WO2019230610A1 - 層を転写するための転写シート及び電極触媒層付きシート - Google Patents

層を転写するための転写シート及び電極触媒層付きシート Download PDF

Info

Publication number
WO2019230610A1
WO2019230610A1 PCT/JP2019/020763 JP2019020763W WO2019230610A1 WO 2019230610 A1 WO2019230610 A1 WO 2019230610A1 JP 2019020763 W JP2019020763 W JP 2019020763W WO 2019230610 A1 WO2019230610 A1 WO 2019230610A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
transfer sheet
transfer
electrode catalyst
sheet
Prior art date
Application number
PCT/JP2019/020763
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
裕太 黒木
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020207037340A priority Critical patent/KR20210018319A/ko
Priority to CN201980036413.6A priority patent/CN112203855A/zh
Publication of WO2019230610A1 publication Critical patent/WO2019230610A1/ja

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a transfer sheet for transferring a layer, and more specifically to a transfer sheet that can be used for supporting and transferring an electrode catalyst layer provided in an electrochemical element such as a fuel cell.
  • the present invention also relates to a sheet with an electrode catalyst layer.
  • a membrane electrode assembly (MEA) is used as a main component.
  • the MEA usually includes an electrolyte membrane and an electrode catalyst layer. More specifically, a pair of electrode catalyst layers for the fuel electrode and the air electrode are respectively laminated on the main surfaces of the electrolyte membrane.
  • An MEA configuration in which a diffusion layer is further formed on the surface of the electrode catalyst layer is also employed.
  • One method of laminating the electrode catalyst layer on the electrolyte membrane is a transfer method.
  • a sheet carrying the electrode catalyst layer on the surface is prepared, and the electrode catalyst layer is thermally transferred to the electrolyte membrane using the sheet as a transfer sheet.
  • Patent Document 1 a belt-shaped electrolyte membrane and a belt-shaped sheet carrying an electrode catalyst layer are laminated to form a laminate, and after passing between a pair of heated thermal transfer rolls, the sheet is peeled off, A method is disclosed in which a catalyst layer is continuously thermally transferred to an electrolyte membrane.
  • Patent Document 2 discloses a method in which an electrode catalyst layer formed on a base material is bonded to a polymer electrolyte membrane by hot pressing, and then the base material is peeled off to thermally transfer the electrode catalyst layer to the electrolyte membrane. Yes.
  • the electrode catalyst layer is becoming thinner with the miniaturization of fuel cells.
  • the thinned electrode catalyst layer is required to improve the homogeneity in the in-plane direction of the MEA, as compared with the prior art.
  • the homogeneity in the state transferred to the electrolyte membrane has a great influence on the power generation characteristics of the fuel cell.
  • an increase in thermal transfer temperature for the purpose of reliably transferring the thinned electrode catalyst layer to the electrolyte membrane is assumed.
  • defects such as deformation, cracks, and loss tend to occur in the electrode catalyst layer after transfer as the thermal transfer temperature rises.
  • An object of the present invention is to provide a transfer sheet that can satisfactorily perform thermal transfer of a transferred layer even when the thermal transfer temperature is high.
  • the present invention A transfer sheet for transferring the layer, A base material layer, and a pair of fluororesin porous layers that are bonded to the base material layer and sandwich the base material layer, A transfer sheet in which at least one of the fluororesin porous layers has a cohesive force of 1.8 N / 20 mm or more, I will provide a.
  • the present invention provides: The transfer sheet of the present invention, and an electrode catalyst layer,
  • the electrode catalyst layer is disposed on the at least one fluororesin porous layer, a sheet with an electrode catalyst layer, I will provide a.
  • the support surface of the transfer layer is constituted by the fluororesin porous layer.
  • the fluororesin constituting the fluororesin porous layer has a high releasability.
  • the contact area with the transfer layer on the carrying surface can be reduced as compared with the non-porous layer. For this reason, in the transfer sheet of the present invention, high releasability of the transfer layer during thermal transfer is ensured.
  • the surface of the fluororesin porous layer having a high cohesive force can be used as the carrying surface of the transfer layer.
  • the cohesive force corresponds to the breaking strength of the layer in the thickness direction.
  • the transfer sheet of the present invention has a structure in which the base material layer is sandwiched between a pair of fluororesin porous layers. For this reason, the deformation
  • the extension of the transfer sheet at the time of thermal transfer is suppressed by the base material layer as compared with the case where it is composed only of the fluororesin porous layer.
  • the transfer sheet of the present invention even when the thermal transfer temperature is high, the transfer layer can be favorably thermally transferred.
  • the transfer sheet 10 includes a base material layer 1 and a pair of fluororesin porous layers 2 a and 2 b that sandwich the base material layer 1.
  • the transfer sheet 10 is a transfer sheet for transferring a transfer layer formed and supported thereon to another member.
  • one fluororesin porous layer 2a has a cohesive force of 1.8 N / 20 mm or more.
  • the support surface of the transfer layer can be constituted by the fluororesin porous layer 2a. More specifically, the main surface (exposed surface) 21 opposite to the side in contact with the base material layer 1 in the fluororesin porous layer 2a can be used as a transfer layer support surface.
  • both the main surface 21 and the main surface 22 may be used as the transfer layer carrying surface.
  • the cohesive force of the fluororesin porous layer corresponds to the breaking strength of the layer in the thickness direction. That is, the higher the cohesive force, the harder the fluororesin porous layer is destroyed by the force applied in the thickness direction.
  • the lower limit of the cohesive force of the fluororesin porous layer 2a may be 1.9 N / 20 mm or more, and further 2.0 N / 20 mm or more.
  • the upper limit of the cohesive force of the fluororesin porous layer 2a is, for example, 4.5 N / 20 mm or less, and may be 4.0 N / 20 mm or less, 3.5 N / 20 mm or less, or even 3.0 N / 20 mm or less. .
  • the cohesive force of the fluororesin porous layer can be evaluated by a 180 ° peeling test.
  • the cohesive force of the fluororesin porous layer can be controlled by characteristics such as the average pore diameter, thickness, and membrane weight per unit area of the fluororesin porous layer. Moreover, each characteristic of a fluororesin porous layer can be controlled by the manufacturing conditions of a fluororesin porous layer, for example, the extending conditions for forming a fluororesin porous layer.
  • the thickness of the fluororesin porous layer 2a is, for example, 100 ⁇ m or less, and may be 70 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or even 10 ⁇ m or less.
  • the thickness of the fluororesin porous layer 2a decreases, the degree of unevenness on the carrying surface tends to decrease.
  • the lower limit of the thickness of the fluororesin porous layer 2a is, for example, 3 ⁇ m or more, 4 ⁇ m or more, and further 5 ⁇ m or more.
  • the thickness of the fluororesin porous layer can be evaluated by analyzing the cross-sectional image of the transfer sheet.
  • the example of a cross-sectional image is an enlarged observation image by an optical microscope or an electron microscope with respect to the cross section of the transfer sheet.
  • the magnification of the magnified observation image may be about 500 times, for example.
  • the thickness at at least 10 measurement points is evaluated while changing the location.
  • the average value of the thickness at each evaluated measurement point can be the thickness of the fluororesin porous layer.
  • the cohesive force of the fluororesin porous layer 2b may be within the range of the cohesive force of the fluororesin porous layer 2a described above.
  • the thickness of the fluororesin porous layer 2b may be within the range of the thickness of the fluororesin porous layer 2a described above.
  • the fluororesin porous layer 2b may have a cohesive force of 1.8 N / 20 mm or more and / or a thickness of 100 ⁇ m or less.
  • the cohesive force and / or thickness of the pair of fluororesin porous layers 2a and 2b provided in the transfer sheet 10 may be the same. This configuration is suitable for the case where the transfer sheet 10 is reused with the main surface 22 as the support surface after the main surface 21 is used as the support surface. Further, when the fluororesin porous layers 2a and 2b have the same thickness, deformation of the transfer sheet 10 due to heat of thermal transfer, typically curl, can be more reliably suppressed. For this reason, even when the thermal transfer temperature is high, thermal transfer of the transfer layer by the transfer sheet 10 can be more satisfactorily performed.
  • the pair of fluororesin porous layers 2a and 2b included in the transfer sheet 10 may have the same configuration.
  • the transfer layer transferred by the transfer sheet 10 is, for example, an electrode catalyst layer used for an electrochemical element such as a fuel cell.
  • the example of an electrode catalyst layer is an electrode catalyst layer with which MEA is provided.
  • the electrode catalyst layer includes a precursor layer thereof.
  • the transfer layer transferred by the transfer sheet 10 is not limited to the electrode catalyst layer.
  • the electrode catalyst layer on the transfer sheet 10 is usually formed by applying a catalyst solution containing a catalyst electrode and a diffusion solvent to the carrying surface of the transfer sheet 10.
  • a catalyst solution having a low solid content concentration and / or a low viscosity is generally used to form a thin electrode catalyst layer.
  • the carrying surface of the transfer sheet 10 is porous. For this reason, even when a catalyst solution having a low solid content concentration and / or a low viscosity is used, the catalyst solution is less likely to be repelled than a non-porous support surface, and the coating property of the catalyst solution can be improved. When the coatability is improved, for example, an electrode catalyst layer having higher homogeneity in the in-plane direction can be formed. Therefore, the transfer sheet 10 has high merit as an electrode catalyst layer transfer sheet (electrode catalyst layer transfer sheet), in particular, a thin electrode catalyst layer transfer sheet.
  • the fluororesin porous layers 2a and 2b and the base material layer 1 are joined by fusion bonding. Bonding by fusion is suitable for forming the transfer sheet 10 having a uniform thickness and reducing the manufacturing cost of the transfer sheet 10.
  • the fusion between the fluororesin porous layers 2a and 2b and the base material layer 1 can be performed by, for example, thermal lamination or hot pressing.
  • the fluororesin porous layers 2a and 2b and the base material layer 1 are fused by pressing a hot roll maintained at 130 to 290 ° C. with a linear pressure of 10 to 40 N / m.
  • the line speed at this time varies depending on the hot roll diameter, the heating temperature, and the like, but is, for example, 3.0 to 20.0 m / min.
  • the method of fusing the fluororesin porous layers 2a and 2b and the base material layer 1 is not limited to the above example.
  • the form of bonding between the fluororesin porous layers 2a and 2b and the base material layer 1 is not limited to fusion.
  • the fluororesin porous layers 2a and 2b and the base material layer 1 may be joined by, for example, an adhesive or a pressure-sensitive adhesive.
  • the thickness of the transfer sheet 10 is, for example, 15 ⁇ m to 400 ⁇ m, and may be 50 ⁇ m to 300 ⁇ m.
  • the base material layer 1 also serves as a reinforcing layer for the fluororesin porous layers 2 a and 2 b in the transfer sheet 10.
  • the base material layer 1 serves as a reinforcing layer for the fluororesin porous layers 2 a and 2 b in the transfer sheet 10.
  • Handleability includes transportability.
  • transfer of the transfer layer by roll-to-roll using the belt-shaped transfer sheet 10 supplied from the roll can be more stably and reliably performed.
  • the base material layer 1 is, for example, a resin layer, a metal layer, a paper layer, or an inorganic layer.
  • the transfer layer is an electrode catalyst layer
  • the base material layer 1 which is a resin layer, particularly a thermoplastic resin layer, is preferable from the viewpoint of preventing the metal from being mixed into the electrode catalyst layer.
  • the fluororesin porous layer is excluded from the resin layer.
  • the metal constituting the base material layer 1 is, for example, aluminum or stainless steel.
  • the melting point of the thermoplastic resin constituting the base material layer 1 is preferably 280 ° C. or lower.
  • the base material layer 1 composed of a thermoplastic resin having a melting point of 280 ° C. or less has good fusion properties with the fluororesin porous layers 2a and 2b.
  • the thermoplastic resin are at least one selected from polyester, polyacetal, polyethylene, ultrahigh molecular weight polyethylene, and polypropylene.
  • polyesters are polyethylene terephthalate (PET) and polybutylene terephthalate.
  • PET polyacetal and PET are preferable, and PET is more preferable because it hardly changes in quality when fused to the fluororesin porous layers 2a and 2b and is excellent in heat resistance and chemical resistance.
  • PET is preferably a grade having a low softening temperature, and in particular, a grade that starts softening at a temperature lower than 233 ° C. is preferable.
  • the base material layer 1 is typically a non-porous layer.
  • the non-porous base material layer 1 is suitable for reducing the surface roughness of the main surface 11 facing the fluororesin porous layer 2a.
  • the degree of unevenness on the main surface 21 (supporting surface) of the fluororesin porous layer 2a can be further reduced.
  • the transfer layer can be stably held.
  • the base material layer 1 is not limited to the non-porous layer, and may be a porous layer constituted by, for example, a woven fabric, a nonwoven fabric, a net, a stretched porous film, a fine particle fusion porous film, or the like.
  • the thickness of the base material layer 1 is, for example, 12.5 ⁇ m to 200 ⁇ m, and may be 25 to 175 ⁇ m.
  • the thickness of the base material layer 1 becomes excessively small, the reinforcing effect by the base material layer 1 is reduced, and the strength and / or handleability of the transfer sheet 10 may be reduced.
  • the thickness of the base material layer 1 is excessively large, for example, when the transfer sheet 10 is a roll, the weight of the roll may be excessive.
  • fluororesin constituting the fluororesin porous layers 2a and 2b are polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer. (FEP).
  • a preferred fluororesin is PTFE.
  • the fluororesin porous layer 2a is preferably a PTFE porous layer. Both the fluororesin porous layers 2a and 2b may be composed of the same fluororesin.
  • the fluororesin porous layers 2a and 2b may not contain components other than the fluororesin, and may not substantially contain components other than the fluororesin. In this specification, “substantially free” means that the content is less than 0.1 wt%, preferably less than 0.01 wt%.
  • the average pore diameter of the fluororesin porous layer 2a is, for example, 0.1 to 20 ⁇ m, and may be 0.2 to 15 ⁇ m, 0.2 to 10 ⁇ m, or even 1.5 to 7.0 ⁇ m.
  • thermal transfer of the transfer layer can be carried out more favorably.
  • the average pore diameter becomes excessively large for example, when the transfer layer is an electrode catalyst layer, carbon particles and catalyst particles contained in the electrode catalyst layer are taken into the pores of the fluororesin porous layer 2a during thermal transfer and thermally transferred.
  • the surface of the transfer layer may become rough.
  • the average pore diameter of both of the fluororesin porous layers 2a and 2b may be in the above range.
  • the average pore diameters of both the fluororesin porous layers 2a and 2b may be the same.
  • the contact angle with water on the main surface 21 of the fluororesin porous layer 2a is, for example, 100 degrees or more, 120 degrees or more, and 130 degrees or more.
  • the main surface having a high contact angle with water is particularly excellent in releasability from the transfer layer.
  • the contact angle with water on the main surface 22 of the fluororesin porous layer 2b may be in the above range.
  • the contact angle with water is a value evaluated by a sessile drop method defined in Japanese Industrial Standard (hereinafter referred to as “JIS”) R3257.
  • JIS R3257 is a standard relating to a method for evaluating the contact angle of the substrate glass surface.
  • the contact angle with water on the main surface of the transfer sheet 10 can be evaluated according to the test conditions defined in this standard.
  • the curl height at the end when the transfer sheet 10 is allowed to stand in an atmosphere of 120 ° C. for 5 minutes is, for example, 10 mm or less, preferably 7 mm or less, more preferably 5 mm or less.
  • An evaluation method of the curl height at the end will be described with reference to FIGS. 3A and 3B show cross sections obtained by cutting the test piece 31 and the plane 32 shown in FIGS. 2A and 2B in the width direction of the test piece 31, respectively.
  • the left-right direction of the paper surface of FIG. “Width” is, for example, the TD direction of the sheet, and in the case of a belt-like sheet, the width direction.
  • “Length” is, for example, the MD direction of the sheet, and in the case of a belt-like sheet, it is the longitudinal direction thereof.
  • a test sheet 31 is obtained by cutting out a transfer sheet, which is an evaluation object, into a width of 490 mm and a length of 500 mm.
  • the test piece 31 is accommodated in a dryer maintained at 120 ° C. and allowed to stand for 5 minutes. At that time, the test piece 31 is allowed to stand on a flat surface 32 that does not cause deformation at 120 ° C. that affects the evaluation of the curl height (FIG. 2 and FIG. 3A).
  • the plane 32 is, for example, the surface of a metal plate. After standing for 5 minutes, the test piece 31 together with the plane 32 is taken out of the dryer and cooled to room temperature. After cooling, the amount of lifting from the plane 32 by standing at 120 ° C.
  • the average value can be the curl height at the end of the transfer sheet 10.
  • the transfer sheet cut out with a smaller size is used as a test piece, and the end of the transfer sheet is measured by the above method.
  • the curl height can be obtained.
  • the coefficient according to the size of the test piece used for the measurement is multiplied by the measurement value, and converted to a value when a test piece having a width of 490 mm ⁇ 500 mm is used for the measurement. This converted value can be the curl height at the end of the transfer sheet.
  • FIG. 4 An example of the sheet with an electrode catalyst layer of the present disclosure is shown in FIG.
  • the sheet 15 with an electrode catalyst layer shown in FIG. 4 is a laminated sheet including the transfer sheet 10 and the transfer layer 3 disposed on the main surface 21 of the fluororesin porous layer 2a in the transfer sheet 10.
  • the transfer layer 3 is an electrode catalyst layer.
  • the sheet 15 with an electrode catalyst layer is configured by laminating a fluororesin porous layer 2b, a base material layer 1, a fluororesin porous layer 2a, and a transfer layer 3 in this order.
  • the transfer sheet 10 provided in the electrode catalyst layer-attached sheet 15 is as described above, including preferred forms.
  • the transfer layer 3 can be thermally transferred to the electrolyte membrane to form the MEA. As shown in FIG. 5, the transfer layer 3 thermally transferred onto the electrolyte membrane 5 becomes the electrode catalyst layer 6 of the MEA 20.
  • MEA An example of a product that can be manufactured using the transfer sheet 10 or the electrode catalyst layer-attached sheet 15 is MEA used for an electrochemical element such as PEFC.
  • the product manufactured using the transfer sheet 10 or the electrode catalyst layer-attached sheet 15 is not limited to the MEA.
  • the electrolyte membrane 5 includes an electrolyte membrane (polymer electrolyte membrane) 5 made of a polymer electrolyte and a pair of electrode catalyst layers 6 that sandwich the electrolyte membrane 5.
  • the electrode catalyst layer 6 is, for example, a porous thin film having pores having a diameter of 1 ⁇ m or less.
  • the electrode catalyst layer 6 mainly contains catalyst material-supporting particles (catalyst particles) and a polymer electrolyte.
  • known polymer electrolytes such as fluorine polymer electrolytes and hydrocarbon polymer electrolytes can be used.
  • the manufacturing method of MEA using the transfer sheet 10 includes, for example, an electrode catalyst layer laminating step, an electrolyte membrane laminating step, a thermocompression bonding step, and a peeling step.
  • the electrode catalyst layer laminating step is a step of forming on the transfer sheet 10 a transfer layer 3 that becomes an electrode catalyst layer after thermal transfer.
  • the electrolyte membrane laminating step is a step of laminating the transfer sheet 10 and the electrolyte membrane 5 so that the transfer layer 3 and the electrolyte membrane 5 are in contact with each other.
  • the thermocompression bonding process is a process in which the transfer layer 3 and the electrolyte membrane 5 are thermocompression bonded.
  • the peeling process is a process of peeling the transfer sheet 10 and leaving the transfer layer 3 on the electrolyte membrane 5 as the electrode catalyst layer 6.
  • the electrolyte membrane lamination step, the thermocompression bonding step, and the peeling step constitute a transfer step for the transfer layer 3.
  • the electrode catalyst layer stacking step can be performed, for example, as follows. First, a catalyst solution (electrode catalyst layer paste) in which catalyst particles and a polymer electrolyte are dispersed in a dispersion solvent is applied to the transfer sheet 10 to form a coating film. Next, the whole is heated at a temperature of about 30 to 180 ° C. to dry the coating film, and a laminated sheet (sheet 15 with the electrode catalyst layer) of the transfer sheet 10 and the transfer layer 3 as the electrode catalyst layer is obtained.
  • a known method such as a doctor blade method, a screen printing method, a roll coating method, or a spray method can be employed.
  • the thermocompression bonding step can be performed by, for example, hot pressing the laminated body in a state where the electrolyte membrane 5 and the transfer layer 3 are in contact with each other or passing them through a pair of hot rolls.
  • the thermocompression bonding temperature is, for example, 80 to 150 ° C. although it depends on the type of the electrolyte membrane 5.
  • the transfer layer 3 may be thermocompression bonded to both surfaces of the electrolyte membrane 5 at the same time.
  • the peeling step can be performed by, for example, continuously peeling the transfer sheet 10 from the thermocompression bonding body of the electrolyte membrane 5 and the transfer layer 3 using a roll for winding the transfer sheet 10.
  • the peeled transfer sheet 10 may be reused.
  • FIG. 6 shows an example of an apparatus that performs the thermocompression bonding process and the peeling process as a series of processes.
  • catalyst materials used for the catalyst particles include platinum group elements such as platinum, palladium, ruthenium, iridium, rhodium, osmium; iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, aluminum, etc. Metals; alloys thereof; and oxides and double oxides of these metals. If the particle size of the catalyst particles is too large, the activity of the catalyst is lowered, and if it is too small, the stability of the catalyst is lowered. Therefore, the particle size is preferably 0.5 to 20 nm, more preferably 1 to 5 nm.
  • the catalyst particles composed of one or more metals selected from platinum, gold, palladium, rhodium, ruthenium and iridium are excellent in electrode reactivity. For this reason, the use of the catalyst particles enables an efficient and stable electrode reaction.
  • Carbon particles are suitable for the particles carrying the catalyst substance.
  • the carbon particles are not limited as long as they are in the form of fine particles, have conductivity, and are not exposed to the catalyst.
  • Examples of carbon particles are carbon black, graphite, graphite, activated carbon, carbon fiber, carbon nanotube, and fullerene. If the particle size of the carbon particles is too small, it becomes difficult to form an electron conduction path. If the particle size is too large, the gas diffusibility of the electrode catalyst layer is reduced or the utilization factor of the catalyst is reduced. Preferably, 10 to 100 nm is more preferable.
  • a known material can be used for the polymer electrolyte regardless of the difference in cation conductivity and anion conductivity.
  • the cation conductivity is, for example, proton conductivity.
  • a known fluorine-based polymer electrolyte or hydrocarbon-based polymer electrolyte can be used as the polymer electrolyte having proton conductivity.
  • An example of the fluorine-based polymer electrolyte is Nafion (registered trademark) manufactured by DuPont.
  • hydrocarbon-based polymer electrolyte examples include sulfonated polyether ketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene.
  • the polymer electrolyte constituting the electrolyte membrane and the polymer electrolyte contained in the electrode catalyst layer are preferably the same.
  • the dispersion solvent used for the catalyst solution is not limited as long as the polymer electrolyte can be dissolved or dispersed as a fine gel in a highly fluid state without eroding the catalyst particles.
  • the dispersion solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and pentaanol; acetone Ketone solvents such as methyl ethyl ketone, pentanone, methyl isobutyl ketone, heptanone, cyclohexanone, methyl cyclohexanone, acetonyl acetone, diisobutyl ketone; ether solvents such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, anisole, methoxy toluene, dibutyl ether; Formamide, dimethylacet
  • the catalyst solution may contain a dispersant.
  • the dispersant are an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
  • sulfonic acid type surfactants such as alkylbenzene sulfonic acid, oil-soluble alkyl benzene sulfonic acid, ⁇ -olefin sulfonic acid, sodium alkyl benzene sulfonate, oil-soluble alkyl benzene sulfonate, ⁇ -olefin sulfonate are used as dispersants. It can be preferably used.
  • Example 1 After 100 parts by weight of PTFE fine powder (Daikin Kogyo Co., Ltd., Polyflon F-104) and 20 parts by weight of a liquid lubricant (n-dodecane, Japan Energy Co., Ltd.) are uniformly mixed and compressed in a cylinder A ram extrusion molding was performed to form a sheet-like PTFE molded body. Next, the formed PTFE compact was passed through a pair of rolling rolls and rolled to a thickness of 0.2 mm. Next, after the rolled PTFE molded body is heated to 150 ° C. to remove the liquid lubricant, it is stretched in the MD direction at a stretching temperature of 370 ° C.
  • PTFE fine powder Daikin Kogyo Co., Ltd., Polyflon F-104
  • a liquid lubricant n-dodecane, Japan Energy Co., Ltd.
  • a PTFE porous layer (thickness 45 ⁇ m, average pore diameter 3.0 ⁇ m, membrane weight 0.00975 g / m 2 per unit area).
  • the thickness of the PTFE porous layer which is a single layer was evaluated with a dial gauge. Specifically, the thickness at at least 10 measurement points was evaluated while changing the location, and the average value of the thicknesses at each measured measurement point was taken as the thickness of the PTFE porous layer.
  • the average pore diameter of the PTFE porous layer was evaluated by a commercially available evaluation apparatus (Perm-Porometer manufactured by Porous Materials, Inc.) capable of automatic measurement in accordance with the method defined in the American Society for Testing and Materials (ASTM) F316-86. .
  • the membrane weight per unit area in the PTFE porous layer was determined by dividing the weight of the PTFE porous layer by the area of the layer. In order to ensure measurement accuracy, the area of the PTFE porous layer for evaluating the membrane weight per unit area was set to 5 m 2 or more.
  • a non-porous PET film (Unitika Ltd., EMBLET® SD-75, film thickness 75 ⁇ m) was prepared as a base material layer, and the prepared base material layer and the prepared PTFE porous layer were paired with each other. Lamination was performed such that the base material layer was sandwiched by the PTFE porous layer. Next, the laminate of the base material layer and the PTFE porous layer was hot-pressed at a linear pressure of 20 kN for 60 seconds with a high-temperature press at 280 ° C., and then formed into a predetermined shape (strip shape having a width of 20 mm and a length of 400 mm).
  • Example 1 Cut to obtain a transfer sheet (Sample 1) in which a PET base material layer and a pair of PTFE porous layers sandwiching the PET base material layer were fused. The cutting was performed so that the MD direction of the PTFE porous layer coincided with the length direction of the strip.
  • Example 2 A PTFE porous layer (thickness 50 ⁇ m, average pore diameter 2.9 ⁇ m, membrane weight 0.01000 g / m 2 per unit area) was prepared in the same manner as Sample 1 except that the stretching conditions were changed. Next, a transfer sheet (Sample 2) in which a PET base material layer and a pair of PTFE porous layers sandwiching the PET base material layer were fused in the same manner as Sample 1 except that the produced PTFE porous layer was used. )
  • Example 3 A PTFE porous layer (thickness 60 ⁇ m, average pore diameter 2.8 ⁇ m, membrane weight 0.01025 g / m 2 per unit area) was prepared in the same manner as Sample 1 except that the stretching conditions were changed. Next, a transfer sheet (Sample 3) in which a PET base material layer and a pair of PTFE porous layers sandwiching the PET base material layer were fused in the same manner as Sample 1 except that the produced PTFE porous layer was used. )
  • Example 4 A PTFE porous layer (thickness 40 ⁇ m, average pore diameter 3.3 ⁇ m, membrane weight 0.00950 g / m 2 per unit area) was prepared in the same manner as Sample 1 except that the stretching conditions were changed. Next, a transfer sheet (Sample 4) in which a PET base material layer and a pair of PTFE porous layers sandwiching the PET base material layer were fused in the same manner as in Sample 1 except that the produced PTFE porous layer was used. )
  • Example 5 Comparative example
  • a PTFE porous layer (thickness 30 ⁇ m, average pore diameter 3.5 ⁇ m, membrane weight 0.00930 g / m 2 per unit area) was prepared in the same manner as Sample 1 except that the stretching conditions were changed.
  • a transfer sheet (comparative example) in which a PET base material layer and a pair of PTFE porous layers sandwiching the PET base material layer were fused in the same manner as in Sample 1 except that the produced PTFE porous layer was used. Sample 5) was obtained.
  • Example 6 Comparative example
  • a PTFE porous layer (thickness 25 ⁇ m, average pore diameter 3.7 ⁇ m, membrane weight 0.00900 g / m 2 per unit area) was prepared in the same manner as Sample 1 except that the stretching conditions were changed.
  • a transfer sheet (comparative example) in which a PET base material layer and a pair of PTFE porous layers sandwiching the PET base material layer were fused in the same manner as in Sample 1 except that the produced PTFE porous layer was used.
  • a sample 6 was obtained.
  • the cohesive force of the PTFE porous layer was evaluated as follows using a 180 ° peeling test.
  • the double-sided adhesive tape 51 (Nitto Denko Co., Ltd., No. 5000NS, 160 ⁇ m in thickness, 20 mm in width and 350 mm in length) is attached to the surface (affixed) of stainless steel Affixed to the wearing surface).
  • the double-sided pressure-sensitive adhesive tape 51 had a sufficient sticking force not to peel from the sticking surface of the fixing plate 52 during the test.
  • the fixing plate 52 which has a flat sticking surface, the area of a sticking surface larger than the area of the double-sided adhesive tape 51, and sufficient thickness which does not deform
  • the fixing plate 52 which has a flat sticking surface, the area of a sticking surface larger than the area of the double-sided adhesive tape 51, and sufficient thickness which does not deform
  • Each sample 53 was affixed on the opposite surface of the double-sided pressure-sensitive adhesive tape 51 to the fixed plate 52 side, with 51 as the “test plate” defined in the above item. The sample 53 was attached such that the PTFE porous layer to be evaluated was in contact with the double-sided adhesive tape 51.
  • the sample 53 was attached by making the long side coincide with the fixed plate 52 and setting the length of the attached portion from one end of the sample 53 to 150 mm.
  • the number of reciprocations of the manual roller (mass 2 kg) for pressing the sample 53 and the double-sided pressure-sensitive adhesive tape 51 does not measure the adhesive force of the double-sided pressure-sensitive adhesive tape 51. Only.
  • the laminate of the fixing plate 52, the double-sided pressure-sensitive adhesive tape 51, and the sample 53 was left in an atmosphere at 70 ° C. for 10 minutes to homogenize the adhesive force of the double-sided pressure-sensitive adhesive tape 51 to the sample 53. Thereafter, the whole was naturally cooled to room temperature (23 ° C. ⁇ 1 ° C.).
  • [Coatability of catalyst solution] (Preparation of catalyst solution) Since the catalyst material used for the electrode catalyst layer is generally expensive, in this example, the applicability of a simulated catalyst solution containing only the carbon particles and the polymer electrolyte was evaluated without the catalyst material. It is considered that the catalyst substance does not greatly affect the coating property of the catalyst solution on the transfer sheet. For this reason, the applicability of the catalyst solution can be evaluated with a simulated catalyst solution.
  • a simulated catalyst solution was prepared as follows. First, 25 g of carbon particles, 125 g of polymer electrolyte (Nafion), 302.5 g of isopropyl alcohol, and 47.5 g of water were mixed to obtain a pseudo catalyst electrode ink having a total amount of 500 g.
  • the obtained pseudo catalyst electrode ink and isopropyl alcohol were mixed and diluted at a weight ratio of 1: 0.5 to obtain a simulated catalyst solution.
  • the composition of this solution corresponds to the low solids concentration and low viscosity composition used to form the thinned electrocatalyst layer.
  • the prepared simulated catalyst solution was applied to the main surface (exposed surface) of one PTFE porous layer in each sample using an applicator to form a coating film (thickness 0.25 mm).
  • the direction of application was the length direction of each sample.
  • the whole was heated for 3 minutes using a dryer maintained at 120 ° C., and the coating film was dried to form a simulated electrode catalyst layer on the transfer sheet.
  • the catalyst solution is not repelled on the coating surface, and the formed electrode catalyst layer is visually observed to show no defects such as cracks. ⁇ ) ”, and other cases were evaluated as“ coatability / impossible ( ⁇ ) ”.
  • a nonporous non-porous PTFE sheet was prepared as a transfer sheet (sample 7 as a comparative example).
  • thermo transfer characteristics A sample on which a simulated electrode catalyst layer was formed was evaluated for thermal transfer characteristics, more specifically, whether stable thermal transfer of the electrode catalyst layer was possible as follows.
  • An adhesive tape (manufactured by Nitto Denko Corporation, No. 360UL, 65 ⁇ m in thickness, 20 mm in width ⁇ 150 mm in length) was prepared as a member for thermally transferring the electrode catalyst layer.
  • the adhesive tape and the sample were laminated so that the adhesive surface of the adhesive tape and the electrode catalyst layer formed on the sample were in contact with each other. Lamination was performed such that the entire electrode catalyst layer was in contact with the adhesive tape.
  • a manual roller having a mass of 2 kg was reciprocated once in the length direction of the laminate, and the adhesive tape and the sample were pressure bonded.
  • the manual roller the one specified in JIS Z0237, item 10.3.1 was used.
  • the laminate was hot-pressed for 30 seconds under a pressurizing condition of a linear pressure of 4.5 kN using a hot press set at room temperature, 120 ° C., 150 ° C. or 180 ° C.
  • a hot press set at room temperature, 120 ° C., 150 ° C. or 180 ° C.
  • the sample was peeled by hand and the state of the electrode catalyst layer transferred to the adhesive tape was visually observed.
  • thermo transfer characteristics / good ( ⁇ ) when the electrode catalyst layer did not show any defects such as deformation, damage, surface loss, etc., it was defined as “thermal transfer characteristics / good ( ⁇ )”, and when defects were partially observed, “thermal transfer characteristics / Depending on the conditions of use of the electrode catalyst layer, “Yes ( ⁇ )” was given, and when a defect was found overall, “thermal transfer characteristics / impossible (x)”.
  • the thermal transfer characteristics of Samples 1 to 4 were good ( ⁇ ) under any thermal transfer conditions of room temperature, 120 ° C., 150 ° C., and 180 ° C.
  • the thermal transfer characteristic of Sample 5 as a comparative example was acceptable ( ⁇ ) under the thermal transfer condition of 150 ° C.
  • the thermal transfer characteristic of Sample 6 as a comparative example was not possible (x) under the thermal transfer conditions of 150 ° C. and 180 ° C.
  • a part of the PTFE porous layer is agglomerated and destroyed at the time of thermal transfer under the high-temperature thermal transfer conditions in which thermal transfer characteristics are enabled or disabled, and adhere to the surface of the transferred electrode catalyst layer. It was.
  • the transfer sheet of the present disclosure can be used, for example, for transferring an electrode catalyst layer provided in an electrochemical element such as a fuel cell.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)
  • Laminated Bodies (AREA)
PCT/JP2019/020763 2018-05-30 2019-05-24 層を転写するための転写シート及び電極触媒層付きシート WO2019230610A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020207037340A KR20210018319A (ko) 2018-05-30 2019-05-24 층을 전사하기 위한 전사 시트 및 전극 촉매층을 갖는 시트
CN201980036413.6A CN112203855A (zh) 2018-05-30 2019-05-24 用于转印层的转印片和带有电极催化剂层的片

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-103320 2018-05-30
JP2018103320 2018-05-30

Publications (1)

Publication Number Publication Date
WO2019230610A1 true WO2019230610A1 (ja) 2019-12-05

Family

ID=68696959

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/020763 WO2019230610A1 (ja) 2018-05-30 2019-05-24 層を転写するための転写シート及び電極触媒層付きシート

Country Status (4)

Country Link
JP (1) JP7324615B2 (ko)
KR (1) KR20210018319A (ko)
CN (1) CN112203855A (ko)
WO (1) WO2019230610A1 (ko)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002184415A (ja) * 2000-10-18 2002-06-28 General Motors Corp <Gm> 膜電極アセンブリを準備する方法
JP2015096325A (ja) * 2013-10-11 2015-05-21 日東電工株式会社 薄層転写用シート、電極触媒層付薄層転写用シート、薄層転写用シートの製造方法、および膜電極接合体の製造方法
JP2017013468A (ja) * 2015-07-06 2017-01-19 日東電工株式会社 層を転写するためのシート及びそれを用いた電極触媒層付きシート
WO2018101176A1 (ja) * 2016-11-29 2018-06-07 日東電工株式会社 層を転写するための転写シート及び電極触媒層付きシート

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008103251A (ja) 2006-10-20 2008-05-01 Toyota Motor Corp 電解質膜への触媒層の熱転写方法および装置
JP5508880B2 (ja) * 2010-02-01 2014-06-04 日東電工株式会社 両面粘着テープおよびその製造方法
CN102823040B (zh) * 2010-03-26 2015-03-11 凸版印刷株式会社 燃料电池膜电极组件的制造方法及燃料电池膜电极组件的制造装置
JP2013073892A (ja) 2011-09-29 2013-04-22 Toppan Printing Co Ltd 燃料電池用膜電極接合体の製造方法
TW201420344A (zh) * 2012-09-21 2014-06-01 Nippon Synthetic Chem Ind 聚乙烯醇系膜及其製造方法、以及使用聚乙烯醇系膜之熱轉印用積層體及使用其之熱轉印方法
JP6558244B2 (ja) * 2014-03-31 2019-08-14 東レ株式会社 触媒転写シート、膜電極複合体の製造方法および触媒層被覆電解質膜の製造方法。

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002184415A (ja) * 2000-10-18 2002-06-28 General Motors Corp <Gm> 膜電極アセンブリを準備する方法
JP2015096325A (ja) * 2013-10-11 2015-05-21 日東電工株式会社 薄層転写用シート、電極触媒層付薄層転写用シート、薄層転写用シートの製造方法、および膜電極接合体の製造方法
JP2017013468A (ja) * 2015-07-06 2017-01-19 日東電工株式会社 層を転写するためのシート及びそれを用いた電極触媒層付きシート
WO2018101176A1 (ja) * 2016-11-29 2018-06-07 日東電工株式会社 層を転写するための転写シート及び電極触媒層付きシート

Also Published As

Publication number Publication date
JP7324615B2 (ja) 2023-08-10
KR20210018319A (ko) 2021-02-17
JP2019209687A (ja) 2019-12-12
CN112203855A (zh) 2021-01-08

Similar Documents

Publication Publication Date Title
KR102239198B1 (ko) 박층 전사용 시트, 전극 촉매층을 갖는 박층 전사용 시트, 박층 전사용 시트의 제조 방법 및 막 전극 접합체의 제조 방법
JP5122149B2 (ja) 固体高分子形燃料電池用膜電極接合体の製造方法
US10374245B2 (en) Manufacturing method for reinforced electrolyte membrane and manufacturing apparatus of manufacturing the same
JP2010067493A (ja) 膜電極接合体の製造方法、膜電極接合体、固体高分子形燃料電池
US20200287220A1 (en) Method for producing gas diffusion electrode substrate and fuel cell
US9005839B2 (en) Method for laminating composite sheet using release film, laminate obtained by the method, and release film for use in the method
JP6345863B2 (ja) 層を転写するための転写シート及び電極触媒層付きシート
JP5412860B2 (ja) 膜触媒層接合体の製造装置及び製造方法、並びに膜電極接合体の製造装置及び製造方法
WO2019230610A1 (ja) 層を転写するための転写シート及び電極触媒層付きシート
JP5439710B2 (ja) 触媒層付電解質膜及びその製造方法
WO2018122888A1 (ja) 層を転写するための転写シート及び電極触媒層付きシート
JP6553962B2 (ja) 層を転写するためのシート及びそれを用いた電極触媒層付きシート
TWI739785B (zh) 用於將層轉印之轉印片及附有電極觸媒層之片材
JP5699348B2 (ja) 膜触媒層接合体の製造装置及び製造方法、並びに膜電極接合体の製造装置及び製造方法
US12040497B2 (en) Method of manufacturing and device for manufacturing membrane-catalyst assembly
KR20200119203A (ko) 연료 전지용 막전극 접합체의 제조 방법
JP2014216053A (ja) マスクフィルム・ベースフィルム付き転写シート、マスクフィルム・ベースフィルム付き転写シートの製造方法、触媒層シートの製造方法、触媒層シート及び固体高分子形燃料電池
JP2010123372A (ja) 固体高分子形燃料電池用膜電極接合体の製造方法および膜電極接合体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19812176

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207037340

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 19812176

Country of ref document: EP

Kind code of ref document: A1