CN111087239A - Water-based tape casting slurry, electrolyte film, preparation method and application thereof - Google Patents

Water-based tape casting slurry, electrolyte film, preparation method and application thereof Download PDF

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CN111087239A
CN111087239A CN201911260192.9A CN201911260192A CN111087239A CN 111087239 A CN111087239 A CN 111087239A CN 201911260192 A CN201911260192 A CN 201911260192A CN 111087239 A CN111087239 A CN 111087239A
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electrolyte
slurry
powder
casting
stabilized zirconia
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雷泽
周卫华
王浩然
吴培华
杨志宾
由晓彬
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China University of Mining and Technology Beijing CUMTB
Shenhua New Energy Co Ltd
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China University of Mining and Technology Beijing CUMTB
Shenhua New Energy Co Ltd
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Abstract

The invention discloses a water-based tape casting slurry, an electrolyte film, a preparation method and application thereof. The aqueous casting slurry includes: electrolyte powder, an aluminum-containing compound, a solvent, a dispersant, a binder, a plasticizer and a defoaming agent. The water-based tape casting slurry is environment-friendly and low in cost, and an electrolyte film prepared from the water-based tape casting slurry has excellent sintering capacity, conductivity and mechanical property.

Description

Water-based tape casting slurry, electrolyte film, preparation method and application thereof
Technical Field
The invention belongs to the field of fuel cells/electrolytic cells, and particularly relates to water-based tape casting slurry, an electrolyte film, and a preparation method and application thereof.
Background
Yttria-stabilized zirconia (YSZ) has higher high-temperature conductivity, good stability and relatively lower cost, and is the most widely applied electrolyte material in Solid Oxide Fuel Cells (SOFCs) and electrolytic cells (SOECs) at present; scandia-stabilized zirconia (ScSZ) has higher conductivity and better mechanical properties, and is considered to be a possible substitute for YSZ electrolyte materials. The electrolyte-supported SOFC/SOEC has high conversion efficiency, and it is generally necessary to make the electrolyte thin as much as possible in order to reduce the electrolyte resistance.
Common forming methods of the electrolyte material include a plasma spraying method, a sputtering method, a casting method and the like, wherein the casting method is widely applied to the commercial mass production of electrolyte films. The method is characterized in that slurry is prepared, casting slurry comprises electrolyte powder, a solvent, a dispersing agent, a bonding agent, a plasticizer and a defoaming agent, the prepared slurry is subjected to ball milling for two to three times for several hours to tens of hours, the casting slurry is subjected to defoaming, sieving and other treatments and then discharged from a discharge port of a casting machine, the height of a scraper and the casting speed are adjusted according to the required thickness of a green blank, so that the slurry uniformly flows out of a film belt, and the solvent is volatilized through drying to form the film element blank. And cutting or punching the demoulded biscuit as required, and then removing the glue and sintering to obtain the required flaky electrolyte material.
The prior casting process still mainly uses an organism system, solvents are usually butanone, benzene, xylene and the like, and although green bodies obtained by casting the solvents have good flexibility, the solvents have the defects of high toxicity, harm to human body, environmental pollution, high cost and the like. Moreover, the zirconia-based electrolyte film prepared by the prior art has poor mechanical property and is easy to crack in the assembling and running processes of the battery, thereby reducing the performance and the service life of the battery, and simultaneously, the problem that the densification temperature required by sintering is overhigh and the medium-low temperature conductivity is lower also exists.
Disclosure of Invention
The invention provides a water-based tape casting slurry, an electrolyte film, a preparation method and application thereof, aiming at the problems that the existing organic tape casting slurry is not environment-friendly and the sintering capacity, the conductivity and the mechanical property of the prepared electrolyte film are not good.
In a first aspect the present invention provides an aqueous casting slurry comprising: electrolyte powder, an aluminum-containing compound, a solvent, a dispersant, a binder, a plasticizer and a defoaming agent.
According to some embodiments of the aqueous casting slurry of the present invention, the content of the aluminum-containing compound in terms of alumina is 0.2 to 12% by weight, more preferably 0.5 to 3% by weight, based on the weight of the electrolyte powder. For example, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, and any value therebetween. The aluminum-containing compound in the preferable range of the invention can promote the sintering of electrolyte powder and improve the conductivity and bending strength, for example, when 0.5 weight percent of aluminum-containing compound calculated by aluminum oxide is added, the relative density of the prepared yttria-stabilized zirconia electrolyte film after being sintered for 10 hours at 1350 ℃ can reach more than 98.5 percent; the conductivity at 800 ℃ can reach 0.0535S/cm; the bending strength reaches 250 MPa. The maximum power density of the electrolyte-supported unit cell prepared based on the material and taking hydrogen as fuel at 800 ℃ is 308mW/cm2And exhibits good stability.
According to some embodiments of the aqueous casting paste of the present invention, the content of the electrolyte powder is 40 to 60% by weight based on the total weight of the aqueous casting paste. For example, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, and any value therebetween.
According to some embodiments of the aqueous casting dope of the present invention, the solvent is contained in an amount of 30 to 45% by weight based on the total weight of the aqueous casting dope. For example, 30 wt%, 35 wt%, 40 wt%, 45 wt%, and any value therebetween.
According to some embodiments of the aqueous casting slurry of the present invention, the dispersant is contained in an amount of 0.8 to 4% by weight based on the total weight of the aqueous casting slurry. For example, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and any value therebetween.
According to some embodiments of the aqueous casting dope of the present invention, the binder is contained in an amount of 4.5 to 8.5% by weight based on the total weight of the aqueous casting dope. For example, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, and any value therebetween.
According to some embodiments of the aqueous casting dope according to the present invention, the content of the plasticizer is 3.5 to 10% by weight based on the total weight of the aqueous casting dope. For example, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, and any value therebetween.
According to some embodiments of the aqueous casting dope according to the present invention, the defoaming agent is contained in an amount of 0.3 to 1% by weight based on the total weight of the aqueous casting dope. For example, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, and any value therebetween.
According to some embodiments of the aqueous casting slurry of the present invention, the electrolyte powder is yttria-stabilized zirconia powder (YSZ), scandia-stabilized zirconia powder (ScSZ), scandia-and ceria-stabilized zirconia powder (ScCeSZ), calcia-stabilized zirconia (CSZ), or magnesia-stabilized zirconia (MSZ).
According to some embodiments of the aqueous casting slurry of the present invention, the yttria content in the yttria-stabilized zirconia powder is 3 to 10 mol%. Because different mole percentages of yttria have certain effects on the performance of the electrolyte membrane, in a preferred aspect of the invention, the yttria content in the yttria-stabilized zirconia powder is 7-9 mole%. In this preferable case, the performance of the electrolyte membrane is optimal. In the present invention, for example, 8 mole% yttria-stabilized zirconia powder may be abbreviated as 8 YSZ.
According to some embodiments of the aqueous casting slurry of the present invention, a content of scandia in the scandia stabilized zirconia powder is 5 to 15 mol%. Because different mole percent contents of scandia have certain influence on the performance of the electrolyte thin film, in the preferred case of the present invention, the content of scandia in the scandia-stabilized zirconia powder is 8 to 12 mole%. In this preferable case, the performance of the electrolyte membrane is optimal. In the present invention, for example, 10 mol% of scandia-stabilized zirconia powder may be abbreviated as 10 ScSZ.
According to some embodiments of the aqueous casting slurry of the present invention, in the scandia and ceria stabilized zirconia powder, a content of scandia is 5 to 15 mol% and a content of ceria is 0.5 to 5 mol%. The scandia and ceria stabilized zirconia powder refers to a powder in which scandia and ceria are stabilized together, and in the present invention, scandia and ceria stabilized zirconia may be written as scandia and ceria stabilized zirconia. In the present invention, for example, a 10 mol% scandia, 1 mol% ceria co-stabilized zirconia powder can be written as 10 mol% scandia, 1 mol% ceria stabilized zirconia, abbreviated as 10Sc1 CeSZ.
According to some embodiments of the aqueous casting slurry of the present invention, the content of calcium oxide in the calcium oxide-stabilized zirconia powder is 5 to 10 mol%. For example, 10 mole% calcia stabilized zirconia powder may be abbreviated as 10 CSZ.
According to some embodiments of the aqueous casting slurry of the present invention, the magnesia-stabilized zirconia powder has a magnesia content of 5 to 10 mol%. For example, 10 mole percent magnesia stabilized zirconia powder may be abbreviated as 10 MSZ.
According to some embodiments of the aqueous casting slurry of the present invention, the average particle diameter of the electrolyte powder is 150-250 nm. Such as 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, and any value therebetween.
According to some embodiments of the aqueous casting slurry of the present invention, the aluminum-containing compound is water-soluble aluminum, further preferably, the aluminum-containing compound is aluminum ethoxide and/or aluminum nitrate. In the present invention, the water-soluble aluminum is selected to make the aluminum more uniformly dispersed in the electrolyte matrix.
According to some embodiments of the aqueous casting slurry of the present invention, the dispersant is triethanolamine and/or isopropanol.
According to some embodiments of the aqueous casting dope of the present invention, the binder is polyvinyl alcohol and/or polyacrylic acid.
According to some embodiments of the aqueous casting slurry of the present invention, the plasticizer is glycerol and/or polyethylene glycol.
According to some embodiments of the aqueous casting slurry of the present invention, the defoaming agent is tributyl phosphate and/or n-butanol.
According to some embodiments of the aqueous casting slurry of the present invention, the solvent may have a wide selection range, and may be, for example, ultrapure water, for the purpose of being able to form a pseudoplastic aqueous slurry excellent in rheological properties and being able to uniformly disperse the electrolyte powder, the aluminum-containing compound, the dispersant, the binder, the plasticizer, and the defoaming agent.
The inventor of the present invention has found through research that when the present application selects the preferred raw materials and combines the preferred content range, the casting effect of the water-based casting slurry is better through the synergistic effect of the materials, and the sintering capability, the conductivity and the mechanical property of the electrolyte film prepared by the water-based casting slurry are better.
The second aspect of the present invention provides a method for producing an electrolyte thin film, comprising:
(A) preparation of casting slurry
Mixing a solvent, a dispersant, an aluminum-containing compound and electrolyte powder and performing first ball milling to obtain initial slurry; then mixing the initial slurry with a plasticizer, a defoaming agent and a water-containing binder, and sequentially carrying out second ball milling, defoaming and sieving to obtain water-based tape casting slurry;
(B) preparation of a biscuit
Carrying out tape casting and drying on the water-based tape casting slurry to obtain a biscuit;
(C) preparation of electrolyte film
And sintering the biscuit.
According to some embodiments of the production method of the present invention, the content of the aluminum-containing compound in terms of alumina is 0.2 to 12% by weight, more preferably 0.5 to 3% by weight, based on the weight of the electrolyte powder. For example, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, and any value therebetween. The aluminum-containing compound in the preferable range of the invention can promote the sintering of electrolyte powder and improve the conductivity and bending strength, for example, when 0.5 weight percent of aluminum-containing compound calculated by aluminum oxide is added, the relative density of the prepared yttria-stabilized zirconia electrolyte film after being sintered for 10 hours at 1350 ℃ can reach more than 98.5 percent; the conductivity at 800 ℃ can reach 0.0535S/cm; the bending strength reaches 250 MPa. The maximum power density of the electrolyte-supported unit cell prepared based on the material and taking hydrogen as fuel at 800 ℃ is 308mW/cm2And exhibits good stability.
According to some embodiments of the production method of the present invention, the charged amount of the electrolyte powder is 40 to 60% by weight based on the total weight of the water-based casting slurry. For example, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, and any value therebetween.
According to some embodiments of the method of manufacturing of the present invention, the total charge of water in the solvent and the aqueous binder is 30 to 45% by weight based on the total weight of the aqueous casting slurry. For example, 30 wt%, 35 wt%, 40 wt%, 45 wt%, and any value therebetween.
According to some embodiments of the preparation method of the present invention, the charged amount of the dispersant is 0.8 to 4% by weight based on the total weight of the aqueous casting slurry. For example, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and any value therebetween.
According to some embodiments of the method of manufacturing of the present invention, the charged amount of the binder in the aqueous binder is 4.5 to 8.5 wt% based on the total weight of the water-based casting slurry. For example, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, and any value therebetween.
According to some embodiments of the preparation method of the present invention, the charged amount of the plasticizer is 3.5 to 10% by weight based on the total weight of the water-based casting slurry. For example, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, and any value therebetween.
According to some embodiments of the preparation method of the present invention, the amount of the defoaming agent is fed in an amount of 0.3 to 1% by weight based on the total weight of the aqueous casting slurry. For example, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, and any value therebetween.
According to some embodiments of the method of preparing of the present invention, the electrolyte powder is yttria-stabilized zirconia powder (YSZ), scandia-stabilized zirconia powder (ScSZ), scandia-and ceria-stabilized zirconia powder (ScCeSZ), calcia-stabilized zirconia (CSZ), or magnesia-stabilized zirconia (MSZ).
According to some embodiments of the method of preparing of the present invention, the yttria content in the yttria-stabilized zirconia powder is 3 to 10 mol%. Because different mole percentages of yttria have certain effects on the performance of the electrolyte membrane, in a preferred aspect of the invention, the yttria content in the yttria-stabilized zirconia powder is 7-9 mole%. In this preferable case, the performance of the electrolyte membrane is optimal. In the present invention, for example, 8 mole% yttria-stabilized zirconia powder may be abbreviated as 8 YSZ.
According to some embodiments of the method of manufacturing of the present invention, a content of scandia in the scandia-stabilized zirconia powder is 5 to 15 mol%. Because different mole percent contents of scandia have certain influence on the performance of the electrolyte thin film, in the preferred case of the present invention, the content of scandia in the scandia-stabilized zirconia powder is 8 to 12 mole%. In this preferable case, the performance of the electrolyte membrane is optimal. In the present invention, for example, 10 mol% of scandia-stabilized zirconia powder may be abbreviated as 10 ScSZ.
According to some embodiments of the method of preparing of the present invention, in the scandia and ceria-stabilized zirconia powder, a content of scandia is 5 to 15 mol% and a content of ceria is 0.5 to 5 mol%. The scandia and ceria stabilized zirconia powder refers to a powder in which scandia and ceria are stabilized together, and in the present invention, scandia and ceria stabilized zirconia may be written as scandia and ceria stabilized zirconia. In the present invention, for example, a 10 mol% scandia, 1 mol% ceria co-stabilized zirconia powder can be written as 10 mol% scandia, 1 mol% ceria stabilized zirconia, abbreviated as 10Sc1 CeSZ.
According to some embodiments of the method of preparing of the present invention, the content of calcium oxide in the calcium oxide-stabilized zirconia powder is 5 to 10 mol%. For example, 10 mole% calcia stabilized zirconia powder may be abbreviated as 10 CSZ.
According to some embodiments of the method of preparing of the present invention, the content of magnesium oxide in the magnesium oxide-stabilized zirconia powder is 5 to 10 mol%. For example, 10 mole percent magnesia stabilized zirconia powder may be abbreviated as 10 MSZ.
According to some embodiments of the preparation method of the present invention, the average particle diameter of the electrolyte powder is 150-250 nm. Such as 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, and any value therebetween.
According to some embodiments of the preparation method of the present invention, the aluminum-containing compound is water-soluble aluminum, and further preferably, the aluminum-containing compound is aluminum ethoxide and/or aluminum nitrate. In the present invention, the water-soluble aluminum is selected to make the aluminum more uniformly dispersed in the electrolyte matrix.
According to some embodiments of the method of making of the present invention, the dispersant is triethanolamine and/or isopropanol.
According to some embodiments of the method of manufacturing of the present invention, the binder is polyvinyl alcohol and/or polyacrylic acid. In the preparation process, the binder needs to be compounded with a solvent (preferably ultrapure water), and preferably, the total weight of the mixture of the binder and the ultrapure water is taken as a substrate, and the content of the binder is 10-20 wt%.
According to some embodiments of the method of manufacturing of the present invention, the plasticizer is glycerol and/or polyethylene glycol.
According to some embodiments of the preparation method of the present invention, the defoaming agent is tributyl phosphate and/or n-butanol.
According to some embodiments of the preparation method of the present invention, the solvent may have a wide selection range, and may be, for example, ultrapure water, for the purpose of being able to form a pseudoplastic water-based slurry excellent in rheological properties and being able to uniformly disperse the electrolyte powder, the aluminum-containing compound, the dispersant, the binder, the plasticizer, and the defoaming agent.
According to some embodiments of the method of preparing of the present invention, the initial slurry has a viscosity of 8 to 15Pa · s. When within this preferred range, the properties of the resulting electrolyte film are more excellent.
According to some embodiments of the method of manufacturing of the present invention, the viscosity of the aqueous casting slurry is 5 to 10Pa · s. When within this preferred range, the properties of the resulting electrolyte film are more excellent.
According to some embodiments of the preparation method of the present invention, in the step (a), the solvent, the dispersant and the aluminum-containing compound are mixed, and then mixed with the electrolyte powder and first ball-milled.
According to some embodiments of the method of preparing of the present invention, the conditions of the first ball milling comprise: the time is 10-12 h.
According to some embodiments of the method of preparing of the present invention, the conditions of the second ball milling comprise: the time is 8-16 h.
According to some embodiments of the method of manufacturing of the present invention, the defoaming conditions include: the time is 20-40 min. The debubbling may be carried out in a debubbling machine conventional in the art. Vacuum defoaming is preferred.
According to some embodiments of the method of manufacturing of the present invention, the sieving conditions comprise: the slurry was passed through a 150-mesh 250-mesh screen.
According to some embodiments of the production method of the present invention, the conditions of the casting include: the casting speed is 0.3-1 cm/s. At which the water based casting slurry of the present invention can be uniformly discharged.
According to some embodiments of the method of manufacturing of the present invention, the conditions of the sintering include: the temperature is 1200 ℃ and 1600 ℃ and the time is 5-15 h.
The third aspect of the present invention provides an electrolyte thin film prepared by the above method.
According to some embodiments of the electrolyte thin film of the present invention, the electrolyte thin film is a yttria-stabilized zirconia-based electrolyte thin film, a scandia-stabilized zirconia-based electrolyte thin film, a calcia-stabilized zirconia-based electrolyte thin film, or a magnesia-stabilized zirconia-based electrolyte thin film.
The invention adopts ultrapure water as solvent, overcomes the defects of an organic system, and obtains the electrolyte film with good flexibility, compactness, high conductivity and high strength.
Drawings
Fig. 1 is a flowchart of a method for producing an electrolyte thin film provided in example 1 of the present invention;
fig. 2 is a bad picture of yttria-stabilized zirconia (YSZ) pixel provided in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention easier to understand, the present invention will be described in further detail below with reference to the accompanying drawings and examples. 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 following examples, the test methods involved are as follows:
1. the relative density test method is an Archimedes drainage method;
2. the conductivity test method is an alternating current impedance method: coating silver paste on two sides of an electrolyte wafer, and measuring the conductivity of a sample in an air atmosphere by an alternating current impedance method, wherein the measurement frequency range is 0.1Hz-1 MHz;
3. the bending strength is measured by a three-point bending test method, specifically, a strip sample is subjected to a three-point bending test by using a universal testing machine (ZWICK-Z020).
[ example 1 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 2.6g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 8 mol% yttria-stabilized zirconia (8YSZ) powder (with an average particle size of 200nm and electrolyte powder) and ball-milling for 12h to obtain initial slurry; then mixing and ball-milling the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of the aqueous binder), 6.3g of glycerol (a plasticizer) and 0.5g of tributyl phosphate (a defoaming agent) for 16h, and sieving the mixture through a 200-mesh sieve after vacuum defoaming for 30min to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm, wherein the thickness is shown in figure 2;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1350 deg.C for 10h to obtain sheet-shaped electrolyte material (electrolyte film), with the preparation process shown in FIG. 1, the size of the round sheet-shaped electrolyte film being 1 mm in diameter and 0.2 mm in thickness; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 2 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of isopropanol (dispersant) and 1.13g of aluminum ethoxide (aluminum-containing compound), then mixing with 70g of 8 mol% yttria-stabilized zirconia (8YSZ) powder (with an average particle size of 200nm and electrolyte powder) and carrying out ball milling for 12h to obtain initial slurry; then mixing the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of aqueous binder), 6.3g of glycerol (plasticizer) and 0.5g of n-butyl alcohol (defoaming agent), ball-milling for 16h, defoaming in vacuum for 30min, and sieving with a 200-mesh sieve to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1350 deg.c for 10 hr to obtain disc-shaped electrolyte material with diameter of 1 mm and thickness of 0.2 mm; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 3 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 2.6g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 10 mol% scandium oxide, 1 mol% cerium oxide stabilized zirconia (10Sc1CeSZ) powder (average particle diameter 200nm, electrolyte powder) and ball milling for 12h to obtain initial slurry; then mixing the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of aqueous binder), 6.3g of glycerol (plasticizer) and 0.5g of n-butyl alcohol (defoaming agent), ball-milling for 16h, defoaming in vacuum for 30min, and sieving with a 200-mesh sieve to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1500 ℃ for 5h to obtain a sheet electrolyte material (electrolyte film), wherein the size of the disc electrolyte film is 1 mm in diameter and 0.2 mm in thickness; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 4 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 3g of triethanolamine (dispersant) and 1.13g of aluminum ethoxide (aluminum-containing compound), then mixing with 70g of 10 mol% scandium oxide and 1 mol% cerium oxide stabilized zirconia (10Sc1CeSZ) powder (the average particle size is 200nm, electrolyte powder) and carrying out ball milling for 12h to obtain initial slurry; then mixing and ball-milling the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of the aqueous binder), 6.3g of glycerol (a plasticizer) and 0.5g of tributyl phosphate (a defoaming agent) for 16h, and sieving the mixture through a 200-mesh sieve after vacuum defoaming for 30min to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1500 ℃ for 5h to obtain a sheet electrolyte material (electrolyte film), wherein the size of the disc electrolyte film is 1 mm in diameter and 0.2 mm in thickness; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 5 ]
(A) Preparation of casting slurry
Mixing 15g of ultrapure water (solvent), 2g of isopropanol (dispersant) and 2.6g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 8 mol% yttria-stabilized zirconia (8YSZ) powder (average particle size 20 μm, electrolyte powder) and ball-milling for 12h to obtain an initial slurry; then mixing the initial slurry with 45.3g of polyacrylic acid aqueous solution (the content of polyacrylic acid is 15 wt%, and the content of the polyacrylic acid is water-containing binder), 5.5g of polyethylene glycol (plasticizer) and 0.5g of tributyl phosphate (defoaming agent), carrying out ball milling for 16h, carrying out vacuum defoaming for 30min, and then sieving with a 150-mesh sieve to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1350 deg.c for 10 hr to obtain disc-shaped electrolyte material with diameter of 1 mm and thickness of 0.2 mm; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 6 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 2g of triethanolamine (dispersant) and 2.6g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 8 mol% yttria-stabilized zirconia (8YSZ) powder (with an average particle size of 150nm and electrolyte powder) and ball-milling for 10h to obtain initial slurry; then mixing the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of aqueous binder), 10g of glycerol (plastic agent) and 1g of tributyl phosphate (defoaming agent), ball-milling for 16h, defoaming in vacuum for 30min, and sieving with a 200-mesh sieve to obtain water-based casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.5cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1350 deg.c for 10 hr to obtain disc-shaped electrolyte material with diameter of 1 mm and thickness of 0.2 mm; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 7 ]
(A) Preparation of casting slurry
Mixing 25g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 2.6g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 10 mol% scandium oxide, 1 mol% cerium oxide stabilized zirconia (10Sc1CeSZ) powder (average particle diameter 200nm, electrolyte powder) and ball milling for 12h to obtain initial slurry; then mixing the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 20 wt%, the content of aqueous binder), 10g of glycerol (plastic agent) and 2g of n-butyl alcohol (defoaming agent), ball-milling for 16h, defoaming in vacuum for 30min, and sieving with a 200-mesh sieve to obtain water-based casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1500 ℃ for 5h to obtain a sheet electrolyte material (electrolyte film), wherein the size of the disc electrolyte film is 1 mm in diameter and 0.2 mm in thickness; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 8 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 5.2g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 8 mol% yttria-stabilized zirconia (8YSZ) powder (with an average particle size of 200nm and electrolyte powder) and ball-milling for 10h to obtain initial slurry; then mixing and ball-milling the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of the aqueous binder), 6.3g of glycerol (a plasticizer) and 0.5g of tributyl phosphate (a defoaming agent) for 8 hours, and sieving the mixture through a 150-mesh sieve after vacuum defoaming for 30 minutes to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1350 deg.c for 10 hr to obtain disc-shaped electrolyte material with diameter of 1 mm and thickness of 0.2 mm; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 9 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 5.2g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 10 mol% scandium oxide, 1 mol% cerium oxide stabilized zirconia (10Sc1CeSZ) powder (average particle diameter 200nm, electrolyte powder) and ball milling for 10h to obtain initial slurry; then mixing the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 20 wt%, the content of the polyvinyl alcohol is water-containing binder), 6.3g of glycerol (plasticizer) and 0.5g of tributyl phosphate (defoaming agent), carrying out ball milling for 8 hours, carrying out vacuum defoaming for 30 minutes, and then sieving with a 150-mesh sieve to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1500 ℃ for 5h to obtain a sheet electrolyte material (electrolyte film), wherein the size of the disc electrolyte film is 1 mm in diameter and 0.2 mm in thickness; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 10 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 15.9g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 8 mol% yttria-stabilized zirconia (8YSZ) powder (with an average particle size of 200nm and electrolyte powder) and ball-milling for 12h to obtain initial slurry; then mixing and ball-milling the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of the aqueous binder), 6.3g of glycerol (a plasticizer) and 0.5g of tributyl phosphate (a defoaming agent) for 16h, and sieving the mixture through a 200-mesh sieve after vacuum defoaming for 30min to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1350 deg.c for 10 hr to obtain disc-shaped electrolyte material with diameter of 1 mm and thickness of 0.2 mm; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 11 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 15.9g of aluminum nitrate (aluminum-containing compound), then mixing with 70g of 10 mol% scandium oxide, 1 mol% cerium oxide stabilized zirconia (10Sc1CeSZ) powder (average particle diameter 200nm, electrolyte powder) and ball milling for 12h to obtain initial slurry; then mixing and ball-milling the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of the aqueous binder), 6.3g of glycerol (a plasticizer) and 0.5g of tributyl phosphate (a defoaming agent) for 16h, and sieving the mixture through a 200-mesh sieve after vacuum defoaming for 30min to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1500 ℃ for 5h to obtain a sheet electrolyte material (electrolyte film), wherein the size of the disc electrolyte film is 1 mm in diameter and 0.2 mm in thickness; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
[ example 12 ]
(A) Preparation of casting slurry
Mixing 20g of ultrapure water (solvent), 5g of triethanolamine (dispersant) and 11.7g of aluminum ethoxide (aluminum-containing compound), then mixing with 70g of 8 mol% yttria-stabilized zirconia (8YSZ) powder (with the average particle size of 200nm and electrolyte powder) and carrying out ball milling for 12h to obtain initial slurry; then mixing and ball-milling the initial slurry with 52.5g of polyvinyl alcohol aqueous solution (the content of polyvinyl alcohol is 15 wt%, the content of the aqueous binder), 6.3g of glycerol (a plasticizer) and 0.5g of tributyl phosphate (a defoaming agent) for 16h, and sieving the mixture through a 200-mesh sieve after vacuum defoaming for 30min to obtain water-based tape casting slurry, wherein the content of each substance is shown in table 1;
(B) preparation of a biscuit
Adjusting the height of a scraper of casting equipment, adjusting the casting speed to be 0.3cm/s, slowly pouring the water-based casting slurry obtained in the step (A) into a hopper, enabling the slurry to uniformly flow out on a film belt, and drying for 24 hours to enable a solvent to volatilize to form a plain film with the thickness of 0.25 mm;
(C) preparation of electrolyte film
And (C) cutting the biscuit obtained in the step (B) into a disc shape and a strip shape respectively, wherein the disc shape is used for measuring the conductivity, and the strip shape is used for measuring the bending strength. Sintering at 1350 deg.c for 10 hr to obtain disc-shaped electrolyte material with diameter of 1 mm and thickness of 0.2 mm; the dimensions of the strip-shaped electrolyte thin film were 0.2 mm in thickness, 20 mm in length and 5 mm in width, and the relative density, conductivity and bending strength of the sheet-like electrolyte material were measured, and the results are shown in table 2.
Comparative example 1
According to the procedure of example 1 except that no aluminum-containing compound was added and the contents of the respective substances are shown in Table 1, a sheet-like electrolyte material was obtained and the sheet-like electrolyte material was tested for relative density, electric conductivity and bending strength, the results of which are shown in Table 2.
Comparative example 2
According to the procedure of example 3 except that no aluminum-containing compound was added and the contents of the respective substances are shown in Table 1, a sheet-like electrolyte material was obtained and the sheet-like electrolyte material was tested for relative density, electric conductivity and bending strength, the results of which are shown in Table 2.
TABLE 1
Figure BDA0002311397870000171
Figure BDA0002311397870000181
Note: the amount of solvent in table 1 is based on the total amount of ultrapure water (solvent) and ultrapure water in the aqueous binder; binder based on the amount of binder in the aqueous binder; the content of the aluminum-containing compound is based on the weight of aluminum oxide, and the percentage is based on the total weight of the electrolyte powder.
TABLE 2
Examples Relative density of% Conductivity, S/cm Flexural strength, MPa
Example 1(Y) 98.5 0.0535 250
Example 2(Y) 98.3 0.051 238
Example 3(S) 99 0.13 400
Example 4(S) 98.5 0.12 391
Example 5(Y) 98.3 0.051 246
Example 6(Y) 98.3 0.049 238
Example 7(S) 98.8 0.118 393
Example 8(Y) 98.3 0.048 260
Example 9(S) 98.6 0.09 433
Example 10(Y) 98 0.04 270
Example 11(S) 96.5 0.085 560
Example 12(Y) 94 0.04 240
COMPARATIVE EXAMPLE 1(Y) 95 0.048 198
COMPARATIVE EXAMPLE 2(S) 97.3 0.1 350
Note: in Table 2Y represents 8YSZ and S represents 10Sc1CeSZ
As can be seen from examples 1 to 12 and comparative examples 1 to 2, the aqueous casting pastes according to the present invention are environmentally friendly and low in cost, and the electrolyte thin films prepared from the aqueous casting pastes have excellent sintering ability, conductivity and mechanical properties.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.

Claims (10)

1. An aqueous casting slurry, comprising: electrolyte powder, an aluminum-containing compound, a solvent, a dispersant, a binder, a plasticizer and a defoaming agent.
2. A water-based casting slurry according to claim 1, wherein the content of the aluminum-containing compound in terms of alumina is 0.2 to 12% by weight, more preferably 0.5 to 3% by weight, based on the weight of the electrolyte powder;
preferably, the content of the electrolyte powder is 40 to 60% by weight, the content of the solvent is 30 to 45% by weight, the content of the dispersant is 0.8 to 4% by weight, the content of the binder is 4.5 to 8.5% by weight, the content of the plasticizer is 3.5 to 10% by weight, and the content of the defoaming agent is 0.3 to 1% by weight, based on the total weight of the aqueous casting slurry.
3. The water-based casting slurry according to claim 1 or 2, wherein the electrolyte powder is yttria-stabilized zirconia powder, scandia-and ceria-stabilized zirconia powder, calcia-stabilized zirconia powder, or magnesia-stabilized zirconia powder;
preferably, the average particle diameter of the electrolyte powder is 150-250 nm.
4. A waterbased casting slurry according to any of claims 1-3, characterised in that the aluminium containing compound is water soluble aluminium, preferably the aluminium containing compound is aluminium ethoxide and/or aluminium nitrate;
preferably, the dispersant is triethanolamine and/or isopropanol;
preferably, the binder is polyvinyl alcohol and/or polyacrylic acid;
preferably, the plasticizer is glycerol and/or polyethylene glycol;
preferably, the defoaming agent is tributyl phosphate and/or n-butanol.
5. A method for producing an electrolyte thin film, comprising:
(A) preparation of casting slurry
Mixing a solvent, a dispersant, an aluminum-containing compound and electrolyte powder and performing first ball milling to obtain initial slurry; then mixing the initial slurry with a plasticizer, a defoaming agent and a water-containing binder, and sequentially carrying out second ball milling, defoaming and sieving to obtain water-based tape casting slurry;
(B) preparation of a biscuit
Carrying out tape casting and drying on the water-based tape casting slurry to obtain a biscuit;
(C) preparation of electrolyte film
And sintering the biscuit.
6. The method according to claim 5, wherein the amount of the aluminum-containing compound is 0.2 to 12 wt%, more preferably 0.5 to 3 wt%, calculated as alumina, based on the weight of the electrolyte powder;
preferably, the amount of the electrolyte powder is 40 to 60 wt%, the amount of the solvent is 30 to 45 wt%, the amount of the dispersant is 0.8 to 4 wt%, the amount of the binder is 4.5 to 8.5 wt%, the amount of the plasticizer is 3.5 to 10 wt%, and the amount of the defoaming agent is 0.3 to 1 wt%, based on the total weight of the water-based casting slurry.
7. The method according to claim 5 or 6, characterized in that the viscosity of the initial slurry is 8-15 Pa-s;
preferably, the viscosity of the aqueous casting slurry is 5 to 10Pa · s.
8. The method according to any one of claims 5 to 7, wherein in the step (A), the solvent, the dispersant and the aluminum-containing compound are mixed, and then mixed with the electrolyte powder and first ball-milled;
preferably, the conditions of the first ball milling include: the time is 10-12 h;
preferably, the conditions of the second ball milling include: the time is 8-16 h;
preferably, the defoaming conditions include: the time is 20-40 min;
preferably, the sieving conditions include: passing the slurry through a 150-mesh and 250-mesh screen;
preferably, the conditions of the casting include: the casting speed is 0.3-1 cm/s;
preferably, the sintering conditions include: the temperature is 1200 ℃ and 1600 ℃ and the time is 5-15 h.
9. An electrolyte thin film prepared by the method of any one of claims 5 to 8;
preferably, the electrolyte thin film is an yttria-stabilized zirconia-based electrolyte thin film, a scandia-and ceria-stabilized zirconia-based electrolyte thin film, a calcia-stabilized zirconia-based electrolyte thin film, or a magnesia-stabilized zirconia-based electrolyte thin film.
10. Use of the electrolyte membrane of claim 9 and/or the electrolyte membrane prepared according to the method of any one of claims 5-7 in a fuel cell, an electrolysis cell.
CN201911260192.9A 2019-12-10 2019-12-10 Water-based tape casting slurry, electrolyte film, preparation method and application thereof Pending CN111087239A (en)

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