JP2024151398A - Fluid ejection or application method, secondary battery or all-solid-state battery manufacturing method, solar cell manufacturing method, and nozzle assembly - Google Patents

Abstract

To solve the problem that viscosity of slurry needs to be reduced in coating by making liquid particles of slurry for electrodes of secondary batteries and all-solid batteries or the like and that solid particles precipitate in a flow channel when viscosity is low, and especially at the time of work stop instantly, a narrow flow channel of an on-off valve downstream side is blocked.SOLUTION: An opening for slurry of high viscosity is provided at a fluid-jetting head tip, an opening for a solvent is provided in the periphery of the slurry opening, and a compressed gas opening is provided in the periphery of the solvent opening, so that slurry with a high solid content is stretched while being swelled by the solvent and granulated. In atomization, another compressed gas is jetted toward the fluid from a close distance to cause collision and make fine particles.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for ejecting a fluid, a method for applying a fluid, a method for manufacturing a secondary battery or an all-solid-state battery, a method for manufacturing a solar cell, and a nozzle assembly.

With the increase in electric vehicles (EVs), the production volume of lithium-ion batteries (LIBs) is rapidly increasing. Accordingly, the production volume of LIB electrode forms is also increasing. However, the LIB electrode formation process requires large drying equipment due to the high line speed, which poses the issue of carbon dioxide emissions. In addition, the manufacture of all-solid-state batteries using sulfide-based electrolytes, which are the main candidates for next-generation secondary batteries, requires a dehumidified environment and even larger equipment, so there was a demand for space-saving equipment while maintaining or improving performance. Furthermore, in other fields, such as the formation of electrode layers for solar cell power generation layers, fuel cells, water electrolysis, and carbon dioxide electrolysis, which also contribute to carbon neutrality, there was a high demand for space-saving manufacturing processes as each of these processes was speeded up.

The present invention is applicable to any type of secondary battery, including lithium ion batteries (LIBs), potassium or sodium ion batteries, all-solid-state batteries, and semi-solid-state batteries. Solar cells include organic thin-film solar cells and dye-sensitized solar cells, and are not limited in structure or type, including perovskite solar cells and perovskite-on-silicon tandem solar cells. The fluid can be selected from liquids, melts, powders, supercritical fluids, and compressed gases, and can be a single fluid or a mixture of these fluids, including short fibers.

Furthermore, the manufacturing and forming methods of granulation, capsules, short fibers, webs, etc. using multiple fluids according to the present invention can be handled by a fluid ejection method. The coating method involves applying a fluid to an object, and is effective in the general manufacture of MLCCs, capacitors, and batteries of different shapes, and can be suitably applied to the formation of electrodes for fuel cells, water electrolysis, gas electrolysis, capacitors, etc. It can also be applied to other fields such as electronics and chemicals, general painting and adhesive processes, and can contribute to the manufacturing process of these objects, especially high-speed production lines.

Conventionally, when applying liquid such as electrode slurry to a wide object such as a secondary battery that moves at high speed, the slot die method has been generally used because it can handle high speeds and is simple. The drying device can handle high speeds, for example, the coating speed of a collector at 60 meters per minute or more. On the other hand, normal methylpyrrolidone (NMP) and other solvents are generally used to dissolve the fluorine-based binder in the electrode slurry, and the drying device is large because of its high boiling point. For this reason, a method of heating the back roll to a high temperature has been attempted. However, since the tip of the heated roll and the slot die are configured to contact the object through a liquid film, it was difficult to keep the coating film shape constant because the temperature and deformation of the tip of the slot die change over time due to heat transfer from the heated roll, and the gap changes. On the other hand, a thin film of the electrode is required, and the formation of an electrode using a catalyst ink on the electrolyte membrane of a fuel cell, which is thin and swells instantly, was extremely difficult because it was necessary to heat and adsorb the electrolyte membrane. In addition, in the formation of a power generation layer for a perovskite solar cell, which requires an ultra-thin film at the nano level, the change in the gap in microns between the slot die head or the coating head using surface tension and the heated object was a problem. Not only the straightness of slot dies, etc., but also the flatness of heated tables and conveyors that transport sheets, etc., was a problem, for example, when heating a sheet-like object to 60°C or higher.
On the other hand, the general spray method of spraying a wide gap at a wide angle is simple but has extremely poor coating efficiency and has not been adopted in the field of secondary batteries, which require wide widths and high speeds.

However, the electrode coating film after drying was thick, at around 100 micrometers, and only the surface of the coating film had little contact with the outside air. Therefore, in order to prevent cracks, the drying temperature was set low and the film moved at high speed, which resulted in the drying equipment becoming huge and becoming a source of CO2 emissions. As a result, the solvent recovery equipment also became large.

In the secondary battery industry, there was a strong demand for a method to shorten the drying time during electrode formation and improve electrode performance. Some have proposed electrode formation methods using electrode powders that do not use solvents in order to eliminate drying equipment and solvent recovery equipment. However, unlike previous methods, the binder content is only a few percent or less in order to improve performance, so there is a problem with poor adhesion of the powder to collectors, etc. In addition, it was necessary to efficiently attach conductive assistants such as carbon nanofibers and carbon nanotubes (CNTs), which are also in trace amounts of less than a few percent, to active material particles. A dehumidified atmosphere is essential for sulfide-based all-solid-state batteries, which are considered to be next-generation secondary batteries and are seen as promising for the future, and if the installation area of a large drying device is large, huge initial and running costs will be incurred. Therefore, it was necessary to make the entire electrode formation device smaller. In order to quickly volatilize the solvent in the electrode slurry, it is good to heat the target object, switch to a low-bottom solvent, or use the azeotropic action of a low-boiling point solvent in the desired ratio, increase contact with gas, dry in a vacuum atmosphere, or use a combination of these.

When applying to an object, general sprays that increase contact with gas, especially the air spray method known as the two-fluid spray method, can quickly evaporate the solvent. However, as mentioned above, when spraying at a wide angle to cover a wide width and away from the object, the coating efficiency is extremely poor at around 30. Furthermore, the spray efficiency for secondary battery objects moving at high speeds, for example at speeds of 60 m/min or more, is even worse because the particles are affected by the wind flow generated above the object. Furthermore, even if multiple spray nozzles are arranged in a horizontal row, the film thickness distribution in the width direction is extremely poor. Due to the numerous basic issues such as these, the spray method has been avoided, especially for high-speed production equipment related to secondary batteries.

In addition, the spray method requires low viscosity, for example 200 mPascal seconds or less, otherwise the spray particles become coarse and the coating distribution varies widely. On the other hand, slurries that have low viscosity and high specific gravity, especially those containing particles such as positive electrode active materials, tend to cause significant particle precipitation in the flow path. In particular, when there is no circulation, for example in the flow path downstream of the opening and closing valve of the coating head, when the internal volume is large and the flow rate is slow, or when the work is stopped, there is a fatal problem of particles settling.
The present invention has been made to solve these problems, and solves each of these individual problems.

Cited Document 1 discloses a method in which a shim having a thin groove for a viscous fluid is sandwiched between blocks to form a flow path, a viscous fluid such as a hot melt adhesive is allowed to ooze from the outlet of the flow path, heated compressed air is sprayed into the viscous fluid from two directions to produce particles or fibers, and the particles or fibers are applied to a substrate. Cited Document 2 is a method invented by the present inventor, which proposes a method in which a fluid selected from liquid, heated melt, powder, supercritical fluid, and gas is sprayed from multiple nozzles in a divergent manner so that it can be used on a wide substrate, and the timing of the sprays is staggered so that adjacent spray patterns are buffered in the air or on the substrate to prevent the patterns from being disturbed.
In the method of the document 1, the viscous fluid is divided into thin streams by multiple thin grooves, but heated air is collided with wide slit grooves from two directions at a certain angle to form particles or fibers. However, even if a viscous fluid with high cohesive power such as hot melt is divided into thin streams, it is attracted to the wall or surface of the head tip by surface tension from the moment it oozes out and grows into a continuous film or large droplets. Hot melt is a high-temperature molten material at around 180°C, so heated air is required to prevent the temperature from dropping, but the stretching effect is low when the droplets are collided with from two directions, and the viscous fluid adheres to metal and other materials due to surface tension and spreads to form a liquid film or droplets. Therefore, even if it is heated, the collision of compressed air alone will result in a collection of coarse particles or extremely thick fibers. The desired small particleization was not achieved. The mechanism of finely dividing the liquid with multiple slot grooves and injecting air into the liquid from air grooves is easy to understand from the diagram of JP-A-06-154691, which has a similar structure. This method aims to form a coating film with sharp edges at the desired location of an object that moves relatively at high speed. For this reason, the stretching effect cannot be expected from the collision of compressed air from two directions alone with highly viscous liquids, and so the coating film of the viscous fluid becomes coarse particles, and there are other issues such as air bubbles remaining in the coating film, so detailed explanations are omitted. Applications that require adhesion rarely require functions other than adhesion, so atomization or ultra-fine short fibers were not necessarily required. Also, even if a viscous liquid is extruded thinly and widely through a slot die, it begins to coagulate the moment it leaves the opening edge, as per the theory of the T-die, and transitions into a thick rod-like flow toward the center in the air. The higher the viscosity, the stronger the cohesive force is generally, so it was impossible to turn the thick coagulated flow into small particles or thin short fibers with compressed gas. In other words, when atomization or thin short fibers were required, it was essential to make the opening narrower, thinner, and smaller, and at the moment the liquid or melt leaves the opening edge, stretch the viscous fluid with a high-speed compressed gas flow from all around, tear it into a fiber-like shape, and turn it into particles using surface tension. Before the short fibers turn into particles due to surface tension, solvents with particularly low boiling points evaporate in the air, and resins and other materials turn into solid, thin, short fibers. Also, when the temperature of the short fibers drops below their melting point, low-viscosity heated molten materials turn into a short fiber aggregate without turning into particles. This is generally called angel hair and is used in the manufacture of webs. In other words, high-viscosity fluids require sufficient or effective stretching or tearing force from all sides at the beginning. Furthermore, if fine particle formation is desired, compressed gas must be collided with the flow at high speed.

Special table Hei 8-501974 Patent Publication 2018-089543

Therefore, the present invention aims to solve the following problems.
Conventionally, secondary battery manufacturing has had the following problems: Similarly, there are similar problems to be solved in the manufacture of next-generation solar cells, such as perovskite solar cells, and in the formation of electrodes for fuel cells, water electrolysis, carbon dioxide electrolysis, etc.
1. Shortening drying time: especially for secondary batteries 2. Support for wide width coating: in general 3. Support for high line speeds: in general 4. Prevention of slurry precipitation: in general, especially for secondary batteries including all-solid-state batteries 5. Formation of thin to thick films: in general 6. Improvement of coating film performance: in general.
The present invention was made to solve these problems, and is structured so that the solvent evaporates easily to increase the drying speed. It can also be applied over a wide area and can handle high-speed movement of objects. It is compatible with thin and thick films. It is structured so that slurry containing solid particles does not settle or does not settle easily. The coating performance is at least maintained at the conventional level, while efforts are made to improve it. The goal is to bring the usage efficiency, including the coating efficiency of slurries, etc., closer to that of conventional die head systems.

1. Quick drying:
By stretching and tearing the slurry with compressed gas to form particles, the contact area with the gas increases, which promotes the evaporation of the solvent. In addition, by heating the target object, the spray particles are crushed by impact and spread thinly, which promotes the evaporation of the solvent. Furthermore, by laminating thin films many times, a high solid content coating film is formed the moment it is applied. In other words, in this invention, even if the solid content concentration before application is low, a high solid content coating film called a higher solid can be formed from the moment it is applied, which is usually difficult to apply. In addition, regardless of viscosity, a viscous fluid can be extruded at a low flow rate through a thin and narrow groove, for example 0.2 mm wide, per pitch of 1 mm to 10 mm, and stretched and torn into fine particles with compressed gas, and applied. Furthermore, by pulse-opening and closing the upstream opening and closing valve in milliseconds, the flow rate can be further reduced, for example to 1/10 or less, making it possible to form an even thinner film. The flow rate can be increased easily by increasing the opening of the automatic opening and closing valve or by increasing the liquid pressure, so thick film application is possible. In addition, the flow path of the liquid fluid can be made into a groove of desired size. Even if the groove is thin, it is possible to laminate thin films with a desired thickness by arranging multiple nozzle assemblies in the moving direction of the object and applying the layers. The thickness of the thin plate of the present invention can be selected from 0.05 to 1 mm, and more preferably from 0.05 to 0.5 mm. Therefore, there is no limit to the amount of liquid or the like that can be pumped in the present invention.

2. Wide width coating:
By selecting the number of nozzle assemblies with 1 to 1500 nozzles for ejecting fluid such as slurry, it is possible to flexibly accommodate coatings from narrow to wide. For example, for a slow line speed of an object of 100 mm per minute, it is possible to select a nozzle assembly with one or a small number of nozzles that traverses perpendicularly to the moving direction of the object to apply. Or, for a wide object that moves slowly, even a wide head nozzle assembly with 1500 nozzles can be used to laminate thin films by adjusting the interval in a pulsed manner. For a wide object that moves at a high speed, a wide nozzle assembly can be fixed and applied, and a nozzle assembly with a small number of nozzles can be swung in a short traverse. For example, a nozzle assembly with 1500 nozzles and an aperture pitch of 1 mm can be used to coat a wide width of about 1500 mm. Even if the number of nozzles is reduced and the pitch is widened, multiple nozzle assemblies can be installed in the moving direction of the object to narrow the fluid aperture pitch in total. Even if there are five sets of nozzle assemblies and the fluid aperture pitch is 5 mm, the total is approximately the same as a pitch of 1 mm. The number of layers can be increased by increasing the number of nozzle assemblies. Therefore, in the formation of LIB electrodes, a conductive additive, such as a dispersion of carbon nanofibers with a desired low solid content, can be mixed around the active material particle slurry, stretched from the periphery with compressed gas, and then atomized and applied. Since it is layered, it is possible to disperse and mix a small amount of conductive additive with the desired distribution. The flow paths of the active material and conductive additive can be reversed. Furthermore, by improving electrode performance and increasing contact with compressed gas, the drying time can be significantly shortened.

3. Supports high-speed line speeds:
The distance between the nozzle assembly opening and the target can be selected, for example, from 1 to 70 mm, more preferably from 5 to 50 mm. Therefore, the influence of wind disturbances that adversely affect particles caused by a target moving at high speed can be ignored. Furthermore, the opening pitch can be shortened, so that the movement of the particles proceeds almost straight toward the target, resulting in a high impact, dense adhesion of the particles, and reduced rebound. In other words, by narrowing the nozzle pitch to, for example, 1 mm to 6 mm, and arranging multiple nozzle assemblies in, for example, six rows, a system can be created that also has the effect of thin film lamination.

4. Slurry precipitation prevention measures:
The slurry is made into a high viscosity slurry that is difficult to settle, and is transported to the opening of the flow path. Even if the slurry is highly viscous, the amount of the slurry is divided by a number of elongated comb-like grooves, and the flow rate from each opening is reduced, and the thin slurry flow is stretched from the entire circumference by compressed gas or compressed gas containing solvent fine particles, and broken down into fibers. A further means for better atomizing the high viscosity slurry is to merge the solvent from the outer circumference downstream of the slurry opening, swell the high viscosity slurry with the surrounding solvent, reduce the viscosity, and turn it into fine particles by the stretching and tearing effect of the compressed gas from the entire circumference. If desired, it is also possible to add the above two methods to further fine the slurry by the collision energy of the collision flow of compressed gas from close to the merged fluid or particles. In addition, in the present invention, it is also possible to mix an inert gas into the high viscosity slurry upstream of the flow path, disperse it in the slurry, foam it, and make the bubbles smaller with liquid pressure, and then foam it when it is ejected from the opening, making it easier to tear the slurry by the foaming force and the stretching force of the compressed gas from the surroundings.
In the present invention, since the desired flow path can be formed with multiple thin plates, the volume of the flow path downstream of the opening and closing valve can be made as small as possible even for foamed viscous fluids. The timing of application is such that the compressed gas is ejected faster than the slurry ejection speed and can be ejected until later than the end of the slurry ejection, so that a clean cut of a pulsed application pattern including foamed liquids can be achieved.

5. Thin and thick films:
If the supply flow rate of the liquid fluid is reduced, the coating film thickness automatically becomes thin, and if the supply rate is increased, the coating film becomes thick. From the viewpoint of energy saving, the compressed gas can be increased or decreased according to the flow rate of the liquid fluid. In addition, regardless of viscosity, the viscous fluid can be divided into thin and thin pieces, for example 50 μm to 300 μm, by a thin plate with a long and narrow groove, and then stretched and finely divided by compressed gas or the like from the periphery, to form a nozzle assembly capable of coating from thin to thick films. A plurality of nozzle assemblies, for example 10 rows, can be arranged in the direction of movement of the object. In the present invention, since the desired number of nozzle assemblies can be arranged, there is no limit to the amount of liquid or the like that can be pumped. The nozzle assembly and the object can move relative to each other. In the present invention, the same liquid film can be applied as with a slot die. Since the gap between the tip of the nozzle assembly and the object can be made wider than the liquid coating film thickness, there is no need to worry about damage to the coating film, such as streaks caused by dirt, which is a problem with slot dies. Therefore, in the present invention, the pressure of the compressed gas can be reduced and the object can be coated with a liquid film as a compressed gas supported slot die. With a liquid fluid with a relatively high viscosity, a narrow stripe coat can be formed. Furthermore, when a low viscosity fluid is used and the liquid fluid opening pitch is narrowed, the liquid fluid flows on the target object, allowing continuous coating to be formed.

7. Improved coating performance:
The nozzle assembly of the present invention is structured using a thin plate that does not allow viscous fluid to accumulate on the wall of the opening due to surface tension, so that the granulation of liquids and the like is stable. Therefore, thin film lamination is possible, and active material particles of the electrode can be densely laminated. By heating the object to a desired temperature, wettability after application can be improved and the solvent can be rapidly evaporated. Then, it becomes possible to fix the composite slurry in a well-dispersed state of multiple particles and short fibers selected from active material particles, electrolyte particles, conductive assistants, binders, etc., from the moment of application. In the present invention, multiple individual slurries or a selected number of composite slurries are joined at the moment they leave the nozzle opening, stretched and torn with compressed gas, etc., and thin film lamination coating is applied to the heated object, thereby forming a nozzle assembly structure that allows coating with less energy. In addition, in the present invention, the electrode composite is granulated to a powder with an average particle size of about 7 to 70 μm, mixed mainly with a solvent to make a slurry, and the powder slurry is made into a first fluid, which is then sprayed simultaneously with the second fluid, compressed gas, so that the solvent is instantly volatilized after application to the object to form a powder layer. Since powder slurry has a low dynamic viscosity and is easy to form into spray particles, the compressed gas pressure can be kept low, at 0.2 MPa or less.

As described above, the present invention is effective for granulation and coating in general. It is particularly effective for high-speed production, which is in high demand, such as electrode formation for fuel cells such as SOFC and PEFC, water electrolysis, MEA manufacturing, electrode formation for secondary batteries and capacitors including all-solid-state batteries and semi-solid batteries, formation of functional membranes and electrolyte layers on porous separators for secondary batteries, formation of electrolyte layers for all-solid-state batteries, and formation of power generation layers, functional membranes, and electrodes for organic solar cells.

Therefore, the present invention is as follows:

The present invention is a method for spraying or applying a liquid fluid to an object, comprising the steps of: aligning and stacking a plurality of thin plates and plates or blocks each having a long and narrow groove for the fluid, forming a long and narrow flow path for the fluid and one or more openings for ejecting a first liquid fluid at the end of the thin plate; forming an ejection opening for a second fluid, which is a compressed gas or a compressed gas mixed with solvent particles, or a supercritical fluid, separated by a wall surrounding the opening for ejecting the liquid fluid; and forming a jetting opening for the first liquid fluid and the long and narrow flow path via an upstream flow path. The method for ejecting or applying a fluid includes the steps of: connecting the elongated flow path of the second fluid to a first opening/closing valve that opens and closes the supply of the first liquid fluid; connecting the elongated flow path of the second fluid to a second opening/closing valve that opens and closes the supply of the second fluid via an upstream flow path; and stretching the discharge flow from the opening of the first liquid fluid by opening the first and second opening/closing valves with a jet flow from the entire periphery of the jet port of the second fluid, ejecting the fluid as fibers or particles, or applying the ejected fibers or particles to an object.

The present invention provides a method for ejecting or applying a liquid fluid, characterized in that the number of grooved thin plates is increased to make the number of fluids and openings three or more, the outermost opening is an outlet for compressed gas or compressed gas containing solvent particles or supercritical fluid, the inside is an opening for liquid fluid, and at least one of the openings for liquid fluid is an outlet for solvent.

The present invention provides a method for ejecting or applying a fluid, which is characterized by colliding another compressed gas or a compressed gas containing solvent fine particles with the ejected liquid fluid at an acute angle and from a close distance, thereby finely atomizing the fibers or particles and ejecting them, or applying the finely atomized fibers or particles to a target object.

The present invention provides a method for producing a secondary battery or an all-solid-state battery, characterized in that the first fluid is selected from a slurry having a solid content of 25 to 75 weight percent, a slurry for secondary battery electrodes, a slurry for all-solid-state battery electrodes, and a slurry for all-solid-state battery electrolyte, the second fluid is selected from a compressed gas or a mixture of solvent fine particles and compressed gas, or a supercritical fluid, the two fluids are joined, the first fluid is stretched by the second fluid or the slurry is granulated by collision energy, and the target is selected from a current collector, an electrolyte layer, an electrode layer, and a separator, and the target is coated with the slurry to form an electrode layer, an electrolyte layer, or a functional membrane layer.

The present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, which is characterized in that after the two fluids are joined, a step is added in which a compressed gas or a compressed gas mixed with solvent fine particles is collided with the joined fluid at an acute angle, and the finely-divided slurry is applied to an object selected from a heated current collector, an electrolyte layer, an electrode layer, and a separator to form an electrode layer, an electrolyte layer, or a functional film layer.

The present invention provides a method for manufacturing a secondary battery or an all-solid-state battery, characterized in that the first fluid is selected from a slurry having a solid content of 50 to 85 weight percent, a slurry for secondary battery electrodes, a slurry for all-solid-state battery electrodes, and a slurry for all-solid-state battery electrolytes, the second fluid is a solvent, and the third fluid is a compressed gas or a supercritical fluid, and the three fluids are joined, the slurry is granulated by the stretching or collision energy of the compressed gas or the supercritical fluid, and the particles are collided with compressed gas or compressed gas mixed with solvent fine particles at an acute angle of 30 degrees or less with the ejection direction of the first fluid to atomize the particles, and the microparticulates are applied to an object selected from a current collector, electrolyte layer, electrode layer, and separator to form an electrode layer, electrolyte layer, or functional film layer.

The present invention provides a method for manufacturing solar cells, which involves moving a nozzle assembly that generates liquid particles relative to an object and applying liquid for a power generation layer or gas barrier layer in the form of particles, comprising the steps of manufacturing a nozzle assembly in which a plurality of thin plates and plates or blocks with elongated grooves are stacked on both sides and 1 to 1,500 openings for the second fluid are arranged on the sides of the openings for the first fluid, and the first fluid is a transparent conductive layer, power generation layer or gas barrier layer liquid, and the second fluid is a compressed gas or a supercritical fluid mixed with a compressed gas or fine solvent particles, and the first fluid is stretched by the surrounding compressed gas or supercritical fluid to form fine particles, which are then applied to an object selected from a heated silicon solar cell layer, transparent glass for solar cells, and transparent plastic film to form a transparent conductive film layer, power generation layer, or gas barrier layer.

The present invention provides a method for producing a perovskite solar cell, characterized in that the solar cell is a perovskite solar cell or a perovskite-on-silicon tandem solar cell.

The present invention is a nozzle assembly for ejecting a liquid fluid, which includes one or more elongated grooves for a first fluid that extend from the middle of a first thin plate to an end of one side of the thin plate, and elongated grooves for a second fluid that are located on both sides of the first fluid groove and have a shorter length from the end than the first fluid groove, and at least two second thin plates that are aligned and stacked from both sides of the first thin plate have elongated grooves that connect to a second flow path of the first thin plate, and a third thin plate has a second fluid groove that is at least as wide as the two ends of the multiple elongated grooves for the first fluid of the first thin plate, or a second flow path that is at least wider than the width between the centerlines of the elongated grooves for the second fluid that are located on both sides of the elongated groove for the first fluid of the first thin plate. A nozzle assembly is provided, characterized in that a groove for the body is formed, a second thin plate is aligned with the first thin plate at the center and a third thin plate is aligned with the second thin plate at the center, a flow path connected to an elongated flow path of a selected fluid is formed in the second and third thin plates, plates or blocks having flow paths formed therein that connect to one or more elongated grooves for the first fluid and the second fluid are stacked together to form one or more elongated flow paths and openings for the first fluid, an opening for the second fluid is provided by separating the opening for the first fluid from a wall surrounding the opening for the first fluid, the upstream of the opening for the first fluid is connected to an opening/closing valve that supplies the first fluid via the flow path, and the upstream of the opening for the second fluid is connected to an opening/closing valve that supplies the second fluid via the flow path.

The present invention provides a nozzle assembly characterized in that, instead of a third thin plate, a plate or block having grooves for a second fluid is aligned and overlapped on both sides of the second thin plate.

According to the present invention, as described above, thin grooves can be machined into multiple thin plates and stacked with blocks or the like to form one or multiple fluid flow paths and openings of the same shape. This eliminates the need to combine multiple parts with complex shapes such as spray nozzles. Even with multiple nozzles, for example 1,500 nozzles, it is possible to form roughly the same jet flow without having to worry about variations in the coating distribution of spray nozzles or the like. Therefore, the present invention can also meet the desired requirements for wide-width objects.

The groove processing of the thin plate can be performed by etching, and laser processing, for example, femtosecond laser, has little effect on temperature, so that even a thin plate, for example, a 50 μm thin plate, can be processed without deformation. The range of the thin plate is not particularly limited, but 0.05 to 1 mm is preferable, and 0.05 to 0.5 mm is more preferable. Therefore, as described above, according to the present invention, it is possible to correspond to the desired viscosity of the fluid, and to correspond to the coating width, coating speed, and coating thickness. It can be effectively applied to a wide range of fields, such as electrode layers and electrolyte layers of secondary batteries including all-solid-state batteries, functional film coating on separators, organic thin film systems for forming power generation layers, perovskite-on-silicon tandem type solar cells, next-generation solar cells including perovskite-on-perovskite tandem solar cells, fuel cells for electrode formation, water electrolysis, and carbon dioxide electrolysis. In particular, perevskite-silicon tandem solar cells require the formation of nano-level conductive oxide films and power generation layers along the unevenness on the fine uneven surface, but it is not possible to coat them uniformly with a normal spray because the air cushion cannot be solved. This is possible with the present invention, which can deposit fine particles into a thin film with impact from a close distance. Ideally, the pulsed fine particles with impact can be attached along the unevenness to form a thin film. In addition, ultrafine particles at the nano level generated by the nozzle assembly of the present invention or generated by colliding with an object can be electrostatically charged and attached to an earthed object. Therefore, this method is effective for objects in other fields in general that have fine unevenness.

The first thin plate of the nozzle assembly of the present invention can be selected from, for example, about 50 to 300 micrometers. There is no restriction on whether it is thinner or thicker than that, but considering that the viscous fluid adheres to the end surface due to surface tension, it is preferable that it is thinner. The second thin plate and subsequent thin plates may be thin as described above, but when a supercritical fluid is used, a thickness of about 0.3 millimeters or more is preferable in terms of strength. In particular, for example, the protrusion level of the opening for the first liquid fluid may be the same as that of the other openings, but if the wall end surface is a thick surface, the liquid is likely to wet due to surface tension and accumulate. Therefore, it is preferable that the end surface of the first opening protrudes about 0.1 to 2 mm from the end surface of the second opening so that the liquid does not accumulate on the wall of the second opening. Furthermore, by setting the timing of ejection of the compressed gas longer before and after the ejection of the liquid fluid, the liquid fluid can be prevented from accumulating on the end surface of the thin plate, and uniform liquid particles can be obtained from the beginning to the end of ejection.
For this reason, the thinner the wall thickness of the flow passage for the viscous fluid, the better. Therefore, the thickness of the thin plate can be selected from, for example, 50 to 300 micrometers. The smaller the first opening area, the thinner the opening, the more the viscous fluid can be divided finely, and the thinner the wall thickness, the better the stretching effect of the compressed gas and the more the particle formation can be promoted.
Furthermore, the present invention forms a three-dimensional flow path by aligning and stacking multiple thin plates with thin grooves, so it can be easily disassembled. In other words, each thin plate can be processed. After use, it can be disassembled and the flow path can be completely and easily cleaned using ultrasound, etc. Furthermore, surface processing is possible. Surface modification processing such as corrosion resistance and water repellency can be performed. For example, metal thin plates can be plated or ceramic coated. It is extremely difficult to process the inner surface of a long, thin cylindrical flow path, for example a metal cylinder with an inner diameter of 0.1 mm and a length of 30 mm, such as a syringe needle, but this can be easily done with the method of the present invention.

The present invention can spray particles onto an object at close range and at a narrow spray angle that is nearly straight, for example, 20 degrees or less, or even 15 degrees or less, so it can effectively coat objects moving at high speed. This can increase coating efficiency by minimizing rebound that occurs when the spray flow collides with the object, which occurs when the spray angle is wide. High coating efficiency and high density at the object interface and between particles can be achieved by spraying with impact from close range. It is even more effective to spray in a pulsed manner with impact.

Upstream of the opening and closing valve of the coating head, a circulation circuit for the slurry is formed, allowing it to circulate at high speed. However, the flow path inside the head downstream of the opening and closing valve does not allow circulation. As a result, slurries that settle quickly settle inside the head. For this reason, it is preferable to reduce the internal volume of the head and increase the flow rate. The present invention increases the flow rate and minimizes cavities by forming a narrow flow path with a thin plate. This makes it possible to solve the problem of precipitation by automatically discharging a small amount of slurry inside the head downstream of the opening and closing valve periodically with a solvent, etc., even when the line is stopped. It is also possible to discharge the slurry periodically before it settles.

Fluorine-based materials such as PTFE and PVDF are often used as binders for the slurry, especially for the positive electrodes of secondary batteries, in terms of durability, so solvents with high boiling points have generally been used. Drying has been carried out in huge drying ovens. One of the aims of the present invention is to make the drying process as short and small as possible.

In the present invention, it is possible to manufacture in a small space even with a high line speed for forming electrodes of conventional secondary batteries. And it is dried at the moment of application to the object or in the shortest possible time. To achieve this, the solvent is made easy to volatilize. In the present invention, in the positive electrode of an all-solid-state battery, an active material particle can be coated with a thin film of an electrolyte such as a sulfide-based electrolyte, for example, by dry mixing. Then, the coated core-shell particles can be dispersed in a solvent. A small amount of a binder such as short fibers or fine particles can be added to the solvent. A low boiling point solvent or a mixed solvent is preferable in terms of volatilization. Therefore, the solvent can be made to volatilize at the moment of application to the object. If a plurality of core-shell particles are aggregated into a powder of 10 to several tens of μm and made into a powder slurry, the solvent can be made to volatilize more easily. In this invention, regardless of the type of slurry, the flow path is divided into a thin comb shape, discharged from the opening, and the moment it is discharged, it is stretched with compressed gas into finer fibrous lines or divided fine particles, and at the moment of application, it is collided with a heated object with an impact, spreading the solvent together with it thinly, promoting the evaporation of the solvent and laminating a thin film, thereby achieving the purpose. Therefore, the flow rate can be restricted by making the flow path and opening long and thin enough not to be clogged with solid particles.
In addition, the fine particle application patterns from the liquid fluid openings of the nozzle assemblies may be overlapped on the object as much as possible by arranging a plurality of nozzle assemblies in the direction of movement of the object and overlapping each pattern to achieve a desired distribution.
In addition, in the present invention, a high-speed compressed gas is collided with a mixed flow of compressed gas that stretches or granulates the slurry, etc., from as close as possible, to form fine particles, thereby further increasing the surface area of the slurry particles. This further promotes the evaporation of the solvent and makes drying faster. By increasing the number of layers, a more uniform coating film can be formed. In addition, by colliding the slurry fine particles with speed energy with a heated object, the solvent contained in the slurry particles is crushed, the surface area is increased, and the evaporation of the solvent is promoted, and the adhesion can be increased as an ultra-dense structure such as solid particles. When the evaporation is promoted, the surface temperature of the object decreases due to the heat of vaporization of the solvent vapor, so it is important that the object is vacuum-adsorbed via a heated adsorption drum or heated adsorption belt and moved at the same time as being heated. The heating temperature can be selected from 50 to 180°C.

In the air spray method, a commercially available two-fluid spray, the liquid is atomized by stretching and colliding with compressed air, and the spray flow is applied to the target by spreading the pattern. However, it was common to spray with a relatively low viscosity. It was also not possible to manufacture spray nozzles with the same particle size distribution or spray pattern. For example, even if multiple nozzles were arranged in a horizontal row, it was not possible to obtain the same discharge amount, particle size, particle size distribution, spray pattern, etc. under the same setting conditions. Therefore, even when multiple relatively uniform nozzles selected from a large number of nozzles were lined up in a row and used, it was not possible to obtain a uniform coating, even if an experienced worker made adjustments.

The liquid or melt is stretched or torn into fibers or a particle stream by a compressed gas or a supercritical fluid such as recovered carbon dioxide gas. If further atomization is desired, another compressed gas can be collided with the particle stream at a close distance at a desired angle to atomize the material.
The distance between the opening of the liquid fluid and the object is preferably 60 mm or less, and more preferably 30 mm or less, so that the particles are impacted and collide with the object to adhere to it. Since the coating is performed with a nearly straight particle flow, this is advantageous in terms of improving the density of the coating film and the coating efficiency.

As described above, the impact of the fine particles on impact with the object is large, so the adhesion of the particles to the object interface can be improved. Also, the closer the particles move in a straight line, the narrower the movement angle, so the narrower the incident angle of the particles to the object, and the less reflected flow, which increases the coating efficiency.
The compressed gas may be from one flow path or opening, or from multiple flow paths or openings. Multiple compressed gas flows are effective in, for example, stretching a high-viscosity fluid so as to envelop it from the inner and outer periphery. The compressed gas can be mixed with fine particles of the solvent. In addition, the atomization can be further promoted by colliding the merging flows with compressed gas from another flow path at a close distance at a desired angle. If leveling of the coating is desired, at least one compressed gas can be mixed with fine solvent particles, or an independent opening can be used as a solvent flow.

The present invention is particularly suitable for applications to batteries such as secondary batteries including all-solid-state batteries, which require high speed, fuel cells, water electrolysis, and carbon dioxide gas electrolysis. In the case of secondary batteries, the fluid is selected from electrode active material particles, electrolytes, conductive assistants, conductive assistant dispersions, binder particles or short fibers, binder solutions, composite powders for secondary batteries, all-solid batteries, and semi-solid batteries, composite slurry for electrodes, solvents, compressed gases, and supercritical fluids, and the target object is selected from current collectors, electrode layers, separators, and electrolyte layers, and in particular the liquid fluid can be divided and sprayed.
In particular, separators moving at high speeds can be coated with a thin film of ceramic particles or electrolyte particles such as LLZ. For breathable separators, effective impregnation or coating with ceramic particles is possible when adsorbing with a roll or belt that adsorbs or heats the separator.

In addition, the compressed gas injected at the acute angle can be injected from a close distance, for example, 2 mm or less, before the speed energy decreases, to obtain the desired fine particles. The compressed gas outlet for collision may be round, rectangular, or slit nozzle-shaped, but is not limited thereto. However, a shim structure is more cost-effective, so a square or rectangular one is preferable. For example, a shim having a plurality of narrow or wide grooves may be sandwiched between the faces of a block or a plate and stacked to form a slit groove that is long in the length direction of the nozzle assembly with a flow path of about 100 micrometers in thickness. The slit groove may be a width that covers the openings of all the fluids, and each opening may be short, for example, 1 mm or less. In order to increase the collision energy by atomization, if the particles are collided at an acute angle from two directions, the particle distribution group after the collision moves at a narrow angle, and a high impact on the target object can be formed and a high density particle layer can be formed, thereby increasing the coating efficiency. On the other hand, if the angle is obtuse, the pattern can be widened, but the coating efficiency will be poor. Since the compressed gas expands adiabatically and the collision energy decreases as the distance increases, the distance until the collision is preferably a close distance, for example, within 5 mm, and more preferably within 2 mm, and it is preferable to collide as close as possible. The particle collision energy with the target is desirably from a narrow angle, for example an ejection angle of 30 degrees or less, more preferably 20 degrees or less, and collision from close range. After granulation, the distance between the targets is desirably 60 mm or less, more preferably 30 mm or less.
The supercritical fluid obtained from the recovered carbon dioxide can be made high pressure, about 9 MPa, so it can collide with high viscosity slurry at high speed, and after the collision, it is effective in promoting the evaporation of the high boiling point solvent contained in the slurry by azeotropy. The evaporated carbon dioxide can be recovered.

The target object can be a long object such as a film or foil, or it can be a sheet or a three-dimensional structure. It can be any size, shape, material, number, mass, etc., and can be silicon plates, glass plates, plastic films, etc. for next-generation solar cells. The fluid can be a supercritical fluid such as carbon dioxide gas made supercritical, compressed gas, gas-powder mixture, liquid fluid or paste, heated and molten material, etc., and fluids with solid content can be used for particle granulation, short fiber and web production in addition to film formation. Particles can also be directly applied to the target object.

Therefore, in addition to batteries, it can be used for capacitor manufacturing, multilayer ceramic capacitor manufacturing, and in the electronics, food, pharmaceutical, and chemical fields. It can also be used favorably for providing functional layers for fuel cells, secondary batteries, and all-solid-state batteries, forming electrodes and electrolyte layers, and forming functional films, power generation layers, and gas barrier layers for solar cells.

The present invention is particularly effective when you want to increase productivity, particularly in roll-to-roll or sheet-to-sheet processes, because it can handle a wide range of materials. It is also effective for composite materials that tend to separate even when mixed and dispersed, because it can be mixed and dispersed at the moment of application. Furthermore, when you want to form a thin, multi-layer coating layer, or when you want to mix even more different types of fluids, you can stack multiple nozzle assemblies (coating devices) in series in the direction of movement of the object.

The present invention can spread a fluid such as a liquid, convert it into fine particles as necessary, and apply it to an object in a coating pattern of fine particles of about 1 mm. A spray pattern of 1 mm or a desired size, for example 5 mm, can be applied to a desired width even on a wide object, for example a coating width of 1 m or more, by arranging the desired number of particles, for example 1,500 particles, in a row. A liquid fluid can be pattern coated from a pair of openings, and high-speed production can be achieved by moving the nozzle assembly, which uses a comb-shaped flow path for the wide liquid fluid, relative to the object.

The thin, narrow grooves or comb-like shapes of thin metal plates, for example, can be produced with high precision by exposure and etching. Fine comb-like shapes can be formed on thin plates such as ceramics using femtosecond laser processing, which is less affected by heat. The thin plate can be made of metal such as stainless steel (SUS), or it can be a ceramic or plastic plate. Therefore, the present invention can produce multiple grooves of the same structure simultaneously with high precision, and since the assembly has the same structure, individual variations in multiple flow paths and openings can be ignored. Therefore, there is no variation like with commercially available air spray nozzles, so almost the same particle ejection quality can be obtained even with a wide width, and coating quality can be maintained.

In the present invention, a combination of a plurality of fluids and a combination of a plurality of nozzle assemblies, and further, for example, a combination in which the on-off valve of a desired fluid is operated at high speed pulse, and individual conditions, such as the on-off or on-off time of each fluid, the pressure of each fluid, and the distance between the nozzle assembly and the target object, can be managed to obtain a composite distribution that cannot be obtained by ordinary mixing of a plurality of fluids. It can also handle slurries containing particles that cannot be obtained by inkjet and high viscosity liquids. Furthermore, by making high pressure compressed gas pressure or recovered carbon dioxide gas into a supercritical fluid and spraying it at high pressure, it is possible to generate fine particles even with high viscosity fluids. Furthermore, even in wide-area high-speed production, multiple fluids can be instantly mixed and applied outside the nozzle assembly. The present invention has the characteristic that the ratio of the flow rates of multiple different fluids and the thin film lamination of different mixed fluids can be easily and instantly changed by the above management. The flow rate can be changed by a method suitable for each, and any means may be used, such as a pressure type such as a pump, an electric volume type, or a pulse type in which an on-off valve is opened and closed at high speed. The lamination means is not limited.
The lamination may be performed by laminating the same liquid, or different types of liquids or powders may be laminated in thin films as required.

Conventionally, the slot die method was widely used when applying liquids such as electrode slurry to wide objects that move at high speed, such as secondary batteries. The boiling point of the solvent used to dissolve the binder in the slurry is high, so a method of heating the back roll to a high temperature is good. However, since the heated roll and the tip of the slot die are in contact with the object through a liquid film, the temperature changes and the tip of the slot die deforms, changing the gap, making it difficult to maintain a constant coating shape. On the other hand, the method of directly applying a thin film of catalyst ink to the electrolyte membrane of a fuel cell required a roll with a complex internal structure that combines both adsorption and heating functions, because the electrolyte membrane of about 10 micrometers instantly swells with the solvent. However, this heated adsorption roll had a fatal problem of deformation of the roll at high temperatures, even if the roundness was kept low at room temperature. Therefore, the gap between the electrolyte membrane and the slot die changed, making it impossible to form a thin film. The electrode layer of a perovskite solar cell also requires a nano-level thin film, and it was not possible to manage it accordingly. Therefore, although spraying with a wider gap is possible, the problem of wide-width compatibility and extremely low coating efficiency was a problem.

The present invention was made to solve these problems, and is capable of coating over a wide area and is compatible with the high speed movement speed of objects. It also prevents or makes it more difficult for slurry containing particles that are particularly prone to settling to settle in the flow paths following the circulation circuit. It creates a coating system that makes it easy to volatilize the solvent from the moment it is sprayed. It is also compatible with high production speeds. And when coating film performance is required for electrodes, etc., it forms an electrode layer with a high density of active material, etc.

For example, slurries containing particles of active materials are often used for electrode materials in batteries such as secondary batteries and all-solid-state batteries, and supercapacitors. The lower the viscosity of the slurry, the better it is suited for spraying. However, when the viscosity is low, particles with a high specific gravity in particular tend to settle in the flow path. For this reason, a method has been proposed in which the slurry is circulated through the flow path at high speed to prevent settling. However, even if settling can be prevented upstream of the opening and closing valve, settling occurs downstream of the opening and closing valve, causing the inside of the nozzle to become clogged. For example, in the case of a slurry using a ternary active material with a solid content of 40 percent or less by weight, when application is stopped, the particles inside the nozzle will settle within a few minutes, causing the nozzle to become clogged, even if the nozzle diameter is 0.3 mm.
Therefore, when production is stopped, it is necessary to constantly or automatically discharge a desired amount of slurry from the nozzle periodically.
In the present invention, the slurry has a high solid content and is less likely to settle, so that the slurry inside the nozzle is less likely to settle in a short time. In addition, the slurry, including the inside of the nozzle downstream of the opening and closing valve, can be pushed with the solvent and replaced with the solvent. At the start of production, production can be started simply by purging the solvent from the flow path after the opening and closing valve.

The present invention can be designed to push the slurry in the narrow flow path downstream of the opening and closing valve with a solvent flow from the upstream of the flow path.

The present invention is also effective for external mixing and coating of liquid fluids that react when two or more liquids come into contact or are mixed. Therefore, a solvent opening can be provided between the openings of the two liquids to prevent reaction near the openings after coating. The present invention can also be effectively applied to perovskite solar cells, in which two different liquids are layered or mixed and coated on an object to form a power generation layer. For perovskite solar cells, a method for accurately coating a thin film of a power generation layer liquid such as lead iodide, which has low viscosity, on an object has been required. Coating devices used include inkjet, slot die, and devices that apply surface tension to form a thin film with a constant gap. However, in all cases, it was necessary to control the gap between the object and the tip of the nozzle or the like to within a micron unit.
When the object is heated, the straightness of the coating head such as the slot die head changes slightly due to the heat, and the gap between the object also changes, making it extremely difficult to maintain the coating accuracy. The present invention can widen the gap to the object in a non-contact manner, and as described above, it is possible to coat a wide width of, for example, 1m or more, and can also handle high-speed production. In addition, the present invention can apply coating by impacting fine particles in a pulsed manner at high speed and colliding them with the object. Therefore, even if the silicon substrate has unevenness, such as a perovskite-on-silicon solar cell, it is possible to apply the fine particles in a thin film to the fine uneven surface by applying an impact in a pulsed manner to prevent air cushions. The particle size can be made finer than inkjet particles, and the number of particles per pulse in one opening can be several hundred times greater. In addition, up to 1,500 openings can be installed, so it has a high advantage in terms of high speed. On the other hand, when the electrode powder particles of about 5 to 70 μm used in the dry method are made into a powder slurry, it was impossible to do this with an inkjet. However, in the present invention, if the primary or aggregated particle diameter is less than 1/3 of the flow path, it can be handled without any problems.

In the present invention, a desired number of liquids can be merged and then granulated with compressed gas for application. The type of liquid can be one or more, for example, three or more. In addition, in the present invention, a solvent can be ejected from the openings around the liquid fluid having solids. At least one of a solvent, a plasticizer, a dispersant, and a surfactant can be selected and mixed into the compressed gas at the outermost opening as fine particles, and then ejected from the opening. In particular, the solvent attached to the liquid fluid opening has the effect of preventing the liquid fluid leading-edge opening from drying up.
The solvent may be a good solvent, a poor solvent, or a mixed solvent. In the case of a water-based liquid, water or a mixed solvent of water and alcohol may be used. In addition, the selected solvent or surfactant can be attached to the particulated liquid particles to support leveling after application to the target object.

In addition, the method of the present invention can be used to apply a liquid material containing a solvent or solids before or after applying a powder to an object.

As mentioned above, it is particularly effective for forming electrodes in secondary batteries including all-solid-state batteries, fuel cells and water electrolysis, forming electrodes in capacitors, applying functional films to secondary battery separators, forming electrolyte layers in all-solid-state batteries, power generation layers and moisture barrier functional films in perovskite and organic solar cells, etc.

1A and 1B are schematic cross-sectional and plan views of a nozzle assembly according to an embodiment of the present invention; 1 is a schematic cross-sectional view of a nozzle assembly according to an embodiment of the present invention. 5 is a schematic diagram showing the associated processes for machining each thin plate groove of the nozzle assembly according to the embodiment of the present invention. 4 is a schematic diagram of a fluid machining groove in a block of a nozzle assembly according to an embodiment of the present invention. 1 is a schematic cross-sectional view of a nozzle assembly according to an embodiment of the present invention.

The following describes a preferred embodiment of the present invention with reference to the drawings. Note that the following embodiment is merely one example to facilitate understanding of the invention, and does not exclude additions, substitutions, modifications, etc. that can be implemented by a person skilled in the art within the scope of the technical concept of the present invention.

FIG. 1 shows a schematic plan view and a schematic cross-sectional view of a fluid opening of a nozzle assembly. One or more elongated first grooves are formed from the middle of the first thin plate 1 to the end of one side of the thin plate. The thin plate may be polygonal, but is preferably rectangular. When there are one or several fluid grooves, a vertically long rectangular thin plate is preferable, and when there are many, for example, 100 or more, a horizontally long rectangular thin plate is preferable. A thin groove for the first fluid is formed from the middle of the rectangular first thin plate 1, and the groove connects to the end of a desired side. Second thin plates 2, 2' are laminated from both sides to form a first flow path 101 for the first fluid and a first opening 11 at the end. If a plurality of first grooves are formed, a plurality of first openings 11 can also be formed. The first groove becomes the first flow path 101, and the end of the first flow path 101 becomes the opening 11 for the first fluid. Furthermore, on both sides of the groove for the first fluid of the first thin plate 1, elongated grooves for the second fluid are formed, the length from the end being shorter than that of the groove for the first fluid. A groove is formed in two second thin plates 2, 2' at substantially the same position and shape as the second groove. A plurality of thin plates, for example, four, may be used. The second thin plate is aligned with the first thin plate and stacked on both sides of the first thin plate. The first elongated groove is formed such that the second thin plate becomes a wall 13, forming one or more flow paths for the first fluid and one or more openings 11 for the first fluid at the end of the thin plate. The first thin plate 1 and the second thin plate 2, 2' are aligned with each other, and a third thin plate 3, 3' is stacked on both sides. The third thin plate 3, 3' is formed with a groove of a width that connects to two grooves for the second fluid formed on either side of the first flow path of the first thin plate. The third thin plate 3, 3' is aligned with the second thin plate and stacked. A thin plate 4 or plate or block 5 is stacked by aligning it with the outside of the first, second, and third thin plates, and one or more flow paths and openings 11 for the first fluid, and a flow path 103 and opening 12 for the second fluid are formed on the outer periphery of the flow path 101 and opening of the first fluid, separated by a wall 13. The thin plate 4 can be omitted. The alignment means is not limited, but can be achieved, for example, by drilling holes in each thin plate and block and inserting knock pins. Usually, it is preferable to provide knock pins at two or more locations where they do not interfere with the flow paths. A flow path 116 is formed in the thin plates 2, 3, and 4 and the block 6 upstream of the flow path 101 of the first fluid, and is connected to an upstream opening/closing valve 126. A groove 120 is formed on the end face of the block on the thin plate side, and is formed to a width that allows the first fluid to spread to the multiple flow paths of the first fluid. In addition, a flow path connected to the flow path of the first fluid is formed at the same position of each thin plate. Similarly, a second fluid passage or groove is formed in the thin plate or block, and the second fluid opening 12 is connected to an upstream on-off valve 127 via a passage 117 .
Instead of forming grooves in the third thin plate, the grooves may be formed on the inside of the block 5, and the third thin plate and the fourth thin plate may be omitted.

In FIG. 2, openings 214 and 215 are provided on the outside of the block for blowing out another compressed gas, etc., in order to collide another compressed gas, etc. with the fluid blown out by the nozzle assembly in FIG. 1. The extension of the tapered surface of the blocks 25 and 26 is arranged to intersect with the extension line of the flow path 201 of the first fluid. The closer the distance to the intersection, the better, and it is desirable to set it within 2 mm, which is the smaller the deceleration of the compressed gas speed. The tapered surface of the block is preferably acute in order to improve the straightness of the particles, and a grooved thin plate 230 is fixed to a compressed gas block 240 to provide a compressed gas flow path 250. Although grooves may be machined in either block, grooves machined in the thin plate are more versatile because the flow rate, etc. can be changed by changing the thickness of the thin plate and the shape of the opening for the compressed gas. The grooves in the thin plate 230 may be one or more with the same width 214 as the opening 212 for the second fluid, or may be wide groove openings 215 that cover multiple openings for the first fluid.

In FIG. 3, one first thin plate 31, two second thin plates 32, and two third thin plates 33 are aligned and stacked to form a first flow path and an opening, and a plate, block, etc. (not shown) is stacked to form a second flow path and an opening around the first flow path.
The first thin plate 31 is formed with one or more elongated grooves 301 for a first fluid.
Then, flow paths for the second fluid are processed in the first thin plate, the second thin plate, and the third thin plate according to the number of thin grooves for the first fluid, and the second fluid openings can be formed around the first fluid openings by stacking thick plates or blocks (not shown) to separate them by walls. The number of the first and second openings can be selected from 1 to 1,500.

In FIG. 4, one block 46 is formed with a flow path 416 through which the first fluid, a liquid fluid, connects from a first opening/closing valve (not shown), and a groove 420 that connects to the elongated thin plate flow path. The cross section of the groove 420 is preferably semicircular as it provides less resistance and allows the flow of slurry, etc. to be smooth. Also, a flow path 417 for the second fluid, such as compressed gas, and a groove 430 that connects to the second fluid are formed. The other block is formed with a compressed gas flow path 417 for the second fluid, and a groove 430. The flow paths and grooves may be machined into a plate, such as a thick plate, instead of a block.

In FIG. 5, the opening surface for the first fluid formed by the thin plates 51, 52, and 52' protrudes from the tip end surface of the blocks 55 and 56. The thin plate 51 is formed with a groove 501 for the first fluid flow path, and the second thin plates 52 and 52' are stacked from both sides to form an opening for the first fluid. The first, second, and third thin plates with grooves for the second fluid opening around the first fluid opening are aligned with the blocks 55 and 56 to form a nozzle assembly. A flow path 520 connected to the first fluid groove 501 is formed in the block 56 and the thin plates 52 and 53 on one side. A flow path 530 connected to the second fluid groove 502 is also formed in the block 56. A similar flow path connected to the second fluid groove is also formed in the block on the other side. In the figure, the tip surfaces of the third thin plates 52 and 52' are at the same level as the tip surfaces of the blocks 55 and 56, but they may be at the position of the tip surfaces of the second thin plates or between them. Furthermore, a fourth thin plate with a flow path can be laminated on both sides of two third thin plates, so that the opening for the first fluid and all of the opening surfaces for the second fluid are protruded.

The present invention is suitable for a method of ejecting or mixing multiple fluids and spreading them downstream. For example, it can be used to granulate while forming particles, encapsulate multiple fluids, or shorten fibers. In addition, the desired fluids can be merged and applied to the target object alone, but the same or different liquid materials can be made into particles or fibers and applied in a pre-process and/or post-process in which a liquid fluid or a heated melt is extruded from a die head or the like or a powder is applied to the target object using a powder application device. Therefore, it is possible to manufacture granulated, encapsulated, or coated products not only in the fields of painting and adhesive application, but also in the food, pharmaceutical, and chemical fields. It is also suitable for the production of electrodes for fuel cells, water electrolysis, and CO2 electrolysis, secondary batteries including all-solid batteries and semi-solid batteries, electrodes for capacitors, electrolyte layers, and power generation layers for solar cells. And since it can increase productivity, it becomes possible to produce new energy-related general coating manufacturing processes with space-saving, energy-saving, low cost, and high quality.

1, 21, 31 First thin plate 2, 22, 32 Second thin plate 3, 23, 33 Third thin plate 5, 25, 45, 55 First block 6, 26, 46, 56 Second block 11, 211 First fluid opening 12, 212 Second fluid opening 13, 213 Wall 126, 216 First fluid opening/closing valve 127, 217 Second fluid opening/closing valve 101, 201 First flow path 103, 203 Second flow path 116, 416 First fluid supply flow path 117, 417 Second fluid supply flow path 120, 420 First fluid reservoir groove 130, 430 Second fluid reservoir groove 214 Second compressed gas opening 215 Second compressed gas opening 230 Second compressed gas thin plate 240 Second compressed gas block 270, 271 Second fluid opening part 301 First fluid groove 302, 312, 380 Second fluid groove 311 First fluid groove opening 312, 370, 371 Second fluid groove opening

Claims (10)

A method for spraying or applying a liquid fluid to an object, comprising the steps of: aligning and stacking a number of thin plates and plates or blocks each having a long and narrow groove for the fluid, forming a long and narrow flow path for the fluid and one or more openings for ejecting a first liquid fluid at the end of the thin plate; forming an ejection opening for a second fluid, compressed gas or compressed gas mixed with solvent particles, or a supercritical fluid, separated by a wall surrounding the opening for ejecting the liquid fluid; and forming the opening and long and narrow flow path for the first liquid fluid via an upstream flow path. A method for ejecting or applying a fluid, comprising the steps of: connecting the elongated flow path of the second fluid to a first opening/closing valve that opens and closes the supply of the first liquid fluid; connecting the elongated flow path of the second fluid to a second opening/closing valve that opens and closes the supply of the second fluid via an upstream flow path; and stretching the discharge flow from the opening of the first liquid fluid by opening the first and second opening/closing valves with a jet flow from the entire periphery of the jet of the second fluid, ejecting it as fibers or particles, or applying the ejected fibers or particles to an object. The liquid fluid ejection or coating method of claim 1, characterized in that the number of grooved thin plates is increased to make the number of fluids and openings three or more, the outermost openings are used as ejection ports for compressed gas or compressed gas containing solvent particles or supercritical fluid, the inside of which are used as openings for liquid fluid, and at least one of the openings for liquid fluid is used as an ejection port for the solvent. The fluid ejection or application method according to claim 1 or 2, characterized in that another compressed gas or compressed gas containing solvent fine particles is collided with the ejected liquid fluid jet at an acute angle and from a close distance to finely atomize the fibers or particles and eject them, or the finely atomized fibers or particles are applied to the target object. A method for manufacturing a secondary battery or an all-solid-state battery, characterized in that the first fluid is selected from a slurry having a solid content of 25 to 75 weight percent, a slurry for secondary battery electrodes, a slurry for all-solid-state battery electrodes, and a slurry for all-solid-state battery electrolyte, the second fluid is selected from a compressed gas or a mixture of solvent fine particles and compressed gas, or a supercritical fluid, the two fluids are joined, the first fluid is stretched by the second fluid or the slurry is granulated by collision energy, and the target is selected from a current collector, an electrolyte layer, an electrode layer, and a separator, and the target is coated with the slurry to form an electrode layer, an electrolyte layer, or a functional membrane layer. The method for manufacturing a secondary battery or an all-solid-state battery according to claim 3 or 4, characterized in that after the at least two fluids are joined, a step is added in which a compressed gas or a compressed gas mixed with solvent fine particles is collided with the joined fluid at an acute angle, and the finely-divided slurry is applied to an object selected from a heated current collector, an electrolyte layer, an electrode layer, and a separator to form an electrode layer, an electrolyte layer, or a functional film layer. The method for manufacturing a secondary battery or an all-solid-state battery according to claim 5, characterized in that the first fluid is selected from a slurry having a solid content of 50 to 85 weight percent, a slurry for secondary battery electrodes, a slurry for all-solid-state battery electrodes, and a slurry for all-solid-state battery electrolyte, the second fluid is a solvent, and the third fluid is a compressed gas or a supercritical fluid, the three fluids are joined, the slurry is granulated by the stretching or collision energy of the compressed gas or the supercritical fluid, and the particles are collided with compressed gas or compressed gas mixed with fine solvent particles at an acute angle of 30 degrees or less with respect to the ejection direction of the first fluid to atomize the slurry, and the fine particles are heated by impact and applied to a target selected from a collector, electrolyte layer, electrode layer, and separator to form an electrode layer, electrolyte layer, or functional film layer. A method for manufacturing solar cells in which a nozzle assembly that generates liquid particles and an object are moved relative to each other to apply liquid for a power generation layer or gas barrier layer in the form of particles, comprising the steps of manufacturing a nozzle assembly in which multiple thin plates and plates or blocks with elongated grooves are stacked on both sides and 1 to 1,500 openings for the second fluid are arranged separated by walls surrounding the openings for the first fluid, and the first fluid is a transparent conductive layer, power generation layer or gas barrier layer liquid, and the second fluid is a compressed gas or a supercritical fluid mixed with compressed gas or solvent particles, and the first fluid is stretched by the surrounding compressed gas or supercritical fluid to form fine particles, which are then applied to an object selected from a heated silicon solar cell layer, transparent glass for solar cells, and transparent plastic film to form a transparent conductive film layer, power generation layer, or gas barrier layer. The method for manufacturing a perovskite solar cell according to claim 7, characterized in that the solar cell is a perovskite solar cell or a perovskite-on-silicon tandem solar cell. A nozzle assembly for ejecting a liquid fluid, comprising: one or more elongated grooves for a first fluid extending from the middle of a first thin plate to an end of one side of the thin plate; elongated grooves for a second fluid located on both sides of the first fluid groove and shorter in length from the end than the first fluid groove; at least two second thin plates are stacked by aligning the first thin plate from both sides, and each of the at least two second thin plates has an elongated groove connected to a second flow path of the first thin plate; and a third thin plate has a second fluid groove at least as wide as the two ends of the multiple elongated grooves for the first fluid of the first thin plate, or a second fluid groove at least wider than the width between the centerlines of the elongated grooves for the second fluid located on both sides of the elongated groove for the first fluid of the first thin plate. A nozzle assembly characterized in that a fluid groove is formed, a second thin plate is aligned with the first thin plate at the center, and a third thin plate is aligned with the second thin plate at the center, and a flow path that connects to an elongated flow path of a selected fluid is formed in the second and third thin plates, and plates or blocks in which flow paths that connect to one or more elongated grooves for the first fluid and the second fluid are formed are stacked to form one or more elongated flow paths and openings for the first fluid, an opening for the second fluid is provided by separating the opening for the first fluid from a wall surrounding the opening for the first fluid, and the upstream of the opening for the first fluid is connected to an opening/closing valve that supplies the first fluid via the flow path, and the upstream of the opening for the second fluid is connected to an opening/closing valve that supplies the second fluid via the flow path. The nozzle assembly of claim 9, characterized in that a plate or block having grooves for a second fluid is aligned and overlaps the second thin plate from both sides in place of the third thin plate.

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