CN114843543A - Super-hydrophobic condensed water surface, preparation method thereof, battery pole plate and fuel cell - Google Patents
Super-hydrophobic condensed water surface, preparation method thereof, battery pole plate and fuel cell Download PDFInfo
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- CN114843543A CN114843543A CN202210629199.9A CN202210629199A CN114843543A CN 114843543 A CN114843543 A CN 114843543A CN 202210629199 A CN202210629199 A CN 202210629199A CN 114843543 A CN114843543 A CN 114843543A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses an ultraphobic condensed water surface and a preparation method thereof, a battery polar plate and a fuel battery, wherein the preparation method comprises the following steps: a fuel cell polar plate and a graphite target material are arranged in the vacuum cavity, wherein the fuel cell polar plate is arranged above the graphite target material; the air pressure value of the vacuum cavity is reduced to 10 ‑3 Pa to 3X 10 ‑ 4 After Pa, filling argon; emitting a pulse laser beam to the graphite target to bombard the graphite target so as to generate graphite plasma, wherein each pulse of the pulse laser beam has a pulse width of 800 fs-12 ps, and the diameter of the pulse laser beam is 120 um; the graphite plasma collides with the filled argon, decelerates and deposits on the polar plate of the fuel cell to form a porous graphite film layer consisting of nano-scale graphite particles; and forming a silane hydrophobic coating on the porous graphite film layer by using a vapor deposition method to obtain the super-hydrophobic condensed water surface. The preparation method obtainsThe super-hydrophobic condensed water surface can not cause hydrophobic failure due to the existence of condensed water, and has excellent drainage performance.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to an ultraphobic condensed water surface, a preparation method thereof, a cell polar plate and a fuel cell.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the characteristics of cleanness, no pollution, low noise, high efficiency, quick start, good low-temperature environment adaptability and the like, and can be widely applied to the fields of traffic, energy and the like. The bipolar plate is one of the core components of the fuel cell, has structures such as a shared channel, a cathode flow field, an anode flow field, a cooling flow field and the like, and has the main functions of uniformly distributing reaction gas in the fuel cell, removing reaction water, conducting electricity and heat, providing mechanical support and the like.
Fig. 1a is a schematic diagram of a flow field flooding of a fuel cell, in an operating condition with high current density, a large amount of water is generated on a cathode side of the fuel cell due to electrochemical reaction and electro-osmotic drag effect, so that liquid water is accumulated in a cathode flow field of a bipolar plate, and flooding is caused in a severe case, which further hinders effective transmission and diffusion of a reactant gas, and causes performance attenuation of the fuel cell and damage to internal components. Accordingly, bipolar plate flow fields are typically treated to be hydrophobic in fuel cell applications.
In the process of implementing the embodiments of the present specification, the inventors found that:
because the proton exchange membrane fuel cell usually runs at high temperature, a large amount of gaseous water is easily generated in the catalyst layer, and a large temperature difference exists between the catalyst layer and the bipolar plate, so that the temperature of the water vapor in the bipolar plate flow field is easily reduced to form condensed water. In addition, to fully wet the proton exchange membrane, the reactant gases are typically humidified, further exacerbating the condensation effect in the flow field. Fig. 1b shows a schematic diagram of failure of a superhydrophobic surface in a condensation environment in the prior art, when a fuel cell is in operation, condensed water infiltrates micro defects and micro-nano structures of a hydrophobic or superhydrophobic surface of a bipolar plate, so that the hydrophobic surface fails, accumulation of liquid water in a flow field is caused, a flooding phenomenon is caused, transmission and diffusion of water and reaction gas are hindered, and power density and service life of the fuel cell are reduced.
Disclosure of Invention
The invention provides an ultraphobic condensed water surface, a preparation method thereof, a battery polar plate and a fuel battery, which are used for overcoming at least one problem in the prior art.
According to a first aspect of embodiments herein, there is provided a method for preparing an ultraphobic condensed water surface, comprising:
a fuel cell pole plate and a graphite target are arranged in the vacuum cavity, wherein the fuel cell pole plate is arranged above the graphite target;
reducing the air pressure value of the vacuum cavity to 10 -3 Pa to 3X 10 -4 After Pa, filling argon;
emitting a pulse laser beam to the graphite target to bombard the graphite target so as to generate graphite plasma, wherein each pulse of the pulse laser beam has a pulse width of 800 fs-12 ps, and the diameter of the pulse laser beam is 120 um;
the graphite plasma collides with the filled argon and is deposited on the fuel cell polar plate to form a porous graphite film layer consisting of nano-scale graphite particles;
and forming a silane hydrophobic coating on the porous graphite film layer by using a vapor deposition method to obtain the super-hydrophobic condensed water surface.
Optionally, the forming of the silane hydrophobic coating on the porous graphite thin film layer by using a vapor deposition method specifically includes:
and placing the fuel cell pole plate deposited with the porous graphite film layer into another container, dripping fluorosilane into the container, vacuumizing the container, and finally placing the container in an oven with a preset temperature for a preset time to deposit fluorosilane on the porous graphite film layer by a vapor deposition method so as to form a silane hydrophobic coating.
Optionally, the graphite particles are nanoparticles, and the nano-structure size of the nanoparticles is 100 nm.
Optionally, the thickness of porous graphite thin film layer is 1um to 5 um.
Optionally, the pressure of the argon gas filled into the vacuum chamber is 10Pa to 50 Pa.
Optionally, the emitting a pulsed laser beam to the graphite target to bombard the graphite target and deposit a graphite plasma on the fuel cell electrode plate further includes: the average output power of the laser beam is 50W to 200W, the pulse frequency is 100kHz to 1000kHz, the target base distance is 25mm to 50mm, and the deposition time is 5 minutes.
According to a second aspect of the embodiments of the present disclosure, there is provided an ultraphobic condensed water surface, which is prepared by the method for preparing an ultraphobic condensed water surface according to any one of the first aspect, including: a porous graphite film layer deposited on the fuel cell bipolar plate and a silane hydrophobic coating disposed on the porous graphite film layer.
According to a third aspect of embodiments herein, there is provided a fuel cell plate provided with an ultraphobic condensed water surface as described in the second aspect.
According to a fourth aspect of embodiments herein, there is provided a fuel cell comprising the fuel cell plate according to the third aspect.
In the embodiment of the specification, the graphite target material arranged in the vacuum cavity is bombarded by the pulse laser beam, the graphite target material is gasified and diffused, is collided and decelerated with argon gas in the vacuum cavity, and is finally deposited on a flow field structure of a fuel cell substrate arranged above the graphite target material to form a porous graphite film layer consisting of nano-scale graphite particles, and the nano-scale porous structure of the porous graphite film layer is combined with a silane hydrophobic coating obtained by a vapor deposition method, so that on one hand, the nano-scale porous structure is easier to form an ultraphobic condensed water surface and can drain smaller condensed water effectively, and on the other hand, the surface obtained by combining the nano-scale porous graphite structure with the silane hydrophobic coating is not more than the Laplace force of the water drop to the capillary force, so that the condensed water is difficult to infiltrate, and the ultraphobic of the condensed water is realized. The surface prepared by the method is introduced into the design and preparation of the flow field of the fuel cell bipolar plate, so that the flow field of the fuel cell bipolar plate can still maintain effective drainage performance under the working conditions of low operating temperature, high humidification and high current density, and the flooding phenomenon is avoided.
Compared with the prior art, the invention points of the embodiment of the specification at least comprise:
1. bombarding a graphite target material arranged in a vacuum cavity by pulse laser beams to prepare a porous graphite film layer consisting of graphite nano-particles, so that the graphite target material is gasified and diffused and collides with argon filled in the vacuum cavity to decelerate to form the porous graphite film layer consisting of nano-scale graphite particles, and a silane hydrophobic coating is formed on the film layer by a vapor deposition method, the silane hydrophobic coating obtained by the vapor deposition method can more comprehensively cover the porous graphite film layer with a nano porous structure to obtain the super-hydrophobic condensed water surface, the Laplace force and the capillary force of the surface are more easily balanced, the condensed water can not infiltrate the surface micro-defects and microstructures, therefore, the hydrophobic failure of the surface of the polar plate flow field caused by the existence of condensed water can not occur, and the combination of the porous graphite film layer and the silane hydrophobic coating is one of the invention points of the embodiment of the invention.
2. The graphite target material arranged in the vacuum cavity is bombarded by the pulse laser beam, so that the graphite target material is gasified, diffused and collided with argon filled in the vacuum cavity for deceleration, each pulse of the pulse laser beam has a pulse width of 800 fs-12 ps, the diameter of the pulse laser beam is 120um, the gasified graphite plasma is finally deposited on a flow field structure of a fuel cell substrate arranged above the graphite target material to form a porous graphite film layer consisting of nano-scale graphite particles, the pressure of the filled argon is 10 Pa-50 Pa, the pressure can ensure that the porosity of the porous graphite film layer and the average particle size of the graphite particles are in a proper interval, for example, the porosity is 30-80%, the average size of the graphite particles is 1 um-20 um, so that the formed porous structure is more beneficial to balance of Laplace force and capillary force, is one of the points of the embodiment of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1a is a schematic diagram of a fuel cell flow field flooding;
FIG. 1b is a schematic diagram illustrating the failure of a superhydrophobic surface in a condensation environment according to the prior art;
FIG. 2 is a flow chart of a method for preparing an ultraphobic condensate surface according to one embodiment of the present invention;
FIG. 3a is a schematic diagram of the connection of a vacuum chamber, fuel cell plates and graphite targets in accordance with one embodiment of the present invention;
FIG. 3b is a schematic diagram of a process of forming a hydrophobic silane coating on a porous graphite thin film layer by a vapor deposition method according to an embodiment of the present invention;
FIG. 4a is a schematic representation of the superhydrophobic performance of the superhydrophobic condensate surface according to one embodiment of the present invention;
FIG. 4b is a schematic diagram of the superhydrophobicity of the superhydrophobic condensate surface to condensate water droplets of 300um size according to one embodiment of the invention;
FIG. 4c is a schematic diagram of the superhydrophobicity of the superhydrophobic condensate surface to condensate water droplets of 200um size according to one embodiment of the invention;
FIG. 4d is a schematic diagram of a process for self-removing condensed water according to an embodiment of the present invention.
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 obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that the terms "including" and "having" and any variations thereof in the embodiments of the present specification and the drawings are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
The embodiment of the specification discloses an ultraphobic condensed water surface, a preparation method thereof, a battery pole plate and a fuel battery. The following are detailed below.
FIG. 2 is a flow chart of a method for preparing an ultraphobic condensate surface according to one embodiment of the present invention; as shown in fig. 2, the preparation method comprises the following steps:
s210, arranging a fuel cell polar plate and a graphite target in a vacuum cavity, wherein the fuel cell polar plate is arranged above the graphite target;
s220, reducing the air pressure value of the vacuum cavity to 10 -3 Pa to 3X 10 -4 After Pa, filling argon; in an implementation mode, the pressure value of the vacuum cavity is reduced to a preset pressure value, and then the inert gas argon is filled, so that the argon is more stable, and the formation of the following porous graphite film layer is facilitated.
S230, emitting a pulse laser beam to the graphite target to bombard the graphite target so as to generate graphite plasma, wherein each pulse of the pulse laser beam has a pulse width of 800 fs-12 ps, and the diameter of the pulse laser beam is 120 um;
the smaller the pulse width of each pulse of the pulse laser beam is, the smaller the pores of the porous structure of the porous graphite film layer are, and the more favorable the condensed water under the operating environment of the fuel cell can be dealt with.
S240, the graphite plasma collides with the filled argon and is deposited on the fuel cell plate to form a porous graphite film layer consisting of nano-scale graphite particles;
and S250, forming a silane hydrophobic coating on the porous graphite film layer by using a vapor deposition method to obtain the super-hydrophobic condensed water surface.
Fig. 3a is a schematic diagram of the connection of a vacuum chamber, a fuel cell plate, and a graphite target according to an embodiment of the present invention. As shown in fig. 3a, a fuel cell plate is disposed on the top of a vacuum chamber, a graphite target is disposed below the fuel cell plate, a pulse laser beam is emitted to the graphite target, and a porous graphite thin film layer is formed on the surface of a flow field of the fuel cell plate by using an ultrafast pulse laser deposition technique.
Fig. 3b is a schematic diagram of a process of forming a silane hydrophobic coating on the porous graphite thin film layer by using a vapor deposition method according to an embodiment of the present invention. As shown in fig. 3b, a silane hydrophobic coating layer is formed on the porous graphite thin film layer by vapor deposition, and the silane hydrophobic coating layer changes the surface wetting characteristics of the porous thin film layer from super-hydrophilic to super-hydrophobic.
The preparation method of the super-hydrophobic condensed water surface of the embodiment bombards the graphite target material arranged in the vacuum cavity through the pulse laser beam, the graphite target material is gasified and diffused, the argon gas in the vacuum cavity is collided and decelerated, and finally deposited on a flow field structure of a fuel cell substrate arranged above the graphite target material to form a porous graphite film layer consisting of nano-scale graphite particles, the porous structure of the nanometer level of this porous graphite thin film layer combines the silane hydrophobic coating that obtains through the vapor deposition method, and the porous structure of nanometer level forms super hydrophobic condensate water surface more easily on the one hand, more can effectually carry out the hydrophobicity with regard to less comdenstion water itself, and on the other hand, the porous graphite structure of nanometer level combines the surface that the hydrophobic coating of silane gained to be not more than capillary force to the laplace power of water droplet again to make the comdenstion water be difficult to soak, realize super hydrophobic to the comdenstion water. The surface prepared by the method is introduced into the design and preparation of the flow field of the fuel cell bipolar plate, so that the flow field of the fuel cell bipolar plate can still maintain effective drainage performance under the working conditions of low operating temperature, high humidification and high current density, and the flooding phenomenon is avoided.
In one implementation, the forming of the silane hydrophobic coating on the porous graphite thin film layer by using a vapor deposition method specifically includes:
and placing the fuel cell pole plate deposited with the porous graphite film layer into another container, dripping fluorosilane into the container, vacuumizing the container to deposit fluorosilane on the porous graphite film layer by a vapor deposition method, and finally placing the container in an oven with a preset temperature for a preset time to form the silane hydrophobic coating.
In one implementation, the graphite particles are nanoparticles having a nanostructure dimension of 100 nm.
In one implementation, the porous graphite film layer is 1um to 5um thick.
In one implementation, the pressure of the argon gas filled into the vacuum cavity is 10Pa to 50Pa to ensure that the porosity of the porous film layer and the average particle size of the graphite particles meet the requirement that the laplace force is not greater than the capillary force, the preferred porosity is 30% to 80%, and the average size of the particles is 1um to 20 um.
The graphite target material arranged in the vacuum cavity is bombarded by the pulse laser beam to ensure that the graphite target material is gasified and diffused and collides with the argon filled in the vacuum cavity to decelerate, each pulse of the pulse laser beam is set to have a pulse width of 800fs to 12ps, the diameter of the pulse laser beam is 120um, the gasified graphite plasma is finally deposited on a flow field structure of a fuel cell substrate arranged above the graphite target, a porous graphite film layer composed of nano-scale graphite particles is formed, the air pressure of the further filled argon is 10Pa to 50Pa, the air pressure can ensure that the porosity of the porous graphite film layer and the average particle size of the graphite particles are in a proper interval, for example, the porosity is 30% to 80%, and the average size of the graphite particles is 1um to 20um, so that the formed porous structure is more favorable for balancing the Laplace force and the capillary force.
In one implementation, the emitting a pulsed laser beam to the graphite target to bombard the graphite target and deposit a graphite plasma on the fuel cell plate further includes: the average output power of the laser beam is 50W to 200W, the pulse frequency is 100kHz to 1000kHz, the target base distance is 25mm to 50mm, and the deposition time is 5 minutes.
In another embodiment of the present disclosure, there is provided an ultraphobic condensate surface, the ultraphobic condensate surface is prepared by the method for preparing an ultraphobic condensate surface as described in any one of the above method embodiments, and the ultraphobic condensate surface includes: a porous graphite film layer deposited on the fuel cell bipolar plate and a silane hydrophobic coating disposed on the porous graphite film layer.
The porous film layer is composed of nano particles with the particle size of hundred nanometers, the nano structure scale is about 100nm, and the nano structure scale is a better structural parameter of the super-hydrophobic condensed water surface. The thickness of the porous film layer is 1-5 microns. Fig. 4a is a schematic diagram of the superhydrophobic performance of the superhydrophobic condensed water surface according to an embodiment of the invention, and fig. 4d is a schematic diagram of a process for self-removing condensed water according to an embodiment of the invention, as shown in fig. 4a, the surface of the porous thin film layer after hydrophobic treatment has excellent superhydrophobic performance, a contact angle of a water drop of 5uL (or 3uL) is greater than 150 ° and a rolling angle is less than 3 °. Fig. 4b is a schematic diagram of the ultraphobic property of the ultraphobic condensate surface to condensate water drops with a size of 300um according to an embodiment of the present invention, fig. 4c is a schematic diagram of the ultraphobic property of the ultraphobic condensate surface to condensate water drops with a size of 200um according to an embodiment of the present invention, and fig. 4d is a schematic diagram of a condensate water self-removal process according to an embodiment of the present invention, as shown in fig. 4d, in a merging process of two micron-sized water drops, a liquid bridge between the water drops hits the surface to generate a drop bouncing phenomenon, and the self-removal of the water drops from the surface is completed within a time of 2.23 milliseconds. As shown in fig. 4b, 4c and 4d, the surface can be super-hydrophobic for the micro-scale condensed water drops, and the condensed water can be merged to convert the surface energy into kinetic energy to cause the condensed water drops to be self-removed from the surface, thereby solving the problem that the condensed water causes hydrophobic failure on the surface of the bipolar plate cathode flow field.
In another embodiment of the present disclosure, a fuel cell plate is further provided, wherein the fuel cell plate is provided with an ultraphobic condensed water surface according to the embodiment.
In another embodiment of the present specification, there is also provided a fuel cell comprising the fuel cell plate as described in the above embodiments.
Those of ordinary skill in the art will understand that: the figures are merely schematic representations of one embodiment, and the blocks or flow diagrams in the figures are not necessarily required to practice the present invention.
Those of ordinary skill in the art will understand that: modules in the devices in the embodiments may be distributed in the devices in the embodiments according to the description of the embodiments, or may be located in one or more devices different from the embodiments with corresponding changes. The modules of the above embodiments may be combined into one module, or further split into multiple sub-modules.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for preparing an ultraphobic condensed water surface is characterized by comprising the following steps:
a fuel cell polar plate and a graphite target are arranged in the vacuum cavity, wherein the fuel cell polar plate is arranged above the graphite target;
reducing the air pressure value of the vacuum cavity to 10 -3 Pa to 3X 10 -4 After Pa, filling argon;
emitting a pulse laser beam to the graphite target to bombard the graphite target so as to generate graphite plasma, wherein each pulse of the pulse laser beam has a pulse width of 800 fs-12 ps, and the diameter of the pulse laser beam is 120 um;
the graphite plasma collides with the filled argon and is deposited on the fuel cell polar plate to form a porous graphite film layer consisting of nano-scale graphite particles;
and forming a silane hydrophobic coating on the porous graphite film layer by using a vapor deposition method to obtain the super-hydrophobic condensed water surface.
2. The method for preparing the ultraphobic condensed water surface according to claim 1, wherein the forming of the silane hydrophobic coating on the porous graphite thin film layer by using the vapor deposition method specifically comprises:
and placing the fuel cell pole plate deposited with the porous graphite film layer into another container, dripping fluorosilane into the container, vacuumizing the container, and finally placing the container in an oven with a preset temperature for a preset time to deposit fluorosilane on the porous graphite film layer by a vapor deposition method so as to form a silane hydrophobic coating.
3. The method of claim 1, wherein the graphite particles are nanoparticles having a nanostructure dimension of 100 nm.
4. The method of claim 2, wherein the porous graphite film layer has a thickness of 1um to 5 um.
5. The method of claim 1, wherein the pressure of the argon gas introduced into the vacuum chamber is 10 to 50 Pa.
6. The method of any one of claims 1 to 5, wherein said emitting a pulsed laser beam to said graphite target to bombard said graphite target to deposit a graphite plasma on said fuel cell plate, further comprises: the average output power of the laser beam is 50W to 200W, the pulse frequency is 100kHz to 1000kHz, the target base distance is 25mm to 50mm, and the deposition time is 5 minutes.
7. An ultraphobic condensate surface prepared by the method of preparing an ultraphobic condensate surface according to any one of claims 1 to 6, comprising: a porous graphite film layer deposited on the fuel cell bipolar plate and a silane hydrophobic coating disposed on the porous graphite film layer.
8. A fuel cell plate having an ultraphobic condensate surface as defined in claim 7.
9. A fuel cell comprising the fuel cell plate of claim 8.
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