CN110364741B - Composite coating method for CCM membrane electrode of hydrogen fuel cell - Google Patents

Composite coating method for CCM membrane electrode of hydrogen fuel cell Download PDF

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CN110364741B
CN110364741B CN201910631382.0A CN201910631382A CN110364741B CN 110364741 B CN110364741 B CN 110364741B CN 201910631382 A CN201910631382 A CN 201910631382A CN 110364741 B CN110364741 B CN 110364741B
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protective film
proton exchange
membrane electrode
catalyst layer
exchange membrane
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CN110364741A (en
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杨志明
杨星
吴健
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Shenzhen Xinyuren Technology Co Ltd
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Shenzhen Xinyuren Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8875Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8878Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8878Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8896Pressing, rolling, calendering
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1004Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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  • 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)
  • Fuel Cell (AREA)

Abstract

A composite coating method of a hydrogen fuel cell CCM membrane electrode comprises the steps of S1, coating a first catalyst layer on the surface A of a proton exchange membrane; s2, baking the first catalyst layer at a first preset temperature; s3, compacting the density of the first catalytic layer at a preset pressure by using a rolling mechanism; s4, compounding a protective film on the compacted first catalytic layer; s5, uncovering the protective film on the surface B of the proton exchange membrane; s6, coating a second catalytic layer on the surface B of the proton exchange membrane; s7, baking the second catalyst layer at a second preset temperature; and S8, stripping the protective film to obtain the CCM membrane electrode. The invention has the advantage that the catalyst layer can not be taken away by the protective film when the protective film is peeled.

Description

Composite coating method for hydrogen fuel cell CCM membrane electrode
Technical Field
The invention relates to a composite coating method and a device for a hydrogen fuel cell CCM (catalyst coated membrane) membrane electrode.
Technical Field
When the catalyst layer is coated on the double-side of the proton exchange membrane of the hydrogen fuel cell, most of the solvents adopted by the catalyst layer are alcohol substances, such as methanol, ethanol, propanol, isopropanol, n-propanol or glycerol, however, most of the currently adopted proton exchange membranes are perfluorosulfonic acid membranes, and thus, when the catalyst layer is coated on the proton exchange membrane, the proton exchange membrane is swelled due to the presence of the alcohol solvents, and the quality of the proton exchange membrane is affected. In order to solve the swelling problem, chinese patent document CN1084481139a discloses a method and apparatus for manufacturing a fuel cell membrane electrode, wherein the method adopted is: coating a first electrode layer on the surface A of the proton exchange membrane; compounding a first protective film on the surface A of the proton exchange membrane; coating a second electrode layer on the surface B of the proton exchange membrane; performing viscosity reduction treatment on the first protective film to reduce the adhesive force of the first protective film; and stripping the first protective film to obtain the membrane electrode. The core of the method is to compound a first protective film on a first electrode layer coated with the first electrode layer (which is a first catalytic layer), then coat a second electrode layer on the B surface of the proton exchange membrane, then carry out viscosity reduction treatment on the first protective film, and then peel off the first protective film. In practical application, people find that when the protective film is uncovered, partial catalytic layers are more or less removed on the protective film, so that the problems of incomplete catalytic layer surface appearance and uneven catalytic layer thickness distribution are caused, which is not allowed.
Disclosure of Invention
In order to solve the problems, the invention provides a composite coating method and equipment for a proton exchange membrane of a hydrogen fuel cell, wherein the protective membrane does not take away a catalyst layer when the protective membrane is stripped.
The technical scheme of the invention is as follows: the composite coating method of CCM membrane electrode for hydrogen fuel cell includes the following steps:
s1, coating a first catalyst layer on the surface A of a proton exchange membrane;
s2, baking the first catalyst layer at a first preset temperature;
s3, compacting the density of the first catalytic layer at a preset pressure by using a rolling mechanism;
s4, compounding a composite protective film on the compacted first catalytic layer;
s5, uncovering the protective film on the surface B of the proton exchange membrane;
s6, coating a second catalytic layer on the surface B of the proton exchange membrane;
s7, baking the second catalyst layer at a second preset temperature;
and S8, stripping the protective film to obtain the CCM membrane electrode.
As a modification of the invention, a step S71 is also provided between the steps S7 and S8, and the protective film is subjected to viscosity reduction treatment to reduce the adhesive force of the protective film.
As a refinement of the invention, the first predetermined temperature and the second predetermined temperature are selected between 70 degrees celsius and 150 degrees celsius.
As an improvement to the invention, the adhesive force range of the composite protective film after viscosity reduction treatment is as follows: 0-1N/25 mm.
As an improvement to the invention, the viscosity reduction treatment comprises: at least one of heat treatment, light treatment, and chemical treatment.
As an improvement to the invention, said predetermined pressure is chosen between 4 and 12 MPa.
The invention also provides a composite coating device of the hydrogen fuel cell CCM membrane electrode, which comprises,
the unwinding mechanism 1 is used for unwinding the proton exchange membrane 11, wherein the proton exchange membrane has two surfaces, one surface is pasted with a protective film and called a surface B, and the other surface is not pasted with the protective film and called a surface A;
a first coating head 2 for coating a first catalytic layer 12 on a surface a of a proton exchange membrane 11;
a first baking oven 3 for baking the first catalytic layer 12 at a first predetermined temperature;
a rolling mechanism 4 that compacts the density of the first catalytic layer at a predetermined pressure;
a composite protective film bonding mechanism 5 for bonding a composite protective film 51 on the compacted first catalytic layer;
the protective film winding mechanism 6 is used for collecting the protective film 13 stripped from the surface B of the proton exchange membrane 11;
a second coating head 7 for coating a second catalytic layer 14 from the B-side of the proton exchange membrane 11;
a second baking oven 8 for baking the second catalytic layer 14 at a second predetermined temperature;
the composite protective film winding mechanism 10 is used for collecting the composite protective film 51 stripped from the surface A of the proton exchange membrane 11;
and the winding mechanism 11 is used for winding the CCM membrane electrode.
As an improvement of the present invention, the composite protective film viscosity reduction device 9 performs viscosity reduction treatment on the composite protective film 51 on the first catalytic layer;
as a refinement of the invention, the first predetermined temperature and the second predetermined temperature are selected between 70 degrees celsius and 150 degrees celsius.
As an improvement to the invention, the adhesive force range of the composite protective film after viscosity reduction treatment is as follows: 0-1N/25 mm.
As an improvement to the invention, the viscosity reduction treatment comprises: at least one of heat treatment, light treatment, and chemical treatment.
As a refinement of the invention, the predetermined pressure is chosen between 4 and 12 MPa.
According to the method, the first catalyst layer is dried, the first catalyst layer is immediately compacted by a rolling mechanism, then the composite protective film is compounded, the second catalyst layer is coated on the B surface of the proton exchange membrane, the viscosity of the composite protective film is reduced or not reduced after the second catalyst layer is dried, and the composite protective film is removed to obtain the CCM membrane electrode, so that the purpose that the first catalyst layer cannot be taken away by the composite protective film when the composite protective film is peeled is achieved.
Drawings
FIG. 1 is a block diagram of one embodiment of the method of the present invention.
Fig. 2 is a schematic structural diagram of an embodiment of the apparatus of the present invention.
Detailed Description
Referring to fig. 1, fig. 1 shows a composite coating method for CCM membrane electrode of hydrogen fuel cell, wherein the adopted proton exchange membrane has two sides, one side is coated with a protective film called B side, and the other side is not coated with a protective film called a side, comprising the following steps:
s1, coating a first catalyst layer on the surface A of a proton exchange membrane, wherein the first catalyst layer can be a catalyst layer which takes Pt/C as a main component and takes a solvent as an alcohol substance, and the alcohol substance can be one or more of methanol, ethanol, propanol and isopropanol;
s2, baking the first catalyst layer at a first preset temperature, wherein the first preset temperature can be selected from 70 ℃ to 150 ℃, and the specific temperature is selected according to the components of the first catalyst layer;
s3, compacting the density of the first catalyst layer by using a rolling mechanism at a preset pressure, wherein the preset pressure is selected from 4-12MPa, the rolling mechanism comprises an upper pressing roller and a lower pressing roller, the two pressing rollers are pressed by a hydraulic device, and after a test, when the preset pressure between the two rollers reaches 4MPa, a composite protective film is compounded after being compacted, after the viscosity reduction treatment of the composite protective film, the adhesion of the first catalyst layer on the composite protective film can be obviously reduced, and the effect is improved along with the increase of the pressure; when the pressure reaches more than 8MPa, the viscosity reduction treatment of the composite protective film is not needed, the amount of the first catalyst layer adhered to the composite protective film can be obviously reduced, when the pressure reaches more than 9MPa and less than 12MPa, the viscosity reduction treatment of the composite protective film is not needed, and a good effect can be achieved.
S4, attaching a composite protective film on the compacted first catalytic layer, wherein the attaching method of the composite protective film can be a hot rolling method and the like;
s5, uncovering the protective film on the surface B of the proton exchange membrane;
s6, coating a second catalytic layer on the surface B of the proton exchange membrane, wherein the second catalytic layer can be a catalytic layer which takes Pt/C as a main component and takes a solvent as an alcohol substance, and the alcohol substance can be one or more of methanol, ethanol, propanol and isopropanol;
s7, baking the second catalyst layer at a second preset temperature, wherein the second preset temperature can be selected from 70-150 ℃, and the specific temperature is selected according to the components of the second catalyst layer;
and S8, stripping the protective film to obtain the CCM membrane electrode.
In the present invention, step S71 is further provided between step S7 and step S8, and when the pressure of the rolling mechanism is between 4MPa and 8MPa, the composite protective film is preferably subjected to a viscosity reduction treatment to reduce the adhesive force of the protective film.
The composite protective film can be a thermal viscosity reduction composite protective film, a light viscosity reduction composite protective film (such as UV light viscosity reduction film) or a chemical viscosity reduction composite protective film, and the thermal viscosity reduction composite protective film, the light viscosity reduction composite protective film and the chemical viscosity reduction composite protective film are existing products and can be directly purchased in the market, so the details are not repeated here.
Preferably, the first predetermined temperature and the second predetermined temperature are selected from 70 ℃ to 150 ℃, depending on the composition of the first catalytic layer and the second catalytic layer.
Preferably, the adhesion range of the composite protective film after viscosity reduction treatment is as follows: 0-1N/25 mm.
Referring to fig. 2, fig. 2 discloses a composite coating device for CCM membrane electrode of hydrogen fuel cell, comprising,
the unwinding mechanism 1 is used for unwinding the proton exchange membrane 11, wherein the proton exchange membrane has two surfaces, one surface is pasted with a protective film and called a surface B, and the other surface is not pasted with the protective film and called a surface A;
the first coating head 2 is used for coating a first catalyst layer 12 on the surface A of the proton exchange membrane 11, wherein the first catalyst layer 12 can be a catalyst layer which takes Pt/C as a main component and takes an alcohol substance as a solvent, and the alcohol substance can be one or more of methanol, ethanol, propanol and isopropanol;
the first baking oven 3 is used for baking the first catalytic layer 12 at a first preset temperature, wherein the first preset temperature can be selected from 70-150 ℃, and the specific temperature is determined according to the components of the first catalytic layer;
the roll-pressing mechanism 4 is used for compacting the density of the first catalytic layer at a preset pressure, the preset pressure is selected from 4-12MPa, the roll-pressing mechanism comprises an upper press roll 41 and a lower press roll 42, the two press rolls are pressed through a hydraulic device, through tests, when the preset pressure between the two rolls reaches 4MPa, a composite protective film is compounded after the two rolls are compacted, after the viscosity reduction treatment of the composite protective film, the adhesion of the first catalytic layer on the composite protective film can be obviously reduced, and the effect of the composite protective film is improved along with the increase of the pressure; when the pressure reaches more than 8MPa, the viscosity reduction treatment of the composite protective film is not needed, the amount of the first catalyst layer adhered to the composite protective film can be obviously reduced, when the pressure reaches more than 9MPa and less than 12MPa, the viscosity reduction treatment of the composite protective film is not needed, and a good effect can be achieved;
a composite protective film bonding mechanism 5 for bonding a composite protective film 51 on the compacted first catalytic layer;
the protective film winding mechanism 6 is used for collecting the protective film 13 stripped from the surface B of the proton exchange membrane 11;
the second coating head 7 is used for coating a second catalyst layer 14 on the surface B of the proton exchange membrane 11, wherein the second catalyst layer 14 can be a catalyst layer which takes Pt/C as a main component and takes a solvent as an alcohol substance, and the alcohol substance can be one or more of methanol, ethanol, propanol and isopropanol;
a second baking oven 8, which is used for baking the second catalytic layer 14 at a second predetermined temperature, wherein the second predetermined temperature can be selected from 70 ℃ to 150 ℃, and the specific temperature is determined according to the components of the first catalytic layer;
the composite protective film viscosity reduction device 9 is used for performing viscosity reduction treatment on the composite protective film 51 on the first catalyst layer, the composite protective film can be a thermal viscosity reduction composite protective film, a light viscosity reduction composite protective film (such as UV light-irradiated viscosity reduction film) or a chemical viscosity reduction composite protective film, and the thermal viscosity reduction composite protective film, the light viscosity reduction composite protective film and the chemical viscosity reduction composite protective film are existing products and can be directly purchased in the market, so the details are not repeated;
the composite protective film winding mechanism 10 is used for collecting the composite protective film 51 stripped from the surface A of the proton exchange membrane 11;
and the winding mechanism 11 is used for winding the CCM membrane electrode.
Preferably, the first predetermined temperature and the second predetermined temperature are selected between 70 ℃ and 150 ℃.
Preferably, the adhesive force range of the composite protective film after viscosity reduction treatment is as follows: 0-1N/25 mm.
Preferably, the viscosity reduction treatment comprises: at least one of heat treatment, light treatment, and chemical treatment.

Claims (5)

1. A composite coating method for CCM membrane electrode of hydrogen fuel cell, the proton exchange membrane has two sides, one side is pasted with protective film called B side, the other side is not pasted with protective film called A side, the method is characterized in that: the method comprises the following steps:
s1, coating a first catalytic layer on the surface A of a proton exchange membrane;
s2, baking the first catalyst layer at a first preset temperature;
s3, compacting the density of the first catalytic layer at a preset pressure by using a rolling mechanism;
s4, compounding a protective film on the compacted first catalytic layer;
s5, uncovering the protective film on the surface B of the proton exchange membrane;
s6, coating a second catalyst layer on the surface B of the proton exchange membrane;
s7, baking the second catalyst layer at a second preset temperature;
and S8, stripping the protective film to obtain the CCM membrane electrode.
2. The composite coating method of hydrogen fuel cell CCM membrane electrode according to claim 1, characterized in that: between the above S7 and S8, there is also a step S71 of performing a viscosity reduction treatment on the protective film to reduce the adhesive force of the protective film.
3. The composite coating method of hydrogen fuel cell CCM membrane electrode according to claim 2, characterized in that: the adhesive force range of the composite protective film after viscosity reduction treatment is as follows: 0-1N/25 mm.
4. The composite coating method for the CCM membrane electrode of the hydrogen fuel cell according to claim 2 or 3, which is characterized in that: the viscosity reduction treatment comprises the following steps: at least one of heat treatment, light treatment, and chemical treatment.
5. The composite coating method for the CCM membrane electrode of the hydrogen fuel cell according to claim 1, 2 or 3, which is characterized in that: the predetermined pressure is selected between 4-12 MPa.
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CN112599793B (en) * 2020-12-14 2022-07-19 中国科学院大连化学物理研究所 CCM coating process for realizing anti-swelling by using protective back membrane
CN112846534B (en) * 2020-12-30 2023-03-21 武汉理工氢电科技有限公司 3CCM cutting method
CN117080511B (en) * 2023-10-18 2024-03-08 国家电投集团氢能科技发展有限公司 Proton exchange membrane processing device and processing method

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