CN116288457B - Porous transport layer and PEM electrolyzer - Google Patents
Porous transport layer and PEM electrolyzer Download PDFInfo
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- CN116288457B CN116288457B CN202310581758.8A CN202310581758A CN116288457B CN 116288457 B CN116288457 B CN 116288457B CN 202310581758 A CN202310581758 A CN 202310581758A CN 116288457 B CN116288457 B CN 116288457B
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- 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
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Abstract
The application relates to a porous transport layer, PEM electrolyzer, comprising: the metal substrate comprises a plurality of lattice units which are stacked, the plurality of lattice units which are stacked form a layered structure, the lattice units have a symmetrical structure, the lattice units have pores, and the porosity of the metal substrate is 20% -90%. The porous transmission layer is designed from a microscopic angle, so that the porous transmission layer can meet the requirements in the fields of support, conduction, mass transfer and the like, and more possibilities are provided for improving the performance of the porous transmission layer. Compared with the traditional porous transmission layer prepared from a macroscopic angle, the porous transmission layer has the advantages that the porosity of the technical substrate is uniformly distributed, the porosity adjustment range is wider, and the porous transmission layer has the characteristics of excellent conductivity, water vapor transmission performance and light weight.
Description
Technical Field
The application relates to the technical field of electrolytic cell manufacturing, in particular to a porous transmission layer and a PEM electrolytic cell.
Background
Proton exchange membrane water electrolysis cells (Proton Exchange Membrane, PEM electrolysis cells) are one of the most promising green hydrogen production electrolysis technologies at present. The PEM electrolyzer converts liquid water into hydrogen and oxygen without carbon emissions, powered by renewable energy sources. Since the amount of precious metal required for an electrolyzer is expected to increase substantially on a large scale, there is a need to improve and optimize electrolyzer assemblies to exhibit lower electrolyzer potentials at lower catalyst loadings.
In PEM electrolysers, porous transport layers (Porous Transport Layer, PTL) provide support between the flow channels and the catalytic layer while facilitating interactions in terms of efficient two-phase transport and charge transfer, are key design considerations for PEM electrolyser systems. The prior porous transmission layer is mainly a titanium felt, and is prepared by stretching a titanium substrate into fiber filaments and then forming the fiber filaments into the titanium felt by adopting a hot pressing process, or carrying out tape casting and calcining treatment on a mixture containing a pore-forming agent and titanium powder.
Disclosure of Invention
In view of this, the present application proposes a porous transport layer and PEM electrolyzer, which can maintain excellent conductivity, moisture transport performance and lightweight characteristics of the porous transport layer by having excellent porosity and uniform pore distribution on the premise of ensuring structural strength.
In a first aspect, embodiments of the present application provide a porous transport layer comprising: the metal substrate comprises a plurality of lattice units which are stacked, the plurality of lattice units which are stacked form a layered structure, the lattice units have a symmetrical structure, the lattice units have pores, and the porosity of the metal substrate is 20% -90%.
In some embodiments, the metal substrate has a porosity of 80% -90%.
In some embodiments, the porous transport layer includes at least one of the following features (1) - (4):
(1) The porosity of the lattice unit is 20% -90%;
(2) The thickness of the metal base material is less than or equal to 0.03mm;
(3) The surface of the metal substrate is rough, and the surface roughness of the metal substrate is 0.01-0.1 mu m;
(4) The material of the metal substrate comprises at least one of titanium, titanium alloy, stainless steel, nickel and nickel alloy.
In some embodiments, the porosity of the metal substrate is graded in a direction perpendicular to the plane of the metal substrate.
In some embodiments, the metal substrate includes first lattice units stacked along a first direction and/or first lattice units stacked along a second direction, the second direction is perpendicular to a plane of the metal substrate, and the first direction is perpendicular to the second direction.
In some embodiments, the metal substrate comprises a first layer and a second layer stacked along a first direction, the first layer comprises first lattice cells stacked along a second direction, the second layer comprises second lattice cells stacked along the second direction, the second lattice cells in contact with the first lattice cells are complementary to the first lattice cells in shape along the first direction, the second direction is perpendicular to a plane in which the metal substrate is located, and the first direction is perpendicular to the second direction; or (b)
The metal substrate comprises a first layer and a second layer which are stacked along a second direction, the first layer comprises first lattice units stacked along the first direction, the second layer comprises second lattice units stacked along the first direction, the second lattice units contacted with the first lattice units are complementary to the first lattice units in shape along the second direction, the second direction is perpendicular to a plane where the metal substrate is located, and the first direction is perpendicular to the second direction.
In some embodiments, the lattice units comprise at least one of Simple cube lattice units, body centered cubic lattice units, diamond lattice units, fluorolite lattice units, measured cube lattice units, triangular hose-comb lattice units, face centered cubic foam lattice units, weiire-Phelan lattice units, and isotrus lattice units.
In some embodiments, the length of the lattice unit along the first direction is equal to the length of the lattice unit along the third direction, wherein the third direction is perpendicular to a plane formed by the first direction and the second direction, and the length of the lattice unit along the second direction is 1/6-1/2 of the length of the lattice unit along the first direction.
In some embodiments, the length of the lattice unit in the first direction is 5 μm to 50 μm, the length of the lattice unit in the third direction is 5 μm to 50 μm, and the length of the lattice unit in the second direction is 2 μm to 20 μm.
In a second aspect, embodiments of the present application provide a PEM electrolyser comprising a porous transport layer according to the first aspect.
The technical scheme of the application has at least the following beneficial effects:
the metal substrate is formed by stacking a plurality of lattice units, the lattice units can form a metal substrate with a layered structure, and the lattice units are of a symmetrical structure with pores, so that the metal substrate can obtain 20% -90% of porosity in a wider range and has uniform pore distribution. On the other hand, evenly distributed pores enable the porous transmission layer to be in contact with the runner and the catalytic layer more evenly, so that the contact resistance is uniform as a whole, and the overall conductivity stability is improved. In addition, the lattice unit with larger porosity enables the porous transmission layer to have larger porosity, so that the porous transmission layer has the characteristic of light weight, meanwhile, the porous transmission layer made of metal can ensure the structural strength of the porous transmission layer, and the use of metal substrate raw materials can be saved. The porous transmission layer is designed from a microscopic angle, so that the porous transmission layer can meet the requirements in the fields of support, conduction, mass transfer and the like, and more possibilities are provided for improving the performance of the porous transmission layer. Compared with the traditional porous transmission layer prepared from a macroscopic angle, the porous transmission layer has the advantages that the porosity of the technical substrate is uniformly distributed, the porosity adjustment range is wider, and the porous transmission layer has the characteristics of excellent conductivity, water vapor transmission performance and light weight.
Drawings
For a clearer description of embodiments of the application or of the prior art, the drawings that are used in the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only some embodiments of the application, and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a Simple cubic lattice unit according to the present application;
FIG. 2 is a schematic diagram of a Body centered cubic lattice unit according to the present application;
FIG. 3 is a schematic diagram of a Diamond lattice unit according to the present application;
FIG. 4 is a schematic structural diagram of a fluoroite lattice unit according to the present application;
FIG. 5 is a schematic diagram of a Truncated cube lattice unit according to the present application;
FIG. 6 is a schematic structural view of a Triangular cellphone-comb lattice unit according to the present application;
FIG. 7 is a schematic diagram of a Face centered cubic foam lattice unit according to the present application;
FIG. 8 is a schematic diagram of the structure of a Weiire-Phelan lattice unit of the present application;
FIG. 9 is a schematic diagram of the structure of an IsoTruss lattice unit according to the present application;
FIG. 10 is a schematic structural diagram of a layered metal substrate constructed of lattice cells shown in FIGS. 1-9 according to the present application.
Detailed Description
For a better understanding of the technical solution of the present application, the following detailed description of the embodiments of the present application refers to the accompanying drawings.
It should be understood that the described embodiments are merely some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
The main components of the PEM water electrolyzer are a proton exchange membrane, a cathode-anode catalytic layer, a cathode-anode gas transmission layer, a cathode-anode end plate and the like from inside to outside. The gas transmission layer, the catalytic layer and the proton exchange membrane form a membrane electrode, which is a main place for material transmission and electrochemical reaction of the whole water electrolysis cell, and the characteristics and the structure of the membrane electrode directly influence the performance and the service life of the PEM water electrolysis cell. At present, the main material of the gas transmission layer is titanium felt, or the mixture containing pore-forming agent and titanium powder is subjected to tape casting and calcining treatment to obtain the porous transmission layer, and the porous transmission layer prepared by the process has the advantage of large-scale batch production, but has the defects of uneven overall uniformity distribution of pores and limited improvement of the porosity, so that the porous transmission layer is required to be improved.
In view of this, the present application proposes a porous transport layer comprising:
the metal substrate comprises a plurality of lattice units which are stacked, the plurality of lattice units which are stacked form a layered structure, the lattice units have a symmetrical structure, the lattice units have pores, and the porosity of the metal substrate is 20% -90%.
In the scheme, the metal substrate is formed by stacking a plurality of lattice units, the lattice units can form a layered structure, and the lattice units are of symmetrical structures with pores, so that the metal substrate can obtain 20% -90% of porosity in a wider range and has uniform pore distribution. On the other hand, evenly distributed pores enable the porous transmission layer to be in contact with the runner and the catalytic layer more evenly, so that the contact resistance is uniform as a whole, and the overall conductivity stability is improved. In addition, the lattice unit with larger porosity enables the porous transmission layer to have larger porosity, so that the porous transmission layer has the characteristic of light weight, meanwhile, the porous transmission layer made of metal can ensure the structural strength of the porous transmission layer, and the use of metal substrate raw materials can be saved. The porous transmission layer is designed from a microscopic angle, so that the porous transmission layer can meet the requirements in the fields of support, conduction, mass transfer and the like, and more possibilities are provided for improving the performance of the porous transmission layer. Compared with the traditional porous transmission layer prepared from a macroscopic angle, the porous transmission layer has the advantages of uniform pore distribution and wide porosity adjustment range, and has the characteristics of excellent conductivity, water vapor transmission performance and light weight.
In some embodiments, the lattice unit has a symmetrical structure, and the lattice unit may be at least one of an axisymmetrical structure, a centrosymmetric structure, and a rotationally symmetrical structure.
In some embodiments, the porosity of the metal substrate is 20% -90%, specifically 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, or other values within the above range may be used, which is not limited in this application, and it is understood that the porosity of the lattice unit determines the porosity of the metal substrate, and the porosity of the metal substrate can be selected within a wider range, preferably, the porosity of the metal substrate is 80% -90%, in which a metal porous transmission layer with excellent porosity can be obtained, so that the existing porous transmission layer can greatly improve the two-phase transmission rate.
In some embodiments, the porosity of the lattice unit is 20% -90%, specifically may be 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, or may be other values within the above range, which is not limited in the present application, and the porous transmission layer of the present application has a larger porosity range, and may be selected according to the requirement.
In some embodiments, the porosity of the metal substrate is graded in a direction perpendicular to the plane of the metal substrate. It can be understood that by selecting lattice units with the porosity from high to low or from low to high to be sequentially arranged along the direction perpendicular to the plane where the metal substrate is positioned, the porosity of the metal substrate is in gradient arrangement, one side of the porous transmission layer with lower porosity is close to the catalytic layer of the PEM electrolytic cell, and the porous transmission layer with lower porosity on one side of the porous transmission layer is arranged in such a way that the porosity of the porous transmission layer with lower porosity is lower, the contact resistance can be reduced, the overall stress of the catalytic layer is uniform, and the capillary action is enhanced, so that the reaction efficiency of the PEM electrolytic cell is improved; the porosity of one side close to the flow channel increases progressively, which is beneficial to improving the transmission performance of the flow channel to the catalytic layer. In general, in PEM electrolysers, the porosity of the metal substrate decreases from the flow channel direction toward the catalytic layer.
In some embodiments, the surface roughness of the metal substrate is 0.01 μm to 0.1 μm, specifically, may be 0.01 μm, 0.02 μm, 0.03 μm, 0.05 μm, 0.07 μm, 0.08 μm, 0.09 μm or 0.1 μm, or the like, but may be other values within the above range, and the present application is not limited thereto.
In some embodiments, the thickness of the metal substrate is 0.005mm to 0.5mm, specifically, 0.005mm, 0.01 mm, 0.02 mm, 0.03mm, 0.05mm, 0.07 mm, 0.09 mm, 0.1 mm, 0.2mm, 0.3 mm, 0.4 mm, or 0.5mm, or the like, but other values within the above range are also possible, and the present application is not limited thereto. Compared with the conventional method for adjusting the thickness of the metal substrate from a macroscopic angle (generally, the thickness is 0.05 mm-0.5 mm), the metal substrate has a wide adjusting range, is thinner in overall thickness, and can obtain a better design field. Preferably, the thickness of the metal substrate is 0.005mm to 0.03mm.
In some embodiments, the metal substrate includes first lattice cells stacked in a first direction and/or first lattice cells stacked in a second direction, the second direction being perpendicular to a plane in which the metal substrate lies, the first direction being perpendicular to the second direction. That is, the metal substrate of the present application contains only lattice units of one structure (i.e., first lattice units), and the metal substrate includes a stacking manner of three forms, in which the first lattice units may be stacked in a first direction, or the first lattice units may be stacked in a second direction, or the metal substrate may be stacked by stacking the first lattice units stacked in the first direction and the first lattice units stacked in the second direction, and different stacking manners may be selected according to thickness and size requirements of the target metal substrate.
In the present application, since the metal substrate has a layered structure, the first direction refers to a direction parallel to the plane of the metal substrate, the second direction refers to a direction perpendicular to the plane of the metal substrate, and the first direction may be an X-axis direction or a Y-axis direction, and the second direction is a Z-axis direction. The following description will be given by taking the first direction as the X-axis direction, the second direction as the Z-axis direction, and the third direction as the Y-axis direction.
In some embodiments, the metal substrate includes a first layer and a second layer stacked in a first direction (X-axis direction), the first layer including first lattice cells stacked in a second direction (Z-axis direction), the second layer including second lattice cells stacked in a second direction (Z-axis direction), the second lattice cells in contact with the first lattice cells in the first direction being complementary in shape to the first lattice cells. The arrangement is such that the first lattice unit and the second lattice unit are arranged in the same direction (X-axis direction), and the second lattice unit in contact with the first lattice unit is complementary to the first lattice unit in shape in the second direction (Z-axis direction), so that the metal substrate forming the layered structure can be ensured, and in this arrangement, the porosity of the metal substrate is not affected. Meanwhile, the first lattice unit and the second lattice unit with different porosities can be selected according to requirements, and the porosity of the metal substrate is designable by regulating and controlling the total porosity of the metal substrate so as to meet different mass transfer requirements.
In some embodiments, the metal substrate includes a first layer and a second layer stacked in a second direction (Z-axis direction), the first layer including first lattice cells stacked in the first direction (X-axis direction), the second layer including second lattice cells stacked in the first direction (X-axis direction), and the second lattice cells in contact with the first lattice cells in the second direction being complementary in shape to the first lattice cells. The arrangement is such that the first lattice unit and the second lattice unit are arranged in the same direction, such that the first lattice unit and the second lattice unit are arranged in the same direction (Z-axis direction), and the second lattice unit in contact with the first lattice unit is complementary to the first lattice unit in shape in the first direction (X-axis direction), so that the metal substrate forming the layered structure can be ensured, and in this arrangement, the porosity of the metal substrate is not affected. Meanwhile, the first lattice unit and the second lattice unit with different porosities can be selected according to requirements, and the porosity of the metal substrate is designable by regulating and controlling the total porosity of the metal substrate so as to meet different mass transfer requirements.
The application is described by taking two different lattice units as examples, of course, the application can also be provided with more than two crystal units, for example, a metal substrate comprises a first layer, a second layer, a third layer and a fourth layer which are stacked, the third layer comprises a third crystal unit, the fourth layer comprises a fourth lattice unit, the reasonable arrangement mode is adopted to enable two adjacent lattice units to be complementary in shape, and finally, the metal substrate with a layered structure is finally formed, and the porous transmission layer with gradient arrangement of porosity can be arranged, so that more possibility is provided for modification treatment of the porous transmission layer.
In some embodiments, the lattice units comprise at least one of Simple cube lattice units, body centered cubic lattice units, diamond lattice units, fluorolite lattice units, measured cube lattice units, triangular resonator-comb lattice units, face centered cubic foam lattice units, weiire-Phelan lattice units, and IsoTruss lattice units, i.e., the metal substrate of the present application may be composed of a single lattice unit or at least two lattice units. Fig. 1 to 9 are schematic structural views of the nine lattice cells, and fig. 10 is a schematic structural view of a metal substrate formed by stacking the nine lattice cells.
In some embodiments, the length of the lattice unit along the first direction is equal to the length of the lattice unit along the third direction, wherein the third direction is perpendicular to a plane formed by the first direction and the second direction, the first direction of the lattice unit is taken as an X-axis direction, the second direction is taken as a Z-axis direction, the third direction is taken as an example, the length of the lattice unit along the first direction is the length of the lattice unit, the length of the lattice unit along the second direction is the height of the lattice unit, the length of the lattice unit along the third direction is the width of the lattice unit, that is, the length and the width of the lattice unit are equal, and the height of the lattice unit is 1/6-1/2 of the length.
In some embodiments, the length of the lattice unit is 5 μm to 50 μm, specifically, may be 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm or 50 μm, or the like, but may be other values within the above range, and the present application is not limited thereto.
In some embodiments, the width of the lattice unit is 5 μm to 50 μm, specifically, may be 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm or 50 μm, or the like, but may be other values within the above range, and the present application is not limited thereto.
In some embodiments, the width of the lattice unit is 2 μm to 20 μm, specifically, may be 2 μm, 5m, 8 μm, 10 μm, 13 μm, 15 μm or 20 μm, etc., but may be other values within the above range, and the present application is not limited thereto.
In some embodiments, the material of the metal substrate comprises at least one of titanium, titanium alloy, stainless steel, nickel, and nickel alloy. The metal material has higher strength and corrosion resistance, can bear larger pressure and flow, can meet the strength requirement of the porous transmission layer, and can play a good role in supporting and protecting the proton exchange membrane.
In some embodiments, the porous transport layer of the present application has a length x, a width y, and a height z, and has a volume of a cuboid of the same length, width, and height as the porous transport layerThe area of (2) is a calculation area, wherein the value V of the volume quantity is the product of the length and width of the porous transmission layer in the calculation area, and the total volume quantity of all lattice units in the porous transmission layer in the calculation area is 0.100V-0.200V, specifically, may be 0.100V, 0.105V, 0.125V, 0.138V, 0.149V, 0.165V, 0.175V, 0.185V or 0.200V, etc., but may also be other values in the above range, which is not limited herein. Within the above-mentioned limits, it is shown that the volume of the present application is small in the same-sized volume region, which can greatly reduce the raw material amount of the porous transport layer. The volume of the porous transmission layer can be measured by a direct method, and the specific measuring method comprises the following steps: the porous transport layer was placed in a container and immersed in water, and the height of the rise in water level was measured. The volume amount is equal to the difference between the volume of the water level rise and the volume of the porous transfer layer.
The embodiment of the application provides an electrolytic tank, in particular to a PEM electrolytic tank, which comprises an anode plate, an anode porous transmission layer, an anode catalytic layer, a proton exchange membrane, a cathode catalytic layer, a cathode porous transmission layer and a cathode plate which are stacked, wherein the anode porous transmission layer and/or the cathode porous transmission layer are/is the porous transmission layer. The porous transmission layer is applied to the electrolytic tank, can improve the corrosion resistance and structural strength of the electrolytic tank, has excellent material transmission performance, can improve the water electrolysis efficiency of the PEM electrolytic tank, and can also prolong the service life of the PEM electrolytic tank.
The embodiment of the application provides a preparation method of a porous transmission layer, which comprises the following steps:
s100, providing or designing a digital model of a lattice unit;
s200, constructing a digital model of the metal substrate according to the digital model of the lattice unit provided by the S100, wherein the porosity of the digital model of the metal substrate is 20% -50%;
s300, the digital model of the metal substrate provided in the S200 is led into 3D printing equipment for printing, and the metal substrate is obtained.
In the scheme, the digital model of the metal base material is built by providing or designing the digital model of the lattice unit in advance, and then the 3D printing equipment is used for printing to prepare a finished product. The preparation process disclosed by the application has high accuracy, can be used for batch production in a mode of pre-establishing a model, can greatly improve the production efficiency of the porous transmission layer, and simultaneously saves the use of the raw materials of the metal base material.
The preparation method of the present application will be described in detail below according to specific preparation steps.
S100, providing or designing a digital model of a lattice unit, wherein the lattice unit comprises nine lattice units shown in fig. 1-9, and can also be other lattice units with symmetrical structures, and the application is not limited herein.
S200, constructing a digital model of the metal substrate according to the digital model of the lattice unit provided in S100.
Specific: stacking the lattice units provided in S100 along a first direction according to the thickness and the size of the lattice units and the thickness and the size of the required metal base material; and/or stacking the lattice units provided in the step S100 along the second direction, and constructing a digital model of the metal base material, so that the digital model of the metal base material is of a layered structure.
In some embodiments, the thickness and size of the lattice elements determine the porosity of the lattice elements, and the thickness and size of the lattice elements can be adjusted according to the desired porosity, thereby controlling the thickness and size of the metal substrate and thus the porosity of the digital model of the metal substrate.
S300, the digital model of the metal substrate provided in the S200 is led into 3D printing equipment for printing, and the metal substrate is obtained.
Specific: before printing, selecting a machining direction, slicing the digital model of the metal substrate constructed in the step S200 according to the machining direction, so as to form a machining path, heating or solidifying powdery metal substrate raw materials by an electron beam according to the machining path, so as to form a three-dimensional metal solid structure, carrying out lamellar processing, stacking a plurality of lamellar sheets, and finally forming the metal substrate solid structure, namely the porous transmission layer. Wherein, the powdery metal base material is generally prepared by adopting a grinding or vapor deposition process.
Embodiments of the present application will be further described below with reference to a number of examples. The embodiments of the present application are not limited to the following specific examples.
In order to facilitate testing of performance data of porous transport layers prepared from different lattice units, the length, width and height of lattice units and the thickness, length and width of the resulting porous transport layers in examples 1 to 10 below were the same.
Example 1
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting a Simple cube lattice unit to construct a digital model of the metal substrate, guiding the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, a Simple cubic lattice unit has a length of 10 μm, a width of 10 μm, and a height of 5 μm, and the resulting titanium felt has a thickness of 0.2mm, a length of 1mm, and a width of 1mm.
Example 2
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting Body centered cubic lattice units to construct a digital model of the metal substrate, introducing the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, body centered cubic lattice units were 10 μm long, 10 μm wide and 5 μm high, and the resulting titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Example 3
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting a Diamond lattice unit to construct a digital model of the metal substrate, guiding the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, the Diamond lattice unit had a length of 10 μm, a width of 10 μm and a height of 5 μm, and the obtained titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Example 4
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting a Fluolite lattice unit to construct a digital model of the metal substrate, introducing the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, the length of the fluoroite lattice unit was 10. Mu.m, the width was 10. Mu.m, and the height was 5. Mu.m, and the thickness of the obtained titanium felt was 0.2mm, the length was 1mm, and the width was 1mm.
Example 5
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting a tested cube lattice unit to construct a digital model of the metal substrate, guiding the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, the measured cube lattice elements were 10 μm long, 10 μm wide and 5 μm high, and the resulting titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Example 6
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting a Triangular-comb lattice unit to construct a digital model of the metal substrate, introducing the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, the Triangular homoher-comb lattice unit had a length of 10 μm, a width of 10 μm and a height of 5. Mu.m, and the obtained titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Example 7
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting Face centered cubic foam lattice units to construct a digital model of the metal substrate, introducing the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, face centered cubic foam lattice units were 10 μm long, 10 μm wide and 5 μm high, and the resulting titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Example 8
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and (3) selecting a Weiire-Phelan lattice unit to construct a digital model of the metal substrate, introducing the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on the titanium metal to obtain the titanium felt.
In this example, the Weaine-Phelan lattice unit had a length of 10 μm, a width of 10 μm and a height of 5 μm, and the obtained titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Example 9
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting an IsoTruss lattice unit to construct a digital model of the metal substrate, guiding the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, an IsoTruss lattice unit was 10 μm long, 10 μm wide and 5 μm high, and the resulting titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Example 10
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting Body centered cubic lattice units and detected cube lattice units to construct a digital model of the metal substrate, introducing the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, body centered cubic lattice units were 10 μm long, 10 μm wide, 5 μm high, and measured lattice units were 10 μm long, 10 μm wide, 5 μm high, and the resulting titanium felt had a thickness of 0.2mm, a length of 1mm, and a width of 1mm.
Example 11
The embodiment obtained in this embodiment provides a method for preparing a porous transmission layer, including the following steps:
and selecting a Simple cube lattice unit to construct a digital model of the metal substrate, guiding the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, a Simple cubic lattice unit has a length of 5 μm, a width of 5 μm, and a height of 2 μm, and the resulting titanium felt has a thickness of 0.2mm, a length of 1mm, and a width of 1mm.
Example 12
The embodiment obtained in this embodiment provides a method for preparing a porous transmission layer, including the following steps:
and selecting a Simple cube lattice unit to construct a digital model of the metal substrate, guiding the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, a Simple cubic lattice unit has a length of 30 μm, a width of 30 μm, and a height of 5 μm, and the resulting titanium felt has a thickness of 0.2mm, a length of 1mm, and a width of 1mm.
Example 13
The embodiment obtained in this embodiment provides a method for preparing a porous transmission layer, including the following steps:
and selecting a Simple cube lattice unit to construct a digital model of the metal substrate, guiding the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, a Simple cubic lattice unit has a length of 50 μm, a width of 50 μm, and a height of 20 μm, and the resulting titanium felt has a thickness of 0.2mm, a length of 1mm, and a width of 1mm.
Example 14
The embodiment provides a method for preparing a porous transmission layer, which comprises the following steps:
and selecting Body centered cubic lattice units to construct a digital model of the metal substrate, introducing the digital model of the metal substrate into 3D printing equipment, and performing 3D printing on titanium metal to obtain the titanium felt.
In this example, body centered cubic lattice units were 100 μm long, 100 μm wide and 50 μm high, and the resulting titanium felt had a thickness of 2mm, a length of 10mm and a width of 10mm.
Comparative example 1
The comparative example provides a method for preparing a porous transport layer, taking titanium metal as an example, comprising the following steps:
(1) The titanium metal base material is prepared by arc melting, vacuum melting and other methods.
(2) Processing the titanium metal base obtained in the step (1) into a titanium plate, and cutting the titanium plate into proper sizes according to the required size and thickness.
(3) And (3) putting the titanium plate obtained in the step (2) into a stretcher, and stretching to change the titanium plate into slender titanium wires.
(4) And (3) weaving the titanium wire stretched in the step (3) into a titanium wire fabric through a spinning machine.
(5) Cutting the titanium wire fabric in the step (4) into titanium felt with proper size according to the required size.
In this comparative example, the titanium felt had a thickness of 0.2mm, a length of 1mm and a width of 1mm.
Test method
(1) Testing the porosity of lattice units by mercury intrusion
Mercury pressing method: the material sample is immersed in mercury and the pressure is increased so that the mercury liquid is fully penetrated in the pores. The porosity can be calculated by measuring the volume of mercury pressed into the sample.
(2) Testing length, width and height of lattice unit by scanning electron microscope
Scanning Electron Microscopy (SEM) is a high resolution microscope that displays microscopic structures on the surface of an article under test at a very high magnification and is used to calculate dimensional information of the article by software.
The length, width and height of the porous transmission layer are directly measured by adopting tools such as a ruler, a caliper, a protractor and the like, so that a relatively accurate length, width and height numerical result can be obtained.
(3) The surface roughness of the metal substrate was measured using an atomic force microscope.
Atomic force microscope (Atomic Force Microscopy AFM), AFM is a high resolution test method suitable for surface roughness testing on the micrometer or sub-micrometer scale, wherein the probe contacts the object surface, the offset of the probe amplitude is recorded, and the roughness of the object surface is calculated therefrom.
(4) And (5) testing the structural strength of the metal substrate by adopting a tension-compression test method.
And (3) tension and compression test: the structure to be tested is placed into a tensile or compressive testing machine, a corresponding tensile or compressive load is applied to the structure, and the change relation between the load and deformation is recorded by a computer of the testing machine, so that the strength of the structure is deduced.
(5) The volume of the metal substrate was measured using a direct measurement method.
Direct measurement: the substrate was placed in a container and immersed in water, and the height of the rise in water level was measured. The volume amount is equal to the difference between the volume of the rise of the water level and the volume of the substrate.
(6) The transmission properties (air permeability) of the metal substrate as a porous transmission layer were tested using a saturation method.
Saturation method: the sample is fixed in an air-tight chamber, with one side being a low pressure face and the other side being a high pressure face. The air permeability is determined by measuring the volume or weight consumed by air passing through the sample from the low pressure side to the high pressure side by filling the chamber with air to obtain a fixed pressure differential.
(7) The conductivity of the metal substrate was measured using the resistivity method.
Resistivity method: the method calculates the conductivity of a material by measuring its resistance or resistivity. Typically, resistivity tests will be performed on a metal sample, electrodes on both ends of the sample are connected and passed with a set current, and the resistance measured to calculate conductivity. The test results are shown in Table 1.
The results of the above performance tests are as follows:
TABLE 1 measurement of Performance of examples and comparative examples
| Lattice unit Porosity of the porous material （%） | Metal substrate Porosity of (2) （%） | Metal substrate Thickness of (2) （mm） | Metal substrate Contact electricity of (a) Resistance (mΩ - cm^2） | Metal substrate Is of the surface roughness of (2) Roughness (mu m) | All lattices Unit body Volume (mm) 3） | All lattices Unit body Volume and titanium Felt same ruler Inch formed Cuboid meter Volume of calculation domain Ratio of integration | Metal substrate Is of air permeability of (2) （mL·mm/ (cm^2· h· mmHg)） | |
| Example 1 | 86.2 | 87.6 | 0.2 | 0.52 | 2 | 0.025 | 0.125 | 1700 |
| Example 2 | 85.4 | 86.2 | 0.2 | 0.64 | 2 | 0.028 | 0.140 | 1580 |
| Example 3 | 85.8 | 86.3 | 0.2 | 0.63 | 2 | 0.027 | 0.135 | 1590 |
| Example 4 | 84.7 | 85.8 | 0.2 | 0.65 | 2 | 0.028 | 0.140 | 1560 |
| Example 5 | 86.3 | 87.1 | 0.2 | 0.54 | 2 | 0.026 | 0.130 | 1600 |
| Example 6 | 83.4 | 84.1 | 0.2 | 0.58 | 2 | 0.032 | 0.160 | 1400 |
| Example 7 | 82.4 | 83.4 | 0.2 | 0.49 | 2 | 0.033 | 0.165 | 1360 |
| Example 8 | 81.6 | 82.5 | 0.2 | 0.51 | 2 | 0.035 | 0.175 | 1170 |
| Example 9 | 86.3 | 87.1 | 0.2 | 0.50 | 2 | 0.026 | 0.130 | 1600 |
| Example 10 | 85.9 | 86.4 | 0.2 | 0.64 | 2 | 0.027 | 0.135 | 1400 |
| Example 11 | 86.8 | 88.1 | 0.2 | 0.51 | 2 | 0.024 | 0.120 | 1720 |
| Example 12 | 88.5 | 89.2 | 0.2 | 0.47 | 2 | 0.022 | 0.11 | 1810 |
| Example 13 | 86.8 | 88.1 | 0.2 | 0.51 | 2 | 0.024 | 0.120 | 1720 |
| Example 14 | 85.4 | 86.2 | 2 | 0.57 | 2 | 27.6 | 0.138 | 1580 |
| Comparative example 1 | 65.4 | 57.4 | 0.2 | 1.6 | 20 | 0.085 | 0.425 | 650 |
It will be appreciated that in table 1, the volume amounts of the calculated domains formed with the titanium felt dimensions refer to: volume of rectangular parallelepiped of the same size as titanium felt.
As can be seen from the data in table 1: the porous transmission layer prepared in the embodiments 1 to 14 can obtain a metal substrate with higher porosity, has uniform porosity distribution, and can improve the water vapor transmission between the flow channel and the catalytic membrane in the membrane electrode, thereby enhancing the water vapor transmission performance of the porous transmission layer. On the basis, the volume of the porous transmission layer in the calculation domain is smaller, the porous transmission layer made of metal can ensure certain structural strength, meanwhile, the use of metal base materials can be saved, the conductivity of the porous transmission layer is ensured, and the porous transmission layer can meet the requirements of various fields such as filtration, separation, mass transfer and the like by being designed from a microscopic angle, so that more possibilities are provided for the improvement of the performance of the porous transmission layer.
Compared with the titanium felt of the comparative example 1, the porosity of the metal substrate of the example 1 is obviously larger than that of the comparative document 1, and the ratio of the volume of the titanium felt of the example 1 to the volume of the cuboid under the same volume as the titanium felt is obviously smaller than that of the titanium felt of the comparative example 1, which shows that the porous transmission layer constructed in a microscopic manner can greatly reduce the consumption of the titanium felt raw material and improve the water vapor transmission performance.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (9)
1. A porous transmission layer comprising: the metal substrate comprises a plurality of lattice units which are stacked, the plurality of lattice units which are stacked form a layered structure, the lattice units are of symmetrical structures, the lattice units are provided with pores, the porosity of the metal substrate is 20% -90%, the length of the lattice units along a first direction is 5-50 mu m, the length of the lattice units along a third direction is 5-50 mu m, the length of the lattice units along a second direction is 2-20 mu m, the second direction is perpendicular to a plane where the metal substrate is located, the first direction is perpendicular to the second direction, and the third direction is perpendicular to a plane formed by the first direction and the second direction.
2. The porous transmission layer of claim 1, wherein the metal substrate has a porosity of 80% -90%.
3. The porous transmission layer according to claim 1, characterized in that the porous transmission layer comprises at least one of the following features (1) - (4):
(1) The porosity of the lattice unit is 20% -90%;
(2) The thickness of the metal base material is 0.005 mm-0.5 mm;
(3) The surface of the metal substrate is rough, and the surface roughness of the metal substrate is 0.01-0.1 mu m;
(4) The metal substrate is made of any one of titanium, titanium alloy, stainless steel, nickel and nickel alloy.
4. The porous transport layer of claim 1, wherein the porosity of the metal substrate is arranged in a gradient along a direction perpendicular to the plane of the metal substrate.
5. The porous transport layer of claim 1, wherein the metal substrate comprises first lattice cells stacked in a first direction and first lattice cells stacked in a second direction.
6. The porous transmission layer according to claim 1, wherein the metal substrate comprises a first layer and a second layer stacked in a first direction, the first layer comprising first lattice cells stacked in a second direction, the second layer comprising second lattice cells stacked in the second direction, the second lattice cells in contact with the first lattice cells being complementary in shape to the first lattice cells in the first direction; or (b)
The metal substrate comprises a first layer and a second layer which are stacked along a second direction, the first layer comprises first lattice units stacked along the first direction, the second layer comprises second lattice units stacked along the first direction, and the second lattice units contacted with the first lattice units are complementary to the first lattice units in shape along the second direction.
7. The porous transport layer of claim 1, wherein the lattice cells comprise at least one of Simple cubic lattice cells, body centered cubic lattice cells, diamond lattice cells, fluoroite lattice cells, sampled cube lattice cells, triangular resonator-comb lattice cells, face centered cubic foam lattice cells, weiire-Phelan lattice cells, or isotrus lattice cells.
8. The porous transport layer of claim 1, wherein the length of the lattice cells in the first direction is equal to the length of the lattice cells in the third direction, and the length of the lattice cells in the second direction is 1/6 to 1/2 of the length of the lattice cells in the first direction.
9. A PEM electrolyser, characterized in that it comprises a porous transport layer according to any one of claims 1 to 8.
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| DE102020132271A1 (en) * | 2020-12-04 | 2022-06-09 | Christian Mangold | Porous transport layer PTL, stack with PTL, manufacturing process for a PTL |
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| EP4166691A1 (en) * | 2021-10-14 | 2023-04-19 | iGas energy GmbH | Frame for pem electrolytic cells and pem electrolytic cell stack for producing high pressure hydrogen by means of differential pressure electrolysis |
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| US20230117377A1 (en) * | 2021-10-19 | 2023-04-20 | National Taiwan University Of Science And Technology | Composite additive structure and composite additive manufacturing equipment |
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| WO1996029621A1 (en) * | 1995-03-17 | 1996-09-26 | Massachusetts Institute Of Technology | Metallodielectric photonic crystal |
| CN115917046A (en) * | 2020-06-10 | 2023-04-04 | 荷兰应用自然科学研究组织Tno | Proton exchange membrane based electrolyzer apparatus and method for manufacturing such apparatus |
| DE102020132271A1 (en) * | 2020-12-04 | 2022-06-09 | Christian Mangold | Porous transport layer PTL, stack with PTL, manufacturing process for a PTL |
| EP4166691A1 (en) * | 2021-10-14 | 2023-04-19 | iGas energy GmbH | Frame for pem electrolytic cells and pem electrolytic cell stack for producing high pressure hydrogen by means of differential pressure electrolysis |
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