CN113173785B - YSZ electrolyte slurry and preparation method thereof - Google Patents

YSZ electrolyte slurry and preparation method thereof Download PDF

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CN113173785B
CN113173785B CN202110590154.0A CN202110590154A CN113173785B CN 113173785 B CN113173785 B CN 113173785B CN 202110590154 A CN202110590154 A CN 202110590154A CN 113173785 B CN113173785 B CN 113173785B
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ysz
ysz powder
powder
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submicron
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CN113173785A (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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Abstract

The invention provides YSZ electrolyte slurry which comprises YSZ powder, a binder and a dispersing agent, wherein the YSZ powder comprises nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder; the grain size of the nano-scale YSZ powder is D50=0.05-0.07 μm, the grain size of the submicron-scale YSZ powder is D50=0.1-0.5 μm, and the grain size of the micron-scale YSZ powder is D50=1-1.2 μm. The invention adopts the nanoscale, submicron and micron YSZ powder with the particle size range to carry out particle grading, and the large-size powder inhibits abnormal growth of crystal grains, inhibits sintering shrinkage of the membrane layer and reduces defects when preparing the electrolyte membrane layer; the small-size powder is filled in the pores, is sintered preferentially at high temperature and contacts with the large-size powder to generate mass transfer, so that the growth and rearrangement of crystal grains are promoted, and the densification of the electrolyte membrane layer is promoted. According to the invention, on the premise of reducing the defect of the electrolyte membrane layer and ensuring compactness, the sintering temperature required by the densification of the electrolyte membrane layer is reduced by the particle grading. In addition, the dispersing agent inhibits agglomeration of the powder, improves the dispersity 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
Solid Oxide Fuel Cells (SOFC) are a class of energy conversion devices that can generate electricity, and are clean and efficient without noise pollution. One of the key technologies for SOFC fabrication is to obtain a dense defect-free electrolyte film that is thin enough and gas impermeable, yttria Stabilized Zirconia (YSZ) being the best CSZ of the electrolyte cubic structure (doped with 8mol% y 2 O 3 ZrO of (2) 2 I.e., 8 YSZ) exhibits maximum ionic conductivity (up to 0.1s cm at 1000 ℃ C.) -1 ) The ion conductor has the advantages that the ion conductor is kept unchanged within the range of larger fluctuation of oxygen partial pressure, the physical and chemical properties are kept stable at high temperature, and the ion conductor has higher mechanical strength at high temperatureYttria-stabilized zirconia (YSZ) is the most widely used SOFC electrolyte material with advantages such as degree and ionic conductivity.
At present, YSZ powder used for preparing the SOFC electrolyte is mainly in submicron level, the finer the powder is, the larger the specific surface area is, and agglomerated particles are easy to appear after slurry is prepared; the finer the powder material is, the higher the surface energy is, and abnormal growth of crystal grains is easy to occur in the sintering process, so that defects are brought to the functional layer; agglomerates formed after particle agglomeration and abnormally grown large grains seriously affect the compactness of the electrolyte layer. On the other hand, submicron YSZ powder has high cost, increasing the preparation cost of the electrolyte.
Disclosure of Invention
The invention provides YSZ electrolyte slurry and a preparation method thereof, which solve the problems of easy agglomeration, defect generation due to abnormal growth of crystal grains during sintering, poor compactness of an electrolyte layer, high cost and the like when submicron YSZ powder is prepared into slurry in the prior art.
In one aspect, the invention provides a YSZ electrolyte slurry, which comprises YSZ powder, a binder and a dispersing agent, wherein the YSZ powder comprises nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder; the particle size of the nano-scale YSZ powder is D50=0.05-0.07 mu m, the particle size of the submicron-scale YSZ powder is D50=0.1-0.5 mu m, and the particle size of the micron-scale YSZ powder is D50=1-1.2 mu m.
Compared with the prior art, the invention has the following beneficial effects: the YSZ powder in the YSZ electrolyte slurry carries out nano-scale, submicron-scale and micron-scale particle grading according to the proportion of D50=0.05-0.07 mu m, D50=0.1-0.5 mu m and D50=1-1.2 mu m, and the large-size powder can inhibit abnormal growth of crystal grains during the sintering step of preparing an electrolyte membrane layer, and can inhibit sintering shrinkage of the membrane layer and reduce defects; from the aspect of surface energy, on the premise of the same quality, the surface area of the small particles is large, the surface phase atoms occupy larger area, the energy level is higher than that of the large particles, the small particle powder has higher sintering activity and is easier to melt, the small-size powder is filled in gaps among the large-size powder and is adhered and adsorbed on the large-size powder, the contact area among the powder particles is increased, the neck connection is favorably generated in the sintering process, the small-size powder is preferentially sintered at high temperature, and the contact of the small-size powder and the large-size powder is favorable for promoting mass transfer and grain growth rearrangement of substances, so that the sintering densification of an electrolyte membrane layer is promoted. The YSZ powder in the YSZ electrolyte slurry is subjected to particle grading by adopting nanoscale, submicron and micron YSZ powder, and when the sintering step of preparing the electrolyte membrane layer is carried out, the sintering temperature required by the densification of the electrolyte membrane layer is reduced on the premise of reducing the defect of the electrolyte membrane layer and ensuring the compactness of the electrolyte membrane layer. Compared with the prior art, the YSZ powder mainly comprises submicron YSZ powder, and the preparation method of the electrolyte membrane layer has the advantages of low cost and low preparation cost. 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 slurry can be uniformly dispersed.
In some embodiments of the invention, the YSZ electrolyte slurry comprises, in parts by weight, 75-108 parts YSZ powder, 61-88 parts binder and 0.7-2 parts dispersant.
The further technical scheme has the beneficial effects that the YSZ powder in the YSZ electrolyte slurry is 75-108 parts, the binder is 61-88 parts and the dispersing agent is 0.7-2 parts, and under the action of the binder and the dispersing agent, the nano-scale, submicron-scale and micron-scale YSZ powder is more uniformly distributed, the dispersibility is better, 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, in parts by weight, 5-8 parts nanoscale YSZ powder, 55-80 parts submicron YSZ powder, and 15-20 parts micron YSZ powder.
The technical scheme has the advantages that the nanometer YSZ powder is 5-8 parts, the submicron YSZ powder is 55-80 parts, and the micron YSZ powder is 15-20 parts, the mixed small-size powder can be fully filled into gaps among the large-size powder, the contact area between the small-size powder and the large-size powder which are melted preferentially during sintering is larger, mass transfer occurs, grain growth rearrangement is promoted, and further the densification effect of the electrolyte layer is better.
In some embodiments of the invention, the submicron YSZ powder comprises submicron YSZ powder having a particle size d50=0.1-0.2 μm and submicron YSZ powder having a particle size d50=0.3-0.5 μm.
The technical scheme has the advantages that the submicron YSZ powder is further divided into the D50=0.1-0.2 μm and D50=0.3-0.5 μm, and the nanometer YSZ powder and the micron YSZ powder are matched, so that the better mutual filling of the YSZ powder in each grain size range in the slurry is realized after the YSZ powder in each grain size range is mixed, the mixing of the YSZ powder in each grain size range in the slurry is more uniform, the structure of the electrolyte membrane layer is more uniform and consistent during sintering, and the compactness is further optimized.
In some embodiments of the present invention, the submicron YSZ powder comprises 10-15 parts of submicron YSZ powder having a particle size d50=0.1-0.2 μm and 45-65 parts of submicron YSZ powder having a particle size d50=0.3-0.5 μm in parts by weight.
The technical scheme has the advantages that the submicron YSZ powder with D50=0.1-0.2 μm is 10-15 parts, the submicron YSZ powder with D50=0.3-0.5 μm is 45-65 parts, and after the submicron YSZ powder is further divided into particle sizes, the content of the submicron YSZ powder in each particle size range is further researched and designed, and under the content, the electrolyte membrane layer prepared by the slurry has fewer defects and higher compactness.
In some embodiments of the invention, the YSZ powder comprises, in parts by weight, 7 parts of nano-sized YSZ powder having a particle size d50=0.06 μm, 12 parts of sub-micron sized YSZ powder having a particle size d50=0.15 μm, 55 parts of sub-micron sized YSZ powder having a particle size d50=0.4 μm, and 18 parts of micro-sized YSZ powder having a particle size d50=1.1 μm.
The YSZ powder has the beneficial effects that when the slurry prepared by the formula content is sintered to prepare the electrolyte membrane layer, the sintering shrinkage of the membrane layer is greatly reduced, and the defects are fewer; the densification degree of the electrolyte membrane layer is higher, the sintering temperature required by the densification of the electrolyte membrane layer is greatly reduced, and the sintering temperature can be reduced by about 50-100 ℃.
In some embodiments of 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 mixture of ethylcellulose and terpineol.
The dispersing agent used in the invention is a coupling agent, and the coupling agent is a silane coupling agent and/or an aluminate coupling agent, so that agglomeration of finer powder can be inhibited, the dispersing degree of slurry can be improved, and slurry can be uniformly dispersed. On the other hand, in the research test, it was found that the addition of the coupling agent (silane coupling agent and/or aluminate coupling agent) can significantly improve the compactness of the electrolyte membrane layer as compared with the case where no coupling agent is added, in addition to improving the dispersibility.
On the other hand, the invention also provides a preparation method of the YSZ electrolyte slurry, which comprises the following steps: ball milling the YSZ powder to obtain submicron YSZ powder with the grain diameter of D50=0.1-0.5 mu m and micron YSZ powder with the grain diameter of D50=1-1.2 mu m respectively, and preparing nano YSZ powder with the grain diameter of D50=0.05-0.07 mu m by a sol-gel method; weighing ethyl cellulose and terpineol, stirring and dissolving until the mixed solution is clear, and obtaining a binder; mixing nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder with a binder, adding a dispersing agent, and ball-milling and uniformly 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, so that the realization is facilitated, and the difficulty that the nanoscale YSZ is difficult to prepare by ball milling is overcome; the YSZ electrolyte slurry is formed by ball milling and mixing of YSZ powder, a binder and a dispersing agent, ball milling is carried out under the condition that the binder and the dispersing agent exist, the ball milling cannot influence the particle size of the YSZ powder, the ball milling mainly plays a role of a mixed material, in addition, the probability of agglomeration of the YSZ powder can be reduced by adding the dispersing agent, and the uniformity of the slurry is further ensured.
In some embodiments of the invention, grinding aid is added during YSZ powder ball milling, the ball milling balls comprise zirconia balls with diameters of 0.3mm, 3mm and 6mm, and 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 from small diameter to large diameter; the ball milling rotating speed is 300-500r/min, and the ball milling time is 4-16h.
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, pollution to the YSZ powder can be avoided, the uniformity of ball milling can be ensured by diameter selection of the zirconia balls, mass ratio of the zirconia balls with different diameters, ball material ratio, ball milling speed and time limitation, and the YSZ powder obtained after ball milling meets the requirements of submicron and micron ranges.
In yet another aspect, the present invention also provides a YSZ electrolyte membrane layer prepared from the YSZ electrolyte slurry of any one of the 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 the advantages of high compactness, uniform and consistent membrane layer structure and few defects.
Drawings
In order to more clearly describe the technical solution in the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be described below.
FIG. 1 is an SEM image of an electrolyte membrane layer prepared by sintering a YSZ electrolyte slurry of an embodiment of the invention at 1300℃for 5 hours;
FIG. 2 is an SEM image of an electrolyte membrane layer prepared by sintering a YSZ electrolyte slurry of another embodiment of the invention at 1300 ℃ for 5 hours;
FIG. 3 is an SEM image of an electrolyte membrane layer prepared by sintering a YSZ electrolyte slurry of yet another embodiment of the invention at 1300 ℃ for 5 hours;
FIG. 4 is an SEM image of an electrolyte membrane layer prepared by sintering a YSZ electrolyte slurry, which has not been subjected to particle size grading, at 1350℃for 5 hours;
FIG. 5 is an SEM image of a cross-section of the electrolyte membrane layer of FIG. 2;
fig. 6 is an SEM image of a cross section of an electrolyte membrane layer without a coupling agent, wherein the YSZ electrolyte slurry prepared in fig. 6 differs from the YSZ electrolyte slurry corresponding to fig. 2 only in whether a coupling agent is added or not.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, various aspects related to the present invention will be described in detail with reference to the following specific embodiments, which are only for illustrating the present invention, but do not limit the scope and spirit of the present invention in any way.
The invention provides YSZ electrolyte slurry which comprises YSZ powder, a binder and a dispersing agent, wherein the YSZ powder comprises nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder; the grain size of the nano-scale YSZ powder is D50=0.05-0.07 μm, the grain size of the submicron-scale YSZ powder is D50=0.1-0.5 μm, and the grain size of the micron-scale YSZ powder is D50=1-1.2 μm.
In the invention, the YSZ electrolyte slurry comprises 75-108 parts by weight of YSZ powder, 61-88 parts by weight of binder and 0.7-2 parts by weight of dispersing agent.
In the invention, 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 according to parts by weight.
In the present invention, the submicron YSZ powder includes submicron YSZ powder having a particle diameter d50=0.1 to 0.2 μm and submicron YSZ powder having a particle diameter d50=0.3 to 0.5 μm.
In the invention, the submicron YSZ powder comprises 10-15 parts of submicron YSZ powder with the particle size of D50=0.1-0.2 μm and 45-65 parts of submicron YSZ powder with the particle size of D50=0.3-0.5 μm according to parts by weight.
In the invention, the dispersing agent 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 the YSZ powder to obtain submicron YSZ powder with the grain diameter of D50=0.1-0.5 mu m and micron YSZ powder with the grain diameter of D50=1-1.2 mu m respectively, and preparing nano YSZ powder with the grain diameter of D50=0.05-0.07 mu m by a sol-gel method;
weighing ethyl cellulose and terpineol, stirring and dissolving until the mixed solution is clear, and obtaining a binder;
mixing nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder with a binder, adding a dispersing agent, and ball-milling and uniformly mixing to obtain the YSZ electrolyte slurry.
In the invention, grinding aid is added during YSZ powder ball milling, the ball milling balls comprise zirconia balls with diameters of 0.3mm, 3mm and 6mm, and the mass ratio of the zirconia balls is 0.8:1:0.5 and the ball-material ratio is 2-2.5:1 according to the order from small diameter to large diameter; the ball milling rotating speed is 300-500r/min, and the ball milling time is 4-16h.
In the invention, submicron YSZ powder with the grain diameter of D50=0.1-0.5 μm is obtained after the YSZ powder is ball-milled, and the submicron YSZ powder with the grain diameter of D50=0.1-0.2 μm and the submicron YSZ powder with the grain diameter of D50=0.3-0.5 μm can be obtained, wherein submicron YSZ powder with the grain diameter of D50=0.1-0.2 μm, submicron YSZ powder with the grain diameter of D50=0.3-0.5 μm and micron YSZ powder with the grain diameter of D50=1-1.2 μm are respectively obtained by setting different ball milling time in the range of 4-16h.
In the invention, the specific process for preparing the nanoscale YSZ powder with the particle size of D50=0.05-0.07 μm by a sol-gel method is as follows: weighing Y according to the molar ratio of Y to Zr=0.08:0.92 2 O 3 、ZrO 2 Dissolving in nitric acid, respectively, adding succinic acid, heating, stirring, mixing to gel state, drying gel, and sintering at 700-800deg.C to obtain nanometer YSZ powder with particle diameter d50=0.05-0.07 μm.
The invention also provides a YSZ electrolyte membrane layer which is prepared from the YSZ electrolyte slurry. Specifically, a screen printing technology can be selected to screen print the electrolyte slurry into a film layer blank, 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 dispersing agent, wherein the YSZ powder comprises nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder; the particle size of the nano-scale YSZ powder is d50=0.05 μm, the particle size of the submicron-scale YSZ powder is d50=0.1 μm and d50=0.3 μm, and the particle size of the micron-scale YSZ powder is d50=1 μm.
In this example, the YSZ electrolyte slurry includes 75 parts YSZ powder, 61 parts binder and 0.7 parts dispersant in parts by weight.
In this example, the YSZ powder includes 5 parts by weight of the nano-scale YSZ powder, 55 parts by weight of the sub-micron-scale YSZ powder, and 15 parts by weight of the micron-scale YSZ powder. 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 dispersing agent 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 embodiment also provides a preparation method of the YSZ electrolyte slurry of the embodiment, comprising the following steps:
s1, respectively weighing three groups of YSZ powder according to parts by weight, adding grinding aids (the use amount of YSZ powder is determined according to the use amount of submicron-level and micron-level YSZ powder required after particle grading, the mass ratio of YSZ powder to grinding aids is 100:1), selecting zirconia balls with diameters of 0.3mm, 3mm and 6mm as ball milling beads, setting the mass ratio of the zirconia balls to be 0.8:1:0.5 according to the sequence from small to large, setting the ball-material ratio to be 2-2.5:1 according to parts by weight, respectively carrying out dry milling in a ball milling tank at a ball milling rotating speed of 300-500r/min, setting the dry milling time to be in a range of 4-16h, and obtaining submicron YSZ powder with the particle diameter of D50=0.1 mu m, submicron YSZ powder with the particle diameter of D50=0.3 mu m and micron YSZ powder with the particle diameter of D50=1 mu m according to the difference of ball milling time after the ball milling. Nanoscale YSZ powder is difficult to prepare by ball milling, and the particle size of the nanoscale YSZ powder is D5 by a sol-gel methodNanoscale YSZ powder of 0=0.05 μm, specifically, Y is weighed in a molar ratio of Y: zr=0.08:0.92 2 O 3 、ZrO 2 Dissolving in nitric acid, respectively, adding succinic acid, heating, stirring, mixing to gel state, drying gel, and sintering at 800 deg.C to obtain nanometer YSZ powder with particle diameter D50=0.05 μm.
S2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol according to parts by weight, stirring and dissolving at a 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 of nano-scale YSZ powder with the particle size of D50=0.05 mu m, 10 parts of submicron-scale YSZ powder with the particle size of D50=0.1 mu m, 45 parts of submicron-scale YSZ powder with the particle size of D50=0.3 mu m and 15 parts of micron-scale YSZ powder with the particle size of D50=1 mu m according to parts by weight, uniformly mixing, adding 61 parts of binder and 0.7 part of coupling agent as dispersing agents, ball-milling for 8-12 hours at the rotating speed of 200-250r/min, and ball-milling uniformly mixing to obtain the YSZ electrolyte slurry of the embodiment.
The present embodiment also provides a YSZ electrolyte membrane layer prepared from the YSZ electrolyte slurry of the present embodiment. Specifically, a screen printing technology can be selected to screen print the electrolyte slurry into a film layer blank, 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 dispersing agent, wherein the YSZ powder comprises nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder; the particle size of the nano-scale YSZ powder is d50=0.06 μm, the particle size of the submicron-scale YSZ powder is d50=0.15 μm and d50=0.4 μm, and the particle size of the micron-scale YSZ powder is d50=1.1 μm.
In this example, the YSZ electrolyte slurry includes 92 parts YSZ powder, 75 parts binder and 1.5 parts dispersant in parts by weight.
In this example, the YSZ powder includes 7 parts by weight of the nanoscale YSZ powder, 67 parts by weight of the submicron-sized YSZ powder, and 18 parts by weight of the micron-sized YSZ powder. 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 dispersing agent 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 embodiment also provides a preparation method of the YSZ electrolyte slurry of the embodiment, comprising the following steps:
s1, respectively weighing three groups of YSZ powder according to parts by weight, adding grinding aids (the use amount of YSZ powder is determined according to the use amount of submicron-level and micron-level YSZ powder required after particle grading, the mass ratio of YSZ powder to grinding aids is 100:1), selecting zirconia balls with diameters of 0.3mm, 3mm and 6mm as ball milling beads, setting the mass ratio of the zirconia balls to be 0.8:1:0.5 according to the sequence from small to large, setting the ball material ratio to be 2-2.5:1 according to parts by weight, respectively carrying out dry milling in a ball milling tank at a ball milling rotating speed of 300-500r/min, setting the dry milling time to be in a range of 4-16h, and obtaining submicron YSZ powder with the particle diameter of D50=0.15 mu m, submicron YSZ powder with the particle diameter of D50=0.4 mu m and micron YSZ powder with the particle diameter of D50=1.1 mu m according to the difference of ball milling time after the ball milling. The nanoscale YSZ powder is difficult to prepare by ball milling, and the nanoscale YSZ powder with the particle size d50=0.06 μm is prepared by a sol-gel method in the embodiment, specifically, Y is weighed according to the molar ratio of y:zr=0.08:0.92 2 O 3 、ZrO 2 Dissolving in nitric acid, respectively, adding succinic acid, heating, stirring, mixing to gel state, drying gel, and sintering at 750deg.C to obtain nanometer YSZ powder with particle diameter d50=0.06 μm.
S2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol according to parts by weight, stirring and dissolving at a 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.
And S3, weighing 7 parts of nano-scale YSZ powder with the particle size of D50=0.06 mu m, 12 parts of submicron-scale YSZ powder with the particle size of D50=0.15 mu m, 55 parts of submicron-scale YSZ powder with the particle size of D50=0.4 mu m and 18 parts of micron-scale YSZ powder with the particle size of D50=1.1 mu m according to parts by weight, uniformly mixing, adding 75 parts of binder and 1.5 parts of coupling agent as dispersing agents, ball-milling for 8-12 hours at the rotating speed of 200-250r/min, and ball-milling uniformly mixing to obtain the YSZ electrolyte slurry of the embodiment.
The present embodiment also provides a YSZ electrolyte membrane layer prepared from the YSZ electrolyte slurry of the present embodiment. Specifically, a screen printing technology can be selected to screen print the electrolyte slurry into a film layer blank, 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 dispersing agent, wherein the YSZ powder comprises nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder; the particle size of the nano-scale YSZ powder is d50=0.07 μm, the particle size of the submicron-scale YSZ powder is d50=0.2 μm and d50=0.5 μm, and the particle size of the micron-scale YSZ powder is d50=1.2 μm.
In this example, the YSZ electrolyte slurry includes 108 parts YSZ powder, 88 parts binder, and 2 parts dispersant in parts by weight.
In this embodiment, the YSZ powder includes 8 parts by weight of nano-scale YSZ powder, 80 parts by weight of sub-micron-scale YSZ powder, and 20 parts by weight of micron-scale YSZ powder. 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 dispersing agent 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 embodiment also provides a preparation method of the YSZ electrolyte slurry of the embodiment, comprising the following steps:
s1, respectively weighing three groups of YSZ powder according to parts by weight, adding grinding aid (the use amount of YSZ powder is determined according to the use amount of submicron-level and micron-level YSZ powder required after particle grading, the mass ratio of YSZ powder to grinding aid is 100:1), and selecting zirconia balls with diameters of 0.3mm, 3mm and 6mm as ball milling ballsThe mass ratio of the zirconia balls is 0.8:1:0.5 in the order of small diameter to large diameter, the ball-material ratio is set to be 2-2.5:1 in parts by weight, the ball-milling speeds are 300-500r/min, the ball-milling tanks are respectively dry-milled, the dry-milling time is set to be 4-16h, and submicron YSZ powder with the grain diameter of D50=0.2 mu m, submicron YSZ powder with the grain diameter of D50=0.5 mu m and micron YSZ powder with the grain diameter of D50=1.2 mu m are obtained according to the difference of the ball-milling time after the ball milling is finished. The nanoscale YSZ powder is difficult to prepare by ball milling, and the nanoscale YSZ powder with the particle size d50=0.07 μm is prepared by a sol-gel method in the embodiment, specifically, Y is weighed according to the molar ratio of y:zr=0.08:0.92 2 O 3 、ZrO 2 Respectively dissolving in nitric acid, adding succinic acid, heating, stirring, mixing to gel state, drying gel, and sintering at 700deg.C to obtain nano-scale YSZ powder with particle diameter d50=0.07 μm.
S2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol according to parts by weight, stirring and dissolving at a 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.
And S3, weighing 8 parts of nano-scale YSZ powder with the particle size of D50=0.07 mu m, 15 parts of submicron-scale YSZ powder with the particle size of D50=0.2 mu m, 65 parts of submicron-scale YSZ powder with the particle size of D50=0.5 mu m and 20 parts of micron-scale YSZ powder with the particle size of D50=1.2 mu m according to parts by weight, uniformly mixing, adding 88 parts of binder and 2 parts of coupling agent as dispersing agents, ball-milling for 8-12 hours at the rotating speed of 200-250r/min, and ball-milling uniformly mixing to obtain the YSZ electrolyte slurry of the embodiment.
The present embodiment also provides a YSZ electrolyte membrane layer prepared from the YSZ electrolyte slurry of the present embodiment. Specifically, a screen printing technology can be selected to screen print the electrolyte slurry into a film blank, and the YSZ electrolyte film is obtained after drying and sintering.
Comparative example
The comparative example is different from examples 1 to 3 in that the comparative example is not subjected to particle grading, and specifically, the comparative example provides a YSZ electrolyte slurry including YSZ powder having a particle size d50=0.05 to 1.2 μm, a binder and a dispersant.
In the comparative example, the YSZ electrolyte slurry includes 75 to 108 parts by weight of YSZ powder, 61 to 88 parts by weight of a binder and 0.7 to 2 parts by weight of a dispersant.
In the comparative example, 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 preparation method of the YSZ electrolyte slurry of the comparative example comprises the following steps:
s1, preparing YSZ powder (the commercial YSZ powder) with the particle size of D50=0.05-1.2 μm;
s2, weighing 3 parts of ethyl cellulose and 97 parts of terpineol according to parts by weight, stirring and dissolving at a rotating speed of 150-250r/min until the mixed solution is clear, and obtaining a binder based on the mixed solution of the ethyl cellulose and the terpineol;
and S3, weighing 75-108 parts by weight of YSZ powder, 61-88 parts by weight of binder and 0.7-2 parts by weight of dispersing agent, ball-milling for 8-12 hours at a rotating speed of 200-250r/min, and uniformly ball-milling to obtain the YSZ electrolyte slurry of the comparative example.
Comparative example also provides a YSZ electrolyte membrane layer prepared from the YSZ electrolyte slurry of the comparative example. Specifically, a screen printing technology can be selected to screen print the electrolyte slurry into a film blank, and the YSZ electrolyte film is obtained after drying and sintering.
Fig. 1 to 3 show SEM images of electrolyte membrane layers prepared by sintering the YSZ electrolyte slurries of examples 1 to 3 at 1300 ℃ for 5 hours, and fig. 4 shows SEM images of electrolyte membrane layers prepared by sintering the YSZ electrolyte slurries of comparative examples without grain grading at 1350 ℃ for 5 hours. As can be seen from fig. 1 to 3, the YSZ electrolyte slurries of examples 1 to 3 subjected to particle grading have very few pores of the electrolyte membrane layer obtained by sintering at 1300 ℃, and in particular, the YSZ electrolyte slurry of example 2 has no pores and very good compactness, and the YSZ electrolyte slurries of examples 1 and 3 have very few pores, so that the requirement of the solid fuel cell on the compactness of the electrolyte membrane layer has been met. As can be seen from fig. 4, the YSZ electrolyte slurry of the comparative example, which was not subjected to the particle grading, had a large number of pores even in the electrolyte membrane layer prepared by sintering at 1350 ℃ (50 ℃ higher than the sintering temperature of examples 1 to 3) for 5 hours, and the electrolyte membrane layer was poor in compactness and defective. Therefore, the YSZ electrolyte slurry subjected to particle grading can be sintered at a lower temperature to prepare the electrolyte membrane layer with higher density, and the electrolyte membrane layer has fewer defects, 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 compactness 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 coupling agent added, wherein the YSZ electrolyte slurry prepared for the electrolyte membrane layer of fig. 6 is different from the YSZ electrolyte slurry corresponding to fig. 2 only in whether the coupling agent is added or not. It can be seen from fig. 5 to 6 that the electrolyte membrane layer has almost no pores and extremely high density after the coupling agent is added, and has obvious pores and relatively poor density when the coupling agent is not added. Therefore, in the invention, the coupling agent used as the dispersing agent not only plays roles of inhibiting agglomeration of finer powder and improving the dispersion degree and the dispersion uniformity, but also plays roles of obviously improving the compactness of the electrolyte membrane layer.
Therefore, the invention discovers the effect of the coupling agent in improving the compactness of the electrolyte membrane layer, and greatly improves the compactness of the electrolyte membrane layer prepared by the YSZ electrolyte slurry according to the invention through the two aspects of the grain composition of YSZ powder and the addition of the coupling agent, thereby greatly contributing to the field of solid oxide fuel cells.
The present invention has been described with reference to specific embodiments, which are merely illustrative, and not intended to limit the scope of the invention, and those skilled in the art can make various modifications, changes or substitutions without departing from the spirit of the invention. Thus, various equivalent changes may be made according to this invention, which still fall within the scope of the invention.

Claims (7)

1. A YSZ electrolyte slurry is characterized by comprising YSZ powder, a binder and a dispersing agent,
wherein the YSZ powder comprises nano-scale YSZ powder, submicron-scale YSZ powder and micron-scale YSZ powder;
the particle size of the nano-scale YSZ powder is D50=0.05-0.07 mu m, the particle size of the submicron-scale YSZ powder is D50=0.1-0.5 mu m, and the particle size of the micron-scale YSZ powder is D50=1-1.2 mu m;
wherein the dispersing agent is a coupling agent, and the coupling agent is a silane coupling agent and/or an aluminate coupling agent;
the YSZ electrolyte slurry comprises, by weight, 75-108 parts of YSZ powder, 61-88 parts of binders and 0.7-2 parts of dispersants;
the YSZ powder comprises, by weight, 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 binder is a mixed solution of ethyl cellulose and terpineol, and the weight ratio of the ethyl cellulose to the terpineol is 3:97;
the submicron YSZ powder and the micron YSZ powder are prepared by ball milling; the nanoscale YSZ powder is prepared by a sol-gel method, and the specific process is as follows: weighing Y according to the molar ratio of Y to Zr=0.08:0.92 2 O 3 、ZrO 2 Respectively dissolving in nitric acid, adding succinic acid, heating, stirring, mixing to gel state, drying gel, and sintering at 700-800 deg.C to obtain nanometer YSZ powder.
2. The YSZ electrolyte slurry of claim 1, wherein the submicron YSZ powder comprises submicron YSZ powder having a particle size d50=0.1-0.2 μm and submicron YSZ powder having a particle size d50=0.3-0.5 μm.
3. The YSZ electrolyte slurry according to claim 2, wherein the submicron YSZ powder comprises 10-15 parts by weight of submicron YSZ powder having a particle size d50=0.1-0.2 μm, and 45-65 parts by weight of submicron YSZ powder having a particle size d50=0.3-0.5 μm.
4. The YSZ electrolyte slurry of claim 3, wherein the YSZ powder comprises, in parts by weight, 7 parts of nano-sized YSZ powder having a particle size d50=0.06 μm, 12 parts of sub-micron sized YSZ powder having a particle size d50=0.15 μm, 55 parts of sub-micron sized YSZ powder having a particle size d50=0.4 μm, and 18 parts of micro-sized YSZ powder having a particle size d50=1.1 μm.
5. The method for producing YSZ electrolyte slurry according to any one of claims 1 to 4, comprising the steps of:
ball milling the YSZ powder to obtain submicron YSZ powder with the grain diameter of D50=0.1-0.5 mu m and micron YSZ powder with the grain diameter of D50=1-1.2 mu m respectively, and preparing nano YSZ powder with the grain diameter of D50=0.05-0.07 mu m by a sol-gel method;
weighing ethyl cellulose and terpineol, stirring and dissolving until the mixed solution is clear, and obtaining a binder;
mixing nanoscale YSZ powder, submicron YSZ powder and micron YSZ powder with a binder, adding a dispersing agent, and ball-milling and uniformly mixing to obtain the YSZ electrolyte slurry.
6. The method for preparing YSZ electrolyte slurry according to claim 5, wherein grinding aid is added during the ball milling of YSZ powder,
the ball-milling beads comprise zirconia balls with diameters of 0.3mm, 3mm and 6mm, wherein the mass ratio of the zirconia balls is 0.8:1:0.5 and the ball-material ratio is 2-2.5:1 according to the order from small diameter to large diameter;
the ball milling rotating speed is 300-500r/min, and the ball milling time is 4-16h.
7. A YSZ electrolyte membrane layer, characterized in that the YSZ electrolyte membrane layer is prepared from the YSZ electrolyte slurry according to any one of claims 1 to 4.
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