2-3 mm, air-drying to obtain an original green body, taking down the original green body, stamping and cutting into pieces to obtain the proton-oxygen ion mixed conductor anode support body green body.
Furthermore, mixing SDC and BZCYb according to a set mass ratio to obtain a mixture, wherein the mass fraction of the SDC in the mixture is 0-10%, then adding a binder into the mixture, and finally grinding to obtain electrolyte slurry, wherein the mass fraction of the mixture in the electrolyte slurry is 60-70%.
Further, screen printing the electrolyte slurry on the proton-oxygen ion mixed conductor anode support body green body, firstly carrying out degreasing treatment, then presintering, and finally carrying out sintering, and sintering the proton-oxygen ion mixed conductor anode support body green body and the electrolyte together to obtain the sintered anode support body and the electrolyte.
Further, firstly preserving heat at 230-240 ℃ for 10-12 h, performing degreasing treatment, then heating to 850-950 ℃ and preserving heat for 2-3 h, and finally heating to 1400-1500 ℃ and preserving heat for 3-5 h, thereby completing co-sintering of the proton-oxygen ion mixed conductor anode support body green body and the electrolyte.
According to a second aspect of the present invention, there is also provided a proton-oxygen ion mixed conductor electrolyte obtained by the process as described above.
According to a third aspect of the present invention, there is also provided a solid oxide fuel cell comprising a proton-oxygen ion mixed conductor electrolyte as described above.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
the proton-leading proton-oxygen ion mixed conductor electrolyte and the anode provided by the invention introduce SDC into BZCYb and uniformly distribute the SDC, so that the serial sintering temperature in the battery preparation process can be reduced, a small amount of oxygen ions can be conducted to the anode and react to generate a certain amount of water vapor, the humidity can be regulated and controlled by the content of the oxygen ion conductor SDC, the in-situ humidification of the anode is realized, the external gas circuit and the control system of the battery are simplified, and the production and operation costs are reduced.
In addition, under the condition of using hydrocarbon fuel, the water vapor of the anode can also generate water gas reaction with carbon possibly deposited, so that the carbon is removed by reforming, the effect of carbon deposit resistance is achieved, and the catalytic activity and the working stability of the anode are improved.
Drawings
Fig. 1 is a diagram showing the overall cell reaction in a conventional oxygen ion conductor electrolyte SOFC, using hydrogen as fuel gas for the discharge reaction.
Fig. 2 is a diagram showing the total cell reaction in a conventional proton conductor-type SOFC in which hydrogen gas is used as a fuel gas for a discharge reaction.
FIG. 3 shows the total cell reaction in the discharge reaction of the proton-oxygen ion mixed conductor electrolyte provided by the embodiment of the present invention using hydrogen as fuel gas.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the invention, in order to improve the sintering activity of the BZCYb electrolyte, the anode is humidified controllably at the same time, a proton-oxygen ion mixed conductor electrolyte is developed, and an oxygen ion conductor Ce is used 0.8 Sm 0.2 O 1.9 The electrolyte (SDC-BZCYb) and the anode (SDC-BZCYb-Ni) are mechanically mixed with BZCYb in a lower proportion (1-10%) to realize high-quality and low-internal-resistance functional H-SOFC electrolyte (SDC-BZCYb) and anode (SDC-BZCYb-Ni). Compared with BZCYb, the SDC has higher sintering activity, the densification sintering temperature of the BZCYb electrolyte is usually about 1300 ℃, the densification sintering temperature of the BZCYb electrolyte is not lower than 1600 ℃, and the introduction of the SDC into the BZCYb is expected to reduce the sintering temperature of the electrolyte layer, so that the overall structural stability of the H-SOFC is optimized. In addition, SDC is an oxygen ion conductor, and a small amount of SDC phase is dispersed in BZCYb to realize the conduction of oxygen ions between cathode-electrolyte-anode and participate in electrode reaction with H on the anode side 2 Reaction to form H 2 O plays a role of in-situ humidification, and under the condition of certain gas flow and cell working temperature, the humidity can be regulated and controlled by the content of SDC, so that the gas path and control equipment in the actual operation of the H-SOFC external system are simplified, and the production and operation costs of the H-SOFC external system are reduced。
The process of the invention is further illustrated below with reference to specific examples.
Example 1
Preparing a proton-oxygen ion mixed conductor anode support:
the proton-oxygen ion mixed conductor anode support body is prepared by a casting-screen printing-sintering process and comprises the components of SDC-BZCYb-NiO, wherein the NiO is reduced into metal simple substance Ni in a reducing atmosphere after the battery is packaged. Firstly, weighing mixed powder of 55 wt.% of NiO (standard type), 35 wt.% of BZCYb and 0.1 wt.% of SDC as powder, adding menhaden oil, ethanol, xylene and starch, ball-milling the powder for 20 hours, and uniformly mixing the powder. Subsequently, PVB, PAG, BBP and cyclohexanone were added, and ball milling was continued for 28 hours to uniformly mix the slurry, which was stirred under a vacuum of 0.8MPa to remove bubbles. The casting process comprises the following steps: pouring the slurry onto a casting machine with the flow velocity of 5mm s -1 And the height of the cutter head is fixed to be 3 mm. After 50 hours of air drying, the green body is taken down and cut into a wafer with a certain diameter by a manual button punching machine to obtain a final anode support body green body, and the green body and the electrolyte layer are subjected to co-firing treatment.
Preparing a proton-oxygen ion mixed conductor electrolyte:
SDC-bzcyb electrolyte was attached to the above cast blank by screen printing, where the slurry used was: mixing 4 wt% of ethyl cellulose and 2.5 wt% of fish oil in terpineol as a binder, mixing SDC and BZCYb according to a certain mass ratio to obtain a solid mixture, wherein the mass ratio of the SDC in the solid mixture is 10%, adding the binder into the solid mixture, fully mixing and grinding to obtain electrolyte slurry, and the mass ratio of the solid mixture in the electrolyte slurry is 68%. After the slurry is silk-screened to the surface of a casting blank body, degreasing treatment is firstly carried out: preserving heat for 12h at 240 ℃, and then performing presintering treatment: slowly heating to 900 ℃, preserving heat for 2.5h, and finally preserving heat for 4 h at 1450 ℃, thus finishing co-firing of the anode support and the electrolyte, and further realizing the mechanical strength of the support and the densification of the electrolyte.
Example 2
Preparing a proton-oxygen ion mixed conductor anode support:
the proton-oxygen ion mixed conductor anode support body is prepared by a casting-screen printing-sintering process and comprises the components of SDC-BZCYb-NiO, wherein the NiO is reduced into metal simple substance Ni in a reducing atmosphere after the battery is packaged. Firstly, weighing mixed powder of 45 wt.% of NiO (standard type), 45 wt.% of BZCYb and 5 wt.% of SDC as powder, adding menhaden oil, ethanol, xylene and starch, ball-milling the powder for 20 hours, and uniformly mixing the powder. Subsequently, PVB, PAG, BBP and cyclohexanone were added, and ball milling was continued for 28 hours to uniformly mix the slurry, which was stirred under a vacuum of 0.8MPa to remove bubbles. The casting process comprises the following steps: pouring the slurry onto a casting machine with the flow velocity of 3mm s -1 And the height of the cutter head is fixed to be 2 mm. After air drying for 45 hours, taking off the green body, cutting the green body into wafers with certain diameters by using a manual button punching machine to obtain a final green body of the anode support, and then co-firing the green body and the electrolyte layer.
Preparing a proton-oxygen ion mixed conductor electrolyte:
SDC-bzcyb electrolyte was attached to the above cast blank by screen printing, where the slurry used was: mixing 4 wt% of ethyl cellulose and 2.5 wt% of fish oil in terpineol as a binder, mixing SDC and BZCYb according to a certain mass ratio to obtain a solid mixture, wherein the mass ratio of the SDC in the solid mixture is 7%, adding the binder into the solid mixture, fully mixing and grinding to obtain electrolyte slurry, and the mass ratio of the solid mixture in the electrolyte slurry is 70%. After the slurry is silk-screened to the surface of a casting blank body, degreasing treatment is firstly carried out: keeping the temperature at 230 ℃ for 12h, and then performing pre-sintering treatment: slowly heating to 950 ℃ and preserving heat for 3h, and finally preserving heat for 5 h at 1400 ℃ to finish co-firing the anode support and the electrolyte, thereby realizing the mechanical strength of the support and the densification of the electrolyte.
Example 3
Preparing a proton-oxygen ion mixed conductor anode support:
The proton-oxygen ion mixed conductor anode support in the invention is prepared by a casting-silk screen printing-sintering process, and comprises the following componentsIs SDC-BZCYb-NiO, wherein NiO is reduced into metallic simple substance Ni in the reducing atmosphere after the battery is packaged. Firstly, mixed powder of 48 wt.% NiO (standard type), 40 wt.% BZCYb and 3 wt.% SDC is weighed as powder, menhaden oil, ethanol, xylene and starch are added, and the mixture is ball-milled for 20 hours and is uniformly mixed. Subsequently, PVB, PAG, BBP and cyclohexanone were added, and ball milling was continued for 30 hours to uniformly mix the slurry, which was stirred under a vacuum of 0.8MPa to remove bubbles. The casting process comprises the following steps: pouring the slurry onto a casting machine with the flow velocity of the casting machine being 4.1mm s -1 And the height of the cutter head is fixed to be 2.5 mm. After 49 hours of air drying, the green body is taken down and cut into disks with certain diameters by a manual button punching machine to obtain the final green body of the anode support, and the green body is subjected to co-firing treatment with the electrolyte layer.
Preparing a proton-oxygen ion mixed conductor electrolyte:
SDC-bzcyb electrolyte was attached to the above cast blank by screen printing, where the slurry used was: mixing 4 wt% of ethyl cellulose and 2.5 wt% of fish oil in terpineol as a binder, mixing SDC and BZCYb according to a certain mass ratio to obtain a solid mixture, wherein the mass ratio of the SDC in the solid mixture is 4%, adding the binder into the solid mixture, fully mixing and grinding to obtain electrolyte slurry, and the mass ratio of the solid mixture in the electrolyte slurry is 60%. After the slurry is silk-screened to the surface of a casting blank body, degreasing treatment is firstly carried out: preserving heat for 11h at 230 ℃, and then performing pre-sintering treatment: slowly heating to 850 ℃ and preserving heat for 3h, and finally preserving heat for 3h at 1500 ℃ to finish co-firing of the anode support and the electrolyte, thereby realizing the mechanical strength of the support and the densification of the electrolyte.
Example 4
Preparing a proton-oxygen ion mixed conductor anode support:
the proton-oxygen ion mixed conductor anode support body is prepared by a casting-screen printing-sintering process and comprises the components of SDC-BZCYb-NiO, wherein the NiO is reduced into metal simple substance Ni in a reducing atmosphere after the battery is packaged. Firstly, weighing mixed powder of 52 wt.% NiO (standard type), 37 wt.% BZCYb and 4 wt.% SDC as powder, and adding the powder into the powderHerring oil, ethanol, xylene and starch, and ball milling for 20 hours. Subsequently, PVB, PAG, BBP and cyclohexanone were added, and ball milling was continued for 23 hours to uniformly mix the slurry, which was stirred under a vacuum of 0.8MPa to remove bubbles. The casting process comprises the following steps: pouring the slurry onto a casting machine with the flow velocity of the casting machine being 3.2mm s -1 And the height of the cutter head is fixed to be 2.1 mm. After 50 hours of air drying, the green body is taken down and cut into a wafer with a certain diameter by a manual button punching machine to obtain a final anode support body green body, and the green body and the electrolyte layer are subjected to co-firing treatment.
Preparing a proton-oxygen ion mixed conductor electrolyte:
SDC-bzcyb electrolyte was attached to the above cast blank by screen printing, where the slurry used was: mixing 4 wt% of ethyl cellulose and 2.5 wt% of fish oil in terpineol as a binder, mixing SDC and BZCYb according to a certain mass ratio to obtain a solid mixture, wherein the mass ratio of the SDC in the solid mixture is 2%, adding the binder into the solid mixture, fully mixing and grinding to obtain electrolyte slurry, and the mass ratio of the solid mixture in the electrolyte slurry is 69.5%. After the slurry is silk-screened to the surface of a casting blank body, degreasing treatment is firstly carried out: keeping the temperature at 238 ℃ for 11h, and then performing pre-sintering treatment: slowly heating to 850 ℃ and preserving heat for 2.9h, and finally preserving heat for 3 h at 1401 ℃ to finish co-firing of the anode support and the electrolyte, thereby realizing the mechanical strength of the support and the densification of the electrolyte.
Example 5
Preparing a proton-oxygen ion mixed conductor anode support:
the proton-oxygen ion mixed conductor anode support body is prepared by a casting-screen printing-sintering process and comprises the components of SDC-BZCYb-NiO, wherein the NiO is reduced into metal simple substance Ni in a reducing atmosphere after the battery is packaged. Firstly, weighing mixed powder of 45 wt.% of NiO (standard type), 41 wt.% of BZCYb and 0.9 wt.% of SDC as powder, adding menhaden oil, ethanol, xylene and starch, ball-milling the powder for 20 hours, and uniformly mixing the powder. Subsequently, PVB, PAG, BBP and cyclohexanone were added and ball milling was continued for 28 hours to mix the slurry uniformly, at 0.8Stirring and defoaming are carried out under the vacuum degree of MPa. The casting process comprises the following steps: pouring the slurry onto a casting machine with the flow velocity of the casting machine being 3.4mm s -1 And the height of the cutter head is fixed to be 2.4 mm. After 50 hours of air drying, the green body is taken down and cut into a wafer with a certain diameter by a manual button punching machine to obtain a final anode support body green body, and the green body and the electrolyte layer are subjected to co-firing treatment.
Preparing a proton-oxygen ion mixed conductor electrolyte:
SDC-bzcyb electrolyte was attached to the above cast blank by screen printing, where the slurry used was: mixing 4 wt% of ethyl cellulose and 2.5 wt% of fish oil in terpineol as a binder, mixing SDC and BZCYb according to a certain mass ratio to obtain a solid mixture, wherein the mass ratio of the SDC in the solid mixture is 6%, adding the binder into the solid mixture, fully mixing and grinding to obtain electrolyte slurry, and the mass ratio of the solid mixture in the electrolyte slurry is 67%. After the slurry is silk-screened to the surface of a casting blank body, degreasing treatment is firstly carried out: keeping the temperature at 235 ℃ for 11h, and then performing pre-sintering treatment: slowly heating to 920 ℃ and preserving heat for 2.5h, and finally preserving heat for 4 h at 1480 ℃ to finish the co-firing of the anode support and the electrolyte, thereby realizing the mechanical strength of the support and the densification of the electrolyte.
Fig. 3 shows the total cell reaction in the discharge reaction of the SOFC using hydrogen gas as fuel gas, in which hydrogen gas is catalytically oxidized to hydrogen ions at the porous anode side, and the hydrogen gas is conducted to the porous cathode through the proton-oxygen ion mixed conductor electrolyte, and reacts with the catalytically reduced oxygen ions to produce water, which is the main part of the cell discharge reaction. Meanwhile, because the proton-oxygen ion mixed conductor electrolyte has mixed conductivity, oxygen ions on the cathode side can be conducted to the porous anode through the proton-oxygen ion mixed conductor electrolyte to generate a small amount of water with hydrogen ions, and the in-situ humidification on the anode side is realized.
In actual engineering practice, the humidity on the anode side can be adjusted by adjusting the SDC content of the proton-oxygen ion mixed conductor electrolyte and the SDC content in the proton-oxygen ion mixed conductor anode support.
In the present invention, BZCYb is BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ The value of delta is related to temperature, and can change under different temperatures and test conditions, wherein delta is larger than 0 and smaller than 1. Ce 0.8 Sm 0.2 O 1.9 Is simply referred to as SDC. PVB is short for polyvinyl butyral, PAG is short for polyalkylene glycol, polyalkylene glycol is a copolymer obtained by copolymerization of ethylene oxide and propylene oxide, and BBP is short for butyl benzyl phthalate.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A proton-oxygen ion mixed conductor electrolyte preparation method is characterized in that a proton-oxygen ion mixed conductor anode support body green body is prepared, electrolyte slurry is attached to the proton-oxygen ion mixed conductor anode support body green body, the proton-oxygen ion mixed conductor anode support body green body and the proton-oxygen ion mixed conductor electrolyte are sintered to form the proton-oxygen ion mixed conductor electrolyte, wherein the proton-oxygen ion mixed conductor anode support body green body comprises NiO, BZCYb and SDC, and the electrolyte slurry comprises SDC and BZCYb.
2. The method for preparing the proton-oxygen ion mixed conductor electrolyte as claimed in claim 1, wherein the mass fractions of NiO, BZCYb and SDC in the green body of the anode support of the proton-oxygen ion mixed conductor are 45 wt.% to 55 wt.%, 35 wt.% to 45 wt.%, and 0 wt.% to 10 wt.%, respectively, wherein NiO is a standard type.
3. The method for preparing proton-oxygen ion mixed conductor electrolyte as claimed in claim 2, wherein when preparing the green body of the proton-oxygen ion mixed conductor anode support, NiO, BZCYb and SDC are weighed and mixed, then herring oil, ethanol, xylene and starch are added, the obtained mixed powder is ball milled, then PVB-98, PAG, BBP and cyclohexanone are added, the ball milling is continued to mix the slurry more uniformly, and finally, the ball milled slurry is defoamed under the vacuum degree of 0.8MPa to obtain the slurry of the proton-oxygen ion mixed conductor anode support.
4. The method for preparing the proton-oxygen ion mixed conductor electrolyte as claimed in one of claims 2 or 3, wherein the proton-oxygen ion mixed conductor anode support slurry is poured onto a casting machine with a flow rate of 3mm s -1 ～5mm s -1 And fixing the height of a cutter head to be 2-3 mm, air-drying to obtain an original green body, taking down the original green body, stamping and cutting into pieces to obtain the proton-oxygen ion mixed conductor anode support body green body.
5. A proton-oxygen ion mixed conductor electrolyte preparation method as claimed in claim 4, characterized in that SDC and BZCYb are mixed in a set mass ratio to obtain a mixture, the mass fraction of SDC in the mixture is 0-10%, then a binder is added to the mixture, finally grinding is carried out to obtain an electrolyte slurry, the mass fraction of the mixture in the electrolyte slurry is 60-70%.
6. The method of claim 5, wherein the electrolyte slurry is screen-printed on the green proton-oxygen ion mixed conductor anode support, and the green proton-oxygen ion mixed conductor anode support is degreased, pre-sintered, and the green proton-oxygen ion mixed conductor anode support and the electrolyte are co-sintered to obtain the sintered anode support and the electrolyte.
7. The method for preparing the proton-oxygen ion mixed conductor electrolyte as claimed in claim 6, wherein the temperature is maintained at 230-240 ℃ for 10-12 h, the degreasing treatment is performed, then the temperature is raised to 850-950 ℃ and maintained for 2-3 h, finally the temperature is raised to 1400-1500 ℃ and maintained for 3-5 h, and the co-sintering of the proton-oxygen ion mixed conductor anode support body green body and the electrolyte is completed.
8. A proton-oxygen ion mixed conductor electrolyte obtained by the process as claimed in any one of claims 1 to 7.
9. A solid oxide fuel cell comprising the proton-oxygen ion mixed conductor electrolyte of claim 8.
10. The solid oxide fuel cell of claim 9, wherein during operation, water is spontaneously generated on the anode side for in situ humidification of the anode, and the humidity on the anode side is adjusted by adjusting the SDC content of the proton-oxygen ion mixed conductor anode support and the SDC content of the proton-oxygen ion mixed conductor electrolyte.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090148742A1 (en) * | 2007-12-07 | 2009-06-11 | Day Michael J | High performance multilayer electrodes for use in reducing gases |
| KR20130022828A (en) * | 2011-08-26 | 2013-03-07 | 연세대학교 산학협력단 | Proton conductor for electrolyte of solid oxide fuel cells and solid oxide fuel cells comprising same |
| WO2013048722A1 (en) * | 2011-09-28 | 2013-04-04 | Phillips 66 Company | Optimization of bzcyyb synthesis |
| CN103811788A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method for middle-temperature and low-temperature solid oxide fuel battery |
| CN105140548A (en) * | 2015-07-01 | 2015-12-09 | 北京理工大学 | Sintering method of electrolytes for solid oxide fuel cell |
| KR20190079139A (en) * | 2017-12-27 | 2019-07-05 | 현대자동차주식회사 | A membrane-electrode assembly for a fuel cell having improved durability and a polymer electrolyte membrane fuel cell comprising the same |
-
2022
- 2022-04-02 CN CN202210343884.5A patent/CN114843569B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090148742A1 (en) * | 2007-12-07 | 2009-06-11 | Day Michael J | High performance multilayer electrodes for use in reducing gases |
| KR20130022828A (en) * | 2011-08-26 | 2013-03-07 | 연세대학교 산학협력단 | Proton conductor for electrolyte of solid oxide fuel cells and solid oxide fuel cells comprising same |
| WO2013048722A1 (en) * | 2011-09-28 | 2013-04-04 | Phillips 66 Company | Optimization of bzcyyb synthesis |
| CN103811788A (en) * | 2014-02-27 | 2014-05-21 | 盐城工学院 | Preparation method for middle-temperature and low-temperature solid oxide fuel battery |
| CN105140548A (en) * | 2015-07-01 | 2015-12-09 | 北京理工大学 | Sintering method of electrolytes for solid oxide fuel cell |
| KR20190079139A (en) * | 2017-12-27 | 2019-07-05 | 현대자동차주식회사 | A membrane-electrode assembly for a fuel cell having improved durability and a polymer electrolyte membrane fuel cell comprising the same |
Non-Patent Citations (3)
| Title |
|---|
| MINGFEI LIU等: "An Efficient SOFC Based on Samaria-Doped Ceria (SDC) Electrolyte", 《THE ELECTROCHEMICAL SOCIETY》, vol. 159, no. 6, pages 661 * |
| 夏梦: "复合BaCeO3基材料对CeO2基电解质在固体氧化物燃料电池中的应用性能的影响", 《中国优秀硕士学位论文全文数据库·工程科技Ⅰ辑》, no. 6, pages 015 - 120 * |
| 孙文平: "中低温固体氧化物燃料电池新材料与结构设计及电化学性能研究", 《中国博士学位论文全文数据库·工程科技Ⅱ辑》, no. 10, pages 042 - 76 * |
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