NL2032014B1 - Method of manufacturing an isolated porous material and an isolated porous material - Google Patents
Method of manufacturing an isolated porous material and an isolated porous material Download PDFInfo
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- NL2032014B1 NL2032014B1 NL2032014A NL2032014A NL2032014B1 NL 2032014 B1 NL2032014 B1 NL 2032014B1 NL 2032014 A NL2032014 A NL 2032014A NL 2032014 A NL2032014 A NL 2032014A NL 2032014 B1 NL2032014 B1 NL 2032014B1
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- Prior art keywords
- intermediate layer
- porous
- porous material
- layer
- deposition
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- 239000011148 porous material Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 238000000151 deposition Methods 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 26
- 239000002344 surface layer Substances 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000386 microscopy Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/08—Perforated or foraminous objects, e.g. sieves
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
- C25D1/22—Separating compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a method of manufacturing an isolated porous material, comprising the steps of providing a substrate; applying an electrically conductive intermediate layer on at least part of a surface of the substrate; forming a surface layer on the intermediate layer by electrodeposition using dynamic bubble templating; and removing the intermediate layer from the porous layer to obtain the isolated porous material; wherein the step of removing the intermediate layer takes place during or after deposition of the porous layer. The invention further relates to a porous material obtainable with said method of manufacturing.
Description
TITLE Method of manufacturing an isolated porous material and an isolated porous material
The present invention relates to a method of manufacturing an isolated porous material and an isolated porous material obtained via said method.
Porous materials, also known as foams, are core components in next- generation electrochemical systems including electrolyzers, batteries, fuel cells, ion- selective separations and others. They may also be applied in general chemical systems as well as ultra-light-weight manufacturing and high surface area applications such as sensors, filters or heat exchangers. They must fulfil a set of seemingly contradictory requirements including the facilitation of transport of reactants and products, provide active sites for reactions and conduct electrons and heat. Optimizing these coupled phenomena necessitates the development of very controlled electrode geometries and chemical compositions.
In general, a foam is a dispersion in which a large proportion of gas by volume in the form of gas bubbles, is dispersed in a liquid, solid or gel. Examples of non-electrochemical and electrochemical methods for the preparation of metal foams include selective dissolution, templating, combustion, and the sol-gel method.
Dynamic hydrogen bubble templated (DHBT) electrodeposition is a relatively newly developed, yet very promising method of the preparation of metal foams.
Electrodeposition of metals using DHBT creates characteristic porous materials (foams). They feature a high porosity and a duality in their pore structure where networks of microscopic pores are arranged in such a way that they form larger, macroscopic pore structures. The overall morphology is sometimes referred to as honeycomb-like. Furthermore the macroscopic pore structures feature a pore size gradient from the top of the foam to the bottom with large pores at the top and small pores at the bottom of the material. Both of these features have been shown to improve mass transport phenomena in electrochemical devices such as fuel cells.
The fundamental idea of DHBT is that the generated Hz bubbles disrupt the growth of the metal layer, acting as a dynamic template for the electrodeposition process. Micropores in the submicron range and macropores in the 5-100 um size range are formed as a result of the growth of metal around small or coalesced bubbles generated on the surface, blowing up the specific surface area.
When applying the DHBT method, high cathodic overpotentials are used, so that certain reaction rates become comparable and decisive for the obtained foam structure. Apart from the reaction rates, however, other factors such as the nucleation, growth and detachment of the surface-generated bubbles, the intensive stirring and the related convective effects caused by bubble formation, the local alkalination of the near-electrode solution layers and its consequences on the chemistry of metal deposition, complex formation, the action of additives, etc. may also determine the surface morphology of the deposited foam.
The term DHBT has been used only in recent years. Other terms for this method of manufacturing a porous layer on a substrate include hydrogen evolution assisted (HEA) electroplating, electrochemical deposition mediated by hydrogen bubbles, nanodendritic micro-porous structure, mesoporous foams created using template-assisted electrodeposition, electrodeposition method with in-situ grown dynamic gas bubble templates, and gas bubble dynamic template.
EP1991824A1 discloses a method for forming a surface layer on a substrate wherein the surface layer is deposited by a controlled electrodeposition process or a controlled gas phase deposition process.
US20220085390A1 discloses a porous transport layer having a plurality of sintered porous layers with a permeability for gaseous and liquid substances. The multilayer porous transport layer is assembled between a bipolar plate and a catalyst layer of an electrochemical cell.
State of the art production of this type of material results in the porous material (the foam} being bonded to the substrate (also known as base plate) it its deposited onto. This limitation of the current material prevents a large variety of further treatments and analysis methods to be applied to the porous material and most importantly its use in a vast range of applications is restricted by the presence of the substrate. Examples of such applications include the application as diffusion media, filter material, and catalyst applications. Detachment of the porous material from the substrate is challenging as the structure is quite fragile compared to the strength of attachment to the substate. In prior art, the term “self-standing foam” is often used to refer to a foam that is connected to a substrate. The “self-standing” then refers to the fact that no additional mechanical support is required, but the foam is not isolated (separated) from the substrate.
It is an object of the present invention to provide a method of manufacturing an isolated porous material. With isolated is meant that it is free- standing, i.e. that is not connected to a substrate.
It is a further object of the present invention to provide an improved method of manufacturing a porous material.
It is a further object of the present invention to provide a method of manufacturing a porous material that leads to a porous material with improved permeability and/or flexibility.
It is a further object of the present invention to provide a porous material with improved permeability and/or flexibility.
One or more of these objects are achieved by the method of manufacturing an isolated porous material according to a first aspect of the invention.
In a first aspect, the invention relates to a method of manufacturing an isolated porous material comprising the steps of: - providing a substrate; - applying an electrically conductive intermediate layer on at least part of a surface of the substrate; - forming a surface layer on the intermediate layer by electrodeposition using dynamic bubble templating; and - removing the intermediate layer from the porous layer to obtain the isolated porous material, wherein the step of removing the intermediate layer takes place during or after deposition of the porous layer.
In a second aspect, the invention relates to a porous material obtainable with a method of manufacturing according to the first aspect.
Corresponding embodiments are also applicable for the porous material according to the present invention.
Specifically, applying an electrically conductive intermediate layer on at least part of a surface of the substrate allows for the porous material that is deposited to be disconnected from the substrate by removal of the intermediate layer.
The present invention is described hereinafter with reference to the accompanying drawings in which embodiments of the present invention are shown and in which like reference numbers indicate the same or similar elements.
Figure 1 shows a schematic of the foam generation procedure describing the main steps. Path a) describes the simultaneous foam formation and removal of the intermediate layer while path b) depicts the foam formation followed by a dedicated step to remove the intermediate layer
Figure 2 shows a cross-section image of a flow reactor designed for the formation of the foam material.
Figure 3 presents an image from Scanning Electron Microscopy (SEM) of the top side and cross-section of a typical DHBT foam structure.
Figure 4 presents SEM images at different magnifications of the top side of a typical DHBT foam structure and a schematic depicting the intended use in two phase transport of liquid and gas with the liquid wicking in the porous wall structure and the large pores remaining open for gas transport.
Figure 5 presents SEM images at different magnifications of the top side of a DHBT foam according to the invention (top row) and the bottom side of a
DHBT foam according to the invention (bottom row), which is only attainable since the foam has been successfully isolated and maintains its shape.
Figure 6 shows different views of a DHBT foam according to the present invention: a bottom and top view of a DHBT foam (left column) side view {middle column) and zoom in of the side view towards the top and bottom sections of the foam (right column) indicating the difference in wall structure as the metal deposition mechanism change between the formation of the bottom and the top of the structure.
Figure 7 shows a variation of area specific charge and its influence on the average and maximum pore size as determined by SEM imaging of the top side of the DHBT material.
Figure 8 shows a variation of deposition potential for a solution of 0.1
M CuSO: and 1.5 M H2SO,4 showing the brittle nature of the material at low potentials and the increased mechanical stability at higher potentials.
Figure 9 is an in plane and through plane view of a typical isolated 5 DHBT foam obtained using X-ray tomographic microscopy.
Figure 10 shows an analysis of the pore sizes of the macro- pores (porosity in wall neglected) of a typical isolated DHBT foam obtained from X-ray tomographic microscopy as function of distance from the bottom side of the material.
Figure 11 shows an analysis of porosity of an isolated DHBT foam according to the present invention obtained from X-ray tomographic microscopy.
Binary porosity refers to the porosity of the macro pores (neglecting the wall porosity and assuming solid material in its place). Backbone porosity refers to the porosity of the wall structure only and total porosity depicts the overall combined porosity of the material.
In an embodiment of the first aspect of the present invention, dynamic bubble templating is dynamic hydrogen bubble templating.
In a further embodiment of the first aspect, the electro-deposited surface layer comprises a porous wall structure defining and separating regularly spaced, sized and shaped macro-pores that are interconnected in the general direction normal to the surface of the intermediate layer, wherein the macro-pores have a diameter greater than 5 um and less than 1000 um and wherein the diameter of the pores gradually increases with distance from the intermediate layer.
In an embodiment of the first aspect, the intermediate layer is a metal with a lower standard electrode potential than the material of the surface layer. For instance, when the surface material is made is of copper, the metal for the intermediate layer can be Zn, Fe or Ni for example. Alternatives such as conductive polymers or carbon based variations would also be possible. For example, it is possible for the intermediate layer to be carbon particles held together by a polymer sprayed onto the substrate and later removed by an organic solvent.
When the step of removing the intermediate layer takes place during deposition of the porous layer, this removal may be done for instance by the chemical acting as hydrogen source (e.g. sulfuric acid) or the metal salt used to form the foam (e.g. copper sulphate) present in the plating solution or by an additive (e.g. solvent in case the conductive intermediate layer is comprised of carbon particles held in place by a polymer) that is not partaking in the foam formation process itself.
When the step of removing the intermediate layer takes place after deposition of the porous layer, this removal may be done for instance by slicing with a straight edge blade, optionally while the material is submerged in a liquid, by etching with an acid, by dissolving in a solvent, by increasing the temperature, by UV-light irradiation or by selective chemical degradation of the intermediate layer. Suitable acids for etching include sulfuric acid and hydrochloric acid. Suitable solvents for dissolving include acetone, benzene, and alcohols. It is noted that the porous material will likely separates already by itself from the substrate and means such as the razor just acts as a transport vehicle.
In an embodiment of the first aspect, the step of removing the intermediate layer takes place after deposition of the porous layer, by slicing with a straight edge blade, optionally while the material is submerged in a liquid, by etching with an acid or by dissolving in a solvent.
In an embodiment of the first aspect, the deposited material is a metallic material, preferably wherein the material is a metal chosen from the group consisting of Fe, Ni, Co, Cu, Cr, Au, Mg, Mn, Al, Ag, Ti, Pt, Sn, Zn and any alloys thereof, more preferably wherein the material is Cu.
In an embodiment of the first aspect, the substrate and the surface layer are comprised of the same or different material. The nature of the substrate material is not critical as long is at is compatible with the application of the intermediate layer, which in turn needs to be compatible with the surface layer. In general the substrate needs to be electrically conductive. Ideally, it is resistant or passive towards the chemicals used in the deposition solution. Examples could include Fe, Ni, Co, Cu, Cr,
Au, Mg, Mn, Al, Ag, Ti, Pt, Sn, Zn and any alloys thereof, as well as carbon based materials such as glassy carbon (vitreous carbonj.
In an embodiment of the first aspect, the deposition takes place using a solution comprising copper sulphate, and this solution is mixed with sulfuric acid. In a specific embodiment, the copper sulphate solution has a concentration below 0.2 M and the sulfuric acid concentration is above 0.1 M. In a more specific embodiment, the copper sulphate solution has a concentration below 0.1 M and the sulfuric acid concentration is above 0.5 M.
Other suitable solutions for deposition include solutions containing metal chlorides or acids that act as hydrogen source.
In an embodiment, the potential during deposition is at least 4 V. This potential ensures a stable foam. In a specific embodiment, this potential is at least 6
V.
A person skilled in the art will know the settings and conditions to generate the desired foam morphology. These can include a wide range of electrical currents, potentials, operation modes (constant current, constant potential, pulsed, switching polarity etc.), deposition solution compositions (in terms of metal salts, hydrogen source, supporting salts, further additives that alter the structure in the desired way), deposition solution flow rates, temperatures, pressures, setup orientation and electrode distance and deposition time.
In an embodiment of the first aspect, the porous layer is Cu, and the deposition takes place using a solution of copper and sulphate mixed with sulfuric acid, and wherein the intermediate layer is made of zinc and has a thickness between 200 nm and 500 nm.
In an embodiment of the first aspect, the porosity, binary pore size distribution and the pore-size gradient across the thickness dimension of the porous material are substantially unchanged by removal of the intermediate layer.
In an embodiment of the first aspect, the method of manufacturing according to the present invention further comprises the step of washing the isolated porous material with a low surface tension liquid. This step may be preceded by a first washing with a non-low surface tension liquid. Washing prevents any residual salt from the deposition solution to crystalize.
In an embodiment of the first aspect, method of manufacturing according to the present invention further comprises the step of drying the isolated porous material. This drying takes place after washing.
The method according to the first aspect of the invention may also include the step of modifying the porous material by annealing at 500° C for 5 hours to increase a grain size of the nanoparticles and reduce a boundary effect of the nanoparticles.
The method according to the first aspect of the invention may also include the step of “thickening” or enhancement of the structure by electrochemical or chemical post treatments such as application of an additional metal layer on the entire surface by electrodeposition or coating of the structure in a protective layer or application of a polymer thin film to alter the wettability.
In an embodiment of the second aspect of the present invention, the material is foldable on itself without breaking, up to a bend radius equal to or below 2 mm.
In a further embodiment of the second aspect, the material is permeable by gases and liquids continuously in all directions. Specifically, the material is permeable in the direction that is perpendicular to the direction of face of the material previously attached to the substrate. This direction is also known as the perpendicular direction. This permeation would not be possible if the material would be attached to the substrate as this would block the flow of gases or liquid in the perpendicular direction.
In a further embodiment of the second aspect, the material has a porosity of at least 85%, a binary pore size distribution arranged in a honeycomb-like fashion, and a pore size gradient across its thickness dimension. Porosity for the materials prepared could also be at least 90%, or at least 95% and can reach also up to 98%.
Other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed invention, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage.
The scope of the present invention is defined by the appended claims.
One or more of the objects of the invention are achieved by the appended claims.
The present invention is further elucidated based on the Examples below which are illustrative only and not considered limiting to the present invention.
DHBT deposition and isolation of copper foam
Deposition of the porous copper layer
In this example, zinc was used as the material of the intermediate layer. The material of the porous layer (the foam) was copper.
The DHBT reactor was prepared and it was ensured that all parts are clean and especially the copper parts are free of oxide buildup. The PTFE guides where placed on the side of the counter electrode. The reactor was assembled by placing the mask on the gasket, followed by a zinc coated substrate with the zinc coated side facing into the reactor. Next, the cathode current collector was placed on top of the substrate, and a PTFE spacer was placed on top of the current collector, after which the PTFE backplate was placed on the spacer. The assembly was then connected to a power source. The reactor was set up in a tilted fashion so the exit tube is higher than the inlet tube, at an angle between 20 to 40 degree, and the zinc coated substrate (cathode) was on the bottom side of the reactor assembly with the counter electrode above it.
The specific settings depend on the desired material properties and the deposition solution. In the present example, the deposition solution used was a 0.1
M solution of CuSO. mixed with a 1.5 M solution of H.SO4. The further settings applied were a voltage 6 V, a charge of at least 400 C and a flow rate of 30 ml/min and a deposition area of 4 cm?2.
When the deposition was finished, the plating solution was removed from the system and air was let in.
The substrate with the porous layer (foam) was placed in a solution of 0.1 M sulfuric acid to remove any remaining zinc from the substrate. After this, the substrate with the foam were placed in a water bath to remove any remaining acid.
Isolation of the porous material
The substrate with the porous layer were placed in water. A straight edge razor, was used to pass between the foam and the substrate and aid in separating the foam from the substrate. Specifically, removal was started in a corner of the foam, and sawing motions were avoided. The angel of the razor to the surface was around 20 degrees.
Post-treatment
After isolation of the foam, the foam was washed using isopropyl alcohol. After this, drying took place in a vacuum oven at 50°C for at least 30 minutes.
Results
The results are visualized in the figures. The figures show that an isolated porous material is obtained. Figure 5 shows a bottom side of the obtained porous material that is only attainable when the porous material is successfully isolated and maintains it shape. Figure 9 shows the in plane and through plane view of an isolated porous material obtained using X-ray tomographic microscopy. Figure 10 shows that the isolated porous material has indeed the desired pore sizes and macro- pores. Figure 11 shows that obtained isolated porous material has the desired porosity.
These results show that one or more objects of the invention are achieved by the method of manufacturing according to the first aspect of the present invention and/or the porous material according to the second aspect of the present invention.
Claims (15)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2032014A NL2032014B1 (en) | 2022-05-30 | 2022-05-30 | Method of manufacturing an isolated porous material and an isolated porous material |
| PCT/NL2023/050278 WO2023234770A1 (en) | 2022-05-30 | 2023-05-16 | Method of manufacturing an isolated porous material and an isolated porous material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2032014A NL2032014B1 (en) | 2022-05-30 | 2022-05-30 | Method of manufacturing an isolated porous material and an isolated porous material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL2032014B1 true NL2032014B1 (en) | 2023-12-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL2032014A NL2032014B1 (en) | 2022-05-30 | 2022-05-30 | Method of manufacturing an isolated porous material and an isolated porous material |
Country Status (2)
| Country | Link |
|---|---|
| NL (1) | NL2032014B1 (en) |
| WO (1) | WO2023234770A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1991824A1 (en) | 2006-03-03 | 2008-11-19 | Richard Furberg | Porous layer |
| US20220085390A1 (en) | 2019-01-23 | 2022-03-17 | Paul Scherrer Institut | Porous transport layer based on multiple micro and nano sintered porous layers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3081715A1 (en) * | 2020-05-08 | 2021-11-08 | Institut National De La Recherche Scientifique | Porous ni electrodes and a method of fabrication thereof |
-
2022
- 2022-05-30 NL NL2032014A patent/NL2032014B1/en active
-
2023
- 2023-05-16 WO PCT/NL2023/050278 patent/WO2023234770A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1991824A1 (en) | 2006-03-03 | 2008-11-19 | Richard Furberg | Porous layer |
| US20220085390A1 (en) | 2019-01-23 | 2022-03-17 | Paul Scherrer Institut | Porous transport layer based on multiple micro and nano sintered porous layers |
Non-Patent Citations (3)
| Title |
|---|
| ILIJA NAJDOVSKI ET AL: "Rapid Synthesis of Porous Honeycomb Cu/Pd through a Hydrogen-Bubble Templating Method", CHEMISTRY - A EUROPEAN JOURNAL, JOHN WILEY & SONS, INC, DE, vol. 17, no. 36, 18 July 2011 (2011-07-18), pages 10058 - 10063, XP071833314, ISSN: 0947-6539, DOI: 10.1002/CHEM.201101224 * |
| KURNIAWAN MARIO ET AL: "Electrodeposition of cuprous oxide on a porous copper framework for an improved photoelectrochemical performance", JOURNAL OF MATERIAL SCIENCE, KLUWER ACADEMIC PUBLISHERS, DORDRECHT, vol. 56, no. 20, 9 April 2021 (2021-04-09), pages 11866 - 11880, XP037425659, ISSN: 0022-2461, [retrieved on 20210409], DOI: 10.1007/S10853-021-06058-Y * |
| LINK STEFFEN ET AL: "Enhanced cycling performance of binder free silicon-based anode by application of electrochemically formed microporous substrate", ELECTROCHIMICA ACTA, ELSEVIER, AMSTERDAM, NL, vol. 380, 26 March 2021 (2021-03-26), XP086535610, ISSN: 0013-4686, [retrieved on 20210326], DOI: 10.1016/J.ELECTACTA.2021.138216 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023234770A1 (en) | 2023-12-07 |
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