WO2022202316A1

WO2022202316A1 - Method for ejecting or applying fluid, and method for producing fuel cell or storage battery

Info

Publication number: WO2022202316A1
Application number: PCT/JP2022/010230
Authority: WO
Inventors: 正文松永
Original assignee: エムテックスマート株式会社
Priority date: 2021-03-22
Filing date: 2022-03-09
Publication date: 2022-09-29
Also published as: JP2022146545A

Abstract

A method for applying a liquid fluid to an object, the method comprising a step in which a liquid fluid in a first container among liquid fluids in at least two containers is pressurized, a step in which the liquid fluid is transferred to a second container through a first flow path that brings the at least two containers into communication with each other, and a step in which the liquid fluid in the second container is sucked and pressurized by means of a pump and is subsequently transferred and circulated to the first container through a second flow path. This method for applying a liquid fluid to an object is characterized in that: the levels of the liquid fluid in the first and second containers are managed by measuring the liquid fluid weights in the containers or the total weights of the containers including the liquid fluid; the viscosity of the liquid fluid is stabilized by repeating transfer or circulation between the containers by automatically switching the transfer direction of the liquid fluid; and the liquid fluid is applied to an object under stable conditions by measuring the transfer weight of the liquid fluid per unit time or the time per unit transfer weight.

Description

Fluid discharge or application method, fuel cell or storage battery manufacturing method

The present invention relates to the discharge and application of fluids such as liquid adhesives and coating agents, and in particular to the application and application of liquids and heated melts whose viscosity is lowered by heating, and slurry whose viscosity changes rapidly with changes in shear force. Regarding coating.

In the past, slurries tended to settle more easily when the viscosity was low, the specific gravity of the solid particles was high, and the particle size was large. Therefore, the slurry in the container is sucked in by a pump and pumped, and a large amount of slurry is moved in the downstream flow path to form a circulation circuit that circulates between the tank and the pump upstream. was applying. If you want to handle a small amount of slurry, etc., the method invented by the present inventors as in Reference 1 is used to pressurize the slurry in the syringe with a compressed gas in a coating device between two syringes and control the flow rate with a flow rate restricting member. While moving between a plurality of syringes, it was dispersed and applied to the object. For example, it can be pressurized with a compressed gas such as dehumidified compressed air or an inert gas such as nitrogen gas or argon gas, and furthermore, it can be mixed with a slurry to form a foam, so the present inventor can apply it to all solid-state battery sulfides. can be suitably applied to a slurry containing electrolyte particles of .

JP 2003-300000

An object of the present invention is to make the ejection weight or coating weight of liquid fluid such as slurry constant per unit time. "Per unit time" does not limit the required time unit such as milliseconds, seconds or minutes.
When the viscosity changes, the discharge weight changes even if the pressure is kept constant. Even if a positive displacement means, such as an electric spur gear pump or an electric plunger pump, was used, the coating film structure and surface state changed when the viscosity changed. Also, when the viscosity is low, the liquid fluid leaks from the sliding portion of the pump, making it difficult to secure a certain amount of volume. In particular, when the amount of the binder is small, the hard solid particles wear the gears and the like. Furthermore, when the viscosity changed to a low viscosity over time, it was impossible to move a certain amount and eject. In addition, when the dispersion state changed, the structure of the applied coating film changed. Therefore, in order to confirm the quality of the product during operation, it was necessary to numerically know whether the viscosity and dispersion state of the liquid fluid were uniform.

The basis for discharging or applying all liquid fluids is to stabilize the discharge or application weight by making the viscosity behavior of the liquid fluid as constant as possible.
In addition, application of a slurry or dispersion containing large and small solid particles, short fibers, etc. affects the performance of the coating film.

More specifically, the stable viscosity and stable dispersion state of the liquid material should be maintained at least during ejection or coating. In particular, in the case of a slurry containing solid particles, it is important when the fluid is likely to contain gas or bubbles, or when the gas is intentionally contained to form a foam. It was necessary to not only measure the viscosity and density using in-line measuring equipment, but also to manage them as a system. In particular, the effect can be further exhibited by combining with a method of indirectly measuring the coating amount by measuring the ejection weight at a desired timing, which is owned by the present inventor. It is even better to measure minute changes with a measuring instrument such as a viscometer or a density meter after the viscosity, behavior, and dispersion state of the liquid fluid are stabilized. By measuring the discharge weight and application weight in milliseconds by the method of the above-mentioned patent No. 5840959, etc., which the inventor of the present invention holds, the quality can be controlled in detail and in a timely manner. manufacturing becomes possible.

In the first place, solid particles with a high specific gravity that differ greatly in specific gravity, a solvent with a specific gravity of less than 1, and, if necessary, a binder or binder solution with a specific gravity of about 1 are mixed and dispersed to form a slurry. It was difficult to maintain a uniform dispersion state. Therefore, it was re-dispersed with a commercial stirrer or other dispersing device before the discharge operation. In the case of such a slurry, the amount of discharge and the amount of application cannot be stabilized only by the volumetric supply method or the method of keeping the pressure constant as the method of moving the slurry. For example, the specific gravity of the platinum fine particles in the electrode catalyst slurry of the fuel cell is 20 or more, the specific gravity of the carbon particles is about 2, the electrolyte solution of Nafion is about 1, and the alcoholic solvent is 1 or less. Especially porous carbon microparticles of several tens of nanometers carrying platinum nanoparticles are a typical slurry in which aggregates tend to aggregate and precipitate. Furthermore, when the solvent of the electrode slurry for fuel cells, etc., is a water-rich slurry, even if the static viscosity is high, the dynamic viscosity with the addition of a shearing force drops dramatically, and the discharge amount using a pressure-type moving means change was drastic. Even if a metering pump, such as a gear pump, is used, the viscosity becomes low and the problem of sealing cannot be solved. Moreover, the coating state of the electrode changes microscopically during the dynamic viscosity change, resulting in an unstable quality state.

In addition, when a liquid such as carbon slurry containing a binder with strong adhesion that easily sticks to the walls of two small containers such as a syringe moves up and down in the syringe, the level of light emitted and received at the detection position of the fiber laser sensor at the lower end of the container is detected. was difficult and malfunctioned. Therefore, the inventors have devised a method of setting the desired slurry pressurization time to switch the liquid movement in the two syringes. However, in long-term operation in units of time, if the minimum unit of time is 100 milliseconds, even a slight change in the flow path will gradually change the slurry liquid level over time, and the pressurized gas in one of the containers will flow backwards, which is fatal. I had a problem. Therefore, the present inventors made it possible to adjust the minimum unit of the pressurization time of the two syringes in units of 10 milliseconds or less, or even 1 millisecond or less. Then, it was confirmed that there was no change in the liquid surface level or circulation by running it for at least 10 minutes in advance with a solvent such as water. Therefore, even if the pressurization time in the two separate containers is slightly different, the accuracy of the flow path should be kept within 5%, if possible, 1% or less, in order to stabilize the discharge weight. should be improved. On the other hand, it was possible to detect the liquid level by making it fluid enough not to stick to the side wall of the syringe, but it was necessary to make the solid content extremely low. Therefore, particles containing a large amount of solid particles having a high specific gravity were particularly precipitated. In addition, in order to increase the flow rate of the slurry in the two containers in order to prevent sedimentation with low viscosity slurry, when pressurizing with a relatively high compressed gas pressure, for example, about 50 KPa to 300 KPa or more, when switching slurry between containers At the bottom of the container, the liquid surface is turbulent and turbulent flow is generated, and compressed gas is mixed in, and bubbles are generated in the slurry. There were also changing challenges.

Slurries that tend to stick to walls generally tended to have a high ratio of binder.
Further, in the electrode catalyst slurry of the fuel cell, it is not necessary to increase the ionomer ratio unduly, but if it is increased, not only the cost increases but also the cohesive force is strong and it is difficult to spray and fine particles. In addition, it has been necessary to increase the solvent content of the high-molecular-weight polymer-based binder for the electrode slurry of the storage battery to achieve the desired low-solid slurry with low viscosity. On the other hand, if the viscosity is low, it is difficult to achieve a perfect seal when transferring a constant amount continuously with an electric positive displacement pump such as a spur gear pump or snake pump.
This adversely affects the discharge amount in milliseconds, which is important in forming a desired electrode structure, for example, in a pulsed spray method. On the other hand, even if a plunger pump with good sealing, such as a multi-plunger pump, is used, the pulsation at the switching of each plunger is large. Because it was avoided, the equipment configuration became complicated and the advantage of the positive displacement type was lost. On the other hand, in a production line such as a roll-to-roll line, it is necessary to move a large amount of liquid such as slurry, and the container for filling the liquid and the device for moving the fluid have been enlarged.

Therefore, if a large-sized apparatus is used, the initial investment and a large amount of materials are wasted especially for trial production, such as granulation and encapsulation of reagents, for table test materials for initial performance confirmation of functional materials. In addition, slurries that use platinum catalysts such as fuel cells are expensive, and slurries that are diluted with a solvent and have a low solid content have a short shelf life of about one day, so unused electrode catalysts are discarded. This has led to a huge cost loss. Therefore, a method of manually or automatically mixing a relatively high-viscosity stock solution and a solvent or the like in a coating system at the work site has been sought. There is also a method of reducing the filling amount and filling in small amounts, but with the general method, the viscosity behavior of the slurry could not be confirmed.
When selecting a slurry with a particularly water-rich solvent in the fuel cell catalyst slurry, even when used at room temperature, the viscosity change due to shear stress tends to occur more rapidly than with an alcohol-based solvent-rich slurry. It was necessary to use it in a stable viscosity range by sufficiently dispersing it by circulating it. Therefore, the platinum catalyst slurry remaining in the tank or in the flow path after the coating operation of a large amount of the catalyst slurry had to be discarded.

Roll coating, screen printing, etc. also required a large amount of electrode slurry at one time. It was necessary to make the coating performance constant as well as the coating weight stability per hit. Therefore, it was necessary to stir a large amount of slurry in a large container or circulate the flow path with a pump or the like to sufficiently disperse the slurry and stabilize the viscosity before use. However, there was also the problem of a large amount of slurry being discarded after the work was completed. A recycling system has been established for precious metals such as platinum catalyst slurries and residues, but the recycling costs are high, and in any case, this leads to a large amount of waste in terms of cost.

Electrode formation of fuel cells Especially at the cathode electrode, hydrogen ions and oxygen ions are brought into contact efficiently, and for efficient discharge of the generated water, it is important to construct micropores, mesopores, and macropores as desired. In particular, there are increasing reports that the electrode performance is high by forming with a pulsed spray with an impact. However, in liquid film application using a slot nozzle, attempts have been made to use a foaming agent to leave bubbles on the electrode film, but the foaming agent has an adverse effect on performance, and the electrode structure cannot be formed as intended. rice field.

The present invention has been devised in view of the above-mentioned problems, and is particularly suitable for fluids such as heated solutions, heated melts, slurries, etc., which are affected by changes in the discharge amount due to changes in viscosity. In particular, the sedimentation of slurry for electrodes such as batteries and capacitors is prevented. It is to stabilize the discharge weight and application weight and distribution of the slurry discharged by the discharge device by keeping the viscosity as constant as possible so as to approach the target value in a short time.

Therefore, in order to solve these problems, the present invention manages the weight per unit time of the liquid fluid moving between at least two containers, or the time required per unit weight, and discharges it when those values are stabilized. Or to start the application work. Furthermore, it is to shorten those times as much as possible.

A further object of the present invention is to provide a fluid ejection or application method that suitably disperses fluids such as slurries and dispersions that tend to settle or that have problems in dispersion, and stabilize the ejection amount and application amount. In addition, the structure of electrodes, etc., where battery materials, especially fuel cell electrode slurries using expensive materials such as platinum catalysts, capacitor electrode slurries, electrode slurries for secondary batteries and all-solid-state batteries, electrolyte slurries, etc. are desired. Alternatively, the object is to provide a method of manufacturing a fuel cell or a method of manufacturing a storage battery by forming a film thickness.

The present invention alternately pressurizes the liquid fluid in at least two containers or constantly pressurizes the liquid fluid in one container to move or circulate the fluid flow path communicating between the at least two containers, A method for discharging or applying a fluid to an object with a discharge device communicating with the flow path, wherein the liquid fluid in the first container is pressurized to generate a differential pressure between the first container and the second container. and pressurizing the fluid in the second container to create a differential pressure between the first container and the first flow channel or other transferring or circulating the liquid fluid to the first container through the flow channel, and measuring the weight of the liquid fluid in the first and second containers or the total weight of the entire container containing the liquid fluid in the container; setting at least one transfer switching level of the fluid in the container to automatically control the transfer or circulation of the fluid to the first and second containers; and a discharge communicating with the flow path. Disclosed is a method for ejecting or applying a fluid, comprising a step of ejecting or applying the fluid to an object using an apparatus or an application apparatus.

The timing of movement switching or circulation of the liquid fluid of the present invention is controlled by measuring the weight of at least the upper and lower limits of the fluid in the container or the total weight of the entire container containing the fluid, and the unit of the fluid in at least one of the containers Provided is a method for ejecting or applying a fluid, characterized in that ejection or application of the fluid is started when the movement time per weight or the weight per unit movement time reaches a set value range.

The liquid fluid in said at least two containers of the present invention is at least one of slurry, heated liquid, and heated melt, and the fluid in said at least one container is directly pressurized or indirectly pressurized by compressed gas. A balance feed method of liquid fluid and compressed gas by pressure is used, the weight of the fluid moved per unit time or the time of movement per unit weight of the fluid is controlled, and when the weight or time reaches within the set value range, the fluid is discharged. Disclosed is a method of ejecting or applying a fluid characterized by initiating ejection or application.

Provided is a method for discharging or applying a fluid characterized by providing at least one further flow path between the first container and the second container in addition to the flow path of the present invention to accelerate movement of the fluid. do.

The electrode slurry in at least two containers of the present invention is alternately pressurized or the electrode slurry in one container is constantly pressurized to move or circulate in the electrode slurry channel communicating between the at least two containers. a method for manufacturing a fuel cell or a storage battery by applying the electrode slurry to an object using an applicator communicating with the flow path and drying the object to form an electrode, wherein the electrode slurry in the first container is pressurized. creating a differential pressure between the slurry and the second container to transfer the electrode slurry to the second container through at least the first flow path; and moving or circulating to the first container via the first channel or another channel by creating a differential pressure between and, the weight of the electrode slurry in the first and second containers or The total weight of the entire vessel containing the in-vessel electrode slurry is measured, and at least the lower limit level of the in-vessel electrode slurry is controlled to automatically move or circulate the electrode slurry to the first and second vessels. and applying the fluid to the object with an application device communicating with the flow path.

The present invention comprises the steps of: pressurizing a liquid fluid in a first container of liquid fluid in at least two containers; moving to a container, sucking and pressurizing the fluid in the second container with a pump, moving it to the first container via a second flow path, and circulating the fluid; measuring and managing the level of the fluid by the weight of the liquid fluid or the total weight of the container containing the liquid fluid, controlling the fluid movement timing of the first container or the second container; Disclosed is a fluid ejection method or application method characterized by ejecting or applying a fluid to an object using an apparatus or an application apparatus.

The timing of movement switching or circulation of the liquid fluid of the present invention is controlled by measuring the weight of at least the upper limit or lower limit of the liquid fluid in the container or the total weight of the entire container containing the liquid fluid, and at least one of the fluids in the container Discharging or applying a fluid is started when the movement time per unit weight or the weight per unit movement time reaches a set value range.

The liquid fluid in the at least two containers of the present invention is at least one of slurry, heated liquid, and hot melt, and the liquid fluid in the at least one container is directly pressurized by compressed gas or indirectly pressurized by compressed gas. A balance field pressurization method by pressurization is used, and the liquid fluid in another container is pumped by a pump, the weight of the fluid transferred per unit time or the transfer time per unit weight of the fluid is controlled, and the weight or time is controlled. Disclosed is a fluid ejection method or application method characterized by starting fluid ejection or application when a set value is reached.

A fluid characterized by providing at least one liquid fluid channel between the first container and the second container separately from the liquid fluid channel of the present invention to accelerate the movement of the liquid fluid. To provide a method of discharging or applying a

The present invention is a method of manufacturing a fuel cell or a storage battery, comprising a step of pressurizing the electrode slurry in a first container of the battery electrode slurries in at least two containers; a step of moving the electrode slurry in the second container to a second container via a first channel that communicates between the two containers; measuring and managing the levels of the electrode slurries in the first and second containers by the weight of the electrode slurries in the containers or the total weight of the container containing the electrode slurries; A fuel cell or a storage battery characterized by comprising: a step of controlling the movement timing of the electrode slurry in the second container; A manufacturing method is provided.

The present invention is particularly effective for quality control of the electrode formation of fuel cells, the electrode formation of storage batteries and capacitors, the electrode formation of solar cells, etc., in which slurry, dispersion, etc. are applied during electrode formation. According to this method, stable application timing can be controlled and a stable application amount can be ensured for a slurry or dispersion containing solid particles or short fibers whose viscosity changes with the level of shear force or with time.

The inventor of the present invention can also heat the liquid containing the resin component to lower the viscosity, or control the viscosity of the heated melt that flows in a liquid state and discharge or apply it. In addition, as a manufacturing method for applying to an object to complete the object, the object is also targeted. For example, it includes a fuel cell, a storage battery such as a secondary battery, a capacitor, a solar cell, etc., which are products manufactured by applying an electrode slurry to form electrodes.

The ejection method of the present invention includes ejection methods such as slot nozzles and sprays, and coating methods, and includes granulation, encapsulation, and the like. Moreover, the application means and the object are not limited. Therefore, it can be applied to a wide range of fields, such as pharmaceuticals, foods, fertilizers, chemicals, semiconductors, electronics, and energy fields, as well as to manufacturing methods for such products.
Liquid fluids include paraffin waxes, hot-melt resins, and adhesives that are solid at room temperature or pastes that melt into liquids when heated.Moisture-curing type polyurethane hot-melt (PUR) systems, etc. In the present invention, any material that contains a resin that reacts with , and is in a liquid state at the time of application, such as a melted material such as a low-viscosity, low-melting metal, can be suitably used in the present invention. In that case, it is necessary to heat at least the portion where the hot melt comes into contact. Hereinafter, in the present invention, a material that can flow and be discharged during discharge, including a melt, is treated as a liquid fluid. The means for ejecting or applying the liquid or the like of the present invention includes a slot nozzle, and ejects or ejects desired droplets from a nozzle or the like, which is an ejection port of the liquid, such as an inkjet or a dispenser, and granulates drugs, foods, fertilizers, and the like. It may be attached to the object including ejection such as spray for encapsulation. The present invention also includes a spray-drying method such as a method of trapping spray particles falling into a fluidized bed of an air-powder mixture in a full-size bed that blows hot air or the like. Particles are generated by inkjets, dispensers, methods and devices that spray droplets of these droplets with ultrasonic waves, compressed air or inert gas, etc. to make them finer, airless sprays, two-fluid sprays, rotary atomization methods, etc. It does not matter what means of transformation. In addition to the above, coating devices include multi-spray nozzles such as meltblown sprays, multi-head sprays, and slit nozzles, regardless of whether they are continuous sprays or pulsed sprays. Furthermore, the present inventors can also use a method in which fine particles are generated by a fine particle generator and moved by a carrier gas or the like to be applied, and the fine particles can be wet or dried and conveyed inside a pipe or the like. The fine particles can be electrostatically charged regardless of whether wet or dry, and can be applied locally or over a wide area to an object such as an object to be coated. Furthermore, it can be applied or formed into a film by introducing it into a vacuum and colliding it with an object. Alternatively, dispersion coating can be performed in which the particles are sparsely distributed in a plane. Furthermore, if wet fine particles are combined on an object and laminated as necessary to form a planar thin film, high-speed production can be achieved. The present inventor collides a spray flow against a rotating object such as a belt or a roll at a close distance, or generates ultrafine particles by bubbling or the like. Submicron or less ultrafine particles are transported directly or by carrier gas, etc., and selected at least one additional means such as static electricity, magnetic force, dew condensation, or guiding under vacuum, and continuously or pulse-dispersed coating on the object. Alternatively, a method of laminating a thin film or forming a film using one or more types of liquid fluids may be employed. The object may be coated in advance with liquid containing solid content, powder, or the like, or may be formed into a film. By performing the movement of the spray or the carrier gas in a pulsing manner, it is possible to more efficiently coat the uneven part of the object, in particular. In particular, the present invention is effective in handling and applying dispersions and slurries containing particles and short fibers, and is therefore effective in forming electrodes for fuel cells, storage batteries including all-solid-state batteries, capacitors, solar cells, and the like. Alternatively, the present invention also includes micro-curtain coating in which a desired liquid film is formed by spraying from an airless spray nozzle at a relatively low pressure of about 200 to 600 kPa, and the liquid film is applied to an object. In addition, dot-like or elongated line-like bead coating may be performed by an ink jet or a dispenser nozzle, and compressed gas may be sprayed onto the bead to further fine particles for coating. A slot nozzle for performing continuous or intermittent surface coating of a desired pattern on an object that moves continuously or intermittently is capable of high-speed processing.
Furthermore, the present inventors have proposed a lamination coating method using a slot nozzle having a plurality of discharge ports or a plurality of slot nozzles using one or more kinds of liquid fluids, and a lamination coating method combining a slot nozzle and a particle applicator. can be suitably used for electrode formation of batteries, for example, electrode formation of fuel cells, capacitors, storage batteries, solar cells, and the like, and electrolyte layer formation of all-solid-state batteries.

Since the present invention can solve these problems, it is particularly effective for quality control of the electrode formation of fuel cells, the electrode formation of storage batteries and capacitors, the electrode formation of solar cells, etc., in which slurry, dispersion, etc. are applied during electrode formation. be. According to this method, stable application timing can be controlled and a stable application amount can be ensured for a slurry or dispersion containing solid particles or short fibers whose viscosity changes with the level of shear force or with time.
Alternatively, according to the method of the present invention, the viscosity of the liquid containing the resin is heated to lower the viscosity, or the viscosity of the wetted part of the system including the flow path of the heated melt that flows in a liquid state by heating is controlled, In particular, the viscosity can be stabilized at the time of ejection or application. Further, in the present invention, the object is the object as well as the production method for completing the object by applying it to the object. For example, it includes a fuel cell, a storage battery such as a secondary battery, a capacitor, a solar cell, etc., which are products manufactured by applying an electrode slurry to form an electrode, etc., and furthermore, it is effective in manufacturing methods thereof. The discharge method of the present invention includes ejection methods such as slot nozzles and sprays, and includes at least partial coating of particles such as granulation and encapsulation. Moreover, the application means and the object are not limited. Therefore, it can be applied to a wide range of fields, such as pharmaceuticals, foods, fertilizers, chemicals, semiconductors, electronics, and energy fields, as well as to manufacturing methods for such products.

In addition, the present inventors have found that nitrogen gas, which is in the region of inexpensive air and inert gases, and especially the extremely low humidity, such as negative dew point, that is essential for all-solid battery electrode slurry and electrolyte layer slurry using sulfide-based electrolytes. A gas fluid containing air up to about 90° C., argon gas, nitrogen gas, or argon gas mixed with other gases can be mixed with these to form a foam and applied using a slot nozzle or spray. Regardless of whether foaming is applied or not, the present inventors can combine slot nozzles and sprays as necessary to apply to desired fuel cells and storage batteries. can. This method is particularly effective in forming electrodes for fuel cells, which has both improved performance and improved production speed. Of course, other methods, such as spraying, can also be selected in the present invention as means for forming and applying. In particular, foaming is effective not only for forming a porous coating film, but also for preventing sedimentation and supporting dispersion of slurries such as electrodes of fuel cells, storage batteries, supercapacitors, etc., and is particularly effective for dispersing ultrafine particles in the slurry. . Dehumidified air, dehumidified nitrogen gas, dehumidified argon gas, etc. should be selected when foaming slurry using sulfide-based electrolyte particles for the electrolyte layer and electrodes of storage batteries, particularly all-solid-state batteries.

In addition, as described above, in order to waste valuable and expensive materials such as fuel cell electrode catalysts, for example, the volume of the liquid contacting flow path of the electrode catalyst slurry is made as small as possible, and even in the production line, the minimum required amount is small. A filling method was desired. Therefore, in order to reduce the amount of waste after use of fuel cells, etc., the inner diameter of the flow path such as PTFE, PFA, or stainless steel is 6 mm or less, or even 4 mm or less, and the viscosity of the liquid material such as slurry is about 50 mPa s. may be about 2 mm, and it is important to make the length as short as possible, such as 300 mm or 2 m. Even if there is an R to R production equipment, even if the internal volume of a container such as a tank is 10 liters or more, the shape, especially the bottom of the container, should be a sharp conical structure with an acute angle of 60 degrees or less, or even 30 degrees or less. It is important to make the cylindrical part thin and long so that even a small amount of liquid can be finally discharged while moving or circulating in the channel.

Therefore, in the present invention, the remaining amount of catalyst ink in two containers, for example, a fuel cell, can be reduced to 100 ml or less even in a large container, and even in the case of a small container, such as a 70 ml syringe, the residual amount can be reduced to 5 ml or less. Furthermore, in the present invention, a small amount of residual slurry can be further diluted with a solvent and applied while moving between containers so that the slurry does not settle, and the catalyst can be almost used up.

As mentioned above, vinylidene fluoride (PVDF) is often used as a binder for storage batteries, which are secondary batteries such as lithium ion batteries, and only limited high boiling point solvents such as normal methylpyrrolidone (NMP) and DMF can be used to dissolve it. become. As a result, the drying time after application of the electrode slurry or the like becomes long, and when a thick film is formed, cracks occur. In the present invention, the binder can be encapsulated in a thin film in the active material particles or the like, or can be partially adhered in a minute amount and granulated. The active material, electrolyte particles and the like granulated by this method can be handled and applied even as powder. For the application, it is convenient to use Japanese Patent No. 6328104 and Japanese Patent No. 6481154 which the present inventor invented and has the right to apply. When applied as a powder, a film can be formed by a hot press after application.
Furthermore, in the present invention, a solvent such as normal heptane having a relatively low boiling point and a high evaporation speed is added to form a slurry, or a desired material such as a conductive aid is added to form a slurry, which is coated and dried quickly to achieve a desired film thickness. can do.

For n-heptane, which is a particularly poor solvent with a low boiling point for PVDF, etc., the outlet of another automatic opening and closing discharge device is connected to the slurry discharge device or nozzle to make the mixing part a small cavity or to instantaneously mix and disperse in the air. can be applied.
Either method can be adopted by the present inventors, and it can also be used as a method that can solve the problem of extending the shelf life of the catalyst electrode ink when adding a solvent to the original electrode slurry of the fuel cell to reduce the solid content. In addition, the latter is used for storage batteries in general that use binders such as PVDF, which can only be dissolved in solvents with a limited high boiling point such as NMP, especially for the electrode formation of all-solid-state batteries and the formation of electrolyte layers. A solvent such as normal heptane can be preferably used to increase the evaporation rate of the entire slurry.
Furthermore, by heating the object and laminating thin films, the dry formation of the slurry can be done densely and quickly, so that the desired electrodes can be formed.
In addition, the active material and the fine binder particles can be thin-layered by separate handling devices as in the case of powder lamination, and the desired electrodes can be formed by making separate slurries or by mixing them into slurries. Furthermore, it is also possible to add a suitable amount of fine particle binder to a slurry containing active material particles and a small amount of binder solution to prepare a slurry having a low cohesive force and apply the slurry.

In the present invention, in order to disperse the slurry better, it is possible to disperse with a dispersing device installed in a simple flow path, a static mixer, or the like. Although the dispersion device is not limited, for example, a net (screen) made of SUS of up to about 300 mesh is provided in one or more channels, and the slurry, etc. is moved or circulated and passed through it to break up aggregates in the slurry, etc. Ideally. can be distributed easily. Dispersion may be carried out by a static mixer, or by mixing and dispersing by a dynamic mixer which stirs by power such as a motor. Further, according to the invention of the present inventor, for example, collisional mixing or The device itself can be made small or very small by using a dispersion method based on collision dispersion.

Such a small device is effective in reducing the solid content at the tip of the device such as the discharge device (head) or nozzle, and mixes solvent or solvent-rich fluid during discharge such as electrode slurry spray of fuel cells. It can be sprayed on its own or mixed with a compressed gas. Furthermore, normal heptane, which has a lower boiling point than a new solvent such as NMP, can be mixed at the tip or mixed with compressed gas and sprayed before applying the electrode slurry of the storage battery. In the case of a fuel cell electrode catalyst slurry with a viscosity of 100 mPa s or less, if the slurry pressure is about 150 KPa or less and the flow rate is about 1000 ml/min or less, at least one sheet of wire mesh such as SUS with up to about 300 mesh is used as described above. If necessary, a large aggregate can be finely divided by moving or circulating the slurry at least once or multiple times with a plurality of sheets from upstream to downstream, sequentially decreasing the opening and decreasing the wire diameter. A filtration area of about 1 to 100 square centimeters is sufficient, and a simple filter and dispersing device can be obtained by simply setting a sheet of punching metal for reinforcement downstream of the wire mesh.

In the present invention, it is generally desirable that the small container or container has a volume of 50 ml to 15 liters. Of course, it may be 15 liters or more, and may be 50 ml or less or 20 ml or less.
When the volume of the container exceeds 200 ml and the viscosity is 500 mPa·s or less, the flow velocity of the slurry or the like may be increased by setting the average inner diameter of the piping such as the PFA tube to the coating head to 4 mm or less, preferably 2.5 mm or less. Apart from that, the channel between the containers may be as long as 6 meters, for example, due to the structure of the device, but if possible, it should be as close as possible, preferably within 1 meter, especially within 300 mm for small containers. If the liquid filling volume in at least one container exceeds 2 liters, a tube with an average inner diameter of at least 4 mm between the two containers, preferably with an inner diameter of 6 mm, if the liquid filling volume in the container exceeds 5 liters. A large amount of slurry in the connecting tank is moved by piping such as the above tubes to prevent precipitation of the slurry, and the viscosity of the slurry is reduced in a short time by the shear force of the slurry, so that the coating work can be performed in a stable range where the viscosity width is desired. It is important to The slurry in the container may be stirred with a stirring device such as a propeller. These tubes can have a large inner diameter separately from the piping of the discharge device, and the tube piping to the discharge device or the like may be one, or a plurality of smaller diameter piping means may be used. The confluence portion may have a structure capable of dispersing collisions. Also, other dispersing means or flow rate adjusting means may be provided in the path.

Furthermore, the flow path to the discharge device is not particularly limited, but it may be from the top of the container in consideration of the case of removing and cleaning the dispersing device installed in the pipe such as a tube that is the flow path. A channel for increasing the amount of movement of the liquid can be separately provided without being limited to the upper portion and the lower portion of the container. A single channel or a plurality of channels may be provided between containers, and one channel may be further branched to form a plurality of channels. Also, if the diameter of the flow path is small, it may be shortened, and the average diameter may be larger than that of the flow path provided in the discharge device, for example, twice or three times. .

In the present invention, two or more containers may be used, and two or more discharge devices may be used. Furthermore, it is possible to use a plurality of systems such as circulation by using a plurality of liquid fluids of different types. Whether or not the present invention is used to take advantage of this feature, the present inventors are able to stack different materials to form a desired electrode structure, for example, alternately layering thin films to achieve a desired mixed and dispersed application. . Alternatively, different types of liquid fluids can be mixed downstream of the ejection head and ejected, or can be applied while being impinged and mixed inside or outside the nozzle. Therefore, for example, the structure of the fuel cell electrode can be made up of a plurality of layers having different ionomer ratios and catalyst loading ratios such as platinum. For example, it is possible to increase the ratio of ionomer such as Nafion only on the electrode interface or surface of the transfer film compared to the internal porous structure, so that even the thermocompression transfer method can improve adhesion and improve performance in high-speed production. Further, for example, in an all-solid-state battery, it is possible to accurately and easily perform a tilting method in which layers are laminated continuously or stepwise while changing the ratio of the active material and the electrolyte. For example, the active material and the conductive agent of the storage battery can be uniformly mixed and dispersed by using separate circulation systems or the like.

To summarize the above, in order to improve the dispersion of the liquid by increasing the speed in the liquid flow path and the container, and furthermore, to prevent the sedimentation of the liquid such as slurry in the container, the flow rate is higher than that of the flow path such as the discharge device, preferably By installing a pipe such as a tube with a large diameter or a short length, the flow rate per unit time of a liquid such as slurry can be increased and dispersion can be improved. When the viscosity of the liquid fluid is low, eg, 100 mPa·s or less, and the pressure of the liquid fluid is relatively high, eg, 150 KPa or more, the inner diameter of the tube may be 6 mm or less, or 4 mm or less. 1.5 mm may be sufficient. By reducing the distance between the containers, for example, within 1 m, the inner diameter of the tube can be reduced, leading to a reduction in the amount of final waste liquid such as fuel cell electrode slurry.

As described above, for example, materials for medical research, electrode slurries for fuel cells, next-generation secondary batteries that are storage batteries, such as all-solid battery electrode slurries, etc. It is possible to handle slurries, etc., and discharge and apply with stable viscosity, so high-performance and high-quality products can be manufactured. In other words, it is possible to visualize the kinematic viscosity by confirming the change in the moving weight per unit time or the amount of change in time per unit weight, especially slurry, etc., and can perform the work such as coating in a stable area while measuring them. . Furthermore, sedimentation of slurry particles, which is the original purpose, can be reliably prevented. In addition, the present invention makes it possible to check not only changes in viscosity in the apparatus over time but also entrapment of bubbles and inclusion of bubbles in the slurry to be filled.

1 is a schematic cross-sectional view of a container and system fitted with a liquid flow path and weight measurement communicating with a dispensing device between at least two containers according to an embodiment of the invention; FIG. FIG. 4 is a schematic cross-sectional view of managing the upper limit and the lower surface level by weight measurement according to the embodiment of the present invention. 1 is a schematic cross-sectional view of pressurizing a liquid fluid with a compressed gas via a piston (plunger) according to an embodiment of the present invention; FIG. 1 is a table showing the relationship between viscosity and shear force, showing the viscosity behavior peculiar to slurry that changes from static viscosity to dynamic viscosity according to the embodiment of the present invention. FIG. 5 is a schematic cross-sectional view of a flow path provided for increasing the flow rate of movement separately from the discharge device flow path that connects via the upper portions of the two containers according to the embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of forming a circulation circuit with a discharge channel and a channel moved by a pump according to the embodiment of the present invention, and forming another channel for further increasing the amount of movement.

A preferred embodiment of the present invention will be described below with reference to the drawings. It should be noted that the following embodiments are merely examples for facilitating understanding of the invention, and exclude additions, replacements, modifications, etc. that can be implemented by those skilled in the art without departing from the technical idea of the invention. not a thing

The drawings schematically show preferred embodiments of the present invention.

In FIG. 1, a first container 1 is connected to a second container 2 via a discharge device 8 which is connected by a liquid fluid channel 7 and further via a liquid fluid channel 7'. The upper portions of the first and second containers are connected to the respective containers via

regulators

103 and 104 for compressed gas such as compressed air, nitrogen gas and argon gas, and

automatic switching valves

101 and 102 . The

containers

1 and 2 are fixed by struts 9 and 9', and weight scales (scales) 5 and 6 can measure the total weight of the

liquid fluids

3 and 4 or the total weight of the container containing the liquid fluid. The weighing scale may employ an inexpensive load cell to form the desired shape of the measuring device.
The transfer of liquid fluid between containers can be switched at a preset desired weight of liquid fluid in each container. The sharper the angle of the cone at the bottom of the container, the thinner and longer the shape, and the thinner and shorter the diameter of the liquid fluid channel, the less liquid fluid can be discarded after the end of the work. Effective for cell catalyst slurry and the like.
In the present invention, the slurry remaining in the liquid fluid channel is filled with a solvent, diluted to a desired solid content, moved through the channel, dispersed, and applied to an object, so that the expensive catalyst in the channel can be almost completely used up. . Also, at least one screen (not shown) can be installed to filter the aggregates or to further break up the aggregates. In the case of slurry, the screen can be selected from commercially available screens of 300 mesh or less, or a plurality of screens with different meshes can be installed in series. Further, a reinforcing material such as punching metal can be provided after the screen in the moving direction of the liquid fluid. By repeating movement or circulation through a screen (not shown), the mesh can be used as an inexpensive dispersing device. In addition, another commercially available dispersing device (not shown) can be installed in the liquid fluid flow path, and a stirring device such as a rotating blade (not shown) is installed in the tank to prevent the slurry from settling in the tank and to disperse it well. can be maintained.

In FIG. 2, at least an upper limit 260 and a lower limit 261 weight in the container can be set in advance for switching the movement of the liquid fluid 23 in the container 21 . At the upper limit position, movement of liquid fluid from another container or the like stops. On the other hand, at the lower limit it is possible to initiate transfer from another container or to fill from a liquid fluid supply means (not shown). At least one weight level detection means may be provided to control the movement of the slurry to a desired position between the upper and lower limits or outside the range in order to fine-tune the switching control. It may be used as control means.

A piston (or plunger) 310 is provided between the liquid substance 33 of the container 31 and the compressed gas 315 in FIG. This is particularly convenient when the compressed gas is nitrogen gas or compressed air, which is not an inert gas such as argon. If the liquid fluid has a low viscosity, for example, less than 100 mPa·s, the piston (plunger) must be well sealed. Therefore, it is necessary to improve the surface finish of the inner wall of the container to improve the precision of the diameter of the sliding portion, especially the roundness. As for the sealing portion of the piston, it is essential to provide a sealing member such as chemical-resistant fluororubber, PTFE, or the like, particularly outside the piston, to improve sealing performance and reduce sliding resistance. Also, the inside of the container is preferably made of PTFE, PFA, fluorine-based material, ceramic material, or treated with them. Furthermore, when the liquid fluid is mixed with gas and circulated through the tanks and the flow path to foam the liquid fluid, the two tanks are closed with the piston, so that the expansion of the foam in the tank can be eliminated. In particular, the piston (plunger) pressurizing means for the foamed liquid fluid may be electrically pressurized by a servomotor or the like. Of course, the liquid surface can be pressurized directly by compressed gas without providing a piston or the like. Pressure regulating valves for compressed gas need to use products with high-precision pressure regulating mechanisms that have a fine relief structure with fast response speed and excellent followability. For example, a pneumatic pressure regulator manufactured by Fairchild is preferably used to maintain a highly accurate hydraulic pressure.

Fig. 4 shows the behavior of liquid fluids, such as slurries, that change viscosity due to changes in shear force. When the application viscosity range 420 is reached, the discharge or application can be started. In the present invention, whether the fluid temperature and viscosity of a liquid fluid to be heated or a thermoplastic resin are stabilized can be conveniently managed by moving time per unit weight or moving weight per unit time. Small containers such as syringes can be installed outside the booth to prevent vibration due to axis movement, and the discharge device can be piped with a flexible tube with a small inner diameter such as PFA to accurately measure the weight of the liquid fluid inside the syringe. . The weight control can be manufactured to the desired shape using commercially available load cells. The object can be moved in the XY direction and coated without moving the discharge device or small device or only by moving it up and down. It can be easily carried out by combining with the method of Japanese Patent No. 5798930 to which the present inventor has the right.

In FIG. 5, apart from the flow paths 57, 57' passing through the top for the discharge device 58 between the

containers

51, 52, another flow path 550 is provided from the bottom of the container. Channels 550 may be provided through the top of each container. Alternatively, the channels 57, 57' may be joined at the bottom of the container. Since the channel 550 accelerates movement of the liquid fluid and supports dispersion, its diameter may be small, for example, an inner diameter of 2 to 6 mm and a length of about 200 to 1000 mm. One or more channels may be provided, and a dispersing device may be installed in the channel.

In FIG. 6, flow paths 67 and 67' of the discharge device 68 between the two containers flow from the bottom of the first container 61 through the top of the first container 61 to the flow path 67, the discharge device 68, and the flow path 67'. It is connected to the bottom of the second container. The flow path may be a metal pipe, a plastic such as PTFE, a rubber hose, or a tube. Chemical resistance is generally desirable for the wetted part, and if pressure resistance is required, it may be covered with reinforcing fibers or SUS blades, for example. The liquid fluid 63 in the first container can be pressurized by the compressed gas and flowed through the flow path to the vicinity of the lower portion of the second container via the upper portion. If the weight of the liquid fluid or the like is detected and the movement is reversed, the operation is the same, so the explanation will be omitted. The inflow of the liquid fluid is preferably carried out by using the side wall of the container to spread the liquid thinly (for example, around several hundred micrometers) widely, while moving the side wall of the container to the liquid surface as a thin film. Liquids in which air is likely to be entrapped can be defoamed by this method. In particular, when a liquid fluid is foamed by mixing gas in the vicinity of the outlet of the container or in the channel, it is important, for example, to defoam the side of the container on the opposite side by the above method and always maintain a constant foaming state in the discharge device. .
In FIG. 6, the liquid fluid 64 that has reached a desired level in the second container is sucked and pressurized by the pump 630 and reaches the first container 61 via the flow path 640 . When the weight of the liquid fluid 63 in the first container reaches the desired upper limit, the operation of the pump 630 is stopped, and when it reaches at least the lower limit, the pump 630 is operated to transfer the liquid fluid, thereby forming a circulation circuit be done. On the other hand, when both the lower limit of the first container and the lower limit of the second container are activated, filling of the second container 62 with the liquid material can be prompted. Further, another channel 650 can be provided when it is desired to increase the circulating weight or the moving weight of the liquid fluid per unit time to improve the viscosity stabilization speed. Furthermore, by installing a dispersing device in at least one channel, a stable liquid fluid with good dispersion can be obtained.

According to the present invention, for example, fields such as granulation and coating for pharmaceuticals and chemicals, and coating slurry materials and liquid fluids for dispersion, such as electronics, fuel cells, super capacitors, solar cells, secondary batteries, etc. Even liquids such as slurries used in small amounts for experiments such as electrode formation can be produced with high quality even when large amounts of liquid fluids are used in large-scale production lines.

1, 2, 21, 31, 51, 52, 61, 62

Containers

3, 4, 23, 33, 53, 54, 63, 64

Liquid fluids

5, 6, 25, 55, 56, 65, 66 Weighing scale (load cell )
7, 7', 27, 27', 37, 37', 57, 57'
67, 67' liquid

fluid flow paths

550, 640, 650 liquid

fluid flow paths

8, 28, 38, 58, 68 discharge device (coating device)
105, 205, 305, 505, 605 ejection head (nozzle)
9, 9', 29, 39, 59, 69

Struts

101, 102, 201, 301

Gas switching valves

103, 104, 203, 303 Gas pressure control valve 260 Liquid level upper limit 261 Liquid level lower limit 310 Piston (plunger)
315 pressurized gas 420 coating start viscosity range 630 pump

Claims

alternately pressurizing the liquid fluid in the two containers or constantly pressurizing the liquid fluid in one container to move or circulate the fluid channel communicating between the at least two containers, and A method of discharging or applying a fluid to an object using a communicating discharge device, wherein the liquid fluid in a first container is pressurized to create a differential pressure between it and the second container, thereby forming a first flow path. and pressurizing the fluid in the second container to create a pressure differential with the first container to flow through the first flow path or another flow path. and measuring the weight of the liquid fluid in the first and second containers or the total weight of the entire container containing the liquid fluid in the container; A step of setting a movement switching level of the fluid in the container to control the movement or circulation of the fluid to the first and second containers automatically; A method of ejecting or applying a fluid, characterized by comprising a step of ejecting or applying the fluid to an object.
The timing of movement switching or circulation of the liquid fluid is controlled by measuring the weight of at least the upper and lower limits of the fluid in the container or the total weight of the entire container containing the fluid, and the weight of the fluid in at least one container per unit weight 2. A method of ejecting or applying a fluid according to claim 1, wherein the ejection or application of the fluid is started when the moving time or the weight per unit moving time reaches a set value range.
The liquid fluid in the at least two containers is at least one of slurry, heated liquid, and hot melt, and the liquid fluid in the at least one container is directly or indirectly pressurized by compressed gas. A balance feed method of liquid fluid and compressed gas is used, the weight of the fluid transferred per unit time or the transfer time per unit weight of the fluid is controlled, and when the weight or time reaches a set value range, the fluid is discharged or discharged. 3. A method of ejecting or applying a fluid according to claim 1, wherein application is started.
Discharge or application of the fluid according to any one of claims 1 to 3, characterized in that at least one channel is further provided between the first container and the second container in addition to the channel to accelerate the movement of the fluid. Method.
The electrode slurry in at least two containers is alternately pressurized or the electrode slurry in one container is constantly pressurized to move or circulate in the electrode slurry channel communicating between the at least two containers, A method for manufacturing a fuel cell or a storage battery by applying the electrode slurry to an object using an applicator communicating with a flow path and drying the object to form an electrode, wherein the electrode slurry in the first container is pressurized to form a second creating a differential pressure between the electrode slurry in the second container and moving it to the second container via at least the first flow path; moving or circulating to the first container via the first flow path or another flow path by creating a differential pressure in the first and second container electrode slurries weight or in the container measuring the total weight of the entire container containing the electrode slurry, and controlling the transfer or circulation of the electrode slurry to the first and second containers automatically at least at the lower limit level of the electrode slurry in the container; 1. A method for manufacturing a fuel cell or a storage battery, comprising the step of applying a fluid to an object with an application device communicating with the flow path.
pressurizing a liquid fluid in a first container of liquid fluid in at least two containers; and moving said fluid to a second container through a first flow path communicating between said at least two containers. a step of sucking and pressurizing the fluid in the second container with a pump and moving it to the first container via the second flow path to circulate; is measured and managed by the weight of the liquid fluid or the total weight of a container containing the liquid fluid, and controlling the fluid movement timing of the first container or the second container; A fluid ejection method or application method characterized by ejecting or applying a fluid to an object using an apparatus.
The timing of movement switching or circulation of the liquid fluid is controlled by measuring at least the weight of the liquid fluid at the upper limit or the lower limit in the container or the total weight of the entire container containing the liquid fluid, and the unit weight of the fluid in at least one container 7. A fluid discharge or application method according to claim 6, wherein the fluid discharge or application is started when the moving time per unit or the weight per unit moving time reaches a set value range.
The liquid fluid in the at least two containers is at least one of slurry, heated liquid, and hot melt, and the liquid fluid in the at least one container is directly or indirectly pressurized by compressed gas. A balance field pressurization method is used, and the liquid fluid in other containers is pressure-fed by a pump, and the weight of the fluid transferred per unit time or the transfer time per unit weight of the fluid is controlled, and the weight or time is within a set value range. 8. A method of ejecting or applying fluid according to claim 6 or 7, wherein the ejection or application of the fluid is started when reaching the inside.
6. Further, in addition to the liquid fluid channel, at least one liquid fluid channel is further provided between the first container and the second container to accelerate movement of the liquid fluid. 8 fluid discharge method or application method.
A method of manufacturing a fuel cell or storage battery, comprising: pressurizing an electrode slurry in a first container of the battery electrode slurries in at least two containers; a step of moving to a second container via a first flow path communicating with the second container, and sucking and pressurizing the electrode slurry in the second container with a pump and transferring it to the first container via the second flow path and measuring and managing the levels of the electrode slurries in the first and second containers by the weight of the electrode slurries in the containers or the total weight of the container containing the electrode slurries, and moving and circulating the first container or the second container. and forming an electrode by applying an electrode slurry to an object with a coating device communicating with the flow path and drying the electrode slurry.