CN113675451A - Electrolyte sheet of molten salt fuel cell and preparation system and method thereof - Google Patents
Electrolyte sheet of molten salt fuel cell and preparation system and method thereof Download PDFInfo
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- CN113675451A CN113675451A CN202110982217.7A CN202110982217A CN113675451A CN 113675451 A CN113675451 A CN 113675451A CN 202110982217 A CN202110982217 A CN 202110982217A CN 113675451 A CN113675451 A CN 113675451A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/144—Fuel cells with fused electrolytes characterised by the electrolyte material
- H01M8/145—Fuel cells with fused electrolytes characterised by the electrolyte material comprising carbonates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses an electrolyte salt sheet of a molten salt fuel cell and a preparation system and a preparation method thereof, wherein the preparation method comprises the following steps: uniformly mixing electrolyte powder and a binder to obtain mixed powder, and simultaneously obtaining a double-sided adhesive tape; hot-press molding: and uniformly distributing the mixed powder, then overlapping the mixed powder with the double-sided adhesive tape, and carrying out hot pressing on the overlapped mixed powder and the double-sided adhesive tape. The invention can realize the preparation of the electrolyte salt sheet with a certain shape and difficult fracture and breakage; the prepared electrolyte salt sheet is a fibrous structure of a binder, wraps and connects electrolyte powder, and forms a space reticular structure which is not only supported by the bottom layer, but also connected by a reticular structure with the sticky double-sided adhesive tape of the bottom layer; the electrolyte salt sheet has a more stable structure, so that after the electrolyte salt sheet is assembled into a battery, the electrolyte can be more effectively uniformly distributed in the diaphragm, the air leakage of the diaphragm and the air leakage of the sealing surface are avoided, and the performance of the battery is ensured.
Description
Technical Field
The invention relates to the field of batteries, in particular to a molten salt fuel cell electrolyte salt sheet and a preparation system and method thereof.
Background
The Molten Carbonate Fuel Cell (MCFC) is a high-temperature Fuel Cell working at 650 ℃, has the advantages of no need of noble metal as a catalyst, wide Fuel source, low noise, nearly zero emission of pollutants, high power generation efficiency, realization of combined heat and power supply and the like, is suitable for distributed power stations or fixed power stations of hundreds kilowatt level to megawatt level, and has good development and application prospects.
The structure of the MCFC can be divided into a cathode, an electrolyte system and an anode, wherein the electrolyte system of the MCFC is composed of a porous diaphragm carrier and carbonate, and the electrolyte in the electrolyte system is molten carbonate. The molten carbonate electrolyte completely fills the pores of the electrolyte membrane by capillary force, and the carbonate electrolyte is fixed in the membrane support to form an electrolyte layer. The electrolyte layer is a carbonate ion conductor and has good ion conductivity, the cathode separator and the anode separator can block gas from passing through, and the plasticity of the electrolyte layer can be used for gas sealing of the battery and preventing gas from leaking, namely, wet sealing.
In the prior art, carbonate electrolyte is typically filled in a cell during MCFC assembly, and the electrolyte is typically pre-filled in the cathode and/or anode gas chambers, slowly melts as the cell temperature increases, and is immersed in the pores in the electrolyte membrane under the capillary force of the electrolyte membrane. Such treatment has the problem that the electrolyte, before melting, affects the distribution of the gases in the flow field, the combustion of the organic substances in the membrane and the volatilization of the combustion products; the electrolyte is likely to be entrained by the gas into the channels, blocking the channels. If the carbonate can be made into a salt film in a manner similar to that for making a separator, it would help solve the above-mentioned problems caused by the electrolyte being placed in the gas cell. For example: the film-shaped salt film can not block a flow field to cause uneven gas distribution, the contact between the salt film and the electrolyte membrane can be improved, and the electrolyte can be promoted to be better distributed in the electrolyte membrane.
Most of the prior methods for preparing carbonate electrolyte membranes are prepared by mixing carbonate electrolyte with organic solvent, binder, plasticizer, defoamer and the like, ball milling for a certain time, and slurry casting. On one hand, the salt film prepared by adopting the carbonate electrolyte slurry casting method needs more mixing and drying time; on the other hand, the carbonate is insoluble in water and organic solvent, the wettability of the surface of the electrolyte powder is poor, the carbonate powder is difficult to combine with the binder, carbonate particles in the slurry are completely wrapped by the binder, the binder in the dried salt film occupies a certain volume, so that the bulk density of the carbonate electrolyte is low, the salt film has a loose structure and low strength, the salt film is fragile and easy to break and crack during assembly, the uniform distribution of the electrolyte in the diaphragm is not facilitated, the air leakage of the diaphragm and the air leakage of a sealing surface can be caused, and the performance of the battery is poor.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems that a salt film prepared by adopting a carbonate electrolyte slurry casting method in the prior art is high in brittleness, easy to break and crack and not beneficial to uniform distribution of electrolyte in a diaphragm, so that a system and a method for preparing an electrolyte salt sheet of a molten salt fuel cell are provided.
A preparation method of electrolyte salt sheets of a molten salt fuel cell comprises the following steps:
raw material acquisition: uniformly mixing electrolyte powder and a binder to obtain mixed powder, and simultaneously obtaining a double-sided adhesive tape;
hot-press molding: and uniformly distributing the mixed powder, then overlapping the mixed powder with the double-sided adhesive tape, and carrying out hot pressing on the overlapped mixed powder and the double-sided adhesive tape.
And uniformly distributing and compacting the mixed powder in a dry-method tape casting manner.
The dry casting process comprises the following steps: and uniformly distributing the mixed powder on a film belt of a dry-method casting machine, and then compacting the mixed powder on the film belt.
In the dry casting process, the mixed powder is processed by a step-by-step compaction method.
The film belt temperature of the dry-method casting machine in the dry-method casting process is 35-45 ℃.
The electrolyte powder is carbonate, and the binder is at least one selected from sodium carboxymethylcellulose (CMC), polyvinyl alcohol (PVA) and polyvinyl butyral (PVB); the mixing ratio of the electrolyte powder to the binder is (4-5) to 1;
the double-sided adhesive tape is a hot melt adhesive film, and the thickness of the hot melt adhesive film is 0.05-0.2mm, preferably 0.1 mm.
The temperature of the hot pressing surface during hot pressing is 90-95 ℃, the pressure of the hot pressing is 5-7MPa, and the pressure maintaining time is 5-7 min.
A system for preparing electrolyte salt sheets for molten salt fuel cells, comprising:
the mixing device is used for uniformly mixing electrolyte powder and a binder to obtain mixed powder;
the material distribution device is used for uniformly distributing the mixed powder;
the double-sided adhesive tape placing mechanism is used for placing the mixed powder and the double-sided adhesive tape in a superposition way;
and the hot pressing device is used for hot pressing the superposed double-sided adhesive tape and the mixed powder.
The preparation system of the invention also comprises a compacting device for compacting the uniformly distributed mixed powder; the material distribution device is a dry-method casting machine and comprises a film belt assembly, and a feeding mechanism and a strickling mechanism which are sequentially arranged along the transmission direction of the film belt assembly;
the compacting device, the double-faced adhesive tape placing mechanism and the hot-pressing device are sequentially arranged at the rear end of the strickling mechanism along the transmission direction of the film tape component.
The film belt assembly comprises a film belt unreeling device, a film belt reeling device and a film belt connected between the film belt unreeling device and the film belt reeling device; preferably, the film tape unwinding device comprises a base with a bottom plate, a film tape unwinding roller arranged on the base, and temperature control equipment arranged on the base and used for controlling the temperature of the bottom plate; the film tape winding device comprises a base with a bottom plate and a film tape winding roller arranged on the base; the film tape is connected to the film tape unwinding roller and the film tape winding roller and is arranged above the bottom plate in parallel;
the feeding mechanism comprises a hopper, a vibrating screen arranged at the bottom of the hopper, a casting trough arranged below the hopper, and a feeding mechanism for promoting mixed powder in the hopper to flow into the casting trough; the delay trough is positioned above the membrane belt;
the scraping mechanism comprises a first scraper and a second scraper; the first scraper and the second scraper are sequentially arranged along the conveying direction of the film belt assembly; preferably, the distance between the lower end of the first scraper and the film belt is larger than the distance between the second scraper and the film belt;
the compaction device is at least one rolling roller; preferably, the compacting device comprises a first rolling roller and a second rolling roller which are arranged in sequence along the conveying direction of the film strip assembly; more preferably, the distance between the first rolling roller and the film belt is larger than the distance between the second rolling roller and the film belt;
the double-sided adhesive tape placing mechanism comprises a double-sided adhesive tape unreeling device and a double-sided adhesive tape reeling device which are sequentially arranged along the transmission direction of the film tape component, and is used for enabling the double-sided adhesive tape arranged on the double-sided adhesive tape unreeling device to be arranged above the film tape in parallel;
the hot-pressing device is a hot press and is arranged between the double-sided adhesive tape unreeling device and the double-sided adhesive tape reeling device, and double-sided adhesive tapes and membrane tapes arranged on the double-sided adhesive tape placing mechanism are positioned between an upper heating plate and a lower heating plate of the hot press and are used for flatly pressing the double-sided adhesive tapes on mixed powder on the membrane tapes to form electrolyte salt sheets;
and the lower heating plate of the hot press and the bottom plate in the film belt assembly are positioned on the same plane.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of electrolyte salt sheets of a molten salt fuel cell, which adopts a mode of carrying out hot press molding on double faced adhesive and mixed powder of electrolyte powder and a binder to realize the preparation of the electrolyte salt sheets with certain shapes and difficult fracture and breakage; the electrolyte salt sheet prepared by the invention is a fibrous structure of a binder, wraps and connects electrolyte powder, and forms a space reticular structure which is not only supported by the bottom layer, but also connected by a reticular structure with the sticky double-sided adhesive tape of the bottom layer; the structure is more stable, and the problem that a salt film prepared by adopting a carbonate electrolyte slurry casting method in the prior art is high in brittleness and easy to break and crack can be effectively solved; after the electrolyte salt sheet is assembled into the battery, the adhesive and the double-sided adhesive in the electrolyte salt sheet can be decomposed under the high-temperature condition when the battery is used, the uniform distribution of electrolyte in the diaphragm cannot be influenced, the gas leakage of the diaphragm and the gas leakage of a sealing surface are effectively avoided, and the performance of the battery is ensured.
2. The preparation method provided by the invention further optimizes the hot press molding step, and specifically, the mixed powder is uniformly distributed and compacted by adopting a dry-method tape casting manner, then is superposed with the double-sided adhesive tape, and finally, the superposed mixed powder and the double-sided adhesive tape are subjected to hot pressing; in the steps, the mixed powder formed by directly mixing the electrolyte powder and the binder is uniformly distributed by adopting a dry casting method, so that the additives such as a solvent, a plasticizer, a defoaming agent and the like are not needed, and the problems of casting and drying time of the slurry and reduction of bulk density caused by coating of carbonate particles by the slurry are solved; meanwhile, the step of compacting the mixed powder is combined, so that the bulk density of the mixed powder on the double-sided adhesive can be further increased; therefore, the optimized scheme not only can improve the preparation efficiency, but also can reduce the loss of the electrolyte of the molten carbonate fuel cell under the high-temperature condition, improve the sealing performance and the service life of the cell and keep higher discharge voltage and power density.
3. In the preparation system of the electrolyte salt sheet of the molten salt fuel cell, provided by the invention, the mixed powder of the carbon electrolyte powder and the binder slowly rotates in the hopper by the feeding mechanism, so that the mixed powder can be uniformly sprayed to the bottom of the hopper, and the mixed powder is uniformly sprayed into the casting trough by matching with the vibrating screen at the bottom of the hopper, so that the influence of larger dry powder particles on the dry casting effect in the casting trough can be prevented. The mixed powder in the casting trough depends on the dragging of a film belt of the dry-method casting machine, and the mixed powder on the film belt is scraped through the first scraper and the second scraper in sequence, so that the consistency of the thickness of the mixed powder on the film belt can be ensured. The temperature control equipment for controlling the temperature of the bottom plate, which is arranged on the base in the film strip assembly, can ensure that the mixed powder on the film strip is dry in the casting process and does not absorb moisture in the air to become damp. The even unanimous bulk density that mixed powder can improve mixed powder through the two-stage of first roller and the second roller that rolls of rolling of thickness on the membrane area to can also further guarantee mixed powder's thickness uniformity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural view of a system for producing electrolyte salt sheets for molten salt fuel cells according to the present invention;
FIG. 2 is a schematic structural diagram of an electrolyte salt sheet prepared according to the present invention;
reference numerals:
the method comprises the following steps of 1-a membrane tape unwinding device, 2-a hopper, 3-a feeding mechanism, 4-a vibrating screen, 5-a casting trough, 6-a first scraper, 7-a second scraper, 8-a temperature control device, 9-a first rolling roller, 10-a second rolling roller, 11-a double-sided adhesive tape unwinding device, 12-a hot press, 13-a double-sided adhesive tape winding device and 14-a membrane tape winding device.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The preparation method of the electrolyte salt sheet of the molten salt fuel cell comprises the steps of raw material acquisition and hot press molding, and specifically comprises the following steps: uniformly mixing electrolyte powder and a binder to obtain mixed powder, and simultaneously obtaining a double-sided adhesive tape; the hot press molding step is as follows: and uniformly distributing the mixed powder, then overlapping the mixed powder with the double-sided adhesive tape, and carrying out hot pressing on the overlapped mixed powder and the double-sided adhesive tape.
The invention adopts the mode of carrying out hot press molding on the double-sided adhesive and the mixed powder of the electrolyte powder and the binder to realize the preparation of the electrolyte salt sheet with a certain shape and difficult fracture and breakage; the electrolyte salt sheet prepared by the invention is a fibrous structure of a binder, wraps and connects electrolyte powder, and forms a space reticular structure which is not only supported by the bottom layer, but also connected by a reticular structure with the sticky double-sided adhesive tape of the bottom layer; the structure is more stable, and the problem that a salt film prepared by adopting a carbonate electrolyte slurry casting method in the prior art is high in brittleness and easy to break and crack can be effectively solved; after the electrolyte salt sheet is assembled into the battery, the adhesive and the double-sided adhesive in the electrolyte salt sheet can be decomposed under the high-temperature condition when the battery is used, the uniform distribution of electrolyte in the diaphragm cannot be influenced, the gas leakage of the diaphragm and the gas leakage of a sealing surface are effectively avoided, and the performance of the battery is ensured.
The raw materials of the present invention include a double-sided adhesive and a mixed powder, where the mixed powder is a mixture of an electrolyte powder and a binder, the electrolyte powder in the present invention may be a conventional electrolyte powder, or an electrolyte powder with an optimized composition and a ratio, and in this embodiment, the electrolyte powder is a carbonate formed by combining lithium carbonate, potassium carbonate, and sodium carbonate according to a specific ratio, for example: the molar ratio is 68: 32 of lithium carbonate and potassium carbonate in a molar ratio of 52: 48 lithium carbonate and sodium carbonate. The mixing ratio of the electrolyte powder and the binder is preferably (4-5): 1; the double-sided adhesive tape in this embodiment is a hot-melt adhesive film, and the thickness of the hot-melt adhesive film is 0.05-0.2mm, preferably 0.1 mm.
In the hot press molding step of the present invention, the mixed powder is preferably uniformly distributed and compacted by a dry casting method, specifically, the mixed powder is uniformly distributed on a film belt of a dry casting machine, and then the mixed powder on the film belt is compacted by a compression roller, wherein the method for compacting the mixed powder includes, but is not limited to, a pressing plate and a compression roller.
In order to ensure the uniformity of the mixed powder on the film belt, the mixed powder after sieving can be selected to uniformly scatter on the film belt, the thickness of the mixed powder on the film belt is accurately limited under the condition of certain thickness by a multi-stage scraper blade coating mode, and the uniformity of the thickness of the mixed powder is further ensured by a multi-stage pressing plate or a compression roller compaction mode. The invention adopts the pressing plate or the pressing roller for compaction so as to ensure the consistency of the thickness of the mixed powder and improve the bulk density of the mixed powder.
In order to ensure that the double-sided adhesive and the mixed powder are better overlapped and are convenient for later hot-pressing treatment, the double-sided adhesive before hot pressing can be arranged on a plane parallel to the membrane tape, and the double-sided adhesive is ensured to be more smoothly overlapped and adhered with the mixed powder on the membrane tape in the hot pressing process.
In the dry casting process, the mixed powder is processed by a step-by-step compaction method.
In order to avoid moisture absorption of the mixed powder on the film belt, the temperature of the film belt of the dry casting machine is controlled to be 35-45 ℃ in the dry casting process.
When hot pressing, it is only necessary to ensure that the double-sided adhesive tape and the binder in the mixed powder are integrated, as shown in fig. 2. Preferably, in order to achieve the best hot pressing effect, the temperature of the hot pressing surface is set to be 90-95 ℃ during hot pressing, the pressure of the hot pressing can be set to be 5-7MPa, and the pressure holding time is set to be 5-7 min.
Example 2
A system for producing electrolyte salt sheets for molten salt fuel cells, as shown in fig. 1, includes: a hot press unit that is used for electrolyte powder and binder homogeneous mixing to obtain mixed powder for with mixed powder evenly distributed's distributing device, be used for the double faced adhesive tape placement mechanism that places mixed powder and double faced adhesive tape coincidence, be used for carrying out the hot pressing with the double faced adhesive tape that the coincidence was placed and mixed powder.
The electrolyte salt sheet with a certain shape and difficult fracture and breakage can be effectively prepared by the system. However, in order to further improve the preparation efficiency and the quality of the prepared salt tablet, the material distribution device is provided with a dry casting machine, and a compaction device for compacting the uniformly distributed mixed powder is additionally arranged on the dry casting machine.
The dry-method casting machine comprises a film belt assembly, and a feeding mechanism and a strickling mechanism which are sequentially arranged along the transmission direction of the film belt assembly; the compacting device, the double-faced adhesive tape placing mechanism and the hot-pressing device are sequentially arranged at the rear end of the strickling mechanism along the transmission direction of the film tape component.
The film belt assembly comprises a film belt unreeling device 1, a film belt reeling device 14 and a film belt connected between the film belt unreeling device 1 and the film belt reeling device 14; the mixed powder is transmitted on the film belt through the film belt winding and unwinding device. Further, the film tape unwinding device 1 comprises a base with a bottom plate, a film tape unwinding roller installed on the base, and a temperature control device 8 arranged on the base and used for controlling the temperature of the bottom plate; the film tape winding device 14 comprises a base with a bottom plate and a film tape winding roller arranged on the base; the film belt is connected to the film belt unwinding roller and the film belt winding roller and is arranged above the bottom plate in parallel.
The feeding mechanism comprises a hopper 2, a vibrating screen 4 arranged at the bottom of the hopper 2, a casting trough 5 arranged below the hopper 2, and a feeding mechanism 3 for promoting the mixed powder in the hopper 2 to flow into the casting trough 5; the casting trough 5 is positioned above the film belt; preferably, the feeding mechanism 3 is a helical feeding shaft mounted in the hopper 2.
The scraping mechanism comprises a first scraper 6 and a second scraper 7; the first scraper 6 and the second scraper 7 are sequentially arranged along the conveying direction of the film belt assembly; preferably, the distance between the lower end of the first blade 6 and the film tape is greater than the distance between the second blade 7 and the film tape.
The compaction device is at least one rolling roller; preferably, the compacting means comprise a first roller 9 and a second roller 10 arranged in succession along the direction of transport of the assembly; more preferably, the distance between the first laminating roller 9 and the film strip is greater than the distance between the second laminating roller 10 and the film strip.
The double-sided tape placing mechanism comprises a double-sided tape unreeling device 11 and a double-sided tape reeling device 13 which are sequentially arranged along the transmission direction of the film tape component, and double-sided tapes which are installed on the double-sided tape unreeling device are arranged above the film tape in parallel.
The hot pressing device is a hot press 12 and is arranged between the double-sided adhesive tape unreeling device 11 and the double-sided adhesive tape reeling device 13, and double-sided adhesive tapes and membrane tapes installed on the double-sided adhesive tape placing mechanism are both positioned between an upper heating plate and a lower heating plate of the hot press 12 and are used for flatly pressing the double-sided adhesive tapes on mixed powder on the membrane tapes to form electrolyte salt sheets.
The lower heating plate of the hot press 12 is located on the same plane as the bottom plate in the film strip assembly.
The specific preparation process of the electrolyte salt sheet by adopting the preparation system of the electrolyte salt sheet of the molten salt fuel cell is as follows:
obtaining a molar ratio of 68: 32 of lithium carbonate and potassium carbonate, then mixing and drying the electrolyte powder and the sodium carboxymethyl cellulose CMC according to the proportion of 4:1 to prepare mixed powder, and feeding the dried mixed powder into a hopper 2.
And starting a hot press 12 for preheating to enable the temperature of the upper heating plate and the lower heating plate to reach 90-95 ℃, starting a temperature control device 8 of the dry casting machine, heating the temperature of the bottom plate to 35-45 ℃, further ensuring that the temperature of the film belt reaches 35-45 ℃, and avoiding moisture absorption of mixed powder on the film belt. The film tape unwinding device 1 and the film tape winding device 14 are started, the unwinding and winding speed is controlled to be 0.1-0.3m/min, in the embodiment, the unwinding and winding speed is controlled to be 0.2m/min, the rotating speed of the feeding mechanism 3 in the hopper 2 is controlled to be synchronous with the unwinding and winding speed of the dry casting machine, the mixed powder is guaranteed to be conveyed to the discharging pipe of the hopper 2 at a constant speed under the rotation of the feeding mechanism 3, and the mixed powder falling from the bottom of the discharging pipe is uniformly sprinkled into the casting trough 5 through the vibrating screen 4.
Through the even mixed powder that spills in curtain coating silo 5 granule of shale shaker 4 first through first scraper 6 under the dragging of membrane area, first scraper 6 highly sets up apart from membrane area surface height 4mm, passes through second scraper 7 again, and second scraper 7 highly sets up apart from membrane area surface height 3 mm.
The mixed powder strickled off through second scraper 7 passes through first roller 9, second roller 10 of rolling in proper order, and first roller is 3mm apart from membrane area surface height, and second roller 10 is 2.5mm apart from membrane area surface height, progressively improves the bulk density of mixed powder, carries the mixed powder of roll-in to hot press 12 under with the membrane area.
After the mixed powder is conveyed to the position under the hot press 12, the film tape unwinding device 1, the film tape winding device 14 and the feeding mechanism 3 are suspended, the double-sided tape unwinding device 11 and the double-sided tape winding device 13 are started, and when the double-sided tape can cover the mixed powder, the double-sided tape unwinding device 11 and the double-sided tape winding device 13 are suspended.
Starting a hot pressing program of the hot press 12, making the upper heating plate move downwards to thermally press and bond the double-sided adhesive and the mixed powder together, wherein the pressure of the hot press is 5-7MPa, and the pressure maintaining time is 5-7min, in the embodiment, the pressure of the hot press is 6MPa, and the pressure maintaining time is 6 min. After the pressure maintaining time is up, the upper heating plate of the hot press 12 automatically moves upwards, and the preparation of one electrolyte salt sheet can be completed.
After the preparation of one electrolyte salt sheet is finished, separating the isolation paper on the double-sided adhesive tape from the pressed electrolyte salt sheet, starting the double-sided adhesive tape unreeling device 11, the double-sided adhesive tape reeling device 13 and the feeding mechanism 3, dragging the first prepared electrolyte salt sheet out of the hot press 12 by using a film tape, then cutting the electrolyte salt sheet at the rear end of the dry-method casting machine, and putting the cut electrolyte salt sheet into a drying box for later use.
The electrolyte salt sheet prepared by the embodiment has a more stable structure, can effectively overcome the problems that a salt film prepared by adopting a carbonate electrolyte slurry casting method in the prior art is high in fragility and easy to break and crack, can effectively ensure the uniform distribution of electrolyte in a diaphragm, effectively avoids the gas blowby and the gas leakage of a sealing surface of the diaphragm, and ensures the performance of a battery.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A method for preparing electrolyte salt sheets of a molten salt fuel cell is characterized by comprising the following steps:
raw material acquisition: uniformly mixing electrolyte powder and a binder to obtain mixed powder, and simultaneously obtaining a double-sided adhesive tape;
hot-press molding: and uniformly distributing the mixed powder, then overlapping the mixed powder with the double-sided adhesive tape, and carrying out hot pressing on the overlapped mixed powder and the double-sided adhesive tape.
2. The manufacturing method according to claim 1, wherein the mixed powder is uniformly distributed and compacted by a dry casting method;
the dry casting process comprises the following steps: and uniformly distributing the mixed powder on a film belt of a dry-method casting machine, and then compacting the mixed powder on the film belt of the dry-method casting machine.
3. The production method according to claim 2, wherein in the dry casting process, the mixed powder is processed by a stepwise compaction method.
4. The production method according to claim 2 or 3, wherein the film tape temperature of the dry casting machine is controlled to 35 to 45 ℃ during the dry casting.
5. The production method according to any one of claims 1 to 4, wherein the electrolyte powder is a carbonate, and the binder is at least one selected from the group consisting of sodium carboxymethylcellulose, polyvinyl alcohol, and polyvinyl butyral; the mixing ratio of the electrolyte powder to the binder is (4-5) to 1;
the double-sided adhesive tape is a hot melt adhesive film, and the thickness of the hot melt adhesive film is 0.05-0.2mm, preferably 0.1 mm.
6. The production method according to any one of claims 1 to 5, wherein the temperature of the hot-pressing surface at the time of hot-pressing is 90 to 95 ℃, the pressure of hot-pressing is 5 to 7MPa, and the dwell time is 5 to 7 min.
7. A molten salt fuel cell electrolyte salt sheet characterized by being produced by the method for producing a molten salt fuel cell electrolyte salt sheet according to any one of claims 1 to 6.
8. A system for producing an electrolyte salt sheet for a molten salt fuel cell, comprising:
the mixing device is used for uniformly mixing electrolyte powder and a binder to obtain mixed powder;
the material distribution device is used for uniformly distributing the mixed powder;
the double-sided adhesive tape placing mechanism is used for placing the mixed powder and the double-sided adhesive tape in a superposition way;
and the hot pressing device is used for hot pressing the superposed double-sided adhesive tape and the mixed powder.
9. The manufacturing system of claim 8, further comprising a compacting device for compacting the uniformly distributed mixed powder; the material distribution device is a dry-method casting machine and comprises a film belt assembly, and a feeding mechanism and a strickling mechanism which are sequentially arranged along the transmission direction of the film belt assembly;
the compacting device, the double-faced adhesive tape placing mechanism and the hot-pressing device are sequentially arranged at the rear end of the strickling mechanism along the transmission direction of the film tape component.
10. The preparation system according to claim 9, wherein the film tape assembly comprises a film tape unwinding device (1), a film tape winding device (14), and a film tape connected between the film tape unwinding device (1) and the film tape winding device (14); preferably, the film tape unwinding device (1) comprises a base with a bottom plate, a film tape unwinding roller installed on the base, and a temperature control device (8) arranged on the base and used for controlling the temperature of the bottom plate; the film tape winding device (14) comprises a base with a bottom plate and a film tape winding roller arranged on the base; the film tape is connected to the film tape unwinding roller and the film tape winding roller and is arranged above the bottom plate in parallel;
the feeding mechanism comprises a hopper (2), a vibrating screen (4) arranged at the bottom of the hopper (2), a casting trough (5) arranged below the hopper (2), and a feeding mechanism (3) for promoting mixed powder in the hopper (2) to flow into the casting trough (5); the casting trough (5) is positioned above the film belt;
the scraping mechanism comprises a first scraper (6) and a second scraper (7); the first scraper (6) and the second scraper (7) are sequentially arranged along the conveying direction of the film belt assembly; preferably, the distance between the lower end of the first scraper (6) and the film belt is larger than the distance between the second scraper (7) and the film belt;
the compaction device is at least one rolling roller; preferably, the compacting device comprises a first rolling roller (9) and a second rolling roller (10) which are arranged in sequence along the conveying direction of the film strip assembly; more preferably, the distance between the first rolling roller (9) and the film belt is larger than the distance between the second rolling roller (10) and the film belt;
the double-sided adhesive tape placing mechanism comprises a double-sided adhesive tape unreeling device (11) and a double-sided adhesive tape reeling device (13) which are sequentially arranged along the transmission direction of the film tape component, and is used for enabling the double-sided adhesive tape arranged on the double-sided adhesive tape to be arranged above the film tape in parallel;
the hot pressing device is a hot press (12) and is arranged between the double-sided adhesive tape unreeling device (11) and the double-sided adhesive tape reeling device (13), and double-sided adhesive tapes and membrane tapes arranged on the double-sided adhesive tape placing mechanism are positioned between an upper heating plate and a lower heating plate of the hot press (12) and are used for flatly pressing the double-sided adhesive tapes on mixed powder on the membrane tapes to form electrolyte salt sheets;
and the lower heating plate of the hot press (12) and the bottom plate in the membrane band assembly are positioned on the same plane.
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| CN202110982217.7A CN113675451B (en) | 2021-08-25 | 2021-08-25 | Electrolyte sheet of molten salt fuel cell and preparation system and method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114927711A (en) * | 2022-05-16 | 2022-08-19 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
| CN114927711B (en) * | 2022-05-16 | 2024-04-26 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
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| US4242426A (en) * | 1979-11-05 | 1980-12-30 | General Electric Company | Process for electrolyte structure with strontium titanate matrix for molten carbonate fuel cells |
| JPS6282655A (en) * | 1985-10-04 | 1987-04-16 | Toshiba Corp | Manufacture of electrolyte plate for molten carbonate fuel cell |
| JPS63224155A (en) * | 1987-03-11 | 1988-09-19 | Toshiba Corp | Electrolyte plate for molten carbonate fuel cell |
| CN110690459A (en) * | 2019-09-25 | 2020-01-14 | 中国华能集团清洁能源技术研究院有限公司 | Method for improving catalytic performance of electrode of molten carbonate fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4242426A (en) * | 1979-11-05 | 1980-12-30 | General Electric Company | Process for electrolyte structure with strontium titanate matrix for molten carbonate fuel cells |
| JPS6282655A (en) * | 1985-10-04 | 1987-04-16 | Toshiba Corp | Manufacture of electrolyte plate for molten carbonate fuel cell |
| JPS63224155A (en) * | 1987-03-11 | 1988-09-19 | Toshiba Corp | Electrolyte plate for molten carbonate fuel cell |
| CN110690459A (en) * | 2019-09-25 | 2020-01-14 | 中国华能集团清洁能源技术研究院有限公司 | Method for improving catalytic performance of electrode of molten carbonate fuel cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114927711A (en) * | 2022-05-16 | 2022-08-19 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
| CN114927711B (en) * | 2022-05-16 | 2024-04-26 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
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| CN113675451B (en) | 2023-02-24 |
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