CN110981527B - Flexible ceramic current-collecting layer film green body - Google Patents

Flexible ceramic current-collecting layer film green body Download PDF

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CN110981527B
CN110981527B CN201911194512.5A CN201911194512A CN110981527B CN 110981527 B CN110981527 B CN 110981527B CN 201911194512 A CN201911194512 A CN 201911194512A CN 110981527 B CN110981527 B CN 110981527B
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powder
collecting layer
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current collecting
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CN110981527A (en
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雷泽
申明海
杨志宾
葛奔
彭苏萍
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China University of Mining and Technology Beijing CUMTB
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Abstract

The invention discloses a flexible ceramic collector layer film green body, which is obtained by casting and drying slurry, wherein the slurry comprises 48-65 parts by weight of raw material powder, 7-21 parts by weight of toughening agent, 0.1-5 parts by weight of sintering aid, 1-10 parts by weight of dispersing agent, 3-8 parts by weight of binder, 10-20 parts by weight of plasticizer, 0.5-2.5 parts by weight of defoaming agent and 50-75 parts by weight of water; the raw material powder is metal oxide and/or metal salt of corresponding metal elements in metal oxide forming the ceramic current collecting layer, and the dosage ratio of the metal elements in the raw material powder is the same as that of the corresponding metal elements in the ceramic current collecting layer; or the raw material powder is the powder formed by crushing a corresponding perovskite phase or a spinel phase formed by metal oxide in the ceramic current collecting layer; the film green body has the characteristics of good flexibility and easy cutting, and is suitable to be installed in a solid oxide fuel cell/electrolytic cell (SOFC/SOEC) to be used as a current collector layer.

Description

Flexible ceramic current-collecting layer film green body
Technical Field
The invention relates to a cuttable flexible ceramic collector layer film green body, and belongs to the technical field of solid oxide fuel cells/electrolytic cells (SOFC/SOEC).
Background
In solid oxide fuel cells/electrolyzers (SOFC/SOEC), the current collector material must be chemically compatible with the interconnect and the electrodes, so using a contact material of the same composition as the electrode material is helpful in improving the conductivity of the cell. The prior air electrode uses perovskite such as lanthanum strontium manganate, lanthanum strontium cobalt iron and the like and (Cu, Mn)3O4、(Co,Mn)3O4When the spinel material is used, the current collecting layers fall off to different degrees in the long-term operation of a solid oxide fuel cell/electrolytic cell (SOFC/SOEC) stack, the conductivity is poor, the preparation process is complex, and the preparation cost of the connector is greatly increased. Meanwhile, when the cell stack is packaged, in order to ensure the integrity and airtightness of the internal cell at high temperature, besides the sealing material, a certain pressure (pressurization) needs to be applied to the cell stack, so that the current collecting layer needs to have certain toughness and hardness.
In addition, the tape casting technology has a series of advantages of simple equipment, continuous operation, high production efficiency, high automation level, stable process, uniform blank performance and the like, so the tape casting technology is widely applied to the production of varistors, solid electrolyte fuel cells, chip capacitors and other functional periods. At present, non-aqueous tape casting is a widely applied process, the development and the application of the non-aqueous tape casting are relatively mature, but the solvent of the non-aqueous tape casting is generally toxic organic matters (toluene, butanone, xylene and the like), so that the non-aqueous tape casting has the problems of harm to human bodies, environmental pollution, flammability, high production cost and the like. Therefore, the development of a water system casting technology which is nontoxic, pollution-free and low in production cost is the hot research at present.
If a ceramic flexible current collector layer can be successfully prepared, which has the characteristics of easy cutting, pressure resistance, easy bending when being used as a green body, porous (for example, the porosity is more than 40 percent), ceramic structure and the like after being sintered at high temperature, and has good electrical conductivity (for example, the electrical conductivity is more than 6.98S/cm), the ceramic flexible current collector layer can be well suitable for the encapsulation of SOFC/SOEC.
However, it is difficult to achieve a good balance between porosity, ceramic structure and electrical conductivity for the current collector layer, especially in water-based casting, since many additives are required to be added to obtain a good film green body.
Disclosure of Invention
The invention aims to prepare a flexible ceramic current-collecting layer film green body which is pressure-resistant and bendable, and has porous property and high electric conductivity after being calcined to form a ceramic structure; due to the casting preparation, the thickness is controllable, for example, 0.2-1.6mm, the area can be randomly regulated and controlled within the range of several square centimeters to hundreds of square centimeters, and the method depends on the size of casting (the width, the length and the casting range of a casting machine) and the later cutting; the method can completely replace the screen printing and spraying technology to prepare the current collecting layer on the battery, and the flexible current collecting layer film green body prepared by the method has the advantages of easy cutting, easy assembly, good performance and the like. The preparation method of the flexible ceramic green body, namely water-based tape casting, is a simple, efficient, low-cost, nontoxic and environment-friendly film production process. The flexible ceramic current collecting layer film which can be cut is a novel current collecting material product with great market potential.
In order to realize the purpose, the invention adopts the following technical scheme:
a green flexible ceramic collector layer film cast and dried from a slurry comprising the following components:
Figure BDA0002294361760000021
the raw material powder is metal oxide or metal salt of corresponding metal elements in metal oxide forming the ceramic current collecting layer, and the dosage ratio of each metal element in the inorganic powder is the same as that of the corresponding metal elements in the ceramic current collecting layer, so that the corresponding ceramic current collecting layer can be obtained after the film green body is calcined.
In one embodiment, the green flexible ceramic current collector film has a thickness of 0.2 to 1.6mm, such as 0.5mm, 0.8mm, 1.0mm, 1.2mm, or 1.5 mm; the tensile break strength is 1.47-6.7MPa, such as 2.0MPa, 3.0MPa, 4.0MPa, 5.0MPa or 6.0 MPa. The flexible ceramic current collecting layer is a casting green body prepared from the components, and is obtained by high-temperature sintering after a battery reactor is assembled; the toughness of a cast green body is generally expressed in terms of tensile strength, and those skilled in the art will appreciate that generally, for a given thickness (e.g., the thickness described above in the context of the present invention), the toughness is better for a green body having greater tensile strength.
In the slurry of the present invention, the amount of the raw material powder is 48 to 65 parts by weight, such as 49, 50, 55, or 60 parts by weight; in one embodiment, the raw powder is selected from the group consisting of basic copper carbonate and manganese carbonate mixtures, cobalt carbonate and manganese carbonate mixtures, (Cu, Mn)3)O4、(Co,Mn)3O4And lanthanum strontium manganate or lanthanum strontium cobalt iron powder, which is nontoxic and harmless, is a common raw material for preparing the current collecting layer material. The particle size is 120 mesh (Taylor standard sieve), i.e. larger than 120 mesh, such as 150 mesh or 200 mesh. In one embodiment, the raw material powder is a metal oxide and/or a metal carbonate; carbonates include among others normal carbonates, bicarbonates (bicarbonates) and basic carbonates.
In the above slurry of the present invention, the dispersant is used in an amount of 1 to 10 parts by weight, such as 2, 4, 6 or 8 parts by weight; in one embodiment, the dispersant may be one or more of polyacrylic acid (PAA, molecular weight preferably 3000-10000g/mol, such as 4000, 5000 or 8000), polyvinylpyrrolidone (PVP, molecular weight preferably 8000-58000g/mol, such as 10000, 15000, 24000 or 58000), triethanolamine, and like organic dispersants.
In the above slurry of the present invention, the binder is used in an amount of 3 to 8 parts by weight, such as 4, 5, 6 or 7 parts by weight; in one embodiment, the binder may be one or more of polyvinyl alcohol (PVA, preferably having an alcoholysis degree of 87-89%, 15 wt%), dextrin, ethyl cellulose, and other water-soluble binders.
In the above slurry of the present invention, the plasticizer is used in an amount of 10 to 20 parts by weight, such as 12, 15 or 18 parts by weight; in one embodiment, the plasticizer may be one or more of polyethylene glycol (PEG, with a degree of polymerization of preferably 400-.
In the above slurry of the present invention, the amount of the defoaming agent is 0.5 to 2.5 parts by weight, for example, 0.8, 1, 1.5, 1.8 or 2 parts by weight; in one embodiment, the defoaming agent can be one or more of water-soluble defoaming agents such as n-butyl alcohol and tributyl phosphate.
In the slurry of the present invention, the sintering aid is used in an amount of 0.1 to 1.5 parts by weight, such as 0.2, 0.5, 0.8, 1 or 1.2 parts by weight; in one embodiment, the sintering aid may be Li2CO3、LiNO3And Bi2O3One or more of (a).
In the above slurry of the present invention, the amount of the toughening agent is 7 to 21 parts by weight, such as 10, 15 or 20 parts by weight; in one embodiment, the toughening agent may be alumina (α -Al)2O3) Or mullite fibers.
In one embodiment, the pH of the slurry is 9-11, such as 10, and when the pH is outside this range it can be adjusted by adding an acid or alkaline agent, such as 25% to 28% ammonia. It was found that the dispersing effect can be increased by controlling the pH value. In the present invention, when alkaline triethanolamine is used, no further pH adjustment is required; for example, PAA is acidic, and has better dispersion effect after pH adjustment. The film green body of the invention can be prepared by the following steps:
(1) adding the raw material powder, a toughening agent and a sintering aid into a ball milling tank, then adding water and a dispersing agent, and adjusting the pH of the suspension to 9-11 by adding a proper amount of ammonia water; after ball milling and dispersion are carried out uniformly, adding a binder, a plasticizer and a defoaming agent, and then continuing ball milling to obtain uniformly dispersed slurry;
(2) transferring the slurry obtained by ball milling in the step (1) to a vacuum defoaming machine for vacuum defoaming to prepare water-based tape casting slurry;
(3) casting the water-based casting slurry obtained in the step (2) on a casting machine, wherein the height of a knife edge of the casting machine is 0.2-1.8mm, and then drying to obtain a film green body; preferably, the thickness of the film green body is controlled to be 0.2-1.6mm by controlling the height of the edge of the casting machine during casting.
In the step (1), the rotation speed of the ball milling is preferably 200-. The research shows that the ball milling dispersing effect is good by the batch feeding.
In the step (2), the vacuum degree of the vacuum defoaming can be as low as-0.1 MPa, so as to facilitate defoaming.
In the above step (3), the drying temperature may be room temperature to 70 ℃, such as 25 ℃, 30 ℃, 40 ℃, 50 ℃ or 60 ℃.
In one embodiment, the aqueous casting slurry is obtained by the following process: weighing 70 parts by weight of nanoscale manganese carbonate, basic copper carbonate, mullite fiber and LiNO3Powder, wherein the molar weight of manganese carbonate and basic copper carbonate is 1:1, the mullite fiber accounts for 10 wt% of the total weight of the powder, and LiNO3Is 1 wt% of the total powder; 40 parts by weight of water was added to the ball mill pot, together with 5 parts by weight of triethanolamine dispersant. Ball milling is carried out for 12 hours, and the ball milling speed is 200 r/min; then, 37.3 parts by weight of 15 wt% PVA (alcoholysis degree 87-89%, e.g., from michelin, viscosity 3.2-3.8mpa.s) binder and 7.5 parts by weight of polyethylene glycol-400, 7.5 parts by weight of glycerin plasticizer, 0.5 part by weight of n-butanol defoaming agent were added to the ball mill jar, ball milling was continued for 24 hours, and then transferred to a vacuum defoaming machine (vacuum degree about-0.1 MPa), defoaming was carried out for 30 minutes to obtain a casting slurry.
In one embodiment, the aqueous casting slurry is obtained by the following process: weighing 70 parts by weight of nanoscale (Cu, Mn)3O4Mullite fiber and Bi2O3Wherein the mullite fiber accounts for 20 percent of the solid content by weight, and Bi2O32 wt% based on the solid content. 30 parts by weight of water and 8 parts by weight of triethanolamine (e.g., from Michelin, AR, 98%) were added as a dispersant to the ball mill jar. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Then 37.3 parts by weight of 15% dextrin (for example, from Mecanne, AR pure) and 10 parts by weight of polyethylene glycol-400, 10 parts by weight of glycerol plasticizer and 1.5 parts by weight of tributyl phosphate are added into a ball milling tank, ball milling is continued for 24 hours, and then the mixture is transferred to a vacuum defoaming machine (the vacuum degree is about-0.1 MPa), and defoaming is carried out for 30 minutes to obtain casting slurry.
In the present invention, if the addition of each component is made in the form of a mixture or a solution of its active ingredient and water, the amount of the component added is calculated as the actual amount of the active ingredient added, and water is added to the component water.
The prepared flexible ceramic film green body has good strength, can be cut, and can be applied to solid oxide fuel cells/electrolytic cells (SOFC/SOEC) stacks, the film green body is heated to 800 plus 900 ℃ at the speed of 0.5-3 ℃/min, and a conductive current collecting layer can be obtained after heat preservation for 0.5-10h, and the current collecting layer film has the properties of high hardness, high porosity, high conductivity and the like, can also control the thickness through multilayer superposition, can completely replace the original current collecting layer preparation technology, can not be influenced after pressurization and heating, and is not easy to break, and is not easy to interfere with gas inlet and outlet and the like.
Drawings
FIG. 1 is a green body prepared by aqueous casting of example 3;
fig. 2 shows the collector layer of the green compact of example 3 after sintering at 850 ℃.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
It should be understood that the difference of the raw materials used in the invention does not affect the preparation process, and only meets the use requirement for preparing the porosity; it should also be understood that the alumina and mullite fibers have a toughening effect, thereby increasing the ceramic structure of the flexible material and improving the strength and integrity of the flexible material to a certain extent. But the electric conductivity influenced by the toughening agent is different, and the toughening effect is also different.
Unless otherwise specified, the following reagents were all analytical grade.
Example 1: preparation of the Current collector layer
Weighing nano manganese carbonate, basic copper carbonate and alpha-Al with the total amount of 70g2O3Powder and Li2CO3Powder, wherein the molar weight of the manganese carbonate and the basic copper carbonate is 1:1, alpha-Al2O3The amount of Li is 15 wt% of the total amount of the powder2CO3The amount of the powder is 0.2 wt% of the total amount of the powder. 20g of water was added to a ball mill pot, and 5g of PAA (molecular weight of 3000g/mol, Mecline, solid content of 30% viscous liquid, average molecular weight of M.W-3000) dispersant was added at the same time, and ammonia was added dropwise to adjust the pH to 10. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Then, 37.3g of 10% PVA (alcoholysis degree of 87-89%, Mecline, viscosity of 3.2-3.8mPa.s) binder, 10g of polyethylene glycol-400 (Mecline, average molecular weight of 400), 10g of glycerol plasticizer (Mecline, AR pure, 99%), 0.5g of tributyl phosphate defoaming agent (Mecline, AR pure, 99%) are added into a ball milling tank, ball milling is continued for 24 hours, and then the mixture is transferred to a vacuum defoaming machine (vacuum degree of-0.1 MPa) to be defoamed for 30 minutes to obtain casting slurry;
and (3) carrying out tape casting on the prepared slurry on a casting machine. The height of the edge of the casting machine is adjusted to be 0.4mm, and the flexible current collecting layer green body with no surface defect and the thickness of 0.241mm is obtained by natural drying at room temperature.
In use, the green body is cut to size consistent with the cathode of the cell, and multiple pieces of the green body can be cold isostatically pressed to the desired thickness. When the cell reactor is assembled, the function is consistent with that of the fuel electrode nickel felt, and the operation is simple. Heating to 850 deg.C at a rate of 0.5-3 deg.C/min, maintaining for 6 hr, volatilizing organic matter, and making spinel phase to obtain stable current collecting layer. The conductivity was determined to be 12.96S/cm and the porosity was determined to be 45%.
Example 2
Weighing nanometer manganese carbonate, basic copper carbonate, mullite fiber and LiNO with total amount of 70g3Wherein the molar weight of the manganese carbonate and the basic copper carbonate is 1:1, the mullite fiber accounts for 10 wt% of the solid content, and the LiNO accounts for3At 1 wt% of the solid content. 40g of water was added to the ball mill jar along with 5g of triethanolamine dispersant. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Then, 37.3g of 15% PVA (polyvinyl alcohol) (alcoholysis degree is 87-89%) binder, 7.5g of polyethylene glycol-400, 7.5g of glycerol plasticizer and 0.5g of n-butyl alcohol defoaming agent (Meclin, AR pure and 99%) are added into a ball milling tank, ball milling is continued for 24 hours, and then the mixture is transferred to a vacuum defoaming machine (vacuum degree is-0.1 MPa) and defoamed for 30 minutes to obtain casting slurry;
and (3) carrying out tape casting on the prepared slurry on a casting machine. The height of the edge of the casting machine is adjusted to be 0.5mm, and the flexible current collecting layer green body with no surface defect and the thickness of 0.331mm is obtained by natural drying at room temperature.
In use, the green body is cut to size consistent with the cathode of the cell, and multiple pieces of the green body can be cold isostatically pressed to the desired thickness. When the cell reactor is assembled, the function is consistent with that of the fuel electrode nickel felt, and the operation is simple. Heating to 850 deg.C at a rate of 0.5-3 deg.C/min, maintaining for 6 hr, volatilizing organic matter, and making spinel phase to obtain stable current collecting layer. The conductivity was determined to be 16.23S/cm and the porosity was determined to be 45%.
Example 3
Weighing a total of 70g of nanoscale (Cu, Mn)3O4Mullite fiber and Bi2O3Wherein the mullite fiber accounts for 20 percent of the solid content by weight, and Bi2O32 wt% based on the solid content. 30g of water were added to the ball mill jar, together with 8g of triethanolamine (Michelin, AR pure, 98%) as dispersant. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Adding 37.3g of 15% dextrin (Mecline, AR pure), 10g of polyethylene glycol-400, 10g of glycerol plasticizer and 1.5g of tributyl phosphate into a ball milling tank, continuing ball milling for 24 hours, transferring to a vacuum defoaming machine (vacuum degree-0.1 MPa), defoaming for 30 minutes, and obtaining casting slurry; the rest is the same as example 1. The conductivity was determined to be 11.88S/cm and the porosity was determined to be 40%.
Example 4
Weighing a total of 70g (Co, Mn)3O4And mullite fiber, Li2CO3Powder, wherein the mullite fiber is30% by weight of solid content, Li2CO3At 3 wt% of the solid content. 20g of water was added to the ball mill jar, while 10g of triethanolamine was added as a dispersant. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Adding 46.67g of 15% ethyl cellulose binder (Mecline, CP), 5g of polyethylene glycol-400, 5g of glycerol plasticizer and 2g of tributyl phosphate into a ball milling tank, continuing ball milling for 24 hours, transferring to a vacuum defoaming machine (vacuum degree-0.1 MPa), defoaming for 30 minutes, and obtaining casting slurry;
and (3) carrying out tape casting on the prepared slurry on a casting machine. The height of the edge of the casting machine is adjusted to be 0.7mm, and the flexible current collecting layer green body with no surface defect and the thickness of 0.572mm is obtained by natural drying at room temperature.
In use, the green body is cut to size consistent with the cathode of the cell, and multiple pieces of the green body can be cold isostatically pressed to the desired thickness. When the cell reactor is assembled, the function is consistent with that of the fuel electrode nickel felt, and the operation is simple. Heating to 900 deg.C at a rate of 0.5-3 deg.C/min, maintaining for 3 hr, volatilizing organic matter, and making spinel phase to obtain stable current collecting layer. The conductivity was determined to be 6.98S/cm and the porosity was determined to be 40%.
Example 5
Weighing 70g of lanthanum strontium manganate and alpha-Al in total2O3And Bi2O3Powder of alpha-Al2O3The powder is 20 wt% of solid content, and Bi2O3The powder content is 4 wt% of the solid content. To a ball mill pot was added 20g of water, and simultaneously 7g of PAA (Meclin, a viscous liquid having a solid content of 40%, and an average molecular weight of M.W of 4000) dispersant, and ammonia was added dropwise to adjust the pH to 10. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Adding 46.67g of 15% ethyl cellulose binder, 5g of polyethylene glycol-400 and 5g of glycerol plasticizer and 2.5g of tributyl phosphate into a ball milling tank, continuing ball milling for 24 hours, transferring to a vacuum defoaming machine (vacuum degree-0.1 MPa), defoaming for 30 minutes, and obtaining casting slurry;
and (3) carrying out tape casting on the prepared slurry on a casting machine. The height of the knife edge of the casting machine is adjusted to be 1.2mm, and the flexible current collecting layer green body with no surface defect and the thickness of 1.023mm is obtained by natural drying at room temperature.
In use, the green body is cut to size consistent with the cathode of the cell, and multiple pieces of the green body can be cold isostatically pressed to the desired thickness. When the cell reactor is assembled, the function is consistent with that of the fuel electrode nickel felt, and the operation is simple. Heating to 900 deg.C at a rate of 0.5-3 deg.C/min, maintaining for 3 hr, volatilizing organic matter, and making spinel phase to obtain stable current collecting layer. The conductivity was determined to be 23.6S/cm and the porosity was determined to be 43%.
Example 6
Weighing 70g of lanthanum strontium manganate and alpha-Al in total2O3And Bi2O3Powder of alpha-Al2O3Powder is 25 wt% of solid content, Bi2O3The powder content is 5 wt% of the solid content. 30g of water was added to a ball mill pot, and 5g of a PAA (Mecline, a viscous liquid having a solid content of 50% and an average molecular weight of M.W of 5000) dispersant was added simultaneously, and ammonia was added dropwise to adjust the pH to 10. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Adding 46.67g of 15% ethyl cellulose binder, 5g of polyethylene glycol-400 and 5g of glycerol plasticizer and 2.5g of tributyl phosphate into a ball milling tank, continuing ball milling for 24 hours, transferring to a vacuum defoaming machine (vacuum degree-0.1 MPa), defoaming for 30 minutes, and obtaining casting slurry; the rest is the same as example 5. The conductivity was determined to be 21.2S/cm and the porosity was determined to be 40%.
Example 7
Weighing lanthanum strontium cobalt iron and alpha-Al with total amount of 70g2O3And Bi2O3Powder of alpha-Al2O3The powder accounts for 30 wt% of the solid content, and Bi accounts for2O3The powder content is 5 wt% of the solid content. 30g of water is added into a ball milling tank, 8g of PVP (avastin, average molecular weight 10000, K13-18) dispersing agent is added at the same time, and ammonia water is added dropwise to adjust the pH value to 10. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Then adding 37.3g of 15% ethyl cellulose binder, 5g of polyethylene glycol-400, 5g of glycerol plasticizer and 2.5g of tributyl phosphate into a ball milling tank, continuing ball milling for 24 hours, transferring to a vacuum defoaming machine (vacuum degree-0.1 MPa), defoaming for 30 minutes, and obtaining casting slurry; the rest is the same as example 5. Through the determination, the method has the advantages that,the conductivity was 18S/cm and the porosity was 40%.
Example 8
Weighing a total of 70g (Co, Mn)3O4、α-Al2O3And LiNO3Powder of alpha-Al2O3The powder is 20 wt% of solid content, LiNO3The powder content is 5 wt% of the solid content. 40g of water was added to the ball mill pot, 5g of PVP (Aladdin, average molecular weight 24000, K23-27) dispersant was added at the same time, and ammonia was added dropwise to adjust the pH to 10. Ball milling was carried out for 12 hours at a ball milling speed of 200 rpm. Then adding 37.3g of 15% PVA (with alcoholysis degree of 87-89%) binder, 10g of polyethylene glycol-400, 10g of glycerol plasticizer and 1.5g of tributyl phosphate into a ball milling tank, continuing ball milling for 24 hours, transferring to a vacuum defoaming machine (with vacuum degree of-0.1 MPa), defoaming for 30 minutes, and obtaining casting slurry; the rest is the same as example 5. The conductivity was determined to be 9.89S/cm and the porosity was determined to be 40%.
The tensile strength data of the green bodies are shown in Table 1.
Table 1 green flexible collector film produced in examples 1-8
Figure BDA0002294361760000101
Figure BDA0002294361760000111
As a flexible current collecting layer material, the better the electrical conductivity is on the basis of ensuring that the porosity reaches more than 40%, the better the electrochemical performance of the assembled SOFC/SOEC is. But also ensures the integrity of the ceramic under pressure, and as the content of the toughening agent is increased, the sintering integrity is higher, but the electrical conductivity is correspondingly reduced. Meanwhile, the thickness of the current collecting layer is determined by the thickness of the used battery, the metal connector and the sealing material, and experiments show that the current collecting effect is optimal when the thickness of the current collecting layer is more than 0.2 mm. Therefore, the current addition amount (10% -30%) of the toughening agent can ensure that the conductivity of the current collecting layer is not lower than 5S/cm, and the current collecting layer can adapt to the pressurizing state, and the thickness of the current collecting layer is selected according to the battery component. Particularly, the examples 2 and 3 have better tensile strength and electrical conductivity meeting the use requirements under the condition of ensuring lower thickness, and the addition amount of the toughening agent is also in an acceptable range, so that the toughening agent can be more ideal.

Claims (8)

1. A green flexible ceramic current collector film for use in a solid oxide fuel cell/electrolyser, cast and dried from a slurry comprising the following components:
Figure FDA0002874172430000011
the raw material powder is metal oxide and/or metal carbonate of corresponding metal elements in metal oxide forming the ceramic current collecting layer, and the dosage ratio of each metal element in the raw material powder is the same as that of the corresponding metal elements in the ceramic current collecting layer; or the raw material powder is the powder formed by crushing a corresponding perovskite phase or a spinel phase formed by metal oxide in the ceramic current collecting layer;
the toughening agent is selected from alumina or mullite fiber; the sintering aid is selected from Li2CO3、LiNO3And Bi2O3One or more of; the dispersing agent is selected from one or more of polyacrylic acid, triethanolamine and polyvinylpyrrolidone; the binder is selected from one or more of polyvinyl alcohol, dextrin and ethyl cellulose; the plasticizer is selected from polyethylene glycol and/or glycerol; the defoaming agent is selected from n-butyl alcohol and/or tributyl phosphate;
the preparation method of the film green body comprises the following steps:
(1) adding the raw material powder, a toughening agent and a sintering aid into a ball milling tank, then adding water and a dispersing agent, and adjusting the pH of the suspension to 9-11 by adding a proper amount of ammonia water; after ball milling and dispersion are carried out uniformly, adding a binder, a plasticizer and a defoaming agent, and then continuing ball milling to obtain uniformly dispersed slurry;
(2) transferring the slurry obtained by ball milling in the step (1) to a vacuum defoaming machine for vacuum defoaming to prepare water-based tape casting slurry;
(3) and (3) casting the water-based casting slurry obtained in the step (2) on a casting machine, wherein the height of a knife edge of the casting machine is 0.2-1.8mm, and then drying to obtain the film green body.
2. The film green compact of claim 1, wherein the raw material powder is a mixture powder of basic copper carbonate and manganese carbonate, a mixture powder of cobalt carbonate and manganese carbonate, (Cu, Mn)3O4Powder, (Co, Mn)3O4One of powder, lanthanum strontium manganate powder or lanthanum strontium cobalt iron powder.
3. The film green of claim 1, wherein said polyacrylic acid has a molecular weight of 3000-10000; the molecular weight of the polyvinylpyrrolidone is 3000-58000 g/mol.
4. The green film of claim 1, wherein the polyvinyl alcohol has an alcoholysis level of 87 to 89%.
5. The film green body according to any one of claims 1 to 4, wherein the film green body is controlled to have a thickness of 0.2 to 1.6mm by controlling a height of a calender edge during casting.
6. A ceramic current collector membrane obtained by calcining the green membrane of any one of claims 1 to 5 at 800-900 ℃ for 0.5-10 h.
7. The ceramic current collecting layer film as claimed in claim 6, wherein the ceramic current collecting layer film is obtained by heating to 800-.
8. Use of a green membrane according to any one of claims 1 to 5 in a solid oxide fuel cell/electrolyser assembly process wherein the green membrane is pressed against the solid oxide fuel cell/electrolyser interconnect and cell electrodes during solid oxide fuel cell/electrolyser assembly and then calcined to form a ceramic current collector membrane and used as a current collector.
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