CN113173785A - YSZ electrolyte slurry and preparation method thereof - Google Patents

YSZ electrolyte slurry and preparation method thereof Download PDF

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CN113173785A
CN113173785A CN202110590154.0A CN202110590154A CN113173785A CN 113173785 A CN113173785 A CN 113173785A CN 202110590154 A CN202110590154 A CN 202110590154A CN 113173785 A CN113173785 A CN 113173785A
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ysz
ysz powder
powder
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micron
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CN113173785B (en
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赵世凯
李洪达
李小勇
徐传伟
马腾飞
陈大明
张晓娇
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Shandong Industrial Ceramics Research and Design Institute Co Ltd
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Shandong Industrial Ceramics Research and Design Institute Co Ltd
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Abstract

The invention provides YSZ electrolyte slurry, which comprises YSZ powder, a binder and a dispersant, wherein the YSZ powder comprises nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder; the grain diameter of the nano-scale YSZ powder is D50-0.05-0.07 μm, the grain diameter of the submicron-scale YSZ powder is D50-0.1-0.5 μm, and the grain diameter of the micron-scale YSZ powder is D50-1.2 μm. The invention adopts the nano-scale, submicron-scale and micron-scale YSZ powder with the grain size range to carry out grain grading, and when preparing the electrolyte film layer, the large-size powder inhibits abnormal growth of crystal grains, inhibits sintering shrinkage of the film layer and reduces defects; the small-size powder is filled into the pores, is sintered preferentially at high temperature and is contacted with the large-size powder to generate mass transfer, so that the growth and rearrangement of crystal grains are promoted, and the densification of an electrolyte membrane layer is promoted. According to the invention, the sintering temperature required by the densification of the electrolyte membrane layer is reduced on the premise of reducing the defects of the electrolyte membrane layer and ensuring the densification through the grain grading. In addition, the dispersing agent inhibits the powder from agglomerating, improves the dispersion degree and ensures that the slurry is uniformly dispersed.

Description

YSZ electrolyte slurry and preparation method thereof
Technical Field
The invention relates to the field of electrolytes for fuel cells, in particular to YSZ electrolyte slurry and a preparation method thereof.
Background
The Solid Oxide Fuel Cell (SOFC) is a high-efficiency clean energy conversion device which can generate electricity and has no noise pollution. One of the key technologies for SOFC preparation is to obtain a dense defect-free electrolyte membrane that is sufficiently thin and gas impermeable, with yttria-stabilized zirconia (YSZ) being the best electrolyte cubic CSZ (doped with 8 mol% Y)2O3ZrO of2I.e., 8YSZ), exhibits maximum ionic conductivity (up to 0.1s cm at 1000 c)-1) The method has the advantages that the pure ion conductor is still kept unchanged in a range with large oxygen partial pressure fluctuation, the physical and chemical properties are kept stable at high temperature, the mechanical strength and the ionic conductivity are high at high temperature, and the like, and the yttria-stabilized zirconia (YSZ) becomes the most widely applied SOFC electrolyte material.
At the present stage, the YSZ powder used for preparing the SOFC electrolyte is mainly in the submicron level, and the finer the powder, the larger the specific surface area, and agglomerated particles are easy to appear after the powder is prepared into slurry; the finer the powder, the higher the surface energy, and the abnormal growth of crystal grains is easy to occur in the sintering process, which brings defects to the functional layer; the aggregation formed after the particles are aggregated and the abnormally grown large grains seriously affect the compactness of the electrolyte layer. On the other hand, the cost of the submicron YSZ powder is high, and the preparation cost of the electrolyte is increased.
Disclosure of Invention
The invention provides a YSZ electrolyte slurry and a preparation method thereof, which solve the problems that submicron YSZ powder in the prior art is easy to agglomerate when being prepared into the slurry, the crystal grains grow abnormally to generate defects when being sintered, the electrolyte layer has poor compactness, high cost and the like.
In one aspect, the invention provides a YSZ electrolyte slurry, comprising YSZ powder, a binder and a dispersant, wherein the YSZ powder comprises nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder; the grain diameter of the nano-scale YSZ powder is D50-0.05-0.07 μm, the grain diameter of the submicron-scale YSZ powder is D50-0.1-0.5 μm, and the grain diameter of the micron-scale YSZ powder is D50-1.2 μm.
Compared with the prior art, the invention has the following beneficial effects: the YSZ powder in the YSZ electrolyte slurry is subjected to nanoscale, submicron and micron particle grading according to the proportion of D50-0.07 mu m, D50-0.1-0.5 mu m and D50-1.2 mu m, the abnormal growth of crystal grains is inhibited by the large-size powder in the sintering step of preparing an electrolyte film, and the sintering shrinkage of the film can be inhibited by the large-size powder, so that the defects are reduced; from the perspective of surface energy, on the premise of the same mass, the small particles have large surface area, the surface phase atom proportion is large, the energy level is higher than that of large particles, the small particle powder has higher sintering activity and is easier to melt, the small powder is filled into gaps among large-size powder and is attached and adsorbed on the large-size powder, the contact area among the powder particles is increased, the generation of neck connection is facilitated in the sintering process, the small powder is preferentially sintered at high temperature, and the contact between the small powder and the large-size powder is helpful to promote mass transfer of substances and growth rearrangement of crystal grains, so that the sintering densification of an electrolyte membrane layer is promoted. The YSZ powder in the YSZ electrolyte slurry is subjected to grain composition by adopting nano-scale, submicron-scale and micron-scale YSZ powder, and the sintering temperature required by the densification of the electrolyte membrane layer is reduced on the premise of reducing the defects of the electrolyte membrane layer and ensuring the densification of the membrane layer during the sintering step for preparing the electrolyte membrane layer. Compared with YSZ powder used in the prior art which takes submicron as a main part, the YSZ powder also comprises nanoscale YSZ powder and micron YSZ powder, so that the cost is low, and the preparation cost of the electrolyte film layer is low. In addition, the dispersing agent is added into the YSZ electrolyte slurry, so that agglomeration of finer powder can be inhibited, the dispersion degree of the slurry can be improved, and the uniform dispersion of the slurry is promoted.
In some embodiments of the invention, the YSZ electrolyte slurry comprises, by weight, 75-108 parts YSZ powder, 61-88 parts binder, and 0.7-2 parts dispersant.
The YSZ electrolyte slurry has the beneficial effects that under the action of the binder and the dispersant, the YSZ powder is 75-108 parts, the binder is 61-88 parts, and the dispersant is 0.7-2 parts, so that the nano-scale, submicron-scale and micron-scale YSZ powder is more uniformly distributed and has better dispersibility, the film layer structure is more uniform and consistent during sintering, and the compactness is better.
In some embodiments of the invention, the YSZ powder comprises, by weight, 5 to 8 parts nanoscale YSZ powder, 55 to 80 parts submicron YSZ powder, and 15 to 20 parts micron YSZ powder.
The beneficial effect of the further technical scheme is that the YSZ powder comprises 5-8 parts of nano-scale YSZ powder, 55-80 parts of submicron-scale YSZ powder and 15-20 parts of micron-scale YSZ powder, the mixed small-size powder can be fully filled in the gap between large-size powder, the contact area between the small-size powder which is preferentially melted during sintering and the large-size powder is larger, mass transfer occurs, the growth and rearrangement of crystal grains are promoted, and the densification effect of the electrolyte layer is better.
In some embodiments of the invention, the sub-micron YSZ powder comprises sub-micron YSZ powder having a particle size of D50-0.1-0.2 μm and sub-micron YSZ powder having a particle size of D50-0.3-0.5 μm.
The beneficial effect of adopting the further technical scheme is that the sub-micron YSZ powder is further divided, the sub-micron YSZ powder is divided into two particle size ranges of D50-0.1-0.2 μm and D50-0.3-0.5 μm, and the nano-scale and micro-scale YSZ powder are matched, so that the YSZ powder in each particle size range in the slurry is better filled with each other after being mixed, meanwhile, the YSZ powder in each particle size range in the slurry is more uniformly mixed, the electrolyte film layer structure is more uniform and consistent during sintering, and the compactness is further optimized.
In some embodiments of the present invention, the sub-micron YSZ powder comprises 10 to 15 parts by weight of sub-micron YSZ powder having a particle size of D50-0.1 to 0.2 μm and 45 to 65 parts by weight of sub-micron YSZ powder having a particle size of D50-0.3 to 0.5 μm.
The beneficial effect of the further technical proposal is that 10-15 parts of submicron YSZ powder with D50 being 0.1-0.2 μm and 45-65 parts of submicron YSZ powder with D50 being 0.3-0.5 μm are adopted, after the submicron YSZ powder is further divided in particle size, the content of the submicron YSZ powder in each particle size range is further researched and designed, and at the content, the electrolyte membrane prepared by the slurry has less defects and higher compactness.
In some embodiments of the present invention, the YSZ powder comprises, in parts by weight, 7 parts of nanoscale YSZ powder having a particle size of D50 ═ 0.06 μm, 12 parts of submicron YSZ powder having a particle size of D50 ═ 0.15 μm, 55 parts of submicron YSZ powder having a particle size of D50 ═ 0.4 μm, and 18 parts of micron YSZ powder having a particle size of D50 ═ 1.1 μm.
The beneficial effects of the further technical scheme are that the sintering shrinkage of the film layer is greatly reduced and the defects are fewer when the slurry prepared by the YSZ powder under the formula content is sintered to prepare the electrolyte film layer; the densification degree of the electrolyte membrane layer is higher, and the sintering temperature required by the densification of the electrolyte membrane layer is greatly reduced and can be reduced by about 50-100 ℃.
In some embodiments of the present invention, the dispersant is a coupling agent, the coupling agent is a silane coupling agent and/or an aluminate coupling agent, and the binder is a mixed solution of ethyl cellulose and terpineol.
The further technical scheme has the beneficial effects that the used dispersing agent is the coupling agent, and the coupling agent is the silane coupling agent and/or the aluminate coupling agent, so that agglomeration of fine powder can be inhibited, the dispersion degree of the slurry can be improved, and the uniform dispersion of the slurry is promoted. On the other hand, in research and experiments, the addition of the coupling agent (silane coupling agent and/or aluminate coupling agent) can obviously improve the compactness of the electrolyte membrane layer compared with the case of not adding the coupling agent besides improving the dispersity.
In another aspect, the present invention further provides a method for preparing YSZ electrolyte slurry as described in any one of the above, including the steps of: ball-milling YSZ powder to obtain submicron YSZ powder with the particle size of D50-0.1-0.5 μm and micron YSZ powder with the particle size of D50-1.2 μm, and preparing nanoscale YSZ powder with the particle size of D50-0.05-0.07 μm by a sol-gel method; weighing ethyl cellulose and terpineol, stirring and dissolving until a mixed solution is clear, and obtaining a binder; mixing nano-scale YSZ powder, sub-micron-scale YSZ powder and micron-scale YSZ powder with a binder, adding a dispersant, and performing ball milling and uniform mixing to obtain the YSZ electrolyte slurry.
Compared with the prior art, the invention has the following beneficial effects: the submicron YSZ powder and the micron YSZ powder are prepared by a ball milling process, and the method is simple; the nanoscale YSZ powder is prepared by a sol-gel method, which is beneficial to realization and overcomes the problem that the nanoscale YSZ is difficult to prepare by ball milling; the YSZ electrolyte slurry is formed by ball-milling and mixing YSZ powder, a binder and a dispersant, the ball milling is carried out in the presence of the binder and the dispersant, the ball milling does not influence the particle size of the YSZ powder, the ball milling mainly plays a role of mixing materials, in addition, the addition of the dispersant can reduce the probability of agglomeration of the YSZ powder, and the uniformity of the slurry is further ensured.
In some embodiments of the invention, grinding aid is added during ball milling of YSZ powder, wherein the ball milling beads comprise zirconia balls with diameters of 0.3mm, 3mm and 6mm, the mass ratio of the zirconia balls is 0.8:1:0.5 and the ball-to-material ratio is 2-2.5:1 in the order of the diameters from small to large; the ball milling speed is 300-500r/min, and the ball milling time is 4-16 h.
The beneficial effects of the further technical scheme are that the grinding aid is added when the submicron and micron YSZ powder is prepared by ball milling, so that the grinding efficiency can be improved, the zirconia balls are selected for ball milling, the pollution to the YSZ powder can be avoided, the uniformity of ball milling can be ensured by the diameter selection of the zirconia balls, the mass ratio of the zirconia balls with different diameters, the ball-material ratio, the ball-milling speed and the limitation of time, and the YSZ powder obtained after ball milling meets the requirements of the submicron and micron range.
In yet another aspect, the present invention also provides a YSZ electrolyte membrane layer prepared from any of the YSZ electrolyte slurries described above.
Compared with the prior art, the invention has the following beneficial effects: the YSZ electrolyte membrane layer is prepared from the YSZ electrolyte slurry containing the grain-graded YSZ powder, and has high compactness, uniform and consistent membrane layer structure and few defects.
Drawings
In order to more clearly illustrate the technical solution in the embodiment of the present invention, the drawings required to be used in the embodiment of the present invention will be described below.
Fig. 1 is an SEM image of an electrolyte membrane layer prepared by sintering YSZ electrolyte slurry at 1300 ℃ for 5 hours according to an embodiment of the present invention;
fig. 2 is an SEM image of an electrolyte membrane layer prepared by sintering YSZ electrolyte slurry at 1300 ℃ for 5 hours according to another embodiment of the present invention;
fig. 3 is an SEM image of an electrolyte membrane layer prepared by sintering YSZ electrolyte slurry of still another embodiment of the present invention at 1300 c for 5 hours;
fig. 4 is an SEM image of an electrolyte membrane layer prepared by sintering YSZ electrolyte slurry without grain grading at 1350 ℃ for 5 h;
FIG. 5 is an SEM image of a cross-section of the electrolyte membrane of FIG. 2;
fig. 6 is an SEM image of a cross-section of the electrolyte membrane layer without the addition of a coupling agent, wherein the YSZ electrolyte paste used to prepare the electrolyte membrane layer in fig. 6 is different from the YSZ electrolyte paste corresponding to fig. 2 only in the presence or absence of the addition of the coupling agent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of various aspects of the present invention is provided with specific examples, which are only used for illustrating the present invention and do not limit the scope and spirit of the present invention.
The invention provides YSZ electrolyte slurry, which comprises YSZ powder, a binder and a dispersant, wherein the YSZ powder comprises nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder; the grain diameter of the nano-scale YSZ powder is D50-0.05-0.07 μm, the grain diameter of the submicron-scale YSZ powder is D50-0.1-0.5 μm, and the grain diameter of the micron-scale YSZ powder is D50-1.2 μm.
In the invention, the YSZ electrolyte slurry comprises 75-108 parts of YSZ powder, 61-88 parts of binder and 0.7-2 parts of dispersant by weight.
In the invention, the YSZ powder comprises, by weight, 5-8 parts of nanoscale YSZ powder, 55-80 parts of submicron YSZ powder and 15-20 parts of micron YSZ powder.
In the present invention, the submicron YSZ powder includes submicron YSZ powder having a particle size of D50-0.1-0.2 μm and submicron YSZ powder having a particle size of D50-0.3-0.5 μm.
In the invention, the submicron YSZ powder comprises 10 to 15 parts by weight of submicron YSZ powder with the grain diameter of D50 being 0.1 to 0.2 μm and 45 to 65 parts by weight of submicron YSZ powder with the grain diameter of D50 being 0.3 to 0.5 μm.
In the invention, the dispersant is a coupling agent, the coupling agent is a silane coupling agent and/or an aluminate coupling agent, and the binder is a mixed solution of ethyl cellulose and terpineol.
The invention also provides a preparation method of the YSZ electrolyte slurry, which comprises the following steps:
ball-milling YSZ powder to obtain submicron YSZ powder with the particle size of D50-0.1-0.5 μm and micron YSZ powder with the particle size of D50-1.2 μm, and preparing nanoscale YSZ powder with the particle size of D50-0.05-0.07 μm by a sol-gel method;
weighing ethyl cellulose and terpineol, stirring and dissolving until a mixed solution is clear, and obtaining a binder;
mixing nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder with a binder, adding a dispersant, and performing ball milling and uniform mixing to obtain the YSZ electrolyte slurry.
In the invention, grinding aid is added when the YSZ powder is ball-milled, the ball-milled beads comprise zirconia balls with the diameters of 0.3mm, 3mm and 6mm, the mass ratio of the zirconia balls is 0.8:1:0.5 and the ball-to-material ratio is 2-2.5:1 according to the sequence from small to large; the ball milling speed is 300-500r/min, and the ball milling time is 4-16 h.
The submicron YSZ powder having a particle size of D50-0.1-0.5 μm obtained by ball milling the YSZ powder may include a submicron YSZ powder having a particle size of D50-0.1-0.2 μm and a submicron YSZ powder having a particle size of D50-0.3-0.5 μm, wherein the submicron YSZ powder having a particle size of D50-0.1-0.2 μm, the submicron YSZ powder having a particle size of D50-0.3-0.5 μm and the micron YSZ powder having a particle size of D50-1.2 μm are obtained by setting different ball milling times within a range of 4-16 h.
In the invention, the specific process for preparing the nano-scale YSZ powder with the grain diameter of D50-0.05-0.07 mu m by a sol-gel method is as follows: weighing Y according to the molar ratio of Y to Zr being 0.08 to 0.922O3、ZrO2Respectively dissolving in nitric acid, adding succinic acid, heating, stirring, mixing to obtain gel, drying the gel, and sintering at 800 deg.C under 700 deg.C to obtain nanoscale YSZ powder with particle size of D50-0.05-0.07 μm.
The invention also provides a YSZ electrolyte membrane layer, and the YSZ electrolyte membrane layer is prepared from the YSZ electrolyte slurry. Specifically, the electrolyte slurry can be screen-printed into a film layer blank by a screen printing technology, and the YSZ electrolyte film layer is obtained after sintering.
Example 1
The embodiment provides a YSZ electrolyte slurry, which comprises YSZ powder, a binder and a dispersant, wherein the YSZ powder comprises nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder; the grain diameter of the nano-scale YSZ powder is D50-0.05 μm, the grain diameter of the submicron-scale YSZ powder is D50-0.1 μm and D50-0.3 μm, and the grain diameter of the micron-scale YSZ powder is D50-1 μm.
In this embodiment, the YSZ electrolyte slurry includes 75 parts by weight of YSZ powder, 61 parts by weight of binder, and 0.7 part by weight of dispersant.
In this embodiment, the YSZ powder includes, by weight, 5 parts of nano-sized YSZ powder, 55 parts of sub-micron sized YSZ powder, and 15 parts of micro-sized YSZ powder. Wherein the submicron YSZ powder comprises 10 parts of submicron YSZ powder with the particle size of D50-0.1 μm and 45 parts of submicron YSZ powder with the particle size of D50-0.3 μm.
In this embodiment, the dispersant is a coupling agent, the coupling agent is a silane coupling agent and/or an aluminate coupling agent, and the binder is a mixed solution of ethyl cellulose and terpineol.
This embodiment also provides a method for preparing the YSZ electrolyte slurry of this embodiment, including the following steps:
s1, respectively weighing three groups of YSZ powder according to parts by weight, adding a grinding aid (the using amount of the YSZ powder is determined according to the using amounts of submicron and micron YSZ powder required after particle grading, the mass ratio of the YSZ powder to the grinding aid is 100:1), selecting zirconia balls with the diameters of 0.3mm, 3mm and 6mm as ball grinding beads, setting the mass ratio of the zirconia balls to be 0.8:1:0.5 according to parts by weight, setting the ball-material ratio to be 2-2.5:1, respectively dry-grinding in a ball grinding tank at a ball grinding speed of 300 and 500r/min, setting the dry-grinding time to be within a range of 4-16h, and obtaining the micron YSZ powder with the particle diameter of D50-0.1 μm, the submicron YSZ powder with the particle diameter of D50-0.3 μm and the micron YSZ powder with the particle diameter of D50-1 μm according to different ball-grinding times after ball grinding. The nano-sized YSZ powder is difficult to be prepared by ball milling, and in this example, the nano-sized YSZ powder with the particle size D50 ═ 0.05 μm is prepared by a sol-gel method, specifically, Y is weighed according to the molar ratio of Y: Zr ═ 0.08:0.922O3、ZrO2Respectively dissolving in nitric acid, adding succinic acid, heating, stirring, mixing to obtain gel, drying, and sintering at 800 deg.C to obtain nanoscale YSZ powder with particle size D50 ═ 0.05 μm.
S2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol by weight, stirring and dissolving at the rotating speed of 150-250r/min until the mixed solution is clear, and obtaining the binder based on the mixed solution of the ethyl cellulose and the terpineol.
S3, weighing 5 parts by weight of nano-scale YSZ powder with the particle size of D50-0.05 μm, 10 parts by weight of submicron-scale YSZ powder with the particle size of D50-0.1 μm, 45 parts by weight of submicron-scale YSZ powder with the particle size of D50-0.3 μm and 15 parts by weight of micron-scale YSZ powder with the particle size of D50-1 μm, uniformly mixing, adding 61 parts of binder and 0.7 part of coupling agent as dispersing agents, ball-milling at the rotating speed of 200 and 250r/min for 8-12h, and obtaining the YSZ electrolyte slurry of the embodiment after ball-milling and uniform mixing.
The present embodiment also provides a YSZ electrolyte membrane layer, which is prepared from the YSZ electrolyte slurry of the present embodiment. Specifically, the electrolyte slurry can be screen-printed into a film layer blank by a screen printing technology, and the YSZ electrolyte film layer is obtained after sintering.
Example 2
The embodiment provides a YSZ electrolyte slurry, which comprises YSZ powder, a binder and a dispersant, wherein the YSZ powder comprises nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder; the grain diameter of the nano-scale YSZ powder is D50-0.06 μm, the grain diameter of the submicron-scale YSZ powder is D50-0.15 μm and D50-0.4 μm, and the grain diameter of the micron-scale YSZ powder is D50-1.1 μm.
In this embodiment, the YSZ electrolyte slurry includes 92 parts by weight of YSZ powder, 75 parts by weight of binder, and 1.5 parts by weight of dispersant.
In this embodiment, the YSZ powder includes 7 parts by weight of nano-sized YSZ powder, 67 parts by weight of sub-micron-sized YSZ powder, and 18 parts by weight of micro-sized YSZ powder. Wherein the submicron YSZ powder comprises 12 parts of submicron YSZ powder with the particle size of D50-0.15 μm and 55 parts of submicron YSZ powder with the particle size of D50-0.4 μm.
In this embodiment, the dispersant is a coupling agent, the coupling agent is a silane coupling agent and/or an aluminate coupling agent, and the binder is a mixed solution of ethyl cellulose and terpineol.
This embodiment also provides a method for preparing the YSZ electrolyte slurry of this embodiment, including the following steps:
s1, respectively weighing three groups of YSZ powder according to parts by weight, adding a grinding aid (the using amount of the YSZ powder is determined according to the using amount of submicron and micron YSZ powder required after particle grading, the mass ratio of the YSZ powder to the grinding aid is 100:1), selecting zirconia balls with the diameters of 0.3mm, 3mm and 6mm as ball grinding beads, setting the mass ratio of the zirconia balls to be 0.8:1:0.5 according to the sequence of the diameters from small to large, setting the ball-material ratio to be 2-2.5:1 according to parts by weight, respectively dry-grinding in a ball grinding tank at a ball grinding speed of 300-After the ball milling, submicron YSZ powder with the grain diameter D50 being 0.15 μm, submicron YSZ powder with the grain diameter D50 being 0.4 μm and micron YSZ powder with the grain diameter D50 being 1.1 μm are obtained according to different ball milling time. The nano-sized YSZ powder is difficult to be prepared by ball milling, and in this example, the nano-sized YSZ powder with the particle size D50 ═ 0.06 μm is prepared by a sol-gel method, specifically, Y is weighed according to the molar ratio of Y: Zr ═ 0.08:0.922O3、ZrO2Respectively dissolving in nitric acid, adding succinic acid, heating, stirring, mixing to obtain gel, drying, and sintering at 750 deg.C to obtain nanoscale YSZ powder with particle size D50 of 0.06 μm.
S2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol by weight, stirring and dissolving at the rotating speed of 150-250r/min until the mixed solution is clear, and obtaining the binder based on the mixed solution of the ethyl cellulose and the terpineol.
S3, weighing 7 parts by weight of nano-YSZ powder with a particle size of D50 ═ 0.06 μm, 12 parts by weight of sub-micron YSZ powder with a particle size of D50 ═ 0.15 μm, 55 parts by weight of sub-micron YSZ powder with a particle size of D50 ═ 0.4 μm, and 18 parts by weight of micro-YSZ powder with a particle size of D50 ═ 1.1 μm, mixing uniformly, adding 75 parts by weight of binder and 1.5 parts by weight of coupling agent as dispersants, ball-milling at a rotation speed of 200 and 250r/min for 8-12h, and ball-milling uniformly to obtain the YSZ electrolyte slurry of the embodiment.
The present embodiment also provides a YSZ electrolyte membrane layer, which is prepared from the YSZ electrolyte slurry of the present embodiment. Specifically, the electrolyte slurry can be screen-printed into a film layer blank by a screen printing technology, and the YSZ electrolyte film layer is obtained after sintering.
Example 3
The embodiment provides a YSZ electrolyte slurry, which comprises YSZ powder, a binder and a dispersant, wherein the YSZ powder comprises nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder; the grain diameter of the nano-scale YSZ powder is D50-0.07 μm, the grain diameter of the submicron-scale YSZ powder is D50-0.2 μm and D50-0.5 μm, and the grain diameter of the micron-scale YSZ powder is D50-1.2 μm.
In this embodiment, the YSZ electrolyte slurry includes 108 parts by weight of YSZ powder, 88 parts by weight of binder, and 2 parts by weight of dispersant.
In this embodiment, the YSZ powder includes, by weight, 8 parts of nano-sized YSZ powder, 80 parts of sub-micron sized YSZ powder, and 20 parts of micro-sized YSZ powder. Wherein the submicron YSZ powder comprises 15 parts of submicron YSZ powder with the particle size of D50-0.2 μm and 65 parts of submicron YSZ powder with the particle size of D50-0.5 μm.
In this embodiment, the dispersant is a coupling agent, the coupling agent is a silane coupling agent and/or an aluminate coupling agent, and the binder is a mixed solution of ethyl cellulose and terpineol.
This embodiment also provides a method for preparing the YSZ electrolyte slurry of this embodiment, including the following steps:
s1, respectively weighing three groups of YSZ powder according to parts by weight, adding a grinding aid (the using amount of the YSZ powder is determined according to the using amounts of submicron and micron YSZ powder required after particle grading, the mass ratio of the YSZ powder to the grinding aid is 100:1), selecting zirconia balls with the diameters of 0.3mm, 3mm and 6mm as ball grinding beads, setting the mass ratio of the zirconia balls to be 0.8:1:0.5 according to parts by weight, setting the ball-material ratio to be 2-2.5:1, respectively dry-grinding in a ball grinding tank at a ball grinding speed of 300 and 500r/min, setting the dry-grinding time to be within a range of 4-16h, and obtaining the micron YSZ powder with the particle diameter of D50-0.2 μm, the submicron YSZ powder with the particle diameter of D50-0.5 μm and the micron YSZ powder with the particle diameter of D50 μm according to different ball-grinding times after ball grinding. The nano-sized YSZ powder is difficult to be prepared by ball milling, and in this example, the nano-sized YSZ powder with the particle size D50 ═ 0.07 μm is prepared by a sol-gel method, specifically, Y is weighed according to the molar ratio of Y: Zr ═ 0.08:0.922O3、ZrO2Respectively dissolving in nitric acid, adding succinic acid, heating, stirring, mixing to obtain gel, drying, and sintering at 700 deg.C to obtain nanoscale YSZ powder with particle size D50 of 0.07 μm.
S2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol by weight, stirring and dissolving at the rotating speed of 150-250r/min until the mixed solution is clear, and obtaining the binder based on the mixed solution of the ethyl cellulose and the terpineol.
S3, weighing 8 parts by weight of nano-scale YSZ powder with the particle size of D50-0.07 mu m, 15 parts by weight of submicron-scale YSZ powder with the particle size of D50-0.2 mu m, 65 parts by weight of submicron-scale YSZ powder with the particle size of D50-0.5 mu m and 20 parts by weight of micron-scale YSZ powder with the particle size of D50-1.2 mu m, uniformly mixing, adding 88 parts of binder and 2 parts of coupling agent as dispersing agents, ball-milling at the rotating speed of 200 and 250r/min for 8-12h, and obtaining the YSZ electrolyte slurry of the embodiment after ball-milling and uniform mixing.
The present embodiment also provides a YSZ electrolyte membrane layer, which is prepared from the YSZ electrolyte slurry of the present embodiment. Specifically, the electrolyte slurry can be screen-printed into a film layer blank by a screen printing technology, and the YSZ electrolyte film layer is obtained after drying and sintering.
Comparative example
The comparative example is different from examples 1 to 3 in that the comparative example does not perform grain grading, and specifically, the comparative example provides a YSZ electrolyte slurry including YSZ powder, a binder, and a dispersant, wherein the particle diameter of the YSZ powder is D50 ═ 0.05 to 1.2 μm.
In the comparative example, the YSZ electrolyte slurry comprises, by weight, 75-108 parts of YSZ powder, 61-88 parts of binder, and 0.7-2 parts of dispersant.
In the comparative example, the dispersant was a coupling agent, the coupling agent was a silane coupling agent and/or an aluminate coupling agent, and the binder was a mixed solution of ethyl cellulose and terpineol.
The preparation method of YSZ electrolyte slurry of the comparative example includes the steps of:
s1, preparing YSZ powder (may be commercially available YSZ powder) with a particle size of D50 ═ 0.05 to 1.2 μm;
s2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol by weight, stirring and dissolving at the rotating speed of 150-250r/min until the mixed solution is clear, and obtaining the binder based on the mixed solution of the ethyl cellulose and the terpineol;
s3, weighing 75-108 parts of YSZ powder, 61-88 parts of binder and 0.7-2 parts of dispersant by weight, ball-milling at the rotating speed of 200-250r/min for 8-12h, and ball-milling and uniformly mixing to obtain the YSZ electrolyte slurry of the comparative example.
The comparative example also provides a YSZ electrolyte membrane layer prepared from the YSZ electrolyte paste of the comparative example. Specifically, the electrolyte slurry can be screen-printed into a film layer blank by a screen printing technology, and the YSZ electrolyte film layer is obtained after drying and sintering.
Fig. 1 to 3 show SEM images of YSZ electrolyte slurries of examples 1 to 3 prepared by sintering at 1300 c for 5h, and fig. 4 shows SEM images of YSZ electrolyte membranes prepared by sintering a YSZ electrolyte slurry of comparative example not subjected to grain grading at 1350 c for 5 h. As can be seen from fig. 1 to 3, the YSZ electrolyte slurries of examples 1 to 3, which were particle graded, sintered at 1300 ℃ gave very few pores in the electrolyte membrane layer, especially the YSZ electrolyte slurry of example 2 gave no pores and very good densification, and the YSZ electrolyte slurries of examples 1 and 3 gave very few pores in the electrolyte membrane layer, which has reached the densification of the electrolyte membrane layer required by the solid fuel cell. As can be seen from fig. 4, the YSZ electrolyte slurry of the comparative example, which was not grain-graded, had a large number of pores even though the electrolyte membrane layer was prepared by sintering at 1350 ℃ (50 ℃ higher than the sintering temperature of examples 1-3) for 5 hours, and the electrolyte membrane layer was poor in compactness and had many defects. Therefore, the YSZ electrolyte slurry with grain composition can be sintered at a lower temperature to prepare an electrolyte membrane layer with higher density, and the defects of the electrolyte membrane layer are few, namely the YSZ electrolyte slurry reduces the sintering temperature required by the densification of the electrolyte membrane layer, and the electrolyte membrane layer obtained by sintering has higher density and fewer defects.
Fig. 5 shows an SEM image of a cross-section of the electrolyte membrane layer of fig. 2, and fig. 6 shows an SEM image of a cross-section of the electrolyte membrane layer without the addition of a coupling agent, wherein the YSZ electrolyte paste from which the electrolyte membrane layer of fig. 6 is prepared differs from the YSZ electrolyte paste corresponding to fig. 2 only in the presence or absence of the addition of a coupling agent. It can be seen from fig. 5-6 that, after the coupling agent is added, the electrolyte film layer has almost no pores and very high density, while when the coupling agent is not added, the electrolyte film layer has obvious pores and poor density. Therefore, the coupling agent used as the dispersing agent not only plays roles of inhibiting fine powder agglomeration and improving the dispersion degree and the dispersion uniformity, but also plays a role of obviously improving the compactness of the electrolyte membrane layer.
Therefore, the invention finds the effect that the coupling agent can improve the compactness of the electrolyte membrane layer, greatly improves the compactness of the electrolyte membrane layer prepared by the YSZ electrolyte slurry through the particle composition of the YSZ powder and the addition of the coupling agent, and has great contribution in the field of solid oxide fuel cells.
The present invention has been described in conjunction with specific embodiments which are intended to be exemplary only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all modifications, variations or alterations that may occur to those skilled in the art without departing from the spirit of the invention. Therefore, various equivalent changes made according to the present invention still fall within the scope covered by the present invention.

Claims (10)

1. The YSZ electrolyte slurry is characterized by comprising YSZ powder, a binder and a dispersant,
wherein the YSZ powder comprises nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder;
the grain diameter of the nano-scale YSZ powder is D50-0.05-0.07 μm, the grain diameter of the submicron-scale YSZ powder is D50-0.1-0.5 μm, and the grain diameter of the micron-scale YSZ powder is D50-1.2 μm.
2. The YSZ electrolyte paste of claim 1, wherein the YSZ electrolyte paste comprises, in parts by weight, 75-108 parts YSZ powder, 61-88 parts binder, and 0.7-2 parts dispersant.
3. The YSZ electrolyte paste of claim 1 or 2, wherein the YSZ powder comprises, by weight, 5-8 parts nanoscale YSZ powder, 55-80 parts submicron YSZ powder, and 15-20 parts micron YSZ powder.
4. The YSZ electrolyte paste of claim 3, wherein the sub-micron YSZ powder comprises sub-micron YSZ powder having a particle size of D50-0.1-0.2 μm and sub-micron YSZ powder having a particle size of D50-0.3-0.5 μm.
5. The YSZ electrolyte slurry of claim 4, wherein the sub-micron YSZ powder comprises, by weight, 10-15 parts of sub-micron YSZ powder with a particle size of D50-0.1-0.2 μm, and 45-65 parts of sub-micron YSZ powder with a particle size of D50-0.3-0.5 μm.
6. The YSZ electrolyte slurry of claim 5, wherein the YSZ powder comprises, in parts by weight, 7 parts of nanoscale YSZ powder with a particle size of D50-0.06 μm, 12 parts of submicron YSZ powder with a particle size of D50-0.15 μm, 55 parts of submicron YSZ powder with a particle size of D50-0.4 μm, and 18 parts of micron YSZ powder with a particle size of D50-1.1 μm.
7. The YSZ electrolyte slurry of claim 1, wherein the dispersant is a coupling agent, the coupling agent is a silane coupling agent and/or an aluminate coupling agent, and the binder is a mixture of ethyl cellulose and terpineol.
8. The method of preparing YSZ electrolyte slurry according to any of claims 1 to 7, comprising the steps of:
ball-milling YSZ powder to obtain submicron YSZ powder with the particle size of D50-0.1-0.5 μm and micron YSZ powder with the particle size of D50-1.2 μm, and preparing nanoscale YSZ powder with the particle size of D50-0.05-0.07 μm by a sol-gel method;
weighing ethyl cellulose and terpineol, stirring and dissolving until a mixed solution is clear, and obtaining a binder;
mixing nano-scale YSZ powder, sub-micron-scale YSZ powder and micron-scale YSZ powder with a binder, adding a dispersant, and performing ball milling and uniform mixing to obtain the YSZ electrolyte slurry.
9. The method of preparing YSZ electrolyte slurry of claim 8, wherein grinding aids are added during the ball milling of the YSZ powder,
the ball milling beads comprise zirconia balls with the diameters of 0.3mm, 3mm and 6mm, the mass ratio of the zirconia balls is 0.8:1:0.5, and the ball-to-material ratio is 2-2.5:1 according to the sequence from small to large;
the ball milling speed is 300-500r/min, and the ball milling time is 4-16 h.
10. A YSZ electrolyte membrane layer prepared from the YSZ electrolyte paste of any one of claims 1 to 7.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108249928A (en) * 2018-01-18 2018-07-06 中国科学院上海硅酸盐研究所 A kind of preparation method of solid-phase sintered silicon carbide ceramics wet moulding low viscosity high solids content water-based slurry
US20210005898A1 (en) * 2019-03-27 2021-01-07 Jingdezhen Ceramic Institute Method for Preparing SOFC anti-coking Ni-YSZ anode materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108249928A (en) * 2018-01-18 2018-07-06 中国科学院上海硅酸盐研究所 A kind of preparation method of solid-phase sintered silicon carbide ceramics wet moulding low viscosity high solids content water-based slurry
US20210005898A1 (en) * 2019-03-27 2021-01-07 Jingdezhen Ceramic Institute Method for Preparing SOFC anti-coking Ni-YSZ anode materials

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