CN118186462A - PTFE-metal substrate with good gas diffusion and conductivity, and preparation method and application thereof - Google Patents
PTFE-metal substrate with good gas diffusion and conductivity, and preparation method and application thereof Download PDFInfo
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- CN118186462A CN118186462A CN202410233916.5A CN202410233916A CN118186462A CN 118186462 A CN118186462 A CN 118186462A CN 202410233916 A CN202410233916 A CN 202410233916A CN 118186462 A CN118186462 A CN 118186462A
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- ptfe
- layer
- breathable film
- metal
- metal substrate
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- 239000002184 metal Substances 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000000758 substrate Substances 0.000 title claims abstract description 34
- 238000009792 diffusion process Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 53
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 53
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 238000002207 thermal evaporation Methods 0.000 claims description 15
- 238000010041 electrostatic spinning Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 238000001771 vacuum deposition Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000005686 electrostatic field Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000007789 gas Substances 0.000 abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 10
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of metal substrate preparation, and discloses a PTFE-metal substrate with good gas diffusion and conductivity, a preparation method and application thereof, wherein the PTFE-metal substrate sequentially comprises a PTFE breathable film layer, a fiber layer and a metal layer from bottom to top; the fiber layer is arranged on the upper layer of the PTFE breathable film layer in a venation manner, the venation-shaped fiber layer forms a hydrophobic framework, the metal layer is plated on the PTFE breathable film layer and the upper layer of the hydrophobic framework, and the metal layer is attached on the hydrophobic framework to form a metal framework; the invention solves the problems that polytetrafluoroethylene breathable films have poor conductivity and the direct use of metal as a catalyst in carbon dioxide electroreduction devices is accompanied by serious hydrogen evolution reaction, and meanwhile, no gaps are unfavorable for gas diffusion, and is suitable for the preparation of PTFE-metal substrates.
Description
Technical Field
The invention relates to the technical field of metal substrate preparation, in particular to a PTFE-metal substrate with good gas diffusion and conductivity, and a preparation method and application thereof.
Background
Fossil raw materials such as coal, petroleum, natural gas and the like are always main energy sources for supporting economic and social development, and a large amount of carbon dioxide discharged from the use of fossil energy sources is an important cause for global climate change and sea level rise.
Among these, in response to the strategy of sustainable development, the conversion of CO2 into valuable chemical products by electrocatalytic means is one of the currently promising solutions. Electrocatalytic CO 2 RR products can be generally classified into C1 compounds (CO, CH 4, etc.); c2 products (C 2H4、C2H5 OH, etc.); c3 compounds (C 3H6、C3H7 OH, etc.). The C2+ products are generally considered to have higher energy storage value than the C1 products, so that the carbon dioxide in the air is reduced into high-value products such as C 2H4、C2H5 OH and the like by utilizing an electric reduction device, thereby realizing carbon circulation and zero emission; currently, there are many methods for controlling the flow of liquid. Various performance indexes of the carbon dioxide electroreduction device are close to the industrialization level; the carbon dioxide electroreduction device mainly comprises a gas diffusion electrode, a catalyst, electrolyte and the like, wherein the air permeability and the electric conductivity of the gas diffusion electrode are extremely important; therefore, polytetrafluoroethylene (PTFE) with strong hydrophobicity and breathability is an ideal material for manufacturing a gas diffusion electrode, but because it is an insulator, it is necessary to carry other conductive materials to use as a gas diffusion electrode, and if metal is directly used as a catalyst in a carbon dioxide electroreduction device, serious hydrogen evolution reaction is accompanied, and at the same time, no void will be detrimental to gas diffusion; therefore, there is a need for a PTFE-metal substrate with good gas diffusion and electrical conductivity.
Disclosure of Invention
The invention aims to provide a PTFE-metal substrate with good gas diffusion and conductivity, and a preparation method and application thereof, so as to solve the problems that a polytetrafluoroethylene breathable film has poor conductivity, and a direct metal is adopted as a catalyst in a carbon dioxide electroreduction device to be accompanied with serious hydrogen evolution reaction, and meanwhile, no gap is harmful to gas diffusion.
In order to achieve the above object, the present invention provides the following technical solutions:
The basic technical scheme provided by the invention is as follows: a PTFE-metal substrate with good gas diffusion and conductivity, which comprises a PTFE breathable film layer, a fiber layer and a metal layer from bottom to top; the fiber layer is arranged on the upper layer of the PTFE breathable film layer in a venation mode, the fiber layer in a venation mode forms a hydrophobic framework, the metal layer is plated on the PTFE breathable film layer and the upper layer of the hydrophobic framework, and the metal layer is attached to the hydrophobic framework to form a metal framework.
Preferably, the metal layer is copper.
The preparation method of the PTFE-metal substrate with good gas diffusion and conductivity comprises the following steps:
s1, fixing a PTFE breathable film on a receiving device of electrostatic spinning equipment, placing a polymer solution or melt into a high-voltage electrostatic field of the electrostatic spinning equipment, enabling the polymer solution or melt to be charged and deform, forming taylor cone liquid drops at the tail end of a spray head of the electrostatic spinning equipment, spraying and depositing the taylor cone liquid drops on the PTFE breathable film, finally forming a venation-shaped hydrophobic fiber skeleton on the PTFE breathable film by controlling the position change of the spray head, and taking out the PTFE breathable film for later use;
S2, placing the polished copper particles in a corresponding evaporation source in a vacuum coating machine, fixing, adhering a PTFE (polytetrafluoroethylene) breathable film with a fiber framework above the evaporation source, enabling one surface of the PTFE breathable film with the fiber framework to face the evaporation source, starting to perform vacuum evaporation, gasifying the copper source into copper particles, and enabling the copper particles to fly to the surface of the PTFE breathable film to be condensed to form a copper film layer, so that the required PTFE-metal substrate is obtained.
Preferably, in S2, the evaporation rate of the vacuum coating machine isThe thermal evaporation current is 85-110A; the pressure of the thermal evaporation vacuum chamber is 5 multiplied by 10 -5～9×10-5 Pa; the thickness of the thermal evaporation coating film is 300nm, and is controlled by a crystal oscillator plate in a thermal evaporation instrument; the temperature of the thermal evaporation substrate is 25-60 ℃.
The PTFE-metal substrate obtained by the preparation method of the PTFE-metal substrate with good gas diffusion and conductivity is applied as a catalyst in catalytic reaction.
The technical proposal has the following principle and beneficial effects: the hydrophobic skeleton is made by electrostatic spinning technology on Polytetrafluoroethylene (PTFE) ventilated membrane, the skeleton has porous characteristic, which is favorable for gas diffusion, then copper or other metals are plated on the Polytetrafluoroethylene (PTFE) ventilated membrane and the skeleton thereof by vacuum thermal evaporation method. In the process of evaporation, metal forms a metal framework on the venuo-shaped fiber, so that the PTFE-metal substrate has better conductivity, and meanwhile, the adsorption of hydrogen on the surface of the metal catalyst is weakened due to strong hydrophobicity, so that the hydrogen evolution reaction rate is greatly reduced; in addition, the metal framework also enables the current distribution to be more uniform during the electrocatalytic carbon dioxide reduction, greatly improves the selectivity of the catalyst to high-value products under higher current density, and enables the carbon dioxide electroreduction under ultra-large current density to be possible to be industrially applied.
Drawings
FIG. 1 is a flow chart of a method of preparing a PTFE-metal substrate according to the present invention;
FIG. 2 is a schematic illustration of a PTFE-metal substrate with good gas diffusion and electrical conductivity in accordance with the present invention;
FIG. 3 is a microscopic schematic of the present invention with and without a skeleton;
in the drawings, a is a skeleton-containing microscopic drawing, and b is a skeleton-free microscopic drawing;
FIG. 4 is a graph of current density versus product Faraday efficiency for both skeletons and non-skeletons;
In the graph, a is a graph of the relation between the current density with a framework and the Faraday efficiency of a product, and b is a graph of the relation between the current density without the framework and the Faraday efficiency of the product;
The names of the corresponding marks in the drawings are:
a PTFE gas-permeable membrane layer 1, a fiber layer 2 and a metal layer 3.
Detailed Description
The invention is described in further detail below with reference to the drawings and the embodiments, but the invention is by no means limited to these examples:
Example 1
As shown in fig. 2, a PTFE-metal substrate with good gas diffusion and conductivity comprises a PTFE gas-permeable membrane layer 1, a fiber layer 2 and copper in order from bottom to top; the fiber layer 2 is arranged on the upper layer of the PTFE ventilated membrane layer 1 in a vein shape, the vein-shaped fiber layer 2 forms a hydrophobic framework, copper is plated on the upper layers of the PTFE ventilated membrane layer 1 and the hydrophobic framework, and copper is attached on the hydrophobic framework to form a metal framework;
as shown in fig. 1, a flowchart of a method for preparing a PTFE-metal substrate according to the present invention is shown, which specifically includes the following steps:
S1, preparing a Polytetrafluoroethylene (PTFE) breathable film, electrostatic spinning equipment and a copper and vacuum coating machine; the electrostatic spinning equipment utilizes an electrostatic spinning technology to manufacture a fiber framework on a Polytetrafluoroethylene (PTFE) breathable film, and the equipment comprises the following specific operation steps and principles: fixing a Polytetrafluoroethylene (PTFE) breathable film on a receiving device of an electrostatic spinning device, placing a polymer solution or melt into a high-voltage electrostatic field of the electrostatic spinning device, enabling the polymer solution or melt to be charged and deform, forming Taylor cone liquid drops at the tail end of a spray head of the electrostatic spinning device, spraying polymer tiny liquid drops, namely 'jet', on the liquid drop surface at a high speed when the charge repulsive force of the liquid drop surface exceeds the surface tension, depositing the jet on the Polytetrafluoroethylene (PTFE) breathable film through high-speed stretching of electric field force, volatilizing and solidifying the solvent, and finally forming a veniform hydrophobic fiber skeleton on the upper layer of the Polytetrafluoroethylene (PTFE) breathable film by controlling the position change of the spray head, and taking out the Polytetrafluoroethylene (PTFE) breathable film for standby.
S2, polishing 6 copper particles with sand paper according to the requirement to remove surface dirt; placing polished copper particles at corresponding evaporation sources in a vacuum coating machine, fixing, adhering a Polytetrafluoroethylene (PTFE) breathable film with a fiber framework above an evaporation copper source, and adjusting parameters of the vacuum coating machine as follows:
The evaporation rate is The thermal evaporation current is 100A; the pressure of the thermal evaporation vacuum chamber is 7 multiplied by 10 < -5 > Pa; the thickness of the thermal evaporation coating film is controlled to be 300nm, and the temperature of the thermal evaporation substrate is controlled to be 50 ℃; after the parameters are set, starting to perform vacuum evaporation, gasifying a copper source into copper particles, enabling the copper particles to fly to the surface of a Polytetrafluoroethylene (PTFE) breathable film to be coagulated to form a copper film layer, and taking out the copper film layer to obtain a PTFE-metal substrate with good gas diffusion and conductivity (shown as a graph in figure 3).
The PTFE-metal substrate prepared by the above procedure was compared with the substrate without a skeleton, and the test data are shown in fig. 4 (a set of bar graphs sequentially shows the faraday efficiency of CH 2、C2H2、CO、H2 from top to bottom), so that it can be seen that more high-value C2 products can be obtained in the case of the metal substrate with a skeleton, and less H 2 is precipitated from the metal substrate with a skeleton, which inhibits the hydrogen evolution reaction efficiency.
The foregoing is merely exemplary embodiments of the present application, and detailed technical solutions or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, and these should also be regarded as the protection scope of the present application, which does not affect the effect of the implementation of the present application and the practical applicability of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (5)
1. A PTFE-metal substrate having good gas diffusion and electrical conductivity, characterized in that: the PTFE breathable film layer, the fiber layer and the metal layer are sequentially arranged from bottom to top; the fiber layer is arranged on the upper layer of the PTFE breathable film layer in a venation mode, the fiber layer in a venation mode forms a hydrophobic framework, the metal layer is plated on the PTFE breathable film layer and the upper layer of the hydrophobic framework, and the metal layer is attached to the hydrophobic framework to form a metal framework.
2. The gas-diffusing and electrically conductive PTFE-metal substrate of claim 1, wherein: the metal layer is copper.
3. The method for producing a PTFE-metal substrate having good gas diffusion and electrical conductivity according to claim 2, comprising the steps of:
s1, fixing a PTFE breathable film on a receiving device of electrostatic spinning equipment, placing a polymer solution or melt into a high-voltage electrostatic field of the electrostatic spinning equipment, enabling the polymer solution or melt to be charged and deform, forming taylor cone liquid drops at the tail end of a spray head of the electrostatic spinning equipment, spraying and depositing the taylor cone liquid drops on the PTFE breathable film, finally forming a venation-shaped hydrophobic fiber skeleton on the PTFE breathable film by controlling the position change of the spray head, and taking out the PTFE breathable film for later use;
S2, placing the polished copper particles in a corresponding evaporation source in a vacuum coating machine, fixing, adhering a PTFE (polytetrafluoroethylene) breathable film with a fiber framework above the evaporation source, enabling one surface of the PTFE breathable film with the fiber framework to face the evaporation source, starting to perform vacuum evaporation, gasifying the copper source into copper particles, and enabling the copper particles to fly to the surface of the PTFE breathable film to be condensed to form a copper film layer, so that the required PTFE-metal substrate is obtained.
4. The method for producing a PTFE-metal substrate having good gas diffusion and electrical conductivity according to claim 3, wherein in S2, the evaporation rate of the vacuum coater isThe thermal evaporation current is 85-110A; the pressure of the thermal evaporation vacuum chamber is 5 multiplied by 10 -5～9×10-5 Pa; the thickness of the thermal evaporation coating film is 300nm, and is controlled by a crystal oscillator plate in a thermal evaporation instrument; the temperature of the thermal evaporation substrate is 25-60 ℃.
5. Use of a PTFE-metal substrate with good gas diffusion and conductivity according to claim 1 as a catalyst in catalytic reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410233916.5A CN118186462A (en) | 2024-03-01 | 2024-03-01 | PTFE-metal substrate with good gas diffusion and conductivity, and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410233916.5A CN118186462A (en) | 2024-03-01 | 2024-03-01 | PTFE-metal substrate with good gas diffusion and conductivity, and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN118186462A true CN118186462A (en) | 2024-06-14 |
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| CN202410233916.5A Pending CN118186462A (en) | 2024-03-01 | 2024-03-01 | PTFE-metal substrate with good gas diffusion and conductivity, and preparation method and application thereof |
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- 2024-03-01 CN CN202410233916.5A patent/CN118186462A/en active Pending
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