CN113839050A - High-performance cathode catalyst layer of fuel cell and manufacturing process thereof - Google Patents
High-performance cathode catalyst layer of fuel cell and manufacturing process thereof Download PDFInfo
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Abstract
The invention relates to the technical field of fuel cells, in particular to a high-performance cathode catalyst layer of a fuel cell and a manufacturing process thereof, which comprises the following process steps: s1, preparing catalyst slurry a; s2, preparing catalyst slurry b: according to the following steps of 3: 1: preparing 4 parts, namely taking three parts of carbon powder, one part of platinum black and four parts of perfluorinated sulfonic acid resin, and fully mixing for later use; s3, forming a first high-efficiency catalyst layer; s4, forming a high-efficiency water-locking proton conducting layer; s5, forming a second efficient catalyst layer, and coating catalyst slurry a and catalyst slurry b on the proton exchange membrane in a staggered manner, wherein the catalyst slurry b is higher in perfluorosulfonic acid resin mass content, so that the efficient water-locking proton conduction layer is ensured to have stronger water-locking capacity and proton conduction efficiency. According to the invention, through the structural change of the catalyst layer, the proton conduction efficiency and the water locking capability of the catalyst layer in the catalyst layer can be improved, and the electrical property of the catalyst layer in a low-humidity environment is improved.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a high-performance cathode catalyst layer of a fuel cell and a manufacturing process thereof.
Background
In order to reduce the commercialization progress of the fuel cell, the purchase cost of the user is reduced. In integrated form, fuel cell systems are continually striving to reduce system components. The complete fuel cell needs some supporting facilities besides the cell plate mainly composed of the bipolar plate and the proton exchange membrane, the proton exchange membrane is kept to work under the humid environment, the generating efficiency can be greatly improved, but due to the structure, the proton exchange membrane without water locking treatment has poor water locking capacity, so a humidifier needs to be added outside the pile to provide water for the pile, and the volume of the complete fuel cell is increased.
The low-humidification or even no external humidification of the fuel cell is realized, and the high-efficiency power generation capacity of the fuel cell is kept, so that a humidifier can be omitted, and the volume of the complete fuel cell is reduced. Is an important development direction among them.
It is a good idea for the membrane electrode to utilize the water produced during the hydrogen-oxygen chemical reaction without the supply of external humidified water.
The chinese patent publication No. CN106684395A discloses a manufacturing process of a cathode catalyst layer with gradient porosity for a fuel cell, and belongs to the technical field of proton exchange membrane fuel cells. A process for manufacturing a cathode catalyst layer with gradient porosity for a fuel cell comprises the steps of uniformly mixing a supported catalyst, a perfluorinated sulfonic acid resin solution with the mass percentage concentration of 5-20%, a low-boiling-point solvent and deionized water to obtain a catalyst slurry, spraying the catalyst slurry on a proton exchange membrane to prepare the cathode catalyst layer, wherein the spraying frequency is controlled to be 2-4 times, and the porosity of the cathode catalyst layer prepared by the process is gradually increased from the proton exchange membrane side to the gas diffusion layer side. The water locking capacity of the inner catalyst layer is ensured during the operation with low current density. But also gives consideration to the oxygen diffusion and the mass transfer capability of the liquid under the condition of high current density.
The cathode catalyst layer is prepared by spraying catalyst slurry on a proton exchange membrane, the spraying frequency is controlled to be 2-4 times, and the cathode catalyst layer prepared by the process is utilized. However, the spraying process has a problem that the inner catalyst layer is horizontally coated in a single layer, and the single-layer horizontal coating needs to be performed on the catalyst layer for achieving a good water locking capability, which increases the processing cost, and the multi-layer coating also causes a problem that the thickness of the whole catalyst layer is increased, which results in an increase in the thickness of the proton exchange membrane and a reduction in the yield.
Therefore, it is desirable to design a high performance cathode catalyst layer for a fuel cell and a manufacturing process thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a high-performance cathode catalyst layer of a fuel cell and a manufacturing process thereof, and aims to solve the problems that the processing cost of a water locking layer provided in the background technology is high, multi-layer coating is needed, the whole thickness of the catalyst layer is increased, the thickness of a proton exchange membrane is increased, and the yield is reduced.
In order to achieve the purpose, the invention provides the following technical scheme: a high-performance cathode catalyst layer of a fuel cell and a manufacturing process thereof comprise the following process steps:
s1, preparing catalyst slurry a: according to the following steps of 3: 1: 1 part of the platinum black is prepared, and three parts of carbon powder, one part of platinum black and one part of perfluorinated sulfonic acid resin are fully mixed for standby;
s2, preparing catalyst slurry b: according to the following steps of 3: 1: preparing 4 parts, namely taking three parts of carbon powder, one part of platinum black and four parts of perfluorinated sulfonic acid resin, and fully mixing for later use;
s3, forming a first high-efficiency catalytic layer: coating by adopting nanoscale coating equipment, namely horizontally coating a layer of catalyst slurry a on a proton exchange membrane to form a first catalytic surface, controlling the thickness to be between 0.1 and 0.5 micrometer, coating a layer of catalyst slurry a on the first catalytic surface at certain intervals to form a second catalytic surface, wherein the coating width is equal to the interval width, the coating width and the interval width are both controlled to be between 0.6 and 1cm, and the coating thickness is controlled to be between 0.1 and 0.5 micrometer, so that an uneven first high-efficiency catalytic layer structure is formed on the surface of the first catalytic surface;
s4, forming a high-efficiency water-locking proton conducting layer: coating by adopting nanoscale coating equipment, firstly coating catalyst slurry b at the interval between two second catalytic surfaces to form a first water locking surface, wherein the first water locking surface is flush with the second catalytic surfaces, the thickness of the first water locking surface is controlled to be 0.1-0.5 micrometer, coating the catalyst slurry b on the second catalytic surfaces to form second water locking surfaces, the width of each second water locking surface is the same as that of each second catalytic surface, the thickness of each second water locking surface is controlled to be 0.1-0.5 micrometer, the first water locking surfaces and the second water locking surfaces form vertically staggered high-efficiency water locking proton conducting layers, and the total mass content of perfluorosulfonic acid resin in the high-efficiency water locking proton conducting layers is controlled to be 50%;
s5, forming a second high-efficiency catalytic layer: coating by adopting nanoscale coating equipment, firstly coating catalyst slurry a on the first water locking surface to form a third catalytic surface, wherein the third catalytic surface is flush with the second water locking surface, the thickness is controlled to be 0.1-0.5 micrometer, then horizontally coating a layer of catalyst slurry a on the third catalytic surface and the second water locking surface to form a fourth catalytic surface, the thickness is controlled to be 0.1-0.5 micrometer, and the third catalytic surface and the fourth catalytic surface form a second high-efficiency catalytic layer.
Preferably, the second catalytic surface is coated obliquely on the first catalytic surface, and the first water-lock surface and the second water-lock surface are also coated obliquely.
Preferably, the second water locking surface is coated at the joint of the first water locking surface and the second catalytic surface, the second water locking surface is respectively overlapped with the first water locking surface and the second catalytic surface, and the width of the overlapped part is one half of the width of the second water locking surface.
Preferably, the coating width of the second catalytic surface is controlled to be 0.3-0.5 cm.
A high-performance cathode catalyst layer of a fuel cell is manufactured by adopting the manufacturing process of the high-performance cathode catalyst layer of the fuel cell according to any one of claims, and comprises a proton exchange membrane, wherein the proton exchange membrane is composed of a cathode surface and an anode surface, a high-efficiency catalyst layer is coated on the cathode surface of the proton exchange membrane, the high-efficiency catalyst layer is composed of a first high-efficiency catalyst layer and a second high-efficiency catalyst layer, and a high-efficiency water-locking proton conducting layer is arranged between the first high-efficiency catalyst layer and the second high-efficiency catalyst layer.
Preferably, the first high-efficiency catalyst layer consists of a first catalyst surface and a second catalyst surface, the high-efficiency water-locking proton conducting layer consists of a first water locking surface and a second water locking surface, the first catalyst surface is coated on the proton exchange membrane, the first catalyst surface is uniformly coated with the second catalyst surface and the first water locking surface, and the second catalyst surface and the first water locking surface are flushed and distributed in a staggered manner.
Preferably, the second high-efficiency catalyst layer consists of a third catalyst surface and a fourth catalyst surface, the third catalyst surface is coated on the first water locking surface and is flush with the second water locking surface, and the fourth catalyst surface is horizontally coated on the third catalyst surface and the second water locking surface.
Compared with the prior art, the invention has the beneficial effects that: the high-performance cathode catalyst layer of the fuel cell and the manufacturing process thereof can improve the proton conduction efficiency and the water locking capacity of the catalyst layer in the catalyst layer and improve the electrical performance of the catalyst layer in a low-humidity environment by changing the structure of the catalyst layer.
(1) The catalyst slurry b is prepared by mixing three parts of carbon powder, one part of platinum black and one part of perfluorinated sulfonic acid resin, and the catalyst slurry b is coated on the catalyst slurry a to form a proton conduction layer with strong water locking capability, so that the low humidification or even no humidification of the fuel cell is realized, the catalyst layer and the proton exchange membrane are kept moist, the proton conduction efficiency is improved, and the power generation capability is improved.
(2) By adopting a double-layer overlapping coating process, the catalyst layers and the water locking layer are arranged in a staggered manner, water can be stored between the catalyst layers in a staggered manner, and the water locking effect is further enhanced.
Drawings
FIG. 1 is a schematic overall structure diagram according to a first embodiment of the present invention;
FIG. 2 is a partial schematic view of the structure of the highly effective catalytic layer and the highly effective water-holding proton conductive layer shown in FIG. 1 according to the present invention;
FIG. 3 is an exploded view of a first embodiment of the present invention;
fig. 4 is a schematic cross-sectional structural view of a third embodiment of the present invention.
In the figure: 1. a proton exchange membrane; 2. a high-efficiency catalyst layer; 21. a first catalytic surface; 22. a second catalytic surface; 23. a third catalytic surface; 24. a fourth catalytic surface; 3. a high efficiency water-retaining proton conducting layer; 31. a first water lock surface; 32. and the second lock water surface.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
referring to fig. 1-4, the present invention provides a high performance cathode catalyst layer for a fuel cell and a manufacturing process thereof; the method comprises the following process steps:
s1, preparing catalyst slurry a: according to the following steps of 3: 1: 1 part of the platinum black is prepared, and three parts of carbon powder, one part of platinum black and one part of perfluorinated sulfonic acid resin are fully mixed for standby;
s2, preparing catalyst slurry b: according to the following steps of 3: 1: preparing 4 parts, namely taking three parts of carbon powder, one part of platinum black and four parts of perfluorinated sulfonic acid resin, and fully mixing for later use;
s3, forming a first high-efficiency catalytic layer: coating by adopting nanoscale coating equipment, firstly, horizontally coating a layer of catalyst slurry a on a proton exchange membrane 1 to form a first catalytic surface 21, controlling the thickness to be between 0.1 and 0.5 micron, controlling the thickness of an excessively thick coating layer to ensure the thickness of the whole coating layer on the proton exchange membrane, avoiding the thickness of the whole coating layer to exceed 3 microns, coating a layer of catalyst slurry a on the first catalytic surface 21 at certain intervals to form a second catalytic surface 22, wherein the coating width is equal to the interval width, the coating width and the interval width are both controlled to be between 0.6 and 1cm, and the coating thickness is controlled to be between 0.1 and 0.5 micron, so that the surface of a first catalytic surface 21 conduction layer forms an uneven first efficient catalytic layer structure, the coating mode can ensure that water-locking protons 3 are staggered with the water-locking protons, and water generated in the reaction process can be staggered and accumulated between the catalytic layers, the water loss caused by a single plane is avoided, and the water locking effect is further improved;
s4, forming the highly efficient water-holding proton conductive layer 3: coating by adopting nanoscale coating equipment, firstly coating catalyst slurry b at the interval between two second catalytic surfaces 22 to form a first water locking surface 31, wherein the first water locking surface 31 is flush with the second catalytic surfaces 22, the thickness of the first water locking surface 31 is controlled to be 0.1-0.5 micrometer, the catalyst slurry b is coated on the second catalytic surfaces 22 to form second water locking surfaces 32, the width of the second water locking surfaces 32 is the same as that of the second catalytic surfaces 22, the thickness of the second water locking surfaces 32 is controlled to be 0.1-0.5 micrometer, the first water locking surfaces 31 and the second water locking surfaces 32 form vertically staggered high-efficiency water locking proton conducting layers 3, the total mass content of perfluorosulfonic acid resin in the high-efficiency water locking proton conducting layers 3 is controlled to be 50%, the mass content of the perfluorosulfonic acid resin is higher, and therefore, the high-efficiency water locking proton conducting 3 layer has stronger water locking capacity and proton conducting efficiency;
s5, forming a second high-efficiency catalytic layer: the coating is carried out by adopting nano-scale coating equipment, firstly, catalyst slurry a is coated on the first water locking surface 31 to form a third catalytic surface 23, the third catalytic surface 23 is flush with the second water locking surface 32, the thickness is controlled to be 0.1-0.5 micrometer, then, a layer of catalyst slurry a is horizontally coated on the third catalytic surface 23 and the second water locking surface 32 to form a fourth catalytic surface 24, the thickness is controlled to be 0.1-0.5 micrometer, the third catalytic surface 23 and the fourth catalytic surface 24 form a second high-efficiency catalytic layer, and finally, the first high-efficiency catalytic layer structure, the high-efficiency water locking proton conducting layer 3 and the second high-efficiency catalytic layer form a staggered superposed structure.
Fuel cell high performance negative pole catalysis layer, including proton exchange membrane 1, proton exchange membrane 1 comprises negative pole face and positive pole face, and the coating has high-efficient catalysis layer 2 on proton exchange membrane 1's the negative pole face, and high-efficient catalysis layer 2 comprises first high-efficient catalysis layer and the high-efficient catalysis layer of second, is provided with high-efficient lock water proton conduction layer 3 between first high-efficient catalysis layer and the high-efficient catalysis layer of second, promotes the lock water effect when guaranteeing catalytic effect.
Further, the first high-efficiency catalyst layer is composed of a first catalyst surface 21 and a second catalyst surface 22, the high-efficiency water-locking proton conducting layer 3 is composed of a first water locking surface 31 and a second water locking surface 32, the first catalyst surface 21 is coated on the proton exchange membrane 1, the first catalyst surface 21 is uniformly coated with the second catalyst surface 22 and the first water locking surface 31, the second catalyst surface 22 and the first water locking surface 31 are flushed and distributed in a staggered mode, the second high-efficiency catalyst layer is composed of a third catalyst surface 23 and a fourth catalyst surface 24, the third catalyst surface 23 is coated on the first water locking surface 31 and flushed with the second water locking surface 32, and the fourth catalyst surface 24 is horizontally coated on the third catalyst surface 23 and the second water locking surface 32, so that water generated in the reaction process can be accumulated between the catalyst layers in a staggered mode, water loss caused by a single plane is avoided, and the water locking effect is further improved.
Example two:
on the basis of the first embodiment, the difference lies in that: the second catalytic surface 22 is obliquely coated on the first catalytic surface 21, and the first water locking surface 31 and the second water locking surface 32 are also obliquely coated, so that the excessive moisture can be discharged obliquely, the effect of height drop is generated, the excessive moisture can be collected towards the tail end more smoothly, and the moisture can be ensured to flow uniformly on the surface of the catalytic layer.
Example three:
on the basis of the first embodiment, the difference lies in that: second lock surface of water 32 coating is in the combination department of first lock surface of water 31 and second catalysis face 22, second lock surface of water 32 overlaps with first lock surface of water 31 and second catalysis face 22 respectively, the overlap portion width is the half of coating width, make and produce the step effect between the 31 second catalysis faces of first lock surface of water 22, prevent water loss, when proton exchange membrane 1 uses on motion products such as new energy automobile, the inside inertia that can produce of fuel cell in the motion, the motion of the water on 2 surfaces of high-efficient catalysis layer has been accelerated, the design of step effect, block moisture in step department, the water locking effect has been improved.
Example four:
on the basis of the first embodiment, the difference lies in that: the coating width of the second catalytic surface 22 is controlled to be 0.3-0.5cm, a more dense step effect is formed, moisture is more densely blocked, and the water locking effect is further improved.
The working principle is as follows: the content of the platinum black and the carbon powder in the high-efficiency water-locking proton conducting layer 3 is lower than that of the platinum black and the carbon powder in the high-efficiency catalyst layer 2, and the quality of the perfluorinated sulfonic acid resin in the high-efficiency water-locking proton conducting layer 3 is higher than that of the perfluorinated sulfonic acid resin in the high-efficiency catalyst layer 2, so that stronger water-locking capacity and proton conducting efficiency are ensured.
Crisscross coincide between high-efficient catalysis layer 2 and the high-efficient water-locking proton conduction layer 3 distributes, the moisture content that produces in the messenger reaction process can crisscross accumulate between the catalysis layer, avoid single plane to cause the moisture content to run off, further improve the water-locking effect, and distribute through crisscross coincide, produce the step effect, carry out the separation to moisture, when proton exchange membrane 1 is used on motion products such as new energy automobile, the inside centrifugal force that can produce of fuel cell in the motion, the separation of the water on high-efficient catalysis layer 2 surface has been accelerated, the design of step effect, the separation has been produced to moisture, the water-locking effect has been improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. A manufacturing process of a high-performance cathode catalyst layer of a fuel cell is characterized by comprising the following process steps:
s1, preparing catalyst slurry a: according to the following steps of 3: 1: 1 part of the platinum black is prepared, and three parts of carbon powder, one part of platinum black and one part of perfluorinated sulfonic acid resin are fully mixed for standby;
s2, preparing catalyst slurry b: according to the following steps of 3: 1: preparing 4 parts, namely taking three parts of carbon powder, one part of platinum black and four parts of perfluorinated sulfonic acid resin, and fully mixing for later use;
s3, forming a first high-efficiency catalytic layer: coating by adopting nanoscale coating equipment, firstly, horizontally coating a layer of catalyst slurry a on a proton exchange membrane (1) to form a first catalytic surface (21), controlling the thickness to be between 0.1 and 0.5 micrometer, coating a layer of catalyst slurry a on the first catalytic surface (21) at certain intervals to form a second catalytic surface (22), wherein the coating width is equal to the interval width, the coating width and the interval width are both controlled to be between 0.6 and 1cm, and the coating thickness is controlled to be between 0.1 and 0.5 micrometer, so that an uneven first high-efficiency catalytic layer structure is formed on the surface of the first catalytic surface (21);
s4, forming the efficient water-locking proton conducting layer (3): coating by adopting nanoscale coating equipment, firstly coating catalyst slurry b at the interval between two second catalytic surfaces (22) to form a first water locking surface (31), wherein the first water locking surface (31) is flush with the second catalytic surfaces (22), the thickness of the first water locking surface is controlled to be 0.1-0.5 micrometer, the second catalytic surfaces (22) are coated with the catalyst slurry b to form second water locking surfaces (32), the width of each second water locking surface (32) is the same as that of each second catalytic surface (22), the thickness of each second water locking surface (32) is controlled to be 0.1-0.5 micrometer, the first water locking surface (31) and the second water locking surface (32) form high-efficiency water locking proton conducting layers (3) which are staggered up and down, and the total mass content of perfluorosulfonic acid resin in the high-efficiency water locking proton (3) is controlled to be 50%;
s5, forming a second high-efficiency catalytic layer: the method comprises the steps of coating by adopting a nanoscale coating device, firstly coating catalyst slurry a on a first water locking surface (31) to form a third catalytic surface (23), leveling the third catalytic surface (23) with a second water locking surface (32), controlling the thickness to be 0.1-0.5 micrometer, then horizontally coating a layer of catalyst slurry a on the third catalytic surface (23) and the second water locking surface (32) to form a fourth catalytic surface (24), controlling the thickness to be 0.1-0.5 micrometer, and forming a second high-efficiency catalytic layer by the third catalytic surface (23) and the fourth catalytic surface (24).
2. The process of manufacturing a high performance cathode catalyst layer for a fuel cell according to claim 1, wherein: the second catalytic surface (22) is coated obliquely on the first catalytic surface (21), and the first water-lock surface (31) and the second water-lock surface (32) are also coated obliquely.
3. The process of manufacturing a high performance cathode catalyst layer for a fuel cell according to claim 1, wherein: the second water locking surface (32) is coated at the joint of the first water locking surface (31) and the second catalytic surface (22), the second water locking surface (32) is respectively overlapped with the first water locking surface (31) and the second catalytic surface (22), and the width of the overlapped part is one half of the width of the second water locking surface (32).
4. The process of manufacturing a high performance cathode catalyst layer for a fuel cell according to claim 1, wherein: the coating width of the second catalytic surface (22) is controlled to be 0.3-0.5 cm.
5. A high-performance cathode catalyst layer of a fuel cell, which is manufactured by adopting the manufacturing process of the high-performance cathode catalyst layer of the fuel cell according to any one of claims 1 to 4, and comprises a proton exchange membrane (1), wherein the proton exchange membrane (1) is composed of a cathode surface and an anode surface, and is characterized in that: the high-efficiency water-locking proton exchange membrane is characterized in that a high-efficiency catalyst layer (2) is coated on the cathode surface of the proton exchange membrane (1), the high-efficiency catalyst layer (2) is composed of a first high-efficiency catalyst layer and a second high-efficiency catalyst layer, and a high-efficiency water-locking proton conducting layer (3) is arranged between the first high-efficiency catalyst layer and the second high-efficiency catalyst layer.
6. The fuel cell high performance cathode catalyst layer of claim 5, wherein: the first high-efficiency catalyst layer consists of a first catalyst surface (21) and a second catalyst surface (22), the high-efficiency water-locking proton conducting layer (3) consists of a first water locking surface (31) and a second water locking surface (32), the first catalyst surface (21) is coated on a proton exchange membrane (1), the first catalyst surface (21) is uniformly coated with the second catalyst surface (22) and the first water locking surface (31), the second catalyst surface (22) and the first water locking surface (31) are flushed and distributed in a staggered manner, and the second water locking surface (32) is coated on the second catalyst surface (22).
7. The fuel cell high performance cathode catalyst layer of claim 6, wherein: the second high-efficiency catalyst layer is composed of a third catalyst surface (23) and a fourth catalyst surface (24), the third catalyst surface (23) is coated on the first water locking surface (31) and is flush with the second water locking surface (32), and the fourth catalyst surface (24) is horizontally coated on the third catalyst surface (23) and the second water locking surface (32).
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| CN111653809A (en) * | 2020-04-28 | 2020-09-11 | 上海电气集团股份有限公司 | Membrane electrode and preparation method thereof |
| CN113140768A (en) * | 2021-04-12 | 2021-07-20 | 上海交通大学 | Cathode side structure of integrated reversible fuel cell membrane electrode |
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