JP2021533532A - Proton conductive two-dimensional amorphous carbon film for gas membrane and fuel cell applications - Google Patents

Abstract

The present disclosure relates generally to two-dimensional amorphous carbon (2DAC) coating techniques. Proton conductive 2DAC films can be used in fuel cells, hydrogen generation and deuterium production applications. More specifically, the present disclosure comprises a fuel containing an aggregate of electrode catalysts and a two-dimensional (2D) amorphous carbon, wherein the 2D amorphous carbon has a crystallinity (C) of 0.8 or less. Regarding batteries.
[Selection diagram] Fig. 1

Description

The present disclosure relates generally to two-dimensional amorphous carbon (2DAC) coating techniques. More specifically, the present disclosure relates to proton conductive 2DAC films for fuel cell, hydrogen generation and deuterium production applications.

Prior art needs to develop and provide improved performance for fuel cell applications.

According to the first broad aspect, the present invention comprises an electrode catalyst assembly and a two-dimensional (2D) amorphous carbon, wherein the 2D amorphous carbon has a crystallinity of 0.8 or less (C). Provides a fuel cell with.

According to the second broad aspect, the present invention comprises an electrode catalyst assembly and a two-dimensional (2D) amorphous carbon, wherein the 2D amorphous carbon has a crystallinity (C) of less than 1. Moreover, a fuel cell having an sp3 / sp2 binding ratio of 0.2 or less is provided.

According to a third broad aspect, the present invention comprises an electrode catalyst assembly and a two-dimensional (2D) amorphous carbon having an atomic structure consisting of a non-hexagonal carbon ring and a hexagonal carbon ring, and. Provided is a fuel cell in which the ratio of the hexagonal carbon ring to the non-hexagonal carbon ring is less than 1.0.

The accompanying drawings, which are incorporated herein and constitute a portion of the specification, illustrate exemplary embodiments of the invention, the general description set forth above and set forth below. Together with a detailed description, it will help explain the features of the invention.
FIG. 6 is a schematic diagram showing a disclosed composite (not graphene) of an atomically thin film showing a random hexagonal ring showing continuity and order according to one embodiment of the present disclosure. TEM images of amorphous films showing hexagonal and non-hexagonal according to one embodiment of the present disclosure are illustrated. Illustrates the measured thickness of the disclosed carbon film on boron nitride by atomic force microscopy (AFM) according to one embodiment of the present disclosure. Illustrative Raman spectra of amorphous films and nanocrystalline graphene on _{SiO 2} according to one embodiment of the present disclosure. TEM diffraction between atomically thin amorphous carbon (left side) and graphene (right side) according to one embodiment of the present disclosure is illustrated. The transmittance of the disclosed carbon film according to one embodiment of the present disclosure is illustrated. Illustrating the mechanical properties of a 2D amorphous film and the demonstration of a suspended carbon film according to one embodiment of the present disclosure. Illustrates the electrical properties of a 2DAC according to one embodiment of the present disclosure. Illustrate composites grown on different substrates according to one embodiment of the present disclosure. Illustrative is X-ray photoelectron spectroscopy (XPS) of 2DAC on Cu according to one embodiment of the present disclosure. The conventional configuration of a proton exchange membrane fuel cell (PEMFC) according to the prior art is illustrated. An embodiment in which 2DAC according to one embodiment of the present disclosure is implemented as a barrier layer between an electrode and a proton exchange membrane is illustrated. An embodiment in which 2DAC according to one embodiment of the present disclosure is implemented in a configuration between an anode aggregate and a cathode aggregate is illustrated. Nafion® is formed on either side of an exemplary 2DAC film according to one embodiment of the present disclosure and illustrates an embodiment confined between an electrode layer and a catalyst layer in a fuel cell configuration. Illustrative fuel cell embodiments in which the 2DAC layer according to one embodiment of the present disclosure is between the electrode / catalyst assembly and the proton / deuteron conductive membrane. It is an exemplary example of how a modified membrane according to one embodiment of the present disclosure can be used to separate a gas mixture.

Detailed description of the invention

(Definition)
If a definition of a term deviates from the commonly used meaning of that term, Applicant will use the definition provided below, unless otherwise indicated.

It should be understood that the above general description and the following description are merely exemplary and descriptive and do not limit the subject matter set forth in the claims. In this application, the use of the singular is meant to be plural, unless otherwise specified. As used herein and in the accompanying claims, the singular form with "a", "an" and "the" is a plurality of references unless the context clearly indicates otherwise. It should be noted that it includes. In this application, the use of "or" (or) means "and / or" (and / or) unless otherwise specified. Moreover, the use of the term "include" (including, including) and other forms (eg, "include", "includes" and "included") is not limiting.

For the purposes of the present invention, the terms "comprising" (including), the term "having" (having), the term "inclating" (including, including), and variants of these terms are intended to be unconstrained. It means that there may be additional elements that are different from the listed elements.

For the purposes of the present invention, directional terms such as "top" (top), "bottom" (bottom), "upper" (upper), "lower" (lower), "above" (upper), " "below" (lower), "left" (left), "right" (right), "horizontal" (horizontal), "vertical" (vertical), "up" (upper), "down" (lower), etc. It is used only for convenience in describing various embodiments of the invention. The embodiments of the present invention may be oriented in various ways. For example, a schematic diagram, a device, or the like shown in a drawing may be turned inside out, rotated by 90 ° in either direction, or inverted.

For the purposes of the present invention, a particular value, if the value is derived by making a mathematical calculation or logical decision using the value, characteristic or other factor. "Based" on characteristics, fulfillment of conditions, or other factors.

It should be noted that, for the purposes of the present invention, in order to provide a more concise description, some of the quantitative representations presented herein are not modified by the term "about". Regardless of whether the term "about" is used explicitly, any quantity shown herein is meant to indicate the actual value shown and is also shown as such. Shows approximations of such indicated values that would be reasonably inferred based on normal skill in the art, including approximations due to experimental and / or measurement conditions for the values. It is understood that this also means.

For the purposes of the present invention, the term "bond strength" refers to the strength of the bond between the disclosed 2DAC film and its growth substrate. Bond strength depends directly on the bond energy between these two materials, which may be measured in units of J / m ^2.

For the purposes of the present invention, the term "amorphous" indicates that it lacks a well-defined form, does not have a specific shape, or is amorphous. As a non-crystalline solid, amorphous represents a solid that lacks the long-range order characteristic of crystals.

For the purposes of the present invention, the term "amorphous carbon" refers to carbon that has no long-range crystalline structure.

For the purposes of the present invention, the term "atomically thin amorphous carbon" has a plane consisting of approximately 1 to 5 layers ^{of carbon atoms, with most sp 2} bonds present between these carbon atoms. Therefore, it shows the amorphous carbon forming the layer. It must be understood that layers may be stacked and this stacking of layers is considered to be within the scope of the invention.

For the purposes of the present invention, the term "carbon coating" refers to a layer of carbon deposited on a substrate.

For the purposes of the present invention, the term "carbon ring size" refers to the size of the ring of carbon atoms. In some disclosed embodiments, the number of atoms in one carbon ring can vary from 4 to 9 atoms.

For the purposes of the present invention, the term "diamond-like carbon" refers to amorphous carbon consisting of sp ³ bonds in most between carbon atoms.

For the purposes of the present invention, the term "differentiate stem cells" refers to the process of directing unspecialized stem cells to specific types of cells with functional traits. In the disclosed embodiments, differentiation results from a combination of chemical factors and substrate-inducing factors.

For the purposes of the present invention, the term "D / G ratio" refers to the intensity ratio of D and G peaks in a Raman spectrum.

For the purposes of the present invention, the term "electrochemical cell (EC)" refers to a device in which it is possible to either generate electrical energy from a chemical reaction or otherwise facilitate it. show. Electrochemical cells that generate electric current are called voltaic cells or galvanic cells, and others are called electrolytic cells that are used to carry out chemical reactions such as electrolysis. A common example of a galvanic cell is a standard 1.5 volt battery for consumer use. The battery may consist of one or more cells connected in either parallel or serial fashion.

For the purposes of the present invention, the term "fuel cell" refers to an electrochemical cell that converts chemical energy from a fuel into electricity through an electrochemical reaction between a hydrogen fuel and oxygen or another oxidizing agent. Fuel cells may differ from batteries in that they require a continuous source of fuel and oxygen (usually air-derived oxygen) to maintain their chemical reaction, whereas batteries. Now, the chemical energy comes from the chemicals that are already present in the battery. Fuel cells can continuously provide electricity as long as fuel and oxygen are supplied.

For the purposes of the present invention, the term "graphene" refers to an allotrope (form) of carbon consisting of a single layer of carbon atoms arranged in a hexagonal lattice. This monolayer is the basic structural element of many other allotropes of carbon, such as graphite, charcoal, carbon nanotubes and fullerenes. This monolayer can be considered the ultimate case of an infinitely large group of aromatic molecules, i.e., a group of flat polycyclic aromatic hydrocarbons. Graphene has many extraordinary properties, including its strong material properties, its ability to efficiently transfer heat and electricity, and is also nearly transparent.

For the purposes of the present invention, the term "membrane" may allow some elements to pass through, but as a selective barrier that blocks others (eg, molecules, ions or other small particles). Shows the layer of action.

For the purposes of the present invention, the term "Nafion®" refers to a sulfonated tetrafluoroethylene fluoropolymer copolymer. Nafion® is the first in a class of ionic synthetic polymers called ionomers. The unique ionicity of Nafion® is the result of incorporating a perfluorovinyl ether group, which is a sulfonic acid group at the end, into the Tetrafluoroethylene backbone. Nafion® acts as a proton conductor for proton exchange membrane (PEM) fuel cells and has excellent thermal and mechanical stability.

For the purposes of the present invention, the term "proton exchange membrane" or the term "polyelectrolyte membrane" (PEM) is generally made from ionomers and is used as an electronic insulator and reactant barrier, eg, oxygen and hydrogen. Shows a semipermeable membrane designed to transfer protons while acting as an electron insulator and reactant barrier to gas. In some embodiments, the proton exchange membrane or polyelectrolyte membrane may also be referred to as a proton conduction membrane. Some of the essential functions of PEMs may include the separation of reactants and the transport of protons, while blocking the direct electronic pathways through the membrane. Various PEMs can be made either from pure polymer membranes or from composite membranes in which other materials are embedded in the polymer matrix. In some disclosed embodiments, the PEM may be characterized primarily by proton conductivity (σ), methanol permeability (P) and thermal stability. In PEM fuel cells, a solid polymer membrane (thin plastic film) may be used as the electrolyte, in which case the polymer is permeable to protons when the water is saturated, but does not transfer electrons.

For the purposes of the present invention, the term "proton exchange membrane fuel cell (PEMFC)" has been developed primarily for transport applications, as well as for stationary and portable fuel cell applications. Indicates a type of fuel cell. Their salient features include a lower temperature / pressure range (50-100 ° C.) and a special polyelectrolyte membrane with proton conductivity. PEMFCs generate and operate electricity on the opposite principle of electrolysis of polymer electrolyte membranes (PEMs), which consume electricity. PEMFCs are a strong candidate to replace aging alkaline fuel cell technology. In some applications, PEMFC may also be known as a polyelectrolyte membrane fuel cell.

For the purposes of the present invention, the term "proton transport" refers to the transport of protons across an electrical insulating film.

For the purposes of the present invention, the term "Raman spectroscopy" refers to spectroscopic techniques used to observe vibrational modes, rotational modes and other low frequency modes in a system. Raman spectroscopy is commonly used in chemistry to provide structural fingerprints that can identify molecules. Raman spectroscopy relies on inelastic scattering of monochromatic light, which is usually inelastic scattering from laser light in the visible, near-infrared or near-ultraviolet range, i.e. Raman scattering. The laser light interacts with molecular vibrations, phonons or other excited states in the system, resulting in an upward or downward shift in the energy of the laser photons. This shift in energy provides information about the vibrational modes in the system.

For the purposes of the present invention, the term "Raman spectrum" refers to the phenomenon of scattering intensity as a function of frequency shift depending on the rotational vibrational state of the molecule. In order for a molecule to exhibit the Raman effect, a change in its electric dipole-electric dipole polarizability must be present with respect to the vibration coordinates corresponding to the vibrational rotational state. The intensity of Raman scattering is proportional to this change in polarizability.

For the purposes of the present invention, the term "self-assembled" refers to the self-assembly of polymer chains in a regular lattice structure covering the disclosed 2DAC surface. In the disclosed embodiments, self-assembly allows the formation of ultra-thin films with different properties compared to bulk properties.

For the purposes of the present invention, the term "sp ³ / sp ² ratio" refers to the type of carbon bond found in 2DAC. Sp ² binding allows higher order growth factor binding.

For the purposes of the present invention, the term "subject" refers to a structural support for a disclosed two-dimensional (2D) amorphous carbon film. In selected applications, the disclosed embodiments provide, for example, a substrate for mechanically supporting a 2DAC film. This is because otherwise the 2DAC film may be too thin to perform its function without being damaged. The substrate may be considered the material used to grow the disclosed 2DAC or 2DAC film on the surface of the substrate.

For the purposes of the present invention, the term "two-dimensional (2D) amorphous carbon film" is used from atomically thin amorphous carbon to as thin as possible amorphous carbon (eg, monoatomic thickness). Amorphous carbon), for example, directly in various substrates including substrates that have low melting temperatures and are non-catalytic, as well as those substrates that also include surfaces of metals, glass and oxides. Show what can be grown. Growth on other substrates is possible due to the low temperature at which the disclosed 2DAC films are grown. Various disclosed embodiments of the 2DAC film may be presented as a self-supporting film or as a coating on a substrate, as disclosed herein. Despite the amorphous nature of the disclosed 2DAC film, carbon atoms are bonded to multiple adjacent carbon atoms in a plane and even when separated from their growth substrate (when self-supporting). It forms a strong network that is very stable. The carbon material also has properties to ensure that it adheres well to the metal surface, thereby completely covering the entire substrate. The inherent thinness and high strength of the disclosed 2DAC thin film also allows the 2DAC thin film to withstand bending of the metal substrate without breaking.

For the purposes of the present invention, the term "two-dimensional (2D) amorphous carbon coating" refers to a 2DAC film that grows and / or deposits directly on a substrate. The disclosed embodiments may also include cases where the 2DAC coating is transferred to or from the substrate.

(explanation)
Various modifications and alternatives of the present invention are possible, but specific embodiments thereof are shown as examples in the drawings and will be described in detail below. However, it is not intended to limit the invention to the particular embodiments disclosed, and on the contrary, the invention spans all modifications, equivalents and alternatives within the spirit and scope of the invention. It must be understood that this will be the case.

Fuel cells provide clean and efficient energy conversion of hydrogen and oxygen sources that provide electrical output and clean water as waste. One of the more promising types of fuel cells is the proton exchange membrane fuel cell (PEMFC), which has been on the market for some time ¹ . In conventional configurations, the PEMFC can basically consist of three components: an anode, a cathode, and a proton exchange membrane. FIG. 11 illustrates the working principle of an exemplary conventional PEMFC (1100). Hydrogen dissociates into protons and electrons at the anode (1106), the protons cross the proton exchange membrane (1104) and reach the cathode (108), while the electrons pass through the external circuit (1110) to the cathode (1108). ) Is reached. At the cathode (108), protons interact with electrons and oxygen, which produces water waste (H ₂ O). Electric power is generated by electrons in the external circuit (1110).

The performance of the PEMFC (1100) is a proton exchange membrane (1104) that transfers protons and prevents hydrogen, methanol, oxygen, nitrogen and other gases that may be present in the system from passing through the membrane. ) Depends on. The electrode / catalyst layer or electrode catalyst assembly (1102) consists of an electrode, typically made of carbon, on which catalyst particles made of platinum, ruthenium or other catalytically active material are deposited. The electrode catalyst assembly (1102) has a porous structure that allows these gases to pass through the layer by diffusion. Hydrogen fuel that passes through the anode electrode catalyst aggregate by diffusion reacts with the catalyst particles and dissociates into protons and electrons. In the cathode electrode catalyst assembly, the oxygen gas continues to pass through the assembly by diffusion and reacts with protons and electrons to form water. In many cases, an inert gas (eg, nitrogen) is flushed through the system to stabilize operating pressure, fuel supply, and to help transport excess gas and liquid to the exhaust. do.

The gas across the proton exchange membrane (1104) not only reduces net efficiency, but also causes the formation of hydrogen peroxide at the electrodes, which causes pinholes and thinning of the proton exchange membrane (104). So I'm worried. These events enhance gas passage and accelerate fuel cell failure ² .

Gas passage can also affect the efficiency of catalytic particles that facilitate chemical reactions at the anode and cathode. The proton exchange membrane (1104) can also be further damaged by ionic contaminants (eg, alkali metals and ammonium ions) ² .

In order to prevent gas passage and deterioration of the proton exchange membrane, various embodiments of the disclosed invention provide a 2DAC layer that can be introduced as a gas passage prevention layer. In some embodiments, the disclosed 2DAC is provided as a film layer. In an exemplary configuration, the disclosed 2DAC film may be attached to a proton exchange membrane (1104). The disclosed 2DAC film does not limit the proton conductivity due to its excellent proton conductivity and ultimate thinness. The disclosed 2DAC film is a barrier to all other gases and ions, thereby increasing the life of the PEMFC used. Further discussion of the disclosed 2DAC films is provided as follows.

The disclosed embodiments relate to new composites composed of atomically thin (single layer) amorphous carbon on a substrate (metal, glass, oxide). This amorphous carbon adheres very well to the substrate on which the amorphous carbon grows. Therefore, this amorphous carbon material provides unique characteristics. For example, the disclosed amorphous carbon material is suitable for applications that utilize a substrate that requires a coating for a specific purpose (s). Exemplary uses may include, but are not limited to, biomedical uses.

The present disclosure provides a new form of carbon called two-dimensional (2D) amorphous carbon (2DAC). According to the disclosed embodiments, 2DACs can be grown directly on a variety of metal substrates, including, for example, substrates that have a low melting temperature and are non-catalytic, as well as substrates that also include glass and oxide surfaces. The thinnest possible amorphous carbon inside (eg, amorphous carbon with a thickness of approximately a single atom) is provided. In one selected embodiment, having a monatomic thickness is a preferred material and may be a lower thickness limit for 2DAC. The disclosed embodiments may include thicknesses that can range to a thickness of a few atoms (eg, a thickness of 10 atoms or about 3 + nm). The disclosed 2DAC may be provided as a two-dimensional (2D) amorphous carbon film. However, as the thickness of the disclosed 2DACs increases, the disclosed 2DACs may still be present in any amorphous carbon material, as disclosed herein. It is still important to note that the thickness and structural differences of the crystalline carbon material (eg, sp ³ to sp ^{2 ratio).}

Growth on other substrates is possible due to the low temperature at which the disclosed 2DAC films are grown. Despite the amorphous nature of the disclosed 2DAC film, carbon atoms are bonded to multiple adjacent carbon atoms in a plane and even when separated from their growth substrate (when self-supporting). It forms a strong network that is very stable. Therefore, each carbon atom is bonded to a plurality of carbon atoms so that a high-density bond (linkage) exists. The disclosed 2DACs also have properties to ensure that they adhere well to the metal surface, thereby ensuring complete coverage. Material properties (eg, material properties disclosed below), such as the inherent thinness and high strength of the disclosed 2DAC thin film, also allow the 2DAC thin film to withstand bending of the metal substrate without breaking. Make it possible.

According to the disclosed embodiments, amorphous carbon may be defined as a form of carbon that does not have long-range structural order. Amorphous carbon exists in several forms, and depending on its form, it is often referred to by different names such as diamond-like carbon, glassy carbon, soot, and so on. Amorphous carbon may be produced, for example, by several techniques including chemical vapor deposition, sputter deposition and cathodic arc deposition, among others. In conventional applications, amorphous carbon has always been present in three-dimensional form (or in bulk). The two-dimensional equivalent form of carbon is graphene, however, graphene only exists as a crystalline material (either single crystal or polycrystalline). Graphene requires high temperatures for it to be synthesized and is most often grown on the copper surface. With the present disclosure, the disclosed embodiments have achieved to produce continuous two-dimensional forms of amorphous carbon that grow at much lower temperatures and on any substrate. The disclosed composite of 2DAC film and substrate has properties that are significantly different from bulk amorphous carbon, and on the contrary, significantly different from monolayer graphene.

Various embodiments of the disclosed 2DAC include a film, eg, a film covering a substrate, a film covering the inner surface of a porous structure, a suspended film, a rolled film, a tube, a fiber, or a hollow ball. May exist as. The disclosed mechanical, electrical, optical, thermal and other properties of the 2DAC are expected to vary, depending on, for example, the shape of the 2DAC. For example, a tube containing the disclosed 2DAC would have a large mechanical strength in the axial direction and a milder response in the radial direction. The disclosed 2DACs can be prepared in various forms to take advantage of the different properties for different uses.

FIG. 1 illustrates a schematic view (100) of the disclosed composite material, along with a TEM image of the carbon material on the upper surface of the substrate. The composition of the disclosed material is a new composite of atomically thin amorphous carbon (102) on a substrate (104) (eg, metal or glass, oxide).

The disclosed composites may exhibit atomically thin 2D amorphous carbon (2DAC) on any substrate. According to the disclosed embodiments, the disclosed 2DAC film on the disclosed substrate may be defined with respect to its atomic structure and its properties.

More rigorous tests and definitions for atomic structure may be expressed as: FIG. 2 illustrates TEM images of amorphous and non-hexagonal films according to one embodiment of the present disclosure. The upper left image of FIG. 2 illustrates a high resolution TEM image of the disclosed 2DAC film including hexagons and non-hexagons. A schematic diagram of the lower left of the TEM image of the upper left image is provided for clarity. Hexagons are colored green, while non-hexagons are colored either red or blue. The upper right display is an FFT illustrating which one exhibits a ring structure that does not have a clear diffraction pattern.

Referring to the TEM image of FIG. 2, the 2DAC film is a monatomic thickness carbon film having a mixture of hexagonal and non-hexagonal rings in its structure. These rings are perfectly connected to each other, thereby forming various polygonal reticulated structures in large area films of at least micron scale. The ratio of hexagons to non-hexagons is a measure of crystallinity (or amorphous) C. The non-hexagon is in the form of a 4-membered ring, a 5-membered ring, a 7-membered ring, an 8-membered ring, and a 9-membered ring. The 2D amorphous film has a C of 0.8 or less when photographed with respect to a minimum imaging area of ^{approximately 8.0 nm 2.} The C value in FIG. 2 is approximately 0.65. The disclosed embodiments may support a C value range (including both ends) between 0.5 and 0.8. This is different from graphene where C = 1 for pure hexagonal reticulum. Non-hexagons can be randomly distributed within the hexagonal matrix or can occur along the boundaries of the hexagonal domain. The domain should not exceed 5 nm. The Fast Fourier Transform (FFT) of the image shall not indicate the diffraction point (Fig. 2, top right). The 2DAC can be separated from the substrate to be self-supporting or transferred to another substrate. Therefore, in some embodiments, the disclosed 2DAC may be separated from the surface of the substrate in order to obtain a self-supporting 2DAC film.

FIG. 3 illustrates the thickness (ie, height) measured by AFM of the isolated disclosed 2DAC film on boron nitride (BN). Based on the disclosed invention, the following properties apply: FIG. 3 shows the AFM of the disclosed transferred 2DAC film to boron nitride (BN). The disclosed thickness of 2DAC is approximately 6 Å, comparable to graphene, which is only one atom thick (thickness ranges from 3.3 Å to 10 Å when measured on BN (both ends). Including)). The thickness is also supported by the TEM image in FIG. In addition, the film is found to be homogeneous.

FIG. 4 illustrates a Raman spectrum (400) of an amorphous film and non-crystalline graphene on _{SiO 2.} Raman spectroscopy of the isolated film did not show a 2D peak (~ 2700 cm-1), but instead showed a wide G peak (at ~ 1600 cm-1) and a D peak (at ~ 1350 cm-1). .. The spread of D-peaks and G-peaks usually indicates a transition from nanocrystalline graphene to an amorphous film, as previously reported ³ . From the intensity ratio of the D peak and the G peak, it is estimated that the domain size is about 1 to 5 nm ³ . Raman spectroscopy serves as a characterization tool for representing the TEM image in FIG. 2 over a large area.

FIG. 5 provides a comparison (500) of TEM diffraction between atomically thin amorphous carbon (left side) and graphene (right side) according to one embodiment of the present disclosure. Further evidence of the amorphousness of the disclosed isolated film is supported by TEM diffraction, where no distinct diffraction points are detected, in contrast to graphene, where crystalline diffraction points are clearly visible. .. The diffraction ring in FIG. 7 (top) indicates that the domain size is less than 5 nm. The diffraction data of the amorphous film 2DAC is consistent with the FFT image in FIG. In this case, the 2DAC film is self-supporting.

Referring to FIG. 6, graph (600) illustrates the transparency of the disclosed carbon film according to one embodiment of the present disclosure. The optical transparency is ~ 98% at a light wavelength of 550 nm, and the transparency increases with increasing wavelength. Therefore, selected embodiments provide 98% or higher optical transparency at wavelengths above 550 nm. Again, the disclosed carbon film differs from graphene: this is a layer in which the transparency of graphene in a single layer is up to 97.7% throughout the visible wavelength (400 nm-700 nm, including both ends). This is because it decreases as the number of. Notably, the transparency of the 2DAC film does not have the rapid decline at short wavelengths (less than 400 nm) as seen in graphene.

The elastic modulus E of the suspended film exceeds 200 GPa, which is larger than the bulky glassy carbon (E = 60 GPa) ⁴ . The limit strain before mechanical failure is 10%, which is much higher than the limit strains of other amorphous carbons reported. FIG. 7 shows the non-surface of the suspended carbon film and the suspended carbon film after applying extreme stress with an atomic force microscope (AFM) (eg, Bruker model number: MPP-11120) chip. Pushing is exemplified. The amorphous nature of the disclosed 2DAC film prevents the suspension film from collapsing in FIG. 7 (bottom). Instead, the film exhibits a ductile response down to the level of extreme stress.

The 2DAC thin film of the disclosed invention has a high electrical resistance, and the electrical resistivity ranges from 0.01Ω-cm to 1000Ω-cm depending on the value of C (which is adjusted by the growth conditions). FIG. 8 is a schematic diagram (800) of the electrical properties of the 2D amorphous carbon, the IV curve (802) of the 2D amorphous film and the histogram of the measured resistance values for a particular C value. 804) and is shown. Measurement techniques / methods aimed at providing resistivity values are used. Ratios are used within the calculation from the data on the IV curve (802) to obtain the respective resistivity data points in the histogram (804). Therefore, the length: width ratio for 2D amorphous carbon in FIG. 8 (left) is 1: 100. In comparison, graphene has a resistivity value of ^10-6 Ω-cm, while bulky glassy carbon (also 100% CC-C sp ² ) starts at 0.01 Ω-cm. It has a value up to 0.001Ω-cm.

When the monolayer film contains more than 6 n-membered rings, it is, of course, a gas, ion, which is small enough in size to pass through the 7-membered ring, 8-membered ring, and 9-membered ring. A membrane through which liquids or other chemical species can be selectively passed. In particular, the disclosed 2DAC film allows protons to pass through at room temperature 10 times more efficiently than crystalline single layer boron nitride ⁵ . For the disclosed 2DAC film, the resistivity to the proton flow across the membrane is 1-10Ω-cm ² at room temperature.

FIG. 9 illustrates composites grown on different substrates according to one embodiment of the present disclosure. Pictures of titanium, glass and copper coated with atomically thin amorphous carbon are illustrated on the left. In the upper right is a Raman spectrum from the covered region showing a similar response regardless of substrate. Finally, in the lower right is a Raman map of the G / D peak ratio of the 2DAC film on titanium, indicating that it is completely covered. The disclosed composites (ie, the disclosed 2DACs and their substrates) can be made from any metal (catalytic or non-catalytic), or in glass or oxide. Accordingly, the disclosed embodiments specify that the 2DAC can be grown directly on any of the disclosed desired substrate materials. This is unlike graphene, which can only be grown on catalytic substrates (eg copper) and requires transfer to all other substrates. Therefore, the disclosed composites bond strongly to the host substrate as compared to the method of depositing amorphous or diamond-like carbon, which cannot be less than 1 nm thick to still be considered continuous. Contains an atomically thin (less than 1 nm) and continuous layer of two-dimensional amorphous carbon.

In general, when the film on the substrate is poorly adhered, various areas of the film may come off the substrate, and thus these areas may or may not provide insufficient protection for the substrate. Become. Accordingly, embodiments of the present disclosure provide an improved film that provides uniformity and strong adhesion over the applied surface of the substrate. Therefore, the disclosed 2DAC film is preferably formed as a continuous film over substantially the entire substrate surface or at least the applied surface. Unlike the conventional design, for example, graphene in the case of Cu which can be easily peeled off (for example, the adhesive force is 10 to 100 J / m2), for example, the disclosed atom arranged in Cu. A thin 2DAC film adheres very well to the substrate with an adhesion energy of over 200 J / m2 ⁶ . This example provides further evidence to distinguish the disclosed 2DAC film from graphene. (Although exemplary embodiments of Cu substrates are described, various embodiments of applying the disclosed 2DAC to any substrate can be applied according to the disclosed embodiments of the present invention.) Adhesive energy is evident in all substrate materials on which the disclosed 2DAC films grow, including, for example, stainless steel, titanium, glass, nickel and aluminum substrates. It should be understood that the above substrates are exemplary and that the teachings of the present disclosure can be applied to any substrate of any desired substrate.

In general, any attempt to transfer a 2D material to a material by conventional materials and processes, whatever the 2D material, has previously been, for example, defects and cracks in the transferred material, and also coating on the substrate. It is causing a drop in the rate. This is due, at least in part, to the fact that many mechanical steps are commonly used in the transfer process and chemicals that induce cracks and defects in conventional film applications can be used. However, the disclosed 2DAC film does not need to be transferred from the growth substrate to the target substrate, for example. In addition to the improved adhesion properties of the disclosed 2DAC film, the enhanced properties of the disclosed 2DAC film result in direct, even and complete coverage of the entire substrate / covering the substrate. Guaranteed. Therefore, it is obtained that it is evenly and completely covered, which is at least because the disclosed 2DAC film is perfectly capable of being directly evenly and successfully grown directly on its host substrate. Because there is no need to do it.

The disclosed 2DAC films are designed to provide such reliable coatings, along with their excellent mechanical properties for adhesion to substrates (eg, carbon, etc.), and further of 2DAC films and 2DAC complexes. Very suitable and reliable for applications that require physical properties / requirements. Such physical properties may include the disclosed 2DAC films and / or 2DAC complexes being able to bend and / or stretch. The disclosed 2DAC adhesion properties and ability to the substrate ensure that this is the case. If there is non-uniform adhesion to the substrate, as in the case of transferred film, cracks in the film will occur in areas of poor adhesion, which is a cause of fragility.

Accordingly, embodiments of the disclosed invention cover the entire substrate (104) on which the amorphous carbon film is grown (Raman map of FIG. 9), which makes it very suitable for applications requiring, for example, a carbon coating. Provides an upper amorphous carbon film (102) that is useful for. The amorphous carbon film (102) on top also acts as a defect-free diffusion barrier, thereby preventing oxidation and corrosion of the underlying substrate. Due to the electrical insulation properties, the disclosed amorphous carbon film (102) prevents any galvanic corrosion of the substrate (104). The low electrical conductivity of the disclosed 2DACs is beneficial for cell adhesion and cell proliferation, as seen in recent reports ⁷ . The cells on the conductive substrate attach to the surface via electrostatic interaction without causing focal adhesions. Desmosomes are very important for cell proliferation and cell growth, and low electrical conductivity is preferred for focal adhesion development and cell proliferation. The low electrical conductivity is a result of the amorphousness of the disclosed 2DAC as observed by the D / G peak intensity of Raman spectroscopy and the sp ³ / sp ^{2 ratio.}

In contrast, graphene is known to exacerbate long term corrosion ^8. The transfer of graphene makes it nearly impossible to produce a flat, continuous film without creating cracks and imperfections along the surface. The disclosed amorphous carbon film (102) material is a composite with the substrate (104), which eliminates the need for transfer and also eliminates the risk of cracks in the film (102). Be taken.

The disclosed 2DAC film consists of sp ^2- bonded carbon similar to glassy carbon; however, the thickness is only about 1 atom layer thickness (6 Å), which is how previously reported. Thinner than the amorphous carbon structure. FIG. 10 illustrates X-ray photoelectron spectroscopy (XPS) measurements of 2D amorphous carbon on Cu, where the measurements show a bond type with ^{a peak position of sp 2} or sp ^{3, while peak intensity.} Shows the percentage of each type of binding. A mixed concentration of sp ² and sp ³ bonds between CC is also possible without sacrificing thickness, but the maximum sp ³ content between CC is set to 20%. Thin structure and strong disclosed 2DAC attached essentially has always protects the underlying substrate, this possibility of peel off is different for thicker films than is evident ^9.

According to the disclosed embodiments, a laser-based growth process uses hydrocarbons as precursors (eg, CH ₄ , C ₂ H _2, etc.) to make the disclosed composite films. Hydrogen gas (H ₂ ) and argon gas (Ar) may also be mixed with the precursor. In this process, the laser has two roles: (1) as an energy source for decomposing the precursor gas in a process called photolysis, and (2) as a local heat source. Assuming that one or both of the aforementioned roles produce the disclosed 2DAC film, in the first case the substrate (104) is said to be at room temperature throughout the growth period and in the second case. In, the laser can heat the substrate (104) to 500 ° C. Typically, a pulse excimer UV laser (eg, 193 nm, 248 nm or 308 nm) is applied to the substrate surface at a fluence of ^{about 50-1000 mJ / cm 2 at various growth times, depending on the substrate used.} It can be oriented parallel to the substrate. Other possible combinations for producing the disclosed complexes may include any combination of laser, plasma and / or substrate heaters. A heater may be used to heat the substrate (104) to 500 ° C. The plasma output may be used in the range of 1 to 100 W (including both ends). Typical combinations using hydrocarbons as precursors would be: (i) laser only; (ii) laser + low power plasma (5W); (iii) laser + low power plasma (5W). + Heater (300 ° C to 500 ° C); (iv) Low power plasma (5W) + 500 ° C heater; (v) High power plasma (100W) only.

According to the disclosed embodiments, complete growth / deposition of the disclosed 2DAC and 2DAC complexes may be accomplished in the chamber. Various modules for heating, plasma, gas flow and pressure control may all be set up and established inside the chamber for a controlled growth environment. According to one embodiment, the process pressure of the chamber may be established in the range 10-1E-4mbar (including both ends).

Process parameters for 2DAC disclosed may include: (i) Process gas: CH ₄ ; (ii) Chamber pressure: 2.0 E-2mbar; (iii) Laser fluence: 70 mJ / cm ² ; (iv) Growth time: 1 minute; (v) Plasma output: 5 W; (vi) Substrate: Cu foil.

In the process for producing the disclosed 2DAC film, _{it may be used that methane (CH 4} ) is used inside the growth chamber for the growth process. The gas pressure in the chamber during the growing period is controlled at 2E-2 mbar throughout the period. This gas is in the presence of a plasma generator operating at an output of 5 W. Growth begins when exposure to a 248 nm excimer laser is performed on the surface of a copper foil substrate with a fluence of ^{70 mJ / cm 2 with a pulse frequency of 50 Hz.} The laser exposure time (ie, growth duration) is set in 1 minute to obtain a continuous 2DAC coating on the substrate. No stage heaters are used in this growth. Multiple parameters disclosed herein include hydrocarbons as precursors, precursor mixtures, photodecomposition processes and adjustments to photodecomposition equipment, temperature adjustments, substrate temperature adjustments, changes in C-values, number of atomic layers. Adjusted to control and / or alter the properties of the disclosed 2DACs, including, but not limited to, changes in the sp ² to sp ^{3 ratio, as well as changes in adhesion to the substrate.} In some cases.

The disclosed carbon film may be constructed with a minimum thickness that ensures that the disclosed metal surface of the substrate is evenly and completely covered for the life of the applied usage. In one exemplary embodiment, the disclosed 2DAC thickness may be designed to be approximately one atomic layer thickness. The disclosed carbon film (102) may be grown directly on some substrates (104), for example in materials such as stainless steel and titanium. Since the growth takes place at a much lower temperature than, for example, graphene synthesis, the disclosed 2DAC is directly relative to other substrates (104) that cannot withstand high temperatures, such as glass and hard disks. Can be grown ¹⁰ . The disclosed 2DAC film (102) is ultra-tough and binds strongly to the substrate (104), making it suitable for applications that may require deformation such as bending and elongation. The strong mechanical properties of the disclosed 2DAC film are due to the absence of grain boundaries. Due to the insulating properties of the disclosed carbon film (102), galvanic corrosion of the substrate (104) is prevented, unlike graphene, which enhances this corrosion. 7-membered ring of carbon film as seen in the TEM images, 8-membered ring and 9-membered rings are useful as an efficient membrane for the, or proton transport for various gases ^5.

According to a selected embodiment of the disclosed invention, the disclosed 2DAC is, for example, as a self-supporting example when the substrate is not suitable for growth and therefore the disclosed 2DAC needs to be transferred. May be caused. Suitable methods and techniques for transporting the disclosed 2DAC (1202), such as dry transport as described in the patent application below, may be used: cvd graphene using a polarized ferroelectric polymer. Defect-free direct dry peeling (International Publication WO2016126208A1). Other transfer methods may include, but are not limited to, thermal release tapes, pressure sensitive adhesives, spin coatings, spray coatings, and Langmuir Brodget techniques.

However, various additional advantages of the present disclosure stipulate that, in some embodiments, the disclosed 2DAC (1202) can be grown directly on the substrate. Such an advantage of the disclosed 2DAC film is that, for example, when compared to graphene for the transfer process, the disclosed 2DAC film does not require a sacrificial support layer for transfer (unlike graphene). .. For graphene, the film layer is required to prevent cracks and defects during the transfer period, and the film layer needs to be removed after transfer. Even with respect to removal, there remains a residue from the sacrificial layer that cannot be completely removed. For the disclosed 2DACs, the transfer can be carried out without the use of sacrificial layers, without inducing defects, without treating the residue, or without damaging the structure.

The various advantages of the disclosed embodiments of the 2DAC layer can be implemented in a wide variety of applications, including but not limited to fuel cell, hydrogen generation and deuterium production applications. In such applications, the advantages of the disclosed 2DAC layers are used, including, for example, an exemplary single layer of carbon atoms in an amorphous structure with a C value of 0.8 or less. Again, referring to the amorphousness of the disclosed 2DAC layer (eg, the 2DAC film shown in FIG. 2), the carbon continuous film is between ^{approximately 0.1-10 S / cm 2.} Arranged in a random pattern that allows for very large lateral conductance of protons. The conductance of deuterium (the nucleus of deuterium) is 0.01 to 1 S / cm ² , which is roughly an order of magnitude smaller than the conductance of protons. The conductance of triton (tritium nucleus) is approximately 0.003 to 0.3 S / cm ² . Due to the difference in transport rate, the disclosed 2DAC becomes an efficient separation membrane for hydrogen isotopes. At the same time, the membrane is impermeable to other molecules _(e.g., H 2, _{O 2} and CH _4).

Proton transport through the film is limited by electron cloud density ⁵ . The C value represents the degree of crystallinity of the disclosed 2DAC and can be controlled / adjusted between approximately 0.5 and 0.8 by varying the growth parameters. By changing the C value, the electron cloud in the film is changed, and the proton conductance can be increased or decreased. For example, the techniques applied may include adjusting the power, pulse and / or angle of the laser used to the disclosed 2DAC.

In the selected embodiment, the elastic modulus E of the disclosed 2DAC suspension film exceeds 200 GPa and the fracture energy exceeds 20 J / m2, which is more than twice the fracture energy of graphene. Evidence of the same is illustrated, for example, in FIG. In FIG. 3, the nanoindentations in the disclosed suspended 2DAC film indicate that the elastic modulus E exceeds 200 GPa (right), and the suspended 2DAC film after the ultimate stress is applied by the AFM chip has a fracture energy of 20 J. It shows that it exceeds / m ^2. Therefore, the characteristics of these mechanical properties of the disclosed 2DAC layer increase the life of the application. For example, the disclosed barrier prevents gas passage through, thereby preventing corrosion of the electrolyte / catalyst layer. The strong mechanical properties of the disclosed 2DAC layer, specifically its high fracture toughness, guarantee a long life of the barrier used, thereby providing longer overall performance of the fuel cell.

The disclosed 2DAC layer or 2DAC film can be further modified during the growth period or post-treatment period by other unrestricted techniques including, for example, reactive oxygen ion plasma, argon sputtering, ozone treatment or electron beam exposure. .. The disclosed atomic structure of 2DAC may be modified to allow larger molecules to pass through. This is used to create a gas separator.

[Example]
2DAC in a fuel cell as a gas passage prevention layer:
FIG. 12 illustrates an exemplary embodiment of an improved PEMFC (1200) with one disclosed embodiment in which the disclosed 2DAC acts as a proton conduction barrier layer. The PEMFC (1200) comprises the disclosed 2DAC (1202) used as a barrier layer between the electrode catalyst assembly (1102) and the proton exchange membrane (1104). The disclosed 2DAC (1202) allows only protons to cross the 2DAC layer (1202) and prevents other gases and liquids from coming into contact with the proton exchange membrane (1104).

In this exemplary configuration, a plurality of electrode catalyst assemblies (1102) are arranged to confine the disclosed 2DAC (1202) and proton exchange membrane (1104). The disclosed 2DAC (1202) may be disposed between the respective electrode catalyst aggregates (1102) and the proton exchange membrane (1104). Acting as a barrier, the 2DAC (1202) prevents fuel, waste and ion contaminants from leaking into the proton exchange membrane (1104) and crossing over to the opposite electrode catalyst assembly (1102). Such leaks are known to cause destruction of the proton exchange membrane (1104) and deterioration of PEMFC performance. It is readily understood that the disclosed 2DACs can be used as is or in other configurations, eg, in layers, films, films and the like.

Hydrogen and oxygen across the proton conductive membrane (1104) can be a direct cause of fuel loss and direct loss of fuel cell efficiency. The disclosed 2DAC (1202) will prevent this loss and can significantly improve the efficiency of the fuel cell. In the absence of 2DAC (1202), other gases (eg, nitrogen, etc.) may also pass through the proton conduction membrane (1104) in other ways. This can result in fuel deficiency, for example at the catalytic site. Such deficiency, catalyst deterioration, therefore, are known to cause a loss of performance and reliability ^11. The disclosed 2DAC (1202) will prevent other gases from crossing the proton conductive membrane (1104) and will prevent the catalyst deterioration described above.

Proton exchange membranes (1104) often require high levels of hydration to transfer protons. By confining the proton conductive membrane (1104) in a non-permeable barrier, dehydration and drying of the proton conductive membrane (1104) can be prevented. This will result in long-term stability of the performance of the PEMFC (1200).

Those skilled in the art will readily appreciate that the disclosed techniques are not limited to PEMFC applications and may also be implemented in other applications (eg, redox flow batteries, etc.).

[Example 2]
2DAC as a monatomic layer proton exchange membrane:
FIG. 13 illustrates an exemplary embodiment of an improved PEMFC (1300) according to a disclosed embodiment in which the disclosed 2DAC is used as a proton conductive monoatomic membrane. In this embodiment, the disclosed 2DAC (1202) is arranged in a configuration between the anode aggregate and the cathode aggregate. In this configuration, the proton exchange membrane is replaced by a monoatomic layer of 2DAC (1202).

The disclosed monatomic layer of 2DAC (1202) transfers protons and prevents the passage of fuel gas and liquid. This reduces the need for hydration of the conventional proton exchange membrane. Due to the large proton conductivity across the ultrathin 2DAC (1202), a large output occurs with less resistance loss than would otherwise be achieved and observed in conventional proton exchange membranes. The 2DAC layer (1202) is mechanically strong and has great fracture toughness that provides long-term stability. The flexibility of 2DAC (1202) enables the novel fabrication of thin and flexible fuel cells.

[Example 3]
Self-assembled, extremely thin, uniform proton exchange membrane in 2DAC:
FIG. 14 discloses that a proton conductive film (1104) is used as a proton conductive film or coating (1104) of self-assembled Nafion® formed in the disclosed 2DAC (1202). Illustrative embodiments of the improved PEMFC (1400) by embodiment are exemplified. Therefore, the proton exchange membrane (1104) may be composed of a fluoropolymer such as Nafion®. The proton exchange membrane (1104) is typically a minimum thickness of about tens of microns to avoid gas passage, and is approximately hundreds of microns to reduce transport loss across the proton exchange membrane (1104). Is formed by the maximum thickness.

The disclosed 2DAC (1202) may serve as a template for polymer aggregates due to its unoccupied π orbitals. The amorphous structure of 2DAC (1202) disclosed acts as a template for Nafion® polymers to form thin films. Even if the disclosed 2DACs have low crystallinity, the π orbitals in the carbocycle allow alignment of the Nafion® polymer on the surface. Therefore, 2DAC (1202) may be utilized to create a very thin, uniform layer of Nafion® coating (1104) on the surface of 2DAC. The Nafion® coating (1104) described above has no pinholes. Due to the self-assembly in the disclosed 2DAC (1202), the proton conductivity of the ultrathin Nafion® coating (1104) is increased, while leakage and gas passage are reduced.

Therefore, as shown in the exemplary embodiment of FIG. 14, the electrode catalyst assembly (1102) may include a plurality of electrode catalyst aggregates. The proton exchange membrane (1104) may include a plurality of proton exchange membranes. The disclosed 2DAC (1202) may be disposed between a plurality of proton exchange membranes (1104), and the plurality of proton exchange membranes (1104) may be disposed between a plurality of electrode catalyst assemblies (1102). May be done.

Since it acts as a proton exchange membrane (1104), in FIG. 14, a Nafion® film is formed on either side of the 2DAC layer (1202) or the 2DAC film, and the electrode catalyst assembly (1102) in a fuel cell configuration. It is exemplified that it can be configured to be confined between. Thus, the disclosed 2DAC (1202) can be transferred to Nafion® film by ^{, for example, a wet transfer similar to the wet transfer 12 of CVD graphene.}

In another exemplary embodiment, the disclosed 2DAC (1202) can also be transferred to a Nafion® membrane by dry transfer as described in the patent application below: Polarized ferroelectric polymer. Defect-free direct dry exfoliation of cvd graphene using WO2016126208A1. As noted above, other transfer methods may include, but are not limited to, thermal release tapes, pressure sensitive adhesives, spin coatings, spray coatings, and Langmuir Brodget techniques.

[Example 4]
Hydrogen isotope separation:
FIG. 15 illustrates an exemplary embodiment of an improved PEMFC according to a disclosed embodiment in which the fuel cell (1500) is configured to operate in the reverse fashion thereby separating hydrogen isotopes. Will be done. The disclosed 2DAC (1202) facilitates the transport of nuclei of the hydrogen isotopes deuterium and tritium, albeit at a much slower rate than proton transport. Differences in transport rate across 2DAC (1202) are used to separate hydrogen isotopes from protium (standard hydrogen). Such separation is for heavy water production, eg for heavy water production for research and use in reactors, as well as for tritium removal, eg, to maintain performance. Can be used for the removal of tritium from heavy water used in.

FIG. 15 illustrates a fuel cell (1500) in which a 2DAC (1202) is located between an electrode catalyst assembly (1102) assembly and a proton / deuteron conduction membrane (1502). The fuel cell (1500) is operated in reverse mode by applying a bias on both sides of the proton / deuteron conductive film (1502). In this mode, the fuel cell (1500) consumes electricity and produces hydrogen and deuterium. Hydrogen and deuterium dissociate into protons and deuteriums and are transported across the disclosed 2DAC layer (1202) and proton / deuterium conduction membrane (1502).

As disclosed above, the atomic structure and carbon ring size of the disclosed 2DAC (1202) can be modified (eg, by exposure to plasma, electron beam or other irradiation techniques). Thus, the structure of the disclosed 2DAC (1202) is by modifying the ring size, thereby affecting the different transport rates of protons and deuterons across the disclosed 2DAC layer (1202). It may be in sync. The results may include that the hydrogen content is greater than that of deuterium.

Therefore, in one embodiment, the source ratio where _{H 2} / D ₂ is 50% may be the product _{ratio where H 2} / D _{2 is 90%.} However, in some disclosed embodiments, the H ₂ / D ₂ source ratio and product ratio can vary. For example, if the rate of transport of the H + is 10 times the D + transport _speed, a source ratio = 1 H 2 / _{D 2,} the product ratio = 10 H ₂ / _D 2.

[Example 5]
Gas selection membrane:
FIG. 16 illustrates an exemplary system (1600) for gas separation by the disclosed modified 2DAC (1202) according to the disclosed embodiments. The disclosed 2DAC (1202) allows larger molecules to pass, thereby being modified by irradiation techniques (eg, electron beam and ion plasma, etc.) to allow gas selective membranes. Therefore, the disclosed 2DAC (1202) remains a barrier to all molecules larger than specified by the modification parameters.

FIG. 16 illustrates an example of how the disclosed modified 2DAC (1202) can be used, for example, as a membrane or layer utilized to separate a gas mixture. For example, the modified 2DAC film (1602) between step 1 (1604) and step 2 (1606) _{may be modified to allow H 2} and O ₂ to pass through, step. step 2 (1606) and is modified 2DAC film between the process steps 3 (1608) (1604), which may be modified to allow that only _{H 2} passes. By applying a negative pressure gradient from step 1 to step 3 and recirculating the gas through the system (1600), step 1 _{only contains CO 2} and step 2 is O _2. will only contain, process step 3 will only contain H _2. Therefore, gas separation is achieved in the system (1600).

In summary, the two-dimensional amorphous carbon (2DAC) of the disclosed embodiments may include a monatomic layer of carbon atoms in a non-crystalline amorphous structure. In its initial state, the random arrangement of atoms, large lateral proton conductivity, as well as all larger atoms and molecules (e.g., H _{2, O 2,} etc. CH ₄₎ barrier allowing for. This highly proton conductive membrane can be implemented, for example, in fuel cells, hydrogen generation and deuterium production applications.

The atomic structure and carbon ring size of the disclosed 2DAC can be modified by exposure to plasma, electron beam or other irradiation techniques. This allows the passage of larger molecules, thereby extending the use of the disclosed 2DACs to a number of gas separation applications. The disclosed 2DAC is unrivaled in that it has an extremely large proton conductivity while incorporating only the thickness of the monatomic layer. Mechanical toughness means, for example, that the disclosed 2DAC requires approximately 3 times more energy to propagate in the disclosed 2DAC when compared to other 2D materials. The disclosed 2DAC is impermeable to molecular hydrogen and larger molecules. Therefore, the disclosed 2DAC prevents the gas from crossing the proton exchange membrane and thus the loss of function of the electrode catalyst assembly (1102). The disclosed 2DACs have a proton transport rate of approximately 0.1-10 S / cm ^2. Such high transport speeds increase performance beyond conventional fuel cells. The disclosed 2DAC results in the selective transport of hydrogen nuclear isotopes. Therefore, the difference in transport rate makes the disclosed 2DAC a more efficient separation membrane for hydrogen isotopes.

Although many embodiments of the present disclosure have been described in detail, it will be clear that various modifications and variations are possible without departing from the scope of the invention as defined in the appended claims. Moreover, all examples in the present disclosure exemplify many embodiments of the invention, while being provided as non-limiting examples, and thus as limiting the various aspects so exemplified. It must be understood that it should not be interpreted.

[References]
The following references are referenced above and are incorporated herein by reference.
1. 1. Sharaf, O.D. Z. & Orhan, M.D. F. "Anoverview of fuel cell technology: Fundamentals and applications", Renewable and Sustainable Energy Reviews 32,810-853 (2014).
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4. Robertson, J. Mol. "Ultrathin carbon coatings for magnetic story technology", Thin Solid Films 383, 81-88 (2001)
5. Hu, S. et al. "Proton transport throttle one-atom-thick cristals", Nature 516, 227-230 (2014)
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7. Choi, W. J. et al. "Effects of substrate control on cell morphogenesis and proliferation tilored, atomic layer deposition-grown ZnOthin fims", Script20thinfilms,
8. Schriver, M.M. et al. "Graphene as a Long-Term Metal Oxidation Barrier: Worse Than Nothing", ACS Nano 7, 5763-5768 (2013)
9. Wang, J.M. S. et al. "The mechanical performance of DLC films on steel substrates", Thin Solid Films 325,163-174 (1998)
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All documents, patents, journal articles and other materials cited in this application are incorporated herein by reference.

References herein to any prior publication (or information derived from that prior publication), or to any matter known in any matter, are to that prior publication (or such). Information derived from prior publications) or what is known to allow, or allow, to form some of the common general knowledge in the field of effort in which this specification relates. It does not imply any form and should not be construed as such.

Although the invention is disclosed in connection with a particular embodiment, the areas and scope of the invention as defined in the appended claims are numerous modifications, changes and changes to the described embodiments. It is possible without deviating from. Accordingly, it is intended that the invention is not limited to the described embodiments, but that the invention is defined in its full scope by the wording of the claims below and its equivalents.

Claims (31)

Electrode catalyst assembly and
A fuel cell comprising two-dimensional (2D) amorphous carbon, wherein the 2D amorphous carbon has a crystallinity (C) of 0.8 or less. The fuel cell according to claim 1, wherein the 2D amorphous carbon is a film. The fuel cell according to claim 1, wherein the 2D amorphous carbon is a film. The fuel cell according to claim 1, wherein the 2D amorphous carbon has a resistivity of 0.01 to 1000 Ω-cm (including both ends). The fuel cell according to claim 1, further comprising a proton exchange membrane. The fuel cell according to claim 5, wherein the 2D amorphous carbon is arranged between the electrode catalyst assembly and the proton exchange membrane. The electrode catalyst aggregate includes a plurality of electrode catalyst aggregates, and the electrode catalyst aggregate contains a plurality of electrode catalyst aggregates.
The fifth aspect of the present invention, wherein the proton exchange membrane is arranged between the plurality of electrode catalyst aggregates, and the 2D amorphous carbon is arranged between the respective electrode catalyst aggregates and the proton exchange membrane. The described fuel cell. The electrode catalyst aggregate includes a plurality of electrode catalyst aggregates, and the electrode catalyst aggregate contains a plurality of electrode catalyst aggregates.
The proton exchange membrane contains a plurality of proton exchange membranes, and the proton exchange membrane contains a plurality of proton exchange membranes.
The fuel cell according to claim 5, wherein the 2D amorphous carbon is arranged between the plurality of proton exchange membranes, and the plurality of proton exchange membranes are arranged between the plurality of electrode catalyst aggregates. .. The fuel cell according to claim 8, wherein the proton exchange membrane is a fluoropolymer. The fuel cell according to claim 9, wherein the fluoropolymer is Nafion®. Electrode catalyst assembly and
It contains two-dimensional (2D) amorphous carbon, the 2D amorphous carbon has a crystallinity (C) of less than 1, and the sp ³ / sp ² binding ratio is 0.2 or less. Fuel cell. The fuel cell according to claim 11, wherein the 2D amorphous carbon is a film. The fuel cell according to claim 11, wherein the 2D amorphous carbon is a film. The fuel cell according to claim 11, further comprising a proton exchange membrane. The fuel cell according to claim 14, wherein the 2D amorphous carbon is arranged between the electrode catalyst assembly and the proton exchange membrane. The electrode catalyst aggregate includes a plurality of electrode catalyst aggregates, and the electrode catalyst aggregate contains a plurality of electrode catalyst aggregates.
The 14th aspect of the present invention, wherein the proton exchange membrane is arranged between the plurality of electrode catalyst aggregates, and the 2D amorphous carbon is arranged between each electrode catalyst aggregate and the proton exchange membrane. The described fuel cell. The electrode catalyst aggregate includes a plurality of electrode catalyst aggregates, and the electrode catalyst aggregate contains a plurality of electrode catalyst aggregates.
The proton exchange membrane contains a plurality of proton exchange membranes, and the proton exchange membrane contains a plurality of proton exchange membranes.
The fuel cell according to claim 14, wherein the 2D amorphous carbon is arranged between the plurality of proton exchange membranes, and the plurality of proton exchange membranes are arranged between the plurality of electrode catalyst aggregates. .. The fuel cell according to claim 17, wherein the proton exchange membrane is a fluoropolymer. The fuel cell according to claim 18, wherein the fluoropolymer is Nafion®. Electrode catalyst assembly and
It contains a two-dimensional (2D) amorphous carbon having an atomic structure consisting of a non-hexagonal carbon ring and a hexagonal carbon ring, and
A fuel cell in which the ratio of the hexagonal carbon ring to the non-hexagonal carbon ring is less than 1.0. The fuel cell according to claim 20, wherein the two-dimensional (2D) amorphous carbon has ^{an adhesion energy of about 200 J / m 2 or more.} The non-hexagonal carbon ring is in the form of a non-hexagonal carbon ring selected from the group consisting of a 4-membered carbon ring, a 5-membered carbon ring, a 7-membered carbon ring, an 8-membered carbon ring and a 9-membered carbon ring. Item 20. The fuel cell according to Item 20. 20. The fuel cell of claim 20, comprising 98% or higher optical transparency at wavelengths above 550 nm. The fuel cell according to claim 20, wherein the 2D amorphous carbon is a film. The fuel cell according to claim 20, wherein the 2D amorphous carbon is a film. 20. The fuel cell of claim 20, further comprising a proton exchange membrane. 26. The fuel cell of claim 26, wherein the 2D amorphous carbon is disposed between the electrode catalyst assembly and the proton exchange membrane. The electrode catalyst aggregate includes a plurality of electrode catalyst aggregates, and the electrode catalyst aggregate contains a plurality of electrode catalyst aggregates.
26. The proton exchange membrane is arranged between the plurality of electrode catalyst aggregates, and the 2D amorphous carbon is arranged between each electrode catalyst aggregate and the proton exchange membrane. The described fuel cell. The electrode catalyst aggregate includes a plurality of electrode catalyst aggregates, and the electrode catalyst aggregate contains a plurality of electrode catalyst aggregates.
The proton exchange membrane contains a plurality of proton exchange membranes, and the proton exchange membrane contains a plurality of proton exchange membranes.
26. The fuel cell according to claim 26, wherein the 2D amorphous carbon is arranged between the plurality of proton exchange membranes, and the plurality of proton exchange membranes are arranged between the plurality of electrode catalyst aggregates. .. 29. The fuel cell according to claim 29, wherein the proton exchange membrane is a fluoropolymer. 30. The fuel cell of claim 30, wherein the fluoropolymer is Nafion®.

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