CN113517447B - Preparation method of fuel cell membrane electrode - Google Patents
Preparation method of fuel cell membrane electrode Download PDFInfo
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- CN113517447B CN113517447B CN202110796939.3A CN202110796939A CN113517447B CN 113517447 B CN113517447 B CN 113517447B CN 202110796939 A CN202110796939 A CN 202110796939A CN 113517447 B CN113517447 B CN 113517447B
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
- B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
- B05C11/06—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface with a blast of gas or vapour
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C13/00—Means for manipulating or holding work, e.g. for separate articles
- B05C13/02—Means for manipulating or holding work, e.g. for separate articles for particular articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0245—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work for applying liquid or other fluent material to a moving work of indefinite length, e.g. to a moving web
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/08—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation
- B05C9/14—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation the auxiliary operation involving heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0466—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas
- B05D3/0473—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas for heating, e.g. vapour heating
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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 a preparation method of a fuel cell membrane electrode, which mainly comprises a coating process and a drying process. The coating process comprises the following steps: when the flexible film conveyed from the unwinding roll of the winding device passes through the coating roll, uniformly coating the coating material on the flexible film through the slot die to form a coating layer; the coating material is stored in a magazine in communication with the slot die, the coating material in the magazine being continuously supplied by an injection pump. The drying process comprises the following steps: drying the coating layer on the flexible film by a drying oven arranged downstream of the coating roller; a synchronous supporting device is arranged opposite to the drying box and comprises a shell, a conveying belt and a transmission shaft; when the coating layer is dried by the drying oven, the conveyor belt of the synchronous supporting device provides plane support synchronous with the transmission speed of the flexible film for the flexible film, and the flexible film is prevented from sagging in the drying process to cause wrinkling and deformation. And the coating layer on the flexible film is dried to form a flexible film electrode, and then the flexible film electrode is collected by a winding roller.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of a fuel cell membrane electrode.
Background
The fuel cell is an energy conversion device that directly converts chemical energy of fuel into electric energy, has the advantages of high energy conversion efficiency, no exhaust emission and the like, and is considered as the most promising power generation technology for solving the problems of energy crisis and environmental pollution from the viewpoint of energy saving and ecological environment protection.
The membrane electrode is one of the core components of the fuel cell, is a place for electrochemical reaction of the fuel cell, and provides a channel for multiphase substance transfer. The manufacturing cost of the membrane electrode accounts for over 30% of the fuel cell cost. The current widely used membrane electrode preparation method is mainly a coating method, and a catalyst is directly coated on a membrane. Because the film is sensitive to organic solvent, the film is easy to swell and wrinkle during coating, so that the film electrode has quality defects, and the utilization rate of the catalyst and the performance of the film electrode are influenced. In the case of preparing the membrane electrode in a large area by adopting a coating method, the problem of swelling and wrinkling of the membrane caused by a solvent becomes more prominent, slight wrinkling generated on the membrane can influence the uniformity of catalyst coating on the surface of a large-area membrane electrode product, and how to avoid wrinkling of the membrane becomes a key problem for overcoming the technology of preparing the membrane electrode in a large area.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a fuel cell membrane electrode, which is implemented by a winding device and mainly comprises a coating process and a drying process.
The coating process comprises the following steps: when the flexible film conveyed from the unwinding roller of the winding device passes through the coating roller, the coating material is uniformly coated on the flexible film through the slot die to form a coating layer; the coating material is stored in a magazine in communication with the slot die, the coating material in the magazine being continuously supplied by an injection pump.
The drying process comprises the following steps: drying the coating layer on the flexible film by a drying oven arranged downstream of the coating roller; a synchronous supporting device is arranged opposite to the drying box and comprises a shell, a conveying belt and a transmission shaft; when the coating layer is dried by the drying oven, the conveyor belt of the synchronous supporting device provides plane support synchronous with the transmission speed of the flexible film for the flexible film, and the flexible film is prevented from sagging in the drying process to cause wrinkling and deformation.
And the coating layer on the flexible film is dried to form a flexible film electrode, and then the flexible film electrode is collected by a winding roller.
The conveyor belt is driven by the transmission shaft to form an annular conveying path; a transition roller is arranged at the downstream of the advancing section of the annular conveying path; the flexible film is turned over by 180 degrees in the conveying direction after bypassing the transition roller, and is folded back to pass through the return section of the annular conveying path and then is continuously conveyed; the conveying belt forms a supporting action surface on the advancing section and the returning section of the annular conveying path to provide plane support for the flexible film; the rotating speed control of a transmission shaft of the synchronous supporting device is coordinated and unified with the rotating speed control of the coating roller and the transition roller, so that the transmission speed of the conveyor belt and the transmission speed of the flexible film are kept synchronous.
A flattening roller is arranged at the upstream of the coating roller, and the flexible film is flattened by the flattening roller before being coated; the flattening roller is provided with a spiral groove; the spiral groove is divided into two sections on the central section of the flattening roller, and the two sections are respectively extended reversely by taking the central section as a symmetrical plane; the included angle between the spiral line of the spiral groove and the flattening roll axis is 50-85 degrees; along with the rotation of nip roll, the flexible film that the spiral groove can pass through is flat to both sides exhibition, avoids the flexible film fold to appear, influences the coating homogeneity.
The number of the drying boxes is 2, and the drying boxes are respectively a first drying box arranged on the opposite side of the advancing section of the annular conveying path and a second drying box arranged on the opposite side of the returning section of the annular conveying path; the drying temperature of the first drying box is 60-90 ℃, and the drying temperature of the second drying box is 100-120 ℃; the length of the first drying box and the length of the second drying box are both more than 1 m. The second drying box is positioned below the first drying box.
After the drying process, the flexible film is sequentially cooled by a first cooling roller and a second cooling roller; the roll surface temperature of the first cooling roll is set to be within the range of 40-60 ℃, and the roll surface temperature of the second cooling roll is set to be within the range of 10-30 ℃; the wrap angle of the flexible film on the first cooling roller and the second cooling roller is more than 90 degrees. Preferably, the roller bodies of the first cooling roller and the second cooling roller are of hollow structures, constant-temperature water and a coolant are respectively introduced into the first cooling roller and the second cooling roller, and the two-stage cooling rollers are used for preventing the electrode film from being cracked due to stress generated on the surface coating caused by the fact that the temperature of the electrode film is reduced too fast after the drying process.
A plurality of pipelines are arranged in the drying box, each pipeline is provided with a plurality of air outlet channels to form a row of air outlet channels, and a plurality of rows of air outlet channels form a blowing array; and continuously introducing nitrogen with 3-10 atmospheric pressures into the pipeline by an external gas source, heating the nitrogen in the pipeline by a heater around the pipeline, uniformly blowing high-temperature nitrogen to the surface of the flexible film by the blowing array, and drying the coating layer.
An air suction groove is arranged between every two rows of air outlet pore channels and is connected with a vacuum pump through a cavity in the drying box; after the swept high-temperature nitrogen is contacted with the surface of the flexible film, the nitrogen is sucked into the cavity by the air suction groove under the action of the vacuum pump and is discharged out of the drying box; under the balance action of the blowing array and the air suction groove, a uniform non-pressure drying air cushion layer is formed above the flexible film, so that the coating layer on the flexible film is uniformly dried under the condition of keeping the original distribution uniformity. The design can avoid that the pressure of high-temperature nitrogen blown out in a single blowing direction pushes the coating material which is not dried and solidified on the flexible film, and the distribution uniformity of the coating layer is changed.
The shell is provided with openings at corresponding positions of the advancing section and the returning section of the annular conveying path, so that the conveying belt is contacted with the flexible film at the openings to realize support; a slit is formed between the edge of the opening of the shell and the conveyor belt, and the width of the slit is within the range of 100 micrometers-1 mm; the casing and the conveyor belt form a cavity of the synchronous supporting device. And the inflation circulating system positioned outside the working cavity fills heated gas into the cavity of the synchronous supporting device, and the flexible film is heated through the conveyor belt. The conveyor belt is made of a thermally conductive material, and in a preferred embodiment, the conveyor belt is made of an alloy containing at least one of aluminum and copper. The surface roughness of the contact surface of the conveyor belt and the flexible film is 5-20 mu m.
A partition board is arranged in the shell, and a heat insulation layer is arranged on the partition board; the partition plate divides the cavity of the synchronous supporting device into an upper cavity and a lower cavity; 2 inflation circulating systems are provided, and gases with different temperatures are respectively filled into the upper cavity and the lower cavity; the temperature of the gas in the upper cavity is 55-85 ℃, and the flexible film on the advancing section of the annular conveying path is heated through the conveying belt; the temperature of the gas in the upper cavity is 95-115 ℃, and the flexible film on the return section of the annular conveying path is heated through the conveying belt.
The coating material comprises the components of iridium oxide, perfluorosulfonic acid, water, ethanol and propanol; mixing iridium oxide powder serving as a catalyst with water, adding propylene alcohol and ethanol, adding a water-based perfluorosulfonic acid ion dispersion, shearing and mixing the obtained mixed solvent in a mixer, and stirring by using a magnetic stirrer to obtain the coating material for the coating process.
The main function of adding the ethanol is to increase the bonding force between the coating material and the flexible film, and the function of adding the propanol is to reduce the contact angle between the coating material and the flexible film and improve the absorbability of the solute.
In order to improve the wettability of the coating material to the flexible film, the diameter of the roller body of the coating roller is preferably between 100 and 300mm, and the coating uniformity is influenced by too large or too small diameter. The surface of the roller body should be inlaid with soft rubber with the thickness of 0.5-1 mm, the friction force between the flexible film and the roller body is increased, the thickness of the rubber layer cannot be larger than 1mm, otherwise, deformation is easy to occur, and the coating is uneven. The distance between the coating roller and the first drying box cannot be too close, otherwise, the heated air flow of the drying box can cause the deformation of the soft rubber layer of the coating roller, and the coating uniformity is influenced. Preferably, the distance between the coating roller and the first drying oven is 0.5-1 m, and the distance gives sufficient time for mixing the catalyst solution and the membrane layer material, and improves the production stability to a certain extent.
The winding equipment adopted by the preparation method mainly comprises a working cavity, an unwinding roller, a winding roller, a groove die system, a coating roller and a synchronous supporting device; the groove die system comprises a groove die, a material box and an injection pump; the coating roller is positioned at the downstream of the unwinding roller, and the groove die and the coating roller are oppositely arranged; the synchronous supporting device is positioned at the downstream of the coating roller, and a drying box is arranged at the opposite side of the synchronous supporting device; the synchronous supporting device comprises a machine shell, a conveying belt and a transmission shaft; when the drying oven dries the coating on the flexible film, the conveyor belt of the synchronous supporting device can provide plane support synchronous with the transmission speed of the flexible film for the flexible film.
The conveying belt is driven by the transmission shaft to form an annular conveying path; a transition roller is arranged at the downstream of the advancing section of the annular conveying path; the flexible film is turned over by 180 degrees in the conveying direction after bypassing the transition roller, and is folded back to pass through the return section of the annular conveying path and then is continuously conveyed; the conveyor belt forms a supporting action surface on the advancing section and the returning section of the annular conveying path to provide plane support for the flexible film; the lengths of the forward section and the return section of the endless conveying path are both 1m or more. The casing is provided with openings at corresponding positions of the advancing section and the returning section of the annular conveying path; the conveyor belt is supported in contact with the flexible film at the opening.
The number of the drying boxes is 2, and the drying boxes are respectively arranged on the opposite sides of the advancing section and the returning section of the annular conveying path; the drying box is of an embedded structure and is embedded and installed on the shell of the working cavity; the drying temperatures of the 2 drying boxes are different; the length of the drying box is more than 1 m.
A plurality of pipelines are arranged in the drying box, the pipelines are connected with an air source outside the drying box, and the extending direction of the pipelines in the drying box is orthogonal to the transmission direction of the flexible film; a heater is arranged around the pipeline to heat the gas in the pipeline, and the heating temperature of the heater is controlled within the range of 50-200 ℃; each pipeline is provided with a plurality of air outlet channels to form a row of air outlet channels; and the multiple rows of gas outlet channels form a purging array, and high-temperature gas is uniformly purged to the surface of the flexible film.
An air suction groove is arranged between every two rows of air outlet channels and is connected with a vacuum pump through a cavity in the drying box; and after the swept high-temperature gas is contacted with the surface of the flexible film, the high-temperature gas is sucked into the cavity through the air suction groove and is discharged out of the drying box.
A flattening roll is also arranged at the upstream of the coating roll, and is provided with a spiral groove; the spiral groove is divided into two sections on the central section of the flattening roller, and the two sections are respectively extended reversely by taking the central section as a symmetrical plane; the included angle between the spiral line of the spiral groove and the flattening roll axis is 50-85 degrees.
A slit is formed between the edge of the opening of the shell of the synchronous supporting device and the conveyor belt, and the width of the slit is within the range of 100 micrometers-1 mm; the casing and the conveyor belt form a cavity of the synchronous supporting device. The synchronous supporting device further comprises an inflation circulating system, the inflation circulating system is located outside the working cavity of the winding device, the inflation circulating system fills heated gas into the cavity of the synchronous supporting device, and the flexible film is heated through the conveying belt.
A partition plate is arranged in the shell and divides a cavity of the synchronous supporting device into an upper cavity and a lower cavity; 2 inflation circulating systems are provided, and gases with different temperatures are respectively filled into the upper cavity and the lower cavity; the clapboard is provided with a heat insulation layer.
A first cooling roller and a second cooling roller are sequentially arranged at the downstream of the synchronous supporting device; the roll surface temperature of the first cooling roll is set to be within the range of 40-60 ℃, and the roll surface temperature of the second cooling roll is set to be within the range of 10-30 ℃.
The rotating speed control of a transmission shaft of the synchronous supporting device is coordinated and unified with the rotating speed control of the coating roller and the transition roller, so that the transmission speed of the conveyor belt and the transmission speed of the flexible film are kept synchronous.
The wall of the working cavity of the winding equipment is also provided with a supporting shaft, and the shell of the synchronous supporting device is fixedly arranged on the supporting shaft.
The synchronous supporting device also comprises a tension adjusting shaft, and the conveying belt is in a surface straight state on the advancing section and the returning section of the annular conveying path through the adjustment of the tension adjusting shaft.
The transmission shaft comprises a driving shaft and a driven shaft, and the driving shaft and the driven shaft are both arranged on the machine shell; the rotating speed control of the driving shaft is coordinated and unified with the transmission speed control of a winding system of the winding equipment, so that the transmission speed of the conveyor belt and the transmission speed of the flexible film are kept synchronous.
The winding equipment for preparing the membrane electrode is also provided with a tension adjusting roller and a guide roller.
The preparation method is mainly suitable for preparing large-area membrane electrode products. The thickness of the catalyst coating layer of the membrane electrode is generally more than 500 μm, and a longer drying oven is needed for drying in order to ensure that the coating layer is fully dried, so the guide roller span before and after the drying oven is correspondingly increased. In the case of large-area membrane electrode preparation, because the weight of the membrane layer and the span between rollers are both large, and in addition, the flexible film is easy to swell under the action of a solvent in a coating material during coating, the flexible film is easy to drop under the action of gravity in a drying box area, so that the swelling deformation and the wrinkle phenomenon are further aggravated, and the product quality is reduced. In the preparation method, when the drying oven dries the flexible film, the conveyor belt of the synchronous supporting device can provide plane support synchronous with the transmission speed of the flexible film for the flexible film, so that the flexible film with the coating layer attached to the surface is prevented from dropping under the action of gravity to aggravate swelling deformation and wrinkling. In addition, under the balance action of the blowing array of the drying box and the air suction groove, a uniform non-pressure drying air cushion layer can be formed above the flexible film, so that the coating layer on the flexible film is uniformly dried under the condition of keeping the original distribution uniformity, the pressure of high-temperature nitrogen blown out in a single blowing direction is prevented from pushing the coating material which is not dried and solidified on the flexible film, the distribution uniformity of the coating layer is changed, and the flexible film can be prevented from generating wrinkles under the impact of the high-temperature nitrogen flow in the single blowing direction. Therefore, the preparation method of the invention solves the technical problem that the membrane is wrinkled and swelled in the preparation of the large-area membrane electrode, improves the uniformity of the membrane electrode catalyst coating layer in a large-area range, and obviously improves the quality and the qualification rate of the membrane electrode product.
Drawings
FIG. 1 is a schematic view of a winding apparatus used in the production method of the present invention;
FIG. 2 is a schematic front view of the structure of the drying box of the present invention;
FIG. 3 is a schematic bottom view of the structure of the drying box of the present invention;
FIG. 4 is a schematic view of the structure of the synchronous supporting device of the present invention;
FIG. 5 is a schematic view of the structure of a winding apparatus used in comparative example 1;
fig. 6 is a schematic view of the structure of the winding apparatus used in comparative example 2.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
Fig. 1 is a schematic structural diagram of a winding device adopted in the preparation method of the present invention, and as shown in the figure, the winding device mainly includes a working cavity 1, an unwinding roller 2, a winding roller 3, a slot die system 4, a coating roller 5 and a synchronous supporting device 6; the groove die system 4 comprises a groove die 7, a material box 8 and an injection pump 9; the coating roll 5 is positioned at the downstream of the unwinding roll 2, and the slot die 7 is arranged opposite to the coating roll 5; the synchronous supporting device 6 is positioned at the downstream of the coating roller 5, and a drying box is arranged at the opposite side of the synchronous supporting device 6; when the drying oven dries the coating on the flexible film, the conveyor belt of the synchronous supporting device can provide plane support synchronous with the transmission speed of the flexible film for the flexible film.
The synchronous supporting device 6 comprises a machine shell 10, a conveyor belt 11 and a transmission shaft; the conveyor belt 11 forms an annular conveying path under the driving of the transmission shaft; downstream of the advance section 12 of the endless conveying path, a transition roller 13 is arranged; the flexible film turns 180 degrees in the conveying direction after passing around the transition roller 13, turns back to pass through the return section 14 of the annular conveying path and continues to be conveyed; the conveyor belt forms a supporting action surface on the advancing section 12 and the returning section 14 of the annular conveying path, and provides plane support for the flexible film; the lengths of the forward section 12 and the return section 14 of the endless conveying path are each 1m or more. The casing 10 is opened at the corresponding positions of the advancing stage and the returning stage of the endless conveying path; the conveyor belt is supported in contact with the flexible film at the opening.
The drying boxes are 2, namely a first drying box 15 arranged at the opposite side of the advancing section 12 of the annular conveying path and a second drying box 16 arranged at the opposite side of the returning section 14 of the annular conveying path; the drying box is of an embedded structure and is embedded and installed on the shell of the working cavity 1; the drying temperatures of the 2 drying boxes are different; the length of the drying box is more than 1 m. The second drying oven 16 is located below the first drying oven 15.
A flattening roll 17 is also arranged at the upstream of the coating roll 5, and the flattening roll 17 is provided with a spiral groove; the spiral groove is divided into two sections on the central section of the flattening roller, and the two sections are respectively extended reversely by taking the central section as a symmetrical plane; the included angle between the spiral line of the spiral groove and the flattening roll axis is 50-85 degrees.
A first cooling roller 18 and a second cooling roller 19 are further arranged at the downstream of the synchronous supporting device 6 in sequence; the roll surface temperature of the first cooling roll 18 is set within the range of 40-60 ℃, and the roll surface temperature of the second cooling roll 19 is set within the range of 10-30 ℃.
The rotating speed control of a transmission shaft of the synchronous supporting device is coordinated and unified with the rotating speed control of the coating roller and the transition roller, so that the transmission speed of the conveyor belt and the transmission speed of the flexible film are kept synchronous.
A supporting shaft 20 is also arranged on the wall of the working cavity of the winding device, and the shell 10 of the synchronous supporting device is fixedly arranged on the supporting shaft.
The winding equipment for preparing the membrane electrode is also provided with a tension adjusting roller and a guide roller.
FIGS. 2 and 3 are schematic front and bottom views, respectively, of the structure of the drying box of the present invention; as shown in the figure, a plurality of pipelines 21 are arranged in the drying oven, the pipelines are connected with an air source outside the drying oven, and the extending direction of the pipelines in the drying oven is orthogonal to the transmission direction of the flexible film; a heater 22 is arranged around the pipeline to heat the gas in the pipeline, and the heating temperature of the heater is controlled within the range of 50-200 ℃; each pipeline is provided with a plurality of air outlet channels 23 to form a row of air outlet channels 24; and the multiple rows of gas outlet channels form a purging array, and high-temperature gas is uniformly purged to the surface of the flexible film.
An air suction groove 25 is arranged between every two rows of air outlet channels and is connected with a vacuum pump 27 through a cavity 26 in the drying box; and after the swept high-temperature gas is contacted with the surface of the flexible film, the high-temperature gas is sucked into the cavity through the air suction groove and is discharged out of the drying box.
FIG. 4 is a schematic structural diagram of the synchronous supporting device of the present invention, as shown in the figure, a slit exists between the edge of the opening of the casing 10 of the synchronous supporting device and the conveyor belt 11, and the width of the slit is within the range of 100 μm to 1 mm; the housing 10 and the conveyor belt 11 form a cavity of the synchronous supporting device. The synchronous supporting device further comprises an inflation circulating system, the inflation circulating system is located outside the working cavity of the winding device, the inflation circulating system fills heated gas into the cavity of the synchronous supporting device, and the flexible film is heated through the conveying belt. The conveyor belt is made of a thermally conductive material, and in a preferred embodiment, the conveyor belt is made of an alloy containing at least one of aluminum and copper. The surface roughness of the contact surface of the conveyor belt and the flexible film is 5-20 mu m.
A partition plate 28 is arranged in the machine shell 10, and the partition plate 28 divides the cavity of the synchronous supporting device into an upper cavity 29 and a lower cavity 30; the number of the inflation circulating systems is 2, namely an inflation circulating system 31 and an inflation circulating system 32, and the inflation circulating systems respectively fill gas with different temperatures into the upper cavity 29 and the lower cavity 30; the partition plate 28 is provided with a heat insulating layer.
The synchronous supporting device also comprises a tension adjusting shaft 33, and the conveying belt 11 is in a surface straight state on the advancing section 12 and the returning section 14 of the annular conveying path through the adjustment of the tension adjusting shaft 33.
The transmission shaft comprises a driving shaft 34 and a driven shaft 35, and the driving shaft 34 and the driven shaft 35 are both arranged on the machine shell 10; the rotation speed control of the driving shaft 34 is coordinated and unified with the transmission speed control of the winding system of the winding device, so that the transmission speed of the conveyor belt and the transmission speed of the flexible film are kept synchronous.
Comparative example 1
The membrane electrode is prepared by adopting winding equipment shown in figure 5, wherein 2 drying boxes are arranged in the winding equipment, namely a drying box 36 and a drying box 37, the drying temperature in the drying box 36 is 60-90 ℃, the drying temperature in the drying box 37 is 100-120 ℃, and the length of each drying box is 1.5 m. Coating a coating layer on the surface of the flexible film through a slot die, wherein the coating thickness is about 600 mu m; and then drying the coating layer on the flexible film through a drying box. Because 2 drying cabinets are arranged in a linear type, the guide roller span before and after the drying area is large, the flexible film seriously falls under the action of gravity when passing through the drying area, so that the swelling deformation and the wrinkle phenomenon are further intensified, the product quality is reduced, and even a qualified membrane electrode product cannot be prepared.
Comparative example 2
The membrane electrode is prepared by adopting winding equipment shown in figure 6, wherein 2 drying boxes are arranged in the winding equipment, namely a drying box 38 and a drying box 39 respectively, the linear arrangement parallel structure of the two drying boxes is changed into a folding up-down arrangement, the drying temperature in the drying box 38 is 60-90 ℃, the drying temperature in the drying box 39 is 100-120 ℃, and the length of each drying box is 1.5 m. Coating a coating layer on the surface of the flexible film through a slot die, wherein the coating thickness is about 600 mu m; and then drying the coating layer on the flexible film through a drying box. Compared with the comparative example 1, the arrangement form of the drying oven in the comparative example 2 shortens the span of the flexible film between the rollers, the falling degree of the flexible film in the drying area is improved, but the flexible film still has more serious falling due to the lack of reliable support, and the swelling deformation and the wrinkle phenomenon are aggravated. And because the direction of the high-temperature nitrogen blown out by the drying box is single, the coating material on the flexible film moves under the pushing of the gas pressure, the distribution of the coating layer on the flexible film is changed, and on the other hand, the airflow impact also causes the flexible film to generate obvious folds. Therefore, the preparation of the membrane electrode in the comparative example 2 also causes the product quality to be reduced, so that the product yield of the membrane electrode is lower.
Examples
The membrane electrode is prepared by adopting winding equipment shown in figure 1, and the preparation method mainly comprises a coating process and a drying process; wherein the coating process comprises: when the flexible film conveyed from the unwinding roller of the winding device passes through the coating roller, uniformly coating a coating material on the flexible film through a slot die to form a coating layer, wherein the thickness of the coating layer is about 800 mu m; the coating material is stored in a magazine in communication with the slot die, the coating material in the magazine being continuously supplied by an injection pump.
The drying process comprises the following steps: drying the coating layer on the flexible film by a drying oven arranged downstream of the coating roller; a synchronous supporting device is arranged opposite to the drying box and comprises a shell, a conveying belt and a transmission shaft; when the coating layer is dried by the drying oven, the conveyor belt of the synchronous supporting device provides plane support synchronous with the transmission speed of the flexible film for the flexible film, and the flexible film is prevented from sagging in the drying process to cause wrinkling and deformation.
And the coating layer on the flexible film is dried to form a flexible film electrode, and then the flexible film electrode is collected by a winding roller.
Before coating, the flexible film is flattened by a flattening roller; along with the rotation of nip roll, the flexible film that the spiral groove can pass through is to both sides exhibition flat, avoids the flexible film fold to appear, influences the coating homogeneity.
The number of the drying boxes is 2, and the drying boxes are respectively a first drying box arranged on the opposite side of the advancing section of the annular conveying path and a second drying box arranged on the opposite side of the returning section of the annular conveying path; the drying temperature of the first drying box is 60-90 ℃, and the drying temperature of the second drying box is 100-120 ℃; the length of the first drying oven and the second drying oven is 2.5 m. The second drying box is positioned below the first drying box.
After the drying process, the flexible film is sequentially cooled by a first cooling roller and a second cooling roller; the roll surface temperature of the first cooling roll is set to be within the range of 40-60 ℃, and the roll surface temperature of the second cooling roll is set to be within the range of 10-30 ℃; the wrap angle of the flexible film on the first cooling roller and the second cooling roller is more than 90 degrees. The roller bodies of the first cooling roller and the second cooling roller are of hollow structures, constant-temperature water and a coolant are respectively introduced into the first cooling roller and the second cooling roller, and the two cooling rollers are used for preventing the electrode films from being cracked due to stress generated by the surface coating caused by too fast temperature reduction after the drying process.
And continuously introducing nitrogen with 3-10 atmospheric pressures into the pipeline of the drying box by using an external air source, and heating the nitrogen in the pipeline by using a heater around the pipeline to ensure that the purging array uniformly purges high-temperature nitrogen to the surface of the flexible film, and drying the coating. After the swept high-temperature nitrogen is contacted with the surface of the flexible film, the swept high-temperature nitrogen is sucked into the cavity by the air suction groove under the action of the vacuum pump and is discharged out of the drying box; under the balance action of the blowing array and the air suction groove, a uniform non-pressure drying air cushion layer is formed above the flexible film, so that the coating layer on the flexible film is uniformly dried under the condition of keeping the original distribution uniformity. The design can avoid that the pressure of high-temperature nitrogen blown out in a single blowing direction pushes the coating material which is not dried and solidified on the flexible film, and the distribution uniformity of the coating layer is changed.
The inflation circulating system respectively inflates gas with different temperatures into the upper cavity and the lower cavity; the temperature of the gas in the upper cavity is 55-85 ℃, and the flexible film on the advancing section of the annular conveying path is heated through the conveying belt; the temperature of the gas in the upper cavity is 95-115 ℃, and the flexible film on the return section of the annular conveying path is heated through the conveying belt.
In the embodiment, although the thickness of the coating layer on the flexible film is far higher than that of the comparative example 1 and the comparative example 2, and the length of the drying oven is nearly 1.7 times that of the drying oven in the comparative example 1 and the comparative example 2, the flexible film does not generate drop deformation or obvious wrinkles in the drying process, the uniformity of the coating layer of the membrane electrode catalyst in a large area range is improved, the quality and the qualification rate of the membrane electrode product are obviously improved, and the performance of the membrane electrode is improved by about 60-80% compared with that of the comparative example 1 and the comparative example 2.
Claims (6)
1. A preparation method of a fuel cell membrane electrode is implemented by a winding device and mainly comprises a coating process and a drying process;
the coating process comprises the following steps: when the flexible film conveyed from the unwinding roller of the winding device passes through the coating roller, the coating material is uniformly coated on the flexible film through the slot die to form a coating layer; the coating material is stored in a magazine communicated with the slot die, and the coating material in the magazine is continuously supplied by an injection pump;
the drying process comprises the following steps: drying the coating layer on the flexible film by a drying oven arranged downstream of the coating roller; a synchronous supporting device is arranged opposite to the drying box and comprises a shell, a conveying belt and a transmission shaft; when the coating layer is dried by the drying box, the conveyor belt of the synchronous supporting device provides plane support synchronous with the transmission speed of the flexible film for the flexible film, so that the flexible film is prevented from sagging in the drying process to cause wrinkling and deformation;
drying the coating layer on the flexible film to form a flexible film electrode, and collecting the flexible film electrode by a winding roller;
the conveying belt is driven by the transmission shaft to form an annular conveying path; a transition roller is arranged at the downstream of the advancing section of the annular conveying path; the flexible film is turned over by 180 degrees in the conveying direction after bypassing the transition roller, and is folded back to pass through the return section of the annular conveying path and then is continuously conveyed; the conveying belt forms a supporting action surface on the advancing section and the returning section of the annular conveying path to provide plane support for the flexible film; the rotating speed control of a transmission shaft of the synchronous supporting device is coordinated and unified with the rotating speed control of the coating roller and the transition roller, so that the transmission speed of the conveyor belt and the transmission speed of the flexible film are kept synchronous;
the number of the drying boxes is 2, and the drying boxes are respectively a first drying box arranged on the opposite side of the advancing section of the annular conveying path and a second drying box arranged on the opposite side of the returning section of the annular conveying path; the drying temperature of the first drying box is 60-90 ℃, and the drying temperature of the second drying box is 100-120 ℃; the lengths of the first drying box and the second drying box are more than 1 m;
a plurality of pipelines are arranged in the drying box, each pipeline is provided with a plurality of air outlet channels to form a row of air outlet channels, and a plurality of rows of air outlet channels form a blowing array; continuously introducing nitrogen with 3-10 atmospheric pressures into the pipeline by an external gas source, heating the nitrogen in the pipeline by a heater around the pipeline, uniformly blowing high-temperature nitrogen to the surface of the flexible film by the blowing array, and drying the coating layer;
an air suction groove is arranged between every two rows of air outlet pore channels and is connected with a vacuum pump through a cavity in the drying box; after the swept high-temperature nitrogen is contacted with the surface of the flexible film, the nitrogen is sucked into the cavity by the air suction groove under the action of the vacuum pump and is discharged out of the drying box; under the balance action of the blowing array and the air suction groove, a uniform non-pressure drying air cushion layer is formed above the flexible film, so that the coating layer on the flexible film is uniformly dried under the condition of keeping the original distribution uniformity.
2. The method for producing a fuel cell membrane electrode according to claim 1, characterized in that: a flattening roller is arranged at the upstream of the coating roller, and the flexible film is flattened by the flattening roller before being coated; the flattening roller is provided with a spiral groove; the spiral groove is divided into two sections on the central section of the flattening roller, and the two sections are respectively extended reversely by taking the central section as a symmetrical plane; the included angle between the spiral line of the spiral groove and the flattening roll axis is 50-85 degrees; along with the rotation of nip roll, the flexible film that the spiral groove can pass through is to both sides exhibition flat, avoids the flexible film fold to appear.
3. The method for producing a fuel cell membrane electrode according to claim 1, characterized in that: after the drying process, the flexible film is sequentially cooled by a first cooling roller and a second cooling roller; the roll surface temperature of the first cooling roll is set to be within the range of 40-60 ℃, and the roll surface temperature of the second cooling roll is set to be within the range of 10-30 ℃; the wrap angle of the flexible film on the first cooling roller and the second cooling roller is more than 90 degrees.
4. The method for producing a fuel cell membrane electrode according to claim 1, characterized in that: the shell is provided with openings at corresponding positions of the advancing section and the returning section of the annular conveying path, so that the conveying belt is contacted with the flexible film at the openings to realize support; a slit is formed between the edge of the opening of the shell and the conveyor belt, and the width of the slit is within the range of 100 mu m-1 mm; the shell and the conveyor belt form a cavity of the synchronous supporting device; the conveying belt is made of heat conducting materials; and the inflation circulating system positioned outside the working cavity fills heated gas into the cavity of the synchronous supporting device, and the flexible film is heated through the conveyor belt.
5. The method of producing a fuel cell membrane electrode according to claim 4, characterized in that: a partition board is arranged in the shell, and a heat insulation layer is arranged on the partition board; the partition plate divides the cavity of the synchronous supporting device into an upper cavity and a lower cavity; 2 inflation circulating systems are provided, and gases with different temperatures are respectively filled into the upper cavity and the lower cavity; the temperature of the gas in the upper cavity is 55-85 ℃, and the flexible film on the advancing section of the annular conveying path is heated through the conveying belt; the temperature of the gas in the upper cavity is 95-115 ℃, and the flexible film on the return section of the annular conveying path is heated through the conveying belt.
6. The method for producing a fuel cell membrane electrode according to claim 1, characterized in that: the coating material comprises the components of iridium oxide, perfluorosulfonic acid, water, ethanol and propanol; mixing iridium oxide powder serving as a catalyst with water, adding propylene alcohol and ethanol, adding a water-based perfluorosulfonic acid ion dispersion, shearing and mixing the obtained mixed solvent in a mixer, and stirring by using a magnetic stirrer to obtain the coating material for the coating process.
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