Nanoporous structures and assemblies incorporating them

Abstract

To provide a method of forming a composite including a carbon composite structure.SOLUTION: The method includes disposing a precursor composition on a substrate. The composition includes a porogen component, a carbon component, and a catalyst component. The method further includes irradiating the precursor composition to form the carbon composite structure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a nanoporous structure and an assembly incorporating the same.

Background Art

[0002] A binder-free mesoporous hybrid carbon coating on a polymer or metal substrate can be used as a high-surface area electrode to achieve excellent device performance. However, achieving the direct fabrication of such a coating is difficult due to substrate decomposition in the high-temperature carbonization process.

Brief Description of the Drawings

[0003] [Figure 1] Cross-sectional view of a battery including a carbon composite structure according to various embodiments. [Figure 2] Schematic diagram showing a method of fabricating a battery according to various embodiments. [Figure 3] Schematic diagram showing an alternative method of fabricating a battery according to various embodiments. [Figure 4] Diagram of a transmission electron microscope image showing a sample according to various embodiments. [Figure 5] Diagram of a transmission electron microscope image showing a sample according to various embodiments. [Figure 6] Diagram of a transmission electron microscope image showing a sample according to various embodiments. [Figure 7] Graph showing the rate performance and Coulombic efficiency of 50 charge-discharge cycles at various cycle currents of an anode according to various embodiments.

Modes for Carrying Out the Invention

[0004] The present disclosure provides a method of forming a composite including a carbon composite structure. The method includes the step of disposing a precursor composition on a substrate. The composition includes a porogen component, a carbon component, and a catalyst component. The method further includes the step of irradiating the precursor composition to form a carbon composite structure.

[0005] This disclosure further provides electrodes. The electrodes include individual layers of carbon composite structures having elongated profiles. The electrodes are formed by placing a precursor composition on a substrate. The composition includes a pologen component, a carbon component, and a catalyst component. The precursor composition is irradiated to form a carbon composite structure.

[0006] This disclosure further provides articles, each comprising a substrate on which an elongated carbon composite structure is arranged to form an electrode. The electrode is formed by arranging a precursor composition on the substrate. The composition comprises a pologen component, a carbon component, and a catalyst component. The precursor composition is irradiated to form a carbon composite structure.

[0007] This disclosure presents a variety of advantages, some of which are unexpected. According to various embodiments, the structure is well suited to serve as a support for a variety of functional materials, including noble metal or metal oxide nanoparticles (NPs), which can significantly improve device performance, such as the capacity of lithium-ion batteries. For example, the structure is highly conductive, Li + It can exhibit excellent performance as a battery anode (for example, approximately 1000mA / g).

[0008] This disclosure provides a method comprising the steps of: placing a precursor composition comprising a polymer that functions as a pologen; a light-absorbing component; a support phase precursor; and a solvent on a substrate; irradiating the precursor composition with electromagnetic radiation of a wavelength and intensity effective in decomposing the polymer and activating the support phase precursor; and forming a hierarchical structure on the substrate.

[0009] This disclosure provides an article comprising a substrate on which a porous structure is arranged, wherein the porous structure is arranged over an area exceeding 1 square meter of the substrate. This disclosure further provides a battery. The battery includes a substrate. The substrate includes an anode layer. The anode layer includes a carbon composite structure that is disposed on the substrate to form electrodes.

[0010] This disclosure further provides a method for forming a battery. The method includes the step of placing a precursor composition on a substrate. The precursor composition includes a pologen component, a carbon component, and a catalyst component. The method further includes the step of bringing the precursor composition into contact with a mold. The mold includes a plurality of protrusions in contact with the precursor composition. The method further includes at least one of the steps of raising the temperature of the precursor composition to form an anode layer and irradiating the precursor composition to form an anode layer. The method further includes the step of placing a separator layer on the anode layer. The method further includes the step of placing a conductor layer on the anode layer to form a battery.

[0011] According to various embodiments, relatively low-cost iron / iron oxide nanoparticles can be used to catalyze the formation of structures or to provide heat by acting as nanoheaters through light absorption. According to various embodiments, the structures can form anodes for lithium-ion batteries. According to various embodiments, the structures can form high-performance anodes due to several attractive features, including the high surface area of ​​the mesoporous structure, the high energy density provided by the iron oxide nanoparticles, the high conductivity due to the graphite nanowires, as well as the good integrity of the film (no binders), and the good mechanical properties provided by the amorphous carbon matrix.

[0012] According to various embodiments, the method for forming the structure requires a simple coating of a precursor composition, followed by rapid conversion of the carbon component to a desired carbon phase and / or removal of the pologen using sub-millisecond light pulses, which can be easily scaled to high-volume roll-to-roll processing and can be carried out at low temperatures (e.g., below 400°C). Using polymers with defined constructs, such as block copolymers, as the pologen / templating component allows for the formation of materials with extremely well-controlled pore size and pore size distribution.

[0013] According to various embodiments, the method can enable the direct conversion of a precursor composition into a desired carbon composite structure to form an anode structure. Intermediate steps, including the steps of preparing a solution from a graphite intermediate and preparing nanoparticles coated with graphite-like carbon, can be avoided. These intermediate steps may require the addition of polymers or other binders, which may degrade performance. However, the direct conversion from the precursor composition to the carbon composite multilayer structure can avoid the need for intermediate steps, and therefore polymers or binders.

[0014] According to various embodiments, a battery comprising at least an anode having a patterned structure as described herein may have an increased surface area compared to a corresponding battery having an anode without a pattern. According to some examples, this can increase the output of the battery.

[0015] The drawings are generally used to illustrate, and not to limit, the various embodiments described in this document. Throughout this document, values ​​expressed in range form should be interpreted flexibly to include not only the numerical value explicitly stated as the limit of the range, but also all individual numerical values ​​or subranges contained within that range, as if each numerical value and subrange were explicitly stated. For example, the range "approximately 0.1% to approximately 5%" or "approximately 0.1% to approximately 5%" should be interpreted to include not only approximately 0.1% to approximately 5%, but also individual values ​​within the specified range (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%). The notation "approximately X to Y" is equivalent to "approximately X to approximately Y" unless otherwise specified. Similarly, the notation "approximately X, Y, or approximately Z" is equivalent to "approximately X, approximately Y, or approximately Z" unless otherwise specified.

[0016] In this document, the terms “a,” “an,” or “the” are used to include one or more unless the context makes it clear otherwise. The term “or” is used to refer to a non-exclusive “or” unless otherwise noted. The phrase “at least one of A and B” is synonymous with “A, B, or A and B.” Furthermore, any usage or terminology adopted herein without further definition is to be understood as being for illustrative purposes only, and not as limiting. Any use of section headings is intended to aid the reading of the document and should not be interpreted as limiting. Information related to a section heading may appear inside or outside that particular section.

[0017] In the methods described herein, the acts may be performed in any order without departing from the principles of this disclosure, unless the order of time or operations is explicitly stated. Furthermore, the designated acts may be performed simultaneously unless the express claims language details that they are performed separately. For example, the act of doing claimed X and the act of doing claimed Y may be performed simultaneously within a single operation, and the resulting method will fall within the literal scope of the claimed method.

[0018] In this specification, the term “about” means that the value or range is somewhat diverse and may be, for example, within 10%, 5%, or 1% of the specified limit of the specified value or range, and includes the specified exact value or range.

[0019] In this specification, the term “substantially” means a large majority or majority, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.

[0020] In relation to a molecule or organic group as defined herein, the term “substituted” means that one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. In this specification, the terms “functional group” or “substituent” mean a group that can be substituted for or is substituted for a molecule or organic group. Examples of substituents or functional groups include, but are not limited to, halogens (e.g., F, CI, Br, and I); oxygen atoms of groups such as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, and carboxyl groups, including carboxylic acids, carboxylates, and carboxylate esters; sulfur atoms of groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; nitrogen atoms of groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms of various other groups. The substituents that can be bonded to the substituted carbon (or other) atom are not limited, but include, for example, F, CI, Br, I, OR, OCF3, CN, NO, NO2, ONO2, azide, CF3, OCF3, R, O(oxo), S(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OCF3, C(O)R, C(O)N(R)2, OCF3, C(S)N(R)2, (CH2) 0~2 N(R)C(O)R, (CH2) 0~2 Examples include N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, and C(=NOR)R, where R can be a hydrogen or carbon-based part, for example, R is hydrogen, (C1~C 40) may be hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl, or two R groups bonded to a nitrogen atom or an adjacent nitrogen atom may, together with one or more nitrogen atoms, form a heterocyclyl.

[0021] In this specification, the term “alkyl” refers to linear and branched alkyl and cycloalkyl groups having 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbon atoms, or, in some embodiments, 1 to 8 carbon atoms. Examples of linear alkyl groups include those having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. In this specification, the term “alkyl” encompasses n-alkyl, isoalkyl, and anteisoalkyl groups, as well as other branched alkyl groups. Typical substituted alkyl groups can be substituted once or multiple times with any of the groups listed herein, such as amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

[0022] In this specification, the term “alkenyl” refers to linear, branched, and cyclic alkyl groups as defined herein, except that at least one double bond is present between two carbon atoms. Thus, alkenyl groups have 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms, or in some embodiments, 2 to 8 carbon atoms. Examples include, but are not limited to, vinyl, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3), -C(CH2CH3)=CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl.

[0023] In this specification, the term "alkynyl" refers to linear and branched alkyl groups, except that at least one triple bond is present between two carbon atoms. Thus, alkynyl groups have 2 to 40 carbon atoms, 2 to about 20 carbon atoms, or 2 to 12 carbon atoms, or in some embodiments, 2 to 8 carbon atoms. Examples include, but are not limited to, -C≡CH, -C≡C(CH3), -C≡C(CH2CH3), -CH2C≡CH, -CH2C≡C(CH3), and -CH2C≡C(CH2CH3).

[0024] In this specification, the term "aryl" refers to a cyclic aromatic hydrocarbon group that does not contain heteroatoms in the ring. Therefore, examples of aryl groups include, but are not limited to, phenyl, azlenyl, heptarenyl, biphenyl, inludacenyl, fluorenyl, phenantrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, the aryl group contains about 6 to about 14 carbon atoms in the ring portion of the group. The aryl group can be unsubstituted or substituted, as defined herein. Typical substituted aryl groups, which can be monosubstituted or more than once, include, but are not limited to, a phenyl group substituted at any one of the 2, 3, 4, 5, or 6 positions of the phenyl ring, or a naphthyl group substituted at any one of the 2 to 8 positions of the naphthyl group.

[0025] Disclosed herein is a method for rapidly producing large-area nanoporous hybrid films comprising a porous material disposed on a substrate. In one example, the nanoporous hybrid film may have a hierarchical structure disposed on a substrate which may be rigid or flexible. Commercially available rigid or flexible substrates may be used if desired. The hierarchical structure consists of at least two different types of structural features. For example, the porous hierarchical structure may have different pore diameters or pore shapes.

[0026] Further disclosed herein are methods for forming composites comprising a graphite multilayer structure. The graphite multilayer structure is porous and can be placed on a substrate that may include a hybrid film.

[0027] Commercially available rigid or flexible substrates can be used, if desired, and can be fabricated from conductive materials. In some examples, the step of placing the precursor composition on the substrate includes the step of applying the precursor composition by spraying or brushing it onto the substrate. In another example, the substrate can be rolled from end to end. The application of the precursor composition to the substrate can be carried out so that the substrate is fully or partially coated with the precursor composition. For example, about 5% to about 100% of the surface area of ​​the substrate can be coated with the precursor composition, or about 75% to about 100%, about 85% to about 100%, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95%, or less than about 100%, about 5, 10% , 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 100%, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or more than about 100%, can be coated with the precursor composition.

[0028] The substrate can be a rigid substrate or a flexible substrate. The substrate can include many different materials such as aluminum, nickel, copper, and their alloys. The substrate can also include polymers described herein. The substrate can also include metallized polymer films. Examples of metallized polymer films include polymers such as polypropylene, polyethylene terephthalate, nylon, or polyethylene, in which a certain amount of aluminum, nickel, or chromium is arranged. The substrate can take the form of a sheet, rod, or foil and may have a surface area of ​​more than 10 square meters, more than 20 square meters, or more than 50 square meters.

[0029] In some cases, the substrate (after irradiation with a precursor composition) is made windable (e.g., 10) so that it can be used in roll-to-roll processing, for example. 6 It is a flexible substrate having an elastic modulus of less than GPa. Therefore, it is possible to wind the substrate to form rolls with diameters ranging from approximately 0.10 m to approximately 10 m, approximately 0.20 m to approximately 9 m, approximately 1 m to approximately 5 m, or less than approximately 0.10 m, approximately 0.10 m, or more than approximately 0.10 m, approximately 0.20, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or approximately 10 m.

[0030] In one example, the substrate can be a flexible substrate and may contain the first polymer. As described herein, the pologen also comprises a polymer (hereinafter referred to as the second polymer). The first polymer used in the substrate is preferably different from the second polymer used in the precursor composition. In one embodiment, the first polymer used in the substrate has a glass transition temperature, a high melting temperature, and a high decomposition temperature that is at least one higher than the glass transition temperature, melting temperature, and decomposition temperature of the second polymer. In one embodiment, it may be desirable that the first polymer used in the substrate has a decomposition temperature higher than the decomposition temperature of the second polymer. Both the first and second polymers can be selected from the list of polymers described herein.

[0031] The first polymer of the substrate may be in the range of about 50% to about 100% by weight of the substrate, in the range of about 90% to about 100% by weight of the substrate, or less than about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight of the substrate, or about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight, or more than about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight of the substrate.

[0032] The precursor composition may contain a pologen component. The pologen component may be present in amounts of about 5% to about 50% by weight, about 20% to about 40% by weight, or less than about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight of the precursor composition, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight, or more than about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight.

[0033] Pologens can be a large quantity of particles of a specified shape and size, used to create pores in molded structures that can be used for a variety of different applications. In various examples, pologens can be block copolymers or homopolymers. During film formation, pologens are the phase removed to create pores in the final structure. In some examples, pologens are removed by thermal decomposition. In other examples, pologens can dissolve and disappear after the structure has cured. The pores in the final structure can be formed to any appropriate range. For example, pores range from approximately 0.5 nm to approximately 1000 nm, approximately 2 nm to approximately 50 nm, or approximately 0.5, 20, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 620, 640, 660, 680, 700, 720, 740, 760, 780, 800, 820, 840, 860, 880, 900, 920, 940, 960, 980, or less than approximately 1000 nm, approximately 0.5, 20, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 620, 640, 660, 680, 700, 720, 740, 760, 780, 800, 820, 840, 860, 880, 900, 920, 940, 960, 980, or approximately 1000 nm, or approximately 0.5, 20, 60, 80, 100, 120, 140, 160, 180, 200, 220, 24 0, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 620, 640, 660, 680, 700, 720, 740, 760, 780, 800, 820, 840, 860, 880, 900, 920, 940, 960, 980, or possibly over approximately 1000 nm.

[0034] The pologen component includes a second polymer, which is different from the first polymer of the substrate, if one is present. The second polymer is present in amounts ranging from approximately 1% to approximately 100% by weight of the pologen component, or approximately 90% to approximately 100% by weight, or approximately 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or less than 100% by weight, approximately 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight, or approximately 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or more than 100% by weight.

[0035] The first polymer of the substrate and the second polymer of the pologen component can be selected from many suitable polymers. Examples of the first and second polymers are thermoplastic polymers, thermosetting polymers, blends of thermoplastic polymers, blends of thermosetting polymers, and blends of thermoplastic and thermosetting polymers. The polymer can be a homopolymer, copolymer, block copolymer, alternating copolymer, alternating block copolymer, random copolymer, random block copolymer, graft copolymer, star-shaped block copolymer, ionomer, dendrimer, liquid crystal polymer, or a combination comprising at least one of the aforementioned polymers. The first or second polymer may be semicrystalline or amorphous.

[0036] Examples of thermoplastic polymers include polyacetal, polyacrylic, polycarbonate, polystyrene, polyester, polyamide, polyamide-imide, polyarylate, polyacrylate, polymethyl methacrylate, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl chloride, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketone, polybenzoxazole, polyoxadiazole, polybenzothiadinophenothiazine, polybenzothiazole, polypyradinoquinoxaline, polypyromellitoimide, polyquinoxaline, polybenzimidazole, polyoxyindole, and polyoxoisoindole. Phosphorus, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polypyrrolidine, polycarborane, polyoxabicyclononane, polydibenzofuran, polyphthalide, polyacetal, polyanhydride, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl phosphate, polyvinyl nitrile, polyvinyl ester, polysulfonate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, polysiloxane, polyolefin, polyacrylamide, etc., or a mixture comprising at least one of the aforementioned organic polymers.

[0037] Examples of thermosetting polymers suitable for blending with reduced crystallinity cellulose include epoxy polymers, unsaturated polyester polymers, polyimide polymers, bismaleimide polymers, bismaleimide triazine polymers, cyanate ester polymers, vinyl polymers, benzoxazine polymers, benzocyclobutene polymers, acrylics, alkyds, phenol-formaldehyde polymers, novolacs, resols, melamine-formaldehyde polymers, urea-formaldehyde polymers, hydroxymethylfurans, isocyanates, unsaturated polyesterimides, or mixtures comprising at least one of the aforementioned thermosetting polymers.

[0038] An example of a first polymer that can be used in a substrate is a polyester substrate, such as a polyethylene terephthalate substrate. An example of a suitable second polymer is a block copolymer.

[0039] A second polymer can act as a binder for the precursor composition after the precursor composition is placed on the first polymer (which, if present, forms the substrate). As detailed herein, the precursor composition is dried after being placed on the substrate, and the second polymer functions to bind the precursor composition to form a precursor layer on the substrate.

[0040] In one embodiment, the second polymer (used in the precursor composition) can be a block copolymer. A suitable block copolymer, upon phase separation, may have a layered, cylindrical, bicontinuous, or spherical form. The block copolymer can be a diblock or a triblock. A diblock may have a first and a second block, and a triblock may have first, second, and third blocks. In some embodiments, the first and third blocks of a triblock may be chemically identical to each other. Each block can be selected from the list of polymers provided above, insofar as the first and second blocks of a diblock copolymer are different from each other. In one example, in the case of a triblock copolymer, the first and second blocks may be different from each other, and in some cases, the first, second, and third blocks may be different from each other.

[0041] Examples of block copolymers (second polymers) that may be used in the precursor composition include poly(styrene-β-vinylpyridine), poly(styrene-β-butadiene), poly(styrene-β-isoprene), poly(styrene-β-methyl methacrylate), poly(styrene-β-alkenyl aromatic compound), poly(isoprene-β-ethylene oxide), poly(styrene-β-(ethylene-propylene)), poly(ethylene oxide-β-caprolactone), poly(butadiene-β-ethylene oxide), and poly(styrene-β-butyl( Examples include methacrylate, poly(methyl methacrylate-bt-butyl methacrylate), poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(styrene-b-trimethylsilylmethyl methacrylate), poly(methyl methacrylate-b-dimethylsiloxane), poly(methyl methacrylate-b-trimethylsilylmethyl methacrylate), or combinations thereof.

[0042] In another embodiment, the block copolymer can be a block copolymer in which each block has a main chain polymer grafted onto the main chain of a different graft polymer. An exemplary main chain polymer is polynorbornene, and the first and second grafts are selected from the list detailed above. In one embodiment, the first graft is polystyrene and the second graft is polyethylene oxide. Thus, the exemplary block copolymer is (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide)). Such polymers can be produced by ring-opening metathesis polymerization.

[0043] In some cases, the block copolymer is preferably a brush copolymer or bottlebrush block copolymer. A polymer brush comprises polymers tethered to the surface of a substrate. Brush or bottlebrush block copolymers also refer to “molecular brushes” and are a new class of macromolecules in which at least two different types of polymer side chains are densely grafted onto a linear polymer backbone. Due to the strong steric repulsion of the polymer side chains, the backbone of the bottlebrush block copolymer is highly elongated, resulting in a worm-like molecular conformation. Bottlebrushes can be superior to their linear analogues for nanotechnology because entanglement of polymer chains can be significantly reduced between the worm-like polymers, and rapid self-assembly can create ordered nanostructures.

[0044] A brush or bottle brush can be either a solvated state in which the grafted polymer layer contains polymer and solvent, or a molten state in which the grafted chains completely fill the empty spaces. These polymer layers can be grafted onto a flat substrate such as a silicon wafer, or a highly curved substrate such as nanoparticles. Brushes are often characterized by the high density of the grafted chains. Furthermore, the confined spaces lead to strong chain elongation and unusual properties of the system.

[0045] In some examples, at least one block of a block copolymer may have a functional group that can interact with the precursor of the supporting phase. The functional group may be suspended from the main chain (i.e., part of a repeating unit), a terminal group, or both suspended from the main chain and a terminal group. Examples of such functional groups are metal alkoxides such as trialkoxysilanes. In one example, a reactive terminal functional group may be used to anchor the copolymer to a substrate to form a bottlebrush copolymer.

[0046] If a solvent is present, it is an effective solvent for solubilizing the second polymer present in the precursor composition. Depending on the chemical properties of the polymer and other components used, the solvent can be an aprotic polar solvent, a nonpolar protic solvent, a nonpolar solvent, or a combination thereof.

[0047] Examples of aprotic polar solvents include water, propylene carbonate, ethylene carbonate, butyrolactone, acetonitrile, benzonitrile, nitromethane, nitrobenzene, sulfolane, dimethylformamide, N-methylpyrrolidone, or combinations thereof. Polar protic solvents include methanol, acetonitrile, nitromethane, ethanol, propanol, isopropanol, butanol, or combinations thereof. Examples of nonpolar solvents include benzene, toluene, methylene chloride, carbon tetrachloride, hexane, diethyl ether, tetrahydrofuran, or combinations thereof. Cosolvents comprising at least one polar solvent and at least one nonpolar solvent may also be used to modify the degree of swelling of the solvent and thereby adjust the solubility of the solvent in the polymer. The solvent can be used in an amount of 50 to 90% by weight relative to the total weight of the precursor composition.

[0048] The support phase precursor (hereinafter referred to as the support phase precursor) generally comprises reactive species that, upon reaction, generate a skeletal structure to support the hierarchical structure arranged on the substrate. The support phase precursor may include metal alkoxides, polyoctahedral silsesquioxanes (hereinafter referred to as silsesquioxanes), or any other reactive species that, upon heating, can provide structure to the components of the precursor composition.

[0049] Examples of metal alkoxides include silicon alkoxides (e.g., silicon trimethoxysilane, tetraethyl orthosilicate, etc.), titanium alkoxides (e.g., titanium isopropoxide, etc.), zirconium alkoxides (e.g., zirconium isopropoxide), aluminum alkoxides (e.g., aluminum sec-butoxide), etc., or combinations thereof. When included in the precursor composition, the metal alkoxide can react with functional groups and itself to form a network of the framework or a precursor of the framework of the network within the precursor composition. When the precursor composition is heated, the polymer decomposes, and the decomposition of the polymer leaves a porous network of metal oxide particles.

[0050] Silsesquioxane has the structure (RSiO 1.5 ) n , where R represents one or more types of substituents, typically organic substituents. An alternative name is "T-resin", which indicates that there are three oxygen atoms substituting silicon (trisubstituted). These molecules have a hard heat-resistant silicon-oxygen framework structure, and their structure and characteristics are intermediate between those of silica glass (SiO2) n and those of silicone polymer (R2SiO) n . The silsesquioxane moiety in the precursor composition can be selected from among various structural types: the polyhedral cages, ladders, random, or mixtures thereof shown in the following Formulas (1) to (3).

[0051] Formula (1) shows a random type of silsesquioxane moiety.

[0052]

Chemical formula

[0053]

Chemical formula

[0054] [ka] As mentioned above, silsesquioxanes can have cage-like structures. Cage-type silsesquioxanes often take the form of cubes, hexagonal prisms, octagonal prisms, decagonal prisms, dodecagonal prisms, or even open cage-like structures. Various cage-type silsesquioxanes are sold by Hybrid Plastics under the trade name POSS. They are described as polyhedral oligomeric silsesquioxanes, with the general formula (RSiO 1.5 ) n The formula has the following properties, where R is selected from an organic or inorganic part and n is 6, 8, 10, 12 or more. Like all silsesquioxanes, these molecules have a rigid, heat-resistant silicon-oxygen frame structure with an oxygen-to-silicon ratio of 1.5, and most contain covalently bonded organic (and sometimes inorganic) groups that provide an outer layer with functional groups such as hydrocarbons (e.g., vinyl, isooctyl, cyclohexyl, cyclopentyl, isobutyl, or other hydrocarbons) and esters, vinyl, epoxy, acrylate, hydroxyl, or other functional groups. The Si8 (where n=8)POSS structure is illustrated below by formula (4).

[0055] [ka] By altering the R group on the silicon atom, various functional groups can be positioned away from the corners of the POSS frame structure. Each R group can be a reactive group that participates in polymerization and can cure the support phase precursor of the precursor composition, or a non-reactive group that can promote chemical compatibility with other species present in the composition. In addition to their role in enabling polymerization or compatibility, various types of R groups can be selected or combined to impart other desired attributes such as flexibility or rigidity, thermal stability, chemical resistance, curing speed, and refractive index. In exemplary embodiments, the R group on the silicon atom is a reactive functional group that can participate in UV-initiated polymerization and includes acrylates, methacrylates, vinyls, vinyl ethers, thiols or epoxides, hydroxyls, or combinations thereof.

[0056] Another way to describe the above structure of the POSS cage-type silsesquioxane portion is by general formula R n-m T n Y m The formula includes, where R is a reactive functional species that can enable UV-induced polymerization of the coating, n is 6, 8, 10, 12 or more, m is 1 to n, and T is SiO 1.5 The Y group is C1-C 24The polymer contains non-reactive groups such as linear, branched, or cyclic alkyl groups, aliphatic or alicyclic ethers or polyethers, aliphatic or alicyclic esters or polyesters, aliphatic or alicyclic siloxanes or polysiloxanes, aliphatic or alicyclic carbonates or polycarbonates, aliphatic or alicyclic fluorocarbons or other halocarbons, aliphatic or alicyclic urethane ethers, urethane esters, or urethane carbonates. In another exemplary embodiment, the R group is a low molecular weight homopolymer or copolymer having reactive species that are positioned along the main chain or as pendant groups positioned away from the main chain.

[0057] In another embodiment, the R group contains two or more reactive functional groups, three or more reactive functional groups, or four or more reactive functional groups. Diacrylated and triacrylated groups are examples of reactive functional groups that enable UV-induced polymerization of the precursor layer.

[0058] Exemplary POSS silsesquioxane moieties include POSS silsesquioxanes functionalized with acrylate and methacrylate functional groups (e.g., MA0701-acryloisobutyl POSS, MA0702-methacrylateisobutyl POSS, MA0703-methacrylatecyclohexyl POSS, MA0706-methacrylateisobutyl POSS, MA0716-methacrylateethyl POSS, MA0717-methacrylateethyl POSS, MA0718-methacrylateisooctyl POSS, MA0719-methacrylateisooctyl POSS, MA0735-methacrylate POSS cage mixture, MA0736-acrylo POSS cage mixture, etc., or combinations thereof), and POSS silsesquioxanes functionalized with epoxy functional groups (e.g., EP0402-epoxycyclohexylisobutyl POSS) These include S, EP0408-epoxycyclohexyl POSS cage mixture, EP0409-glycidyl POSS cage mixture, EP0417-glycidylethyl POSS, EP0418-glycidyl isobutyl POSS, EP0419-glycidyl isooctyl POSS, EP0423-triglycidyl isobutyl POSS, EP0430-octa-epoxycyclohexyldimethylsilyl POSS, EP0435-octa-glycidyldimethylsilyl POSS, etc., or combinations thereof), POSS silsesquioxanes functionalized with thiol functional groups (TH1550-mercaptopropyl isobutyl POSS, TH1555-mercaptopropyl isooctyl POSS, etc., or combinations thereof), isobutyl acrylate, difunctional heterocages, isooctyl acrylate, difunctional heterocages, or combinations thereof. All of the aforementioned POSS components are commercially available from Hybrid Plastics. POSS silsesquioxanes, which are liquids or oils rather than solids (powder or wax), include MA0718, MA0719, MA0735, MA0736, EP0408, EP0409, EP0423, EP0435, and TH1555.

[0059] The supporting phase precursor is present in amounts of approximately 2% to 15% by weight, or approximately 4.7% to 8.6% by weight, approximately 5.9% to 6.3% by weight, or approximately 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or less than approximately 15% by weight, approximately 2, 2.5, 3, 3.5, 4, 4.5, It can be used in amounts of 0.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or approximately 15% by weight, or in amounts exceeding approximately 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or approximately 15% by weight.

[0060] The precursor composition may contain a light-absorbing component that can selectively absorb electromagnetic radiation of a specific wavelength to decompose the polymer present in the precursor composition and activate the support phase precursor to form a support structure. The light-absorbing composition may generally contain metal nanoparticles or metal oxide nanoparticles that can absorb electromagnetic radiation of one or more frequencies, warming up enough to decompose the second polymer while simultaneously reacting the support phase precursor. In one embodiment, the support phase precursor may also react with reactive functional groups present on or within the light-absorbing component.

[0061] The light-absorbing component may include metal particles, carbonaceous particles, electrically conductive metal oxide nanoparticles, metal nanoparticles, or combinations thereof. The light-absorbing component may also include precursors of metal particles, carbonaceous particles, electrically conductive metal oxide nanoparticles, metal nanoparticles, or combinations thereof, which are converted into nanoparticles upon reaction. The reaction can be induced by irradiation heat or other suitable reactions.

[0062] The particles may be nano-sized or micrometer-sized. There are no particular restrictions on the shape of the particles; for example, they may be spherical, irregular, fractal, plate-like, or whisker-like. Nanometer-sized particles generally have an average particle size of 1 to 100 nanometers, while micrometer-sized particles have an average size of over 10¹ nanometers to about 5,000 nanometers. In one example, it is desirable that the particles are nanoparticles. The average particle size referred to herein is determined by the particle's radius of gyration. Suitable examples of light-absorbing nano-sized particles include metal particles, carbon nanotubes, graphene nanoparticles, carbon black, fullerenes, buckyballs, or combinations comprising at least one of the aforementioned nano-sized particles.

[0063] Metal nanoparticles or metal oxide nanoparticles can be used as light-absorbing components that generate heat when they absorb light. As further described herein, metal nanoparticles or metal oxide nanoparticles can also act as catalysts when there is no light absorption. Some metal nanoparticles or metal oxide nanoparticles can act solely as thermogenerating substances or catalysts, while others can act as both catalysts and thermogenerating substances. These may be conductive metals or alloys that do not melt under the conditions used when they are incorporated into organic polymers and then used to manufacture the finished product. Metals such as aluminum, copper, magnesium, chromium, tin, nickel, silver, iron, titanium, gold, platinum, palladium and mixtures thereof can be incorporated into precursor compositions as conductive fillers. Physical mixtures and true alloys such as stainless steel and bronze can also function as light-absorbing particles.

[0064] Furthermore, some intermetallic chemical compounds of these metals, such as borides and carbides (e.g., titanium diboride), can also function as light-absorbing particles. Solid non-metallic conductive filler particles, such as tin oxide and indium tin oxide, can also be optionally added to absorb light. Solid metallic and non-metallic conductive fillers can exist in the form of powders, drawn wires, twists, fibers, tubes, nanotubes, flakes, laminates, platelets, ellipsoids, disks, and other commercially available geometric shapes.

[0065] The light-absorbing component absorbs electromagnetic radiation of various wavelengths, generating heat and decomposing the polymer. The electromagnetic radiation may be visible light, ultraviolet light, microwave radiation, infrared radiation, or a combination thereof. In a preferred embodiment, the absorbed radiation may be present in the visible light region of the electromagnetic spectrum.

[0066] The light-absorbing component can be used in amounts of approximately 2% to approximately 10% by weight, approximately 3.5% to approximately 5.5% by weight, approximately 4.1% to approximately 4.5% by weight, or approximately 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or less than approximately 10% by weight, approximately 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or approximately 10% by weight, or approximately 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or more than approximately 10% by weight relative to the total weight of the precursor composition.

[0067] In a method for producing an article containing a precursor composition, the precursor composition can be applied to a substrate to form a precursor layer. The precursor composition can be applied to the substrate by methods such as spray coloring, electrostatic spray coloring, spin casting, doctor blade method, immersion method, or a combination thereof.

[0068] Next, the precursor layer is dried using high temperature. High temperature can be achieved using radiation, conduction, or convection. High temperature is used to remove the solvent and, if desired, promote the phase separation of the copolymer. Appropriate high temperatures depend on the components of the precursor composition, and are approximately 50°C to 200°C, approximately 60°C to 150°C, approximately 70°C to 140°C, or approximately 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or less than 200°C, approximately 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 , 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 200°C, or approximately 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or above 200°C.

[0069] Following phase separation, the substrate on which the precursor layer is located is exposed to electromagnetic radiation of a desired wavelength to promote heating of the precursor composition. Light-absorbing components in the precursor composition absorb light, locally warming to temperatures above 300°C, 400°C, or 450°C. This localized heat generation promotes the decomposition of the second polymer (the polymer present in the precursor layer) but does not affect the first polymer (the polymer present in the substrate). The polymer present in the substrate is transparent to the incident radiation. The heat generation also promotes reactions in the supporting phase, facilitating the formation of a porous skeletal structure that supports the hierarchical structure. The hierarchical structure can be a carbon composite. The carbon composite may include one or more layers to form a carbon composite multilayer structure. The carbon composite may also include an amorphous carbon matrix. In some examples, the carbon composite may include only or both a carbon composite multilayer structure and / or an amorphous carbon matrix.

[0070] In some examples, one or more layers of a carbon composite multilayer structure may include individual elongated graphite material (graphene) layers to form a graphite multilayer structure (e.g., a sheet) which may have an elongated profile. For example, the individual layers of the carbon composite multilayer structure may be nanowires, nanotubes, or nanoribbons. The width of the individual layers of the graphite multilayer structure may range from about 5 nanometers to about 70 nanometers, about 20 nanometers to about 50 nanometers, or less than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70 nanometers, or greater than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70 nanometers.

[0071] Carbon composite structures can be formed by a method that includes the step of placing a precursor composition on a substrate. The precursor composition comprises a pologen component, a carbon component, and a catalyst component. The precursor composition can be in fluid or solid form. After the precursor composition is placed on the substrate, the precursor composition is irradiated with electromagnetic radiation. Upon irradiation, the catalyst catalyzes a reaction that grows graphite nanowires, nanoribbons, or nanotubes from the carbon component. Alternatively, the precursor composition may contain a light-absorbing species component that acts as a nanoheater, locally heating a carbon source to form an amorphous carbon matrix.

[0072] To form a carbon composite structure, the precursor composition contains a carbon component. The carbon component provides a carbon source for graphite nanowires, nanotubes, or nanowires. The carbon source may also be a source for growing an amorphous carbon matrix. The carbon component may be about 5% to about 50% by weight, about 20% to about 40% by weight, or less than about 20, 25, 30, 35, 40, 45, or 50% by weight of the precursor composition, or about 20, 25, 30, 35, 40, 45, or 50% by weight, or more than about 20, 25, 30, 35, 40, 45, or 50% by weight. The carbon component may contain one or more carbon-containing molecules. Examples of suitable carbon-containing molecules include phenol-formaldehyde resin (Resol), glucose, cellulose, 4-hydroxybenzoic acid, and mixtures thereof. In some examples, the carbon component includes brown sugar, barley sugar, caramel, coccine sugar, corn syrup, starch, molasses, molasses raffinate (sugar waste), glucan, galactan, xylan, and at least one of the sugar waste. In some examples, the carbonaceous material includes powdered activated carbon, granular activated carbon, carbon black, carbon fibers, carbon honeycomb or plate structures, aerogel carbon films, pyrolysis char, or activated carbon or regenerated activated carbon having a mass-average particle size larger than fly ash in the flue gas stream to be treated. Another example of a suitable carbon source is substituted or unsubstituted hydrocarbons having any suitable number of carbon atoms, e.g., substituted or unsubstituted alkanes, alkenes, alkynes, or combinations thereof, e.g., substituted or unsubstituted (C1-C) 40 ) Alkanes, (C1~C 40 ) Alkenes, (C1~C 40 ) Alkynes, (C4~C 40)Any one or a combination of aryl or a mixture thereof. The carbon component can be in solid, gaseous, or aqueous phase. In short, the carbon component may contain about 40% by weight of carbon to about 90% by weight of carbon, about 60% by weight of carbon to about 80% by weight of carbon, or less than about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or 90% by weight of carbon, or about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or 90% by weight of carbon, or more than about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or 90% by weight of carbon.

[0073] In some examples, the precursor composition may also include a nitrogen source that can act as a dopant for the carbon complex. Examples of nitrogen sources include amides (e.g., dicyandiamide), amines (e.g., glucosamine or melamine), and pyrroles (e.g., polypyrrole or urea). If present, the nitrogen source may be present in amounts ranging from about 0.1% to about 30% by weight, about 1% to about 10% by weight, or about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 10, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, or less than approximately 30% by weight, approximately 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 10, 11.5, 12, 12.5, 13, 13.5, 14 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, or approximately 30% by weight, or approximately 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 8, 8.5, 9, 9.5, 10, 10.5, 10, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, or more than approximately 30% by weight.

[0074] To form a carbon composite structure, the precursor composition also includes a catalytic component. The catalytic component facilitates the formation of graphite nanowires, nanotubes, or nanowires from the carbon component. The catalytic component may be present in amounts ranging from about 0.01% to about 50% by weight, about 1% to about 15% by weight, or less than about 0.01, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight of the precursor composition, or more than about 0.01, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight. The catalytic component can act through chemical reactions or act as a nanoheater that releases heat by absorbing electromagnetic radiation. Nanoheaters can form amorphous carbon matrices.

[0075] The catalyst component comprises at least one metal nanoparticle or metal oxide nanoparticle. The amount of the at least one metal nanoparticle or metal oxide nanoparticle may be about 50% to about 100% by weight, about 90% to about 100% by weight, about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or less than 100% by weight of the catalyst component, about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight, or about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or more than 100% by weight. The catalyst components, which are metal nanoparticles or metal oxide nanoparticles, can have sizes ranging from approximately 1 to approximately 100 nanometers, approximately 1 to approximately 50 nanometers, approximately 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or less than 100 nanometers, approximately 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 nanometers, or approximately 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or more than 100 nanometers.

[0076] Metal nanoparticles or metal oxide nanoparticles may contain one or more metals. Suitable examples of metals or metal oxides include silicon, silicon carbide, iron, iron oxide, copper, nickel, palladium, platinum, ruthenium, rubidium, their alloys, or mixtures thereof. Examples of iron oxides include FeO, Fe2O3, Fe3O4, Fe4O6, Fe5O7, Fe 25 O 32 Fe 13 O 19 Examples include at least one of Fe2O3, (Fe(OH)2), and (Fe(OH)3).

[0077] During the process, the precursor composition containing carbon and catalyst components is irradiated with electromagnetic radiation after being applied to a substrate. In some examples where the catalyst component is a metal oxide, the irradiation reduces the metal oxide to a metal. The electromagnetic radiation can be supplied from a light source. A suitable example of a light source is a xenon flash lamp. The precursor composition can be irradiated with a series of pulses of light. For example, the precursor composition can be irradiated with 1 to 20 pulses, 2 to 15 pulses, or 3 to 6 pulses. Each pulse is approximately 0.1 ms to 15 ms, approximately 0.25 ms to 0.5 ms, approximately 0.1, 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or less than 15 ms, approximately 0.1, 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6 The pulses can last for 0.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or 15 milliseconds, or approximately 0.1, 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or longer than 15 milliseconds. The energy of each light pulse is approximately 5500 mJ / cm². 2 ~Approx. 7000mJ / cm 2, about 6042mJ / cm 2 ~Approx. 6781mJ / cm 2 5500, 6000, 6500, or 7000 mJ / cm² 2 Less than 5500, 6000, 6500, or 7000 mJ / cm² 2 , or 5500, 6000, 6500, or 7000 mJ / cm² 2 It can exceed.

[0078] Irradiation of the precursor composition can form individual layers of at least a carbon composite multilayer structure. These individual layers of the carbon composite multilayer structure can be composite structures containing one or more graphite nanowires, graphite nanotubes, and graphite nanoribbons. The nanowires, nanotubes, or nanoribbons are characterized by having a nanoscale width. For example, nanowires, nanotubes, or nanoribbons can have widths ranging from approximately 5 nanometers to approximately 500 nanometers, approximately 20 nanometers to approximately 50 nanometers, approximately 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or less than 70 nanometers, approximately 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70 nanometers, or more than approximately 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70 nanometers. In some examples, the width may be 1 micrometer (1 micron) or more.

[0079] Nanowires, nanotubes, or nanoribbons are grown from a carbon component by a catalytic component upon irradiation. Individual layers of nanowires, nanotubes, or nanoribbons are stacked on top of each other. In the final structure, at least a portion of the individual layers can be at least partially in contact with metal nanoparticles or metal oxide nanoparticles of the catalytic component.

[0080] Carbon composite structures can also include amorphous carbon matrices. Amorphous carbon matrices can be formed from the thermal conversion of several carbon sources (e.g., Resol) when nanoparticles release heat. At suitable temperatures, Si nanoparticles may be favorable for generating amorphous carbon matrices from Resol. Carbon composite structures can also include residual nanoparticles from catalytic components.

[0081] In some examples of carbon composite structures, there may be mixtures of nanowires, nanotubes, and nanoribbons with amorphous carbon. However, in other examples, the carbon composite structure may consist solely of nanoribbons, nanotubes, nanoribbons, or amorphous carbon.

[0082] Carbon composite structures can be adapted to many different uses in different articles. For example, carbon composite structures can form anodes. Anodes can be part of batteries such as lithium-ion batteries. Anodes can also be used in other electronic products such as capacitors or sensors. In these examples, carbon composite carbon multilayer structures can range from about 0.01% to about 50% by weight of the components, about 5% to about 60% by weight, or less than 0.01, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight, or more than 0.01, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by weight. The carbon composite structure may include additional components, such as known nanoparticle additives having conductive, insulating, or capacitive properties.

[0083] Figure 1 is a cross-sectional view of a battery 50 including a carbon composite structure. As shown in Figure 1, the battery 50 includes an anode 52, a separator 54, and a cathode 56. The battery 50 may further include a substrate on which the anode 52 is mounted. The anode 52 can have many suitable shapes and designs. For example, the anode 52 can be flat. Alternatively, as shown in Figure 1, the anode 52, and therefore the carbon composite structure, can form a patterned structure. The patterned structure shown in Figure 1 shows the anode 52 of a pattern formed from a plurality of protrusions 60 extending in the z direction. The width W of individual protrusions between at least two protrusions 60 can be customized to be substantially the same. Alternatively, the widths between at least two protrusions can be different from one another. The width of the individual protrusions 60 is in the range of approximately 900 nm to approximately 900 μm, approximately 800 nm to approximately 10 μm, or approximately 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, or less than approximately 900 μm, approximately 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 2 The nautical margins may be 00nm, 100nm, 100μm, 200μm, 300μm, 400μm, 500μm, 600μm, 700μm, 800μm, or approximately 900μm, or approximately 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 200nm, 100nm, 100μm, 200μm, 300μm, 400μm, 500μm, 600μm, 700μm, 800μm, or greater than approximately 900μm, but are not limited to these.

[0084] The length of at least one projection in the y-direction can be in the range of approximately 1.5 to approximately 20 times the width, approximately 5 to approximately 15 times the width, or approximately 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, or less than approximately 20 times, approximately 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5 It is possible to have values ​​that are 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, or about 20 times larger, or about 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, or more than about 20 times larger.

[0085] The distance or pitch between adjacent protrusions 60 is in the range of approximately 2000 nm to approximately 500 μm, approximately 1600 nm to approximately 10 μm, or approximately 2000 nm, 1900 nm, 1800 nm, 1700 nm, 1600 nm, 1500 nm, 1400 nm, 1300 nm, 1200 nm, 1100 nm, 1000 nm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 100 μm, 200 μm, 300 μm, 400 μm, or less than approximately 500 μm, approximately 2000 nm, 1900 nm, 1800 nm, 1700 nm, 1600 nm, 1500 nm, 1400 nm, 1300 nm, These may be 1200nm, 1100nm, 1000nm, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 200nm, 100nm, 100μm, 200μm, 300μm, 400μm, or approximately 500μm, or approximately 2000nm, 1900nm, 1800nm, 1700nm, 1600nm, 1500nm, 1400nm, 1300nm, 1200nm, 1100nm, 1000nm, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 200nm, 100nm, 100μm, 200μm, 300μm, 400μm, or approximately over 500μm.

[0086] As shown in Figure 1, the projection 60 has a profile that is square (when viewed from the z direction). However, other shapes are also possible. For example, the profile of the projection 60 can be circular, oval, or other polygonal shapes such as triangle, rectangle, pentagon, hexagon, heptagon, and octagon.

[0087] The separator 54 is positioned between the anode 52 and the cathode 56. The separator is shaped to roughly match the shape of the anode 52. The separator 54 generally contains a dielectric material. The dielectric material may include at least one of a polymer, microparticles, nanoparticles, and a binder. In some examples, the microparticles are in the range of approximately 30% to approximately 100% by weight of separator 54, in the range of approximately 90% to approximately 100% by weight of the separator layer, or approximately 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or less than 100% by weight of separator 54, approximately 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight of separator 54, or approximately 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or more than 100% by weight of separator 54. Microparticles can be selected from polymethylurea, melamine formaldehyde resin, lithium polyacrylate, polyamide, poly(lithium 2-acrylamido-2-methylpropanesulfonate), silicon dioxide (SiO2), aluminum oxide (Al2O3), boehmite (AlO(OH)), titanium dioxide (TiO2), zinc oxide (ZnO), potassium fluoride (KF), lithium fluoride (LiF), zeolite, and calcium carbonate (CaCO3). Furthermore, in some examples, the nanoparticles are in the range of approximately 30% to approximately 100% by weight of separator 54, in the range of approximately 90% to approximately 100% by weight of the separator layer, or less than approximately 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight of separator 54, or approximately 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight of separator 54, or more than approximately 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight of separator 54.Nanoparticles can be selected from silicon dioxide (SiO2), aluminum oxide (Al2O3), boehmite (AlO(OH)), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), titanium dioxide (TiO2), zirconium oxide (ZrO2), tin dioxide (SnO2), zinc oxide (ZnO), potassium fluoride (KF), lithium fluoride (LiF), mesoporous aluminosilicate (Al2SiO5), mesoporous niobium-tantalum composite oxides, and mesoporous magnesium-tantalum composite oxides. The binder may be in the range of approximately 10% to approximately 90% by weight of separator 54, approximately 30% to approximately 50% by weight of the separator layer, or approximately 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or less than approximately 90% by weight of separator 54, approximately 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or approximately 90% by weight, or approximately 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or more than approximately 90% by weight. The polymer can be selected from any suitable polymer having dielectric properties. Examples include homopolymers and copolymers of polyethylene oxide, polyacrylonitrile, and polysiloxane.

[0088] The binder may include polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylic acid, lithium polyacrylate, poly(methyl methacrylate), poly(butyl acrylate), ethyl hydroxyethyl cellulose, styrene-butadiene resin, carboxymethylcellulose, polyimide, polyacrylonitrile, polyurethane, ethyl vinyl acetate copolymer, and polyester.

[0089] The cathode 56 is located in the separator 54. The cathode 56 generally matches the profile of the separator 54. The cathode may contain lithium oxide. The lithium oxide may be in the range of about 50% to about 100% by weight of the cathode 56, in the range of about 90% to about 100% by weight, or less than about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight of the cathode 56, or about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight, or more than about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by weight. Examples of lithium oxides include, but are not limited to, lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), lithium manganese oxide (LiMn2O4), and olivine-type lithium iron phosphate (LiFePO4).

[0090] The battery 50 can be formed by a number of suitable methods. An example of a suitable method is shown in Figure 2. Figure 2 is a schematic diagram showing a thermal nanoimprint method for forming the battery 50. As shown in Figure 2, method 70 includes operation 72. In operation 72, a precursor composition 73 comprising at least the pologen component, carbon component, and catalyst component described herein is deposited on a substrate 74. A mold 75 is placed over the precursor composition 73 and lowered. The mold 75 is formed of a number of cavities 76 that form projections 60 at the anode 52. The cavities 76 form projections 60 therein when they come into contact with the precursor composition 73.

[0091] In operation 80, the template 75 is held in the correct position on the precursor composition 73. The template 75 and optionally the substrate 74 are then heated to form the anode 52. The application of heat can form the carbon composite microstructure described herein. In operation 82, the template 75 is removed after sufficient heating. This leaves the anode 52, including the projection 60, formed on the substrate 74. In operation 84, the anode 53 is optionally processed to remove excess material. In another operation, the separator 54 is deposited on the anode 54 and the cathode 56 is deposited on the separator 54. The separator 54 can be deposited or coated on the anode 53 from the gas phase using any suitable method, such as chemical vapor deposition.

[0092] In an alternative example, the separator 54 can be attached to the precursor composition 73 in operation 72. This allows the anode 52 and separator 54 to be formed simultaneously.

[0093] Figure 3 shows an alternative method for forming the battery 50. Figure 3 is a schematic diagram showing an electromagnetic radiation nanoimprint method for forming the battery 50. As shown in Figure 3, method 90 includes operation 92. In operation 92, a photocrosslinkable precursor composition 73A, comprising at least the pologen component, carbon component, and catalyst component described herein, is deposited onto a substrate 74. A mold 75A is placed over the precursor composition 73A and lowered. The mold 75A is formed of a plurality of cavities 76 that form projections 60 at the anode 52. The mold 75A is substantially transparent. The cavities 76 form projections 60 therein upon contact with the precursor composition 73A.

[0094] In operation 94, the template 75 is held in the correct position on the precursor composition 73. The template 75 and optionally the substrate 74 are then exposed to electromagnetic radiation (e.g., ultraviolet light) to form the anode 52. The application of electromagnetic radiation can form the carbon composite microstructure described herein. In an alternative example, the template 75A may be heated in combination with exposure to electromagnetic radiation. In operation 96, the template 75 is removed after it has been sufficiently heated. This leaves the anode 52, including the projection 60, formed on the substrate 74. In operation 98, the anode 53 is optionally processed to remove excess material. In another operation, the separator 54 is attached to the anode 54 and the cathode 56 is attached to the separator 54.

[0095] In an alternative example, the separator 54 can be deposited onto the precursor composition 73A in operation 98. This allows the anode 52 and the separator 54 to be formed simultaneously.

[0096] (Examples) Various embodiments of this disclosure can be better understood by referring to the following examples presented as examples. This disclosure is not limited to the examples given herein.

[0097] (Example 1) Formation of nanoporous materials Hierarchical nanoporous hybrid materials containing functional nanoparticles (NPs) have been fabricated for a variety of applications, including catalysis, separation, sensing, and energy storage and conversion. The pore size within these materials can be manipulated by the self-assembly of sacrificial soft templates, including low molecular weight surfactants and block copolymers (BCPs).

[0098] Rapid preparation of hierarchical large-area nanoporous films on flexible substrates not only enables the fabrication of lightweight and portable devices, but also reduces manufacturing costs by employing large-scale manufacturing methods such as roll-to-roll processing. In this example, a simple method is provided for the rapid, large-area synthesis of hierarchical nanoporous hybrid films of silica, carbon, and gold on commercially available polyethylene terephthalate (PET) substrates by photothermal processing. The light-absorbing thin film contains gold NP as a nanoheater to convert light energy into heat by strong localized surface plasmon resonance (LSPR), sacrificial (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide))(PS-b-PEO) brush BCP to create mesopores, and crosslinked polyhedral oligomer silsesquioxane (POSS) as a silica source to form the framework of the porous structure. PS-b-PEO brush BCP (Mn=1583 kg / mol, PDI=1.06, f PEOThe gold NPs (48.4% by weight) were synthesized by sequential ring-opening metathesis polymerization (ROMP) according to the inventors' reported synthesis procedure. The molecular weights of the PS and PEO side chains were 3.5 and 2.0 kg / mol, respectively. Gold NPs with a diameter of approximately 2 nm were coated with 4-mercaptophenol, which exhibits strong hydrogen bonding interactions with the PEO domain. Rod coating and thermal annealing were performed to allow maturation of the NPs to larger sizes (>10 nm) and to initiate crosslinking of the POSS, thereby preparing thin films over large areas. A strong LSPR peak at 543 nm was observed after annealing, providing high light absorption efficiency of the film for subsequent photothermal processing. For comparison, in unannealed samples containing smaller NPs (2 nm), it was not possible to identify a clear LSPR. Crosslinking of the POSS cage was achieved by imide formation between the carboxylic acid and secondary amine groups in the POSS upon heating, and was verified by Fourier transform infrared spectroscopy (FTIR). The spherical morphology was formed by the self-assembly of PS, which appeared as spheres during solvent evaporation, and PEO domains incorporated into the gold NP / POSS matrix. This was confirmed by small-angle X-ray scattering (SAXS), field emission scanning electron microscopy (FESEM), and cross-sectional transmission electron microscopy (TEM) of thin sections from annealed samples. Since PS and PEO in unstained samples have similar electron densities, the contrast observed in TEM images is solely due to the gold NP and POSS present in the PEO domains. The domain spacing of the spherical structure was determined by SAXS to be approximately 84 nm. To create a well-defined porous structure, the BCP template was removed, and the crosslinked POSS matrix was oxidized to silica upon heating.

[0099] In photothermal processing, the emission is peak intensity between 400 and 500 nm over a broad wavelength range of 200–1000 nm. The light intensity can be precisely controlled by changing the voltage and / or pulse duration. The optimal method involves repeating the same pulse three times for a duration of 0.3 milliseconds. This is compared to a control sample without photothermal processing, using pulses of 1785, 1837, and 1891 mJ / cm² with different pulse energies. 2 FTIR spectra of four representative samples, including samples 1-3, obtained using [the specified method]. 1800-1200 cm⁻¹ -1 Multiple absorption peaks in this range are attributed to organic components and gradually disappear with increasing pulse energy. Removal of organic matter corresponds to CH expansion and contraction in the range of 3100-2800 cm. -1 This was also confirmed by the absence of peaks in the range. As the pulse energy increased, a blue shift of the O-Si-O stretching peak was observed, indicating oxidation to the POSS cage opening and mesh-like silica structure. In contrast, for the gold-free sample exposed to a xenon flash lamp using the same pulse energy, neither a clear change in FTIR nor evidence of nanoporous structure in the FESEM image was observed, suggesting that the gold NPs converted the light energy into heat, enabling the creation of the nanoporous structure. The oxidation of POSS was further confirmed by a slight change in the binding energy of the silicon (Si) 2p orbital between the control sample and sample 3 (102.2 vs 103.0 eV) according to X-ray photoelectron spectroscopy (XPS). In general, it was observed that the weight percentages of silica (11.2% vs. 37.3% wt%), carbon (0% vs. 18.0% wt%), and gold NP (23.3% vs. 43.0% wt%) increased significantly with increasing pulse energy, while the organic residue decreased remarkably from 65.5% wt% to 1.70% wt%, indicating the high efficiency of the inventors' synthesis method. The pulse energy was increased from 1837 to 1891 mJ / cm². 2It is noteworthy that an unusual increase in silica weight percentage was observed when the material was changed. This can be well explained by a large number of POSS cages oxidized at higher light intensity in air, which is consistent with the clear blue shift of the O-Si-O stretching peak observed in FTIR and the XPS data. This is also the reason why the gold weight percentage decreased from 46.7% to 43.0% by weight. The efficient oxidation of POSS cages enables the creation of porous hybrid materials with good mechanical properties. Furthermore, hybrid materials containing high concentrations of gold NPs exhibit strong LSPR, making them useful for many potential applications, including sensing. For the samples after photothermal treatment, a blue shift of the LSPR peak was observed, indicating high sensitivity of gold NPs to the surrounding chemical environment (organic vs. air / silica / carbon), making them promising for sensor applications.

[0100] The porous structures of samples 1-3 were characterized by FESEM and TEM. Pore diameters were obtained by image analysis of over 400 pores using ImageJ. Well-controlled, uniform pores extending approximately 44-48 nm were formed on the surface of the hybrid coating obtained during rapid photothermal processing on a millisecond scale. For comparison, random porous structures were observed in prepared samples using PEO homopolymer as a template, suggesting that the nanoporous structures were formed by replicating the spherical morphology of self-assembled BCP nanocomposites. Interestingly, a bubbly porous structure with interconnected macropores over 50 nm was observed beneath the surface of sample 3, as indicated by cross-sectional FESEM micrographs. This is likely due to the rapid evaporation of gaseous products during photothermal processing. Similar porous structures were also observed in some small crack areas on the surface where a large amount of gas was released. For comparison, in samples 1 and 2, the material beneath the film surface is not porous. Furthermore, the connections between surface pores and subsequent macropores can be clearly observed in high-magnification FESEM microscopy images. Highly loaded gold NPs (43.0 wt%) are sufficiently dispersed within the porous structural framework without aggregation. The resulting porous hierarchical structure with large surface pores can facilitate the penetration of large biomolecules for separation or sensing applications.

[0101] Energy-dispersive X-ray spectroscopy (EDS) for TEM was used to further verify the elemental distribution of the porous structure of sample 3. TEM shows high-angle annular dark-field scanning TEM (HAADF-STEM) micrographs of the area for EDS mapping, where gold NPs appear as bright regions in the image. Silicon (Si), oxygen (O), carbon (C), and gold (Au) are confirmed in the EDS spectra to be consistent with the XPS results. A uniform distribution of all elements was observed in the porous film, providing a pathway to hybrids with unique physical properties.

[0102] In short, Example 1 provides a robust strategy for synthesizing large-area nanoporous hybrid films on flexible substrates by rapid photothermal processing. This method allows for selective heating of only the top coating without damaging the polymer substrate. Compared to laser writing, this technique offers significant advantages in fabricating large-area films and is compatible with roll-to-roll manufacturing. Furthermore, a porous hierarchical structure with large mesopores on the surface and bubble-like macropores directly beneath was created in a short time of less than 1 millisecond. Hybrid films containing high concentrations of gold NP in their unique porous structure can be applied to sensor and catalytic applications. This strategy can be transferred to the synthesis of various porous hybrid films containing a wide range of functional additives with high surface area and well-controlled pore sizes for many applications, including supercapacitors, sensors, filtration, and catalytic applications.

[0103] (Example 2) Graphite layer formation Mesoporous carbon or its hybrid materials exhibit many attractive features, including high specific surface area, well-controlled pore size, high conductivity, and chemical stability, making them of interest for a variety of important applications in separation, catalysis, sensing, and energy storage. Block copolymers (BCPs) and low molecular weight surfactants can be used as sacrificial templates to generate mesoporous structures with controllable morphology, pore size, and porosity. The resulting nanoporous structures are attractive supports for a variety of functional materials, including noble metal or metal oxide nanoparticles (NPs), which can greatly improve device performance, such as the capacity of lithium-ion batteries.

[0104] Mesoporous carbon or hybrid constructions, with film thicknesses ranging from several micrometers to tens of micrometers, hold great importance for practical applications in optical, electronic, electrochemical, and sensing devices. Preparation methods for mesoporous carbon may require carbonization and graphitization at high temperatures (>800°C) for several hours in an inert atmosphere. These harsh conditions can pose significant challenges to industrial-scale fabrication via roll-to-roll processing. Laser beam writing has been employed to synthesize porous carbon on silicon wafers, where the substrate absorbs light energy, heating the top film and enabling carbonization. However, further heating in a furnace may be required to graphitize the film to some extent, making this method unsuitable for fabricating carbon films on low-temperature substrates. A one-step method for generating and patterning porous graphene films by heating polyimide with a CO2 infrared laser has been reported, but the mesoporous structure of the resulting carbon is not controlled, and only a few polymer materials efficiently absorb light and can be carbonized. In either case, incorporating functional additives into the porous structure would not significantly expand the usefulness of porous carbon. Furthermore, given the limited beam size, achieving rapid, large-area preparation of mesoporous films using lasers remains a challenging task.

[0105] In this embodiment, it is demonstrated that large-area porous silica can be prepared by rapid photothermal processing via sub-millisecond light pulses from a xenon flash lamp. However, the resulting material is not conductive and cannot be used as an electrode in real-world applications such as lithium-ion batteries. This embodiment illustrates that large-area mesoporous hybrid carbon films on polymer and metal substrates containing gold or iron / iron oxide can be readily fabricated using a photothermal processing method.

[0106] This fabrication scheme enables the selective carbonization of light-absorbing films under mild conditions and is compatible with industrial-scale processing methods such as roll-to-roll manufacturing. Advantageously, high-density graphite nanowires can be created in a rapid heating method, possibly using iron NP as a catalyst for nanowire growth. Iron NP can be generated by reducing iron oxide NP in the initial stages of heating, depending on the photothermal treatment, and then oxidized to iron oxide in the final product. The resulting hybrid material can be used as an anode for lithium-ion batteries due to several attractive features, including the high surface area of ​​the mesoporous structure, high energy density due to the contribution of iron oxide NP, high conductivity derived from the graphite nanowires, as well as good film integrity (binder-free) and good mechanical properties provided by the amorphous carbon matrix.

[0107] The (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide))(PS-b-PEO) brush BCP is used as a template for creating well-controlled pores by rapid self-assembly. In the gold-based design, both 4-mercaptophenol-coated NPs (approximately 2 nm) and resol are selectively incorporated into the PEO domains, driven by hydrogen bonding interactions, resulting in a spherical morphology with PS as spheres and PEO / gold / resol as the matrix. The bcc spherical morphology was verified by small-angle X-ray scattering (SAXS), with a domain spacing of approximately 79 nm (d=2π / q). Transmission electron microscopy (TEM) of the sample confirmed that the gold NPs were well dispersed within the nanocomposite film. Absorption spectra of the annealed sample revealed a strong localized plasmon resonance (LSPR) of gold NPs at 610 nm, enabling efficient light absorption during subsequent photothermal processing. Prior to photothermal treatment, thermogravimetric analysis was employed to disclose thermal decomposition in air, indicating the presence of approximately 24 wt% gold in the mixture. The light energy density can be precisely controlled by changing the voltage and / or pulse duration. In optimal experiments on a film on ITO-PET, the pulse duration was fixed at 0.3 milliseconds, and the light intensity was adjusted simply by changing the applied voltage. This method involves repeating the same light pulse three times with a 1-second time interval.

[0108] Energy density: 1582 mJ / cm² 2 Fourier transform infrared (FTIR) spectra of the sample before and after photothermal treatment using light pulses show that all absorption peaks attributed to organic components are absent after photothermal treatment, indicating that nearly complete carbonization was achieved in a heating period of less than 1 millisecond. The Raman spectrum of the resulting carbon sample is D(1306cm²). -1 ) and G (1569cm -1The peaks overlap, similar to the Raman spectrum of amorphous carbon prepared using furnace carbide. This was further confirmed by high-resolution TEM and X-ray diffraction (XRD) spectra. Field emission scanning electron microscopy revealed uniform mesopores formed on the surface area of ​​the carbon film, where gold NPs or clusters appeared as bright regions. The pore size was approximately 41 nm, according to image analysis using ImageJ, which is significantly larger than the pore size of mesoporous materials prepared using linear BCP. Naturally, the pore size and shape can be tuned by adjusting the composition of the BCP nanocomposite. Cross-sectional SEM shows a well-controlled porous structure inside the carbon film by replicating the spherical morphology of the precursor composition. The mesoporous structure containing high-load, well-dispersed gold NPs was further characterized by TEM. Furthermore, energy-dispersive X-ray spectroscopy (EDS) was used to further verify the elemental composition (approximately 53 wt%) and distribution in the mesoporous structure.

[0109] Mesoporous carbon films on metal surfaces can be used as binder-free electrodes for supercapacitors, batteries, and sensors, with the metal substrate functioning as a current collector. Aluminum foil was chosen first to demonstrate the rapid creation of mesoporous carbon / gold films by photothermal processing. (6042~6781 mJ / cm²) 2 Six repetitions of light pulses of different energies were used to prepare the carbon film. The carbon content first increased, then decreased, to 6331 mJ / cm³. 2 In samples obtained with this light energy, the highest carbon percentage was 98.5%, and the lowest oxygen level was 1.45%. The sheet resistance was measured at light intensities of 6042 to 6781 mJ / cm². 2 As it increases, the resistance decreases significantly from 67.1 to 16.7 kΩ. 6478 mJ / cm 2 SEM images of samples prepared at this photoenergy density show large-area carbon films up to 3 μm thick obtained on an aluminum surface. An interesting porous hierarchical structure was verified by cross-sectional SEM. The surface area shows a bubbly layer approximately 300 nm thick on top of a uniform mesoporous sublayer with an average pore diameter of approximately 31 nm.

[0110] To explore the generality and scale adaptability of the photothermal method, gold was replaced with low-cost iron / iron oxide NP (approximately 7 nm) as a nanoheater for carbonization. SimPulse, simulation software for photothermal processing systems, allows for short-term evaluation regarding the temperatures that can be reached by different materials when treated with strong light pulses. Iron oxide was found to achieve much higher temperatures than gold. Furthermore, iron oxide exhibits a high theoretical energy density (approximately 1000 mA / h / g) when used as an anode for lithium-ion batteries. The precursor composition was prepared on nickel foil. Similar to the gold system, iron / iron oxide NP coated with 4-hydroxybenzoic acid (HBA) is selectively incorporated into the PEO domain of PS-b-PEO BCP via hydrogen bonding. Spherical morphology was observed in cross-sectional SEM of the precursor composition. TGA indicates multi-step decomposition of the precursor, leaving approximately 24 wt% iron oxide. 6572 mJ / cm 2 A light pulse with a specific energy was selected for optimal photothermal treatment. Different numbers of phototreatment iterations (4, 8, and 12) were used to reveal different carbonization stages.

[0111] FTIR spectra indicate incomplete carbonization in samples treated with 4 iterations, suggesting that complete carbonization can be achieved with more iterations (8 and 12). Sheet resistance decreases significantly from 180 to 0.29 kΩ as pulses increase, indicating efficient carbonization was achieved during rapid photothermal heating.

[0112] Iron oxide (γ-Fe2O3) was confirmed using X-ray diffraction (XRD). SEM showed a bubbly structure on the upper surface and a well-defined porous structure directly below, resulting from the BCP morphology. As shown in Figure 4, the lattice-like carbon nanowires are evident in TEM decorated with iron / iron oxide NPs, consistent with the wire-like features observed in SEM. As shown in Figure 5, high-resolution TEM shows a well-ordered graphite structure in the nanowires, with a lattice spacing of 0.32 nm, very close to the interlayer spacing between fully packed graphene sheets (0.33 nm). The graphite nanowires are likely generated using iron NPs as a catalyst in a millisecond heating method, similar to the mechanism of carbon nanotube growth from iron NPs. Figure 6 shows high-density carbon wires around NPs consisting of monolayers to more than 10 layers of graphene. The photothermal method in this work provides a simple pathway to the rapid, scalable, and low-cost fabrication of graphite-carbon materials for many important applications, including lithium-ion batteries.

[0113] Hybrid mesoporous carbon films are being tested as anodes for lithium-ion batteries. Ultra-high energy densities exceeding 800 mA / h / g were observed with a current density of 70 mA / h during the first discharge cycle, suggesting a high surface area of ​​the anode and efficient lithium-ion transport within the binder-free anode. Initial constant-current cycling tests confirmed the stable performance of the anode with a high specific capacity of approximately 948 mA / h / g, one of the highest figures reported. For comparison, some preparation methods for mesoporous carbon may require carbonization and graphitization at high temperatures (>800°C) for several hours in an inert atmosphere. These harsh conditions pose a significant challenge to industrial-scale fabrication by roll-to-roll processing. Typically, graphite powder prepared using conventional methods needs to be mixed with polymer binders to prepare coatings for metal surfaces for lithium-ion batteries. However, polymer binders can reduce film conductivity and block porous pathways for lithium transport. The method reported herein provides a cost-effective pathway for the industrial-scale production of high-performance anode hybrid materials for lithium-ion batteries.

[0114] The material was tested as an anode for lithium-ion batteries. 0.8V (vs. Li / Li + A separate lithiation plateau was demonstrated in ), indicating good reactivity of iron oxide. Under a current of 200 mA / g, the composite electrode exhibited a high specific capacity of 1550 mA / h / g on the first discharge. As shown in Figure 7, this high capacity, along with a relatively low Coulomb efficiency, points to the high surface area of ​​the porous composite and parasitic irreversible reactions obtained at the interface. These reactions include solid electrolyte interface (SEI) formation and possibly corrosion such as the reaction of the carbon matrix. The capacity of the composite electrode stabilized immediately after the initial 4-5 cycles of lithiation / delithiation, resulting in a specific capacity of approximately 900 mA / h / g, one of the highest values ​​of all capacities reported for carbon / ferrite-based electrodes. The observed graphite-carbon layer wrapped around the particles acts as a flexible cage to accommodate the volume changes of iron oxide and help the particles remain connected to the amorphous carbon matrix. As the current density increased to 300 mA / g and 400 mA / g, the electrodes demonstrated capacities of 600 mA / g and 450 mA / g, respectively. Compared to other electrode materials that can be produced on a large scale, such as graphite, the capacity of the carbon / iron / iron oxide composite in actual testing far exceeded the theoretical capacity of graphite (370 mA / g). The methods and materials described herein provide a viable pathway to the industrial-scale production of high-performance, binder-free anodes for lithium-ion batteries and other batteries.

[0115] (Example 3) Formation of a battery having patterned anodes Commercially available FeO xA nanoparticle aqueous dispersion (particle size 30-100 nm, 20 wt%, Sigma Aldrich) was the first solvent, which was replaced with a dimethylformamide (DMF) dispersion. The DMF and the original dispersion were mixed in a 1:1 volume ratio. The mixture was then left overnight under a nitrogen stream to allow water evaporation. The replaced dispersion contained approximately 20 wt% FeO2 in the DMF. x The commercially available (acid-catalyzed) novolac phenol resin and Pluronic 127 surfactant were dissolved separately in DMF to a solid concentration of approximately 100 mg / ml. FeO x / Carbon precursor ink is FeO x The mixture was prepared by simply mixing three elements in a weight ratio of 5:1:1:phenol resin:Pluronic 127. The mixture was immediately immersed in a bath, ultrasonically treated, and starched for 30 minutes.

[0116] The glass substrate was cleaned with deionized water and dried in a nitrogen stream. A precursor mixture containing iron oxide, phenolic resin, Pluronic 127, and dimethyl fumarate (mass ratio 5:1:1:45) was spin-coated onto the glass substrate in a glove box at 4% relative humidity (800 rpm, 30 seconds). In another example, the precursor mixture could be solvent-free and contain iron oxide, phenolic resin, and Pluronic 127 (mass ratio 5:1:1). A mold formed with a poly(dimethylsiloxane) (PDMS) stamp was then placed on a film. The target imprint dimensions on the mold were a series of line patterns with a width of 2 μm, a height of 4 μm, and a pitch of 10 μm. After being heated briefly on a hot plate at 60°C, the PDMS stamp was peeled off, and the imprint was transferred to an oven and baked for another hour at 120°C to allow crosslinking of the phenolic resin.

[0117] If the precursor mixture is photocurable, the mold is transparent, and photothermal processing is performed using a Novacentrix Pulse Forge 1300 photonic curing system. The pulse duration is fixed at 0.6 milliseconds, a voltage of 500V is applied, and a flux of 4800 mJ / cm² is applied. 2This method yielded the optimal light energy. This method involved repeating the same light pulse three times at 1-second intervals.

[0118] (Example 4) Formation of anode and separator bilayer Commercially available FeO x A nanoparticle aqueous dispersion (particle size 30-100 nm, 20 wt%, Sigma Aldrich) was the first solvent, which was replaced with a dimethylformamide (DMF) dispersion. To do this, the DMF and the original dispersion were mixed in a 1:1 volume ratio. The mixture was then left overnight under a nitrogen stream to allow water evaporation. The replaced dispersion consisted of approximately 20 wt% FeO2 in DMF. x The commercially available (acid-catalyzed) novolac phenol resin and Pluronic 127 surfactant are dissolved separately in DMF to reach a solid concentration of approximately 100 mg / ml. FeO x The carbon precursor ink was prepared by mixing three elements together. In one demonstration, FeO x The weight ratio of phenolic resin to Pluronic 127 is 5:1:1. The mixture was immediately ultrasonically treated in a bath and star-mixed for 30 minutes.

[0119] Alternatively, if an alkaline catalyst phenolic resin (resol phenolic resin) was used, all elements were dissolved in water / ethanol. Preparation followed the same procedure as described in Example 3. FeO x The aqueous dispersion can be used as is.

[0120] The separator layer is supplied by Evonik Corp. and has a surface area of ​​175-225 m². 2 It contains Aerosil 200, a hydrophilic fumed silica, at a concentration of / g, dispersed in water under high shear. A clear and uniform dispersion of 2-8% with thixotropic rheology suitable for imprinting is obtained. This layer is almost transparent to the light spectrum of Pulse Forge 1300.

[0121] The bilayer imprinting process involved spin-coating a precursor film onto an indium / tin oxide (ITO) coated glass. The as-cast precursor film was placed on a hot plate at 60°C for 5 minutes. Upon heating, the solid concentration of the ink increased as the solvent evaporated. This resulted in a rapid increase in ink viscosity. Subsequently, the composite electrolyte was cast onto the annealed film. The bilayer film was heated on the plate for another 5 minutes to concentrate the upper layer. The film was then transferred to a Nanonex imprinting system, and a high-elasticity mold (h-PDMS or PTFE) was placed on the bilayer film. The imprinting was held under pressure at 110°C for 5 minutes, after which the film was removed from the mold. Alternatively, in addition to heating the mold, the bilayer was photothermally processed.

[0122] Photothermal processing was performed using a Novacentrix Pulse Forge 1300 photonic curing system. Light intensity was adjusted by varying the applied voltage and / or pulse duration. In one demonstration, the pulse duration was fixed at 0.6 milliseconds, a voltage of 500V was applied, and a light intensity of 4800 mJ / cm² was applied. 2 This yielded the optimal light energy. This method involved repeating the same light pulse three times with a 1-second time interval. Lower energy levels lead to a large amount of organic residue in the product, while higher energy levels can destroy the imprinted pattern.

[0123] An anode separator bilayer was used to assemble the battery. To assemble the battery, a counter electrode (cathode) slurry was prepared by mixing commercially available LiCoO2, carbon black, and PVDF binder in an 8:1:1 ratio in NMP, followed by sonication in a bath. The slurry was cast and planarized into a bilayer structure. This formed a comb-type cathode / anode array. An aluminum current collector was then sputtered onto the LiCoO2 cathode. Constant current charging / discharging of the full cell was tested using a commercially available potentiostat (Maccor 4304). Lithium perchlorate (LiClO4) or lithium hexafluorophosphate (LiPF6) in an ethylene carbonate (EC) / dimethyl carbonate (DMC) mixture solvent (1 / 1 volume) was used as the liquid electrolyte. Capacity was measured from 0.1C to 10C.

[0124] The terms and expressions used are intended to be used as descriptive terms, not as restrictive terms, and in using such terms and expressions, there is no intention to exclude any equivalent of the exhibited and described features or any part thereof, and it is recognized that various modifications are possible within the scope of the embodiments of this disclosure. Therefore, although this disclosure has been specifically disclosed by specific embodiments and optional features, it should be understood that modifications and changes to the concepts disclosed herein are possible for those skilled in the art, and such modifications and changes are considered to be within the scope of the embodiments of this disclosure.

[0125] Additional Embodiments The following exemplary embodiments are provided, and their numbering should not be interpreted as indicating a level of importance.

[0126] Embodiment 1 is a method for forming a composite having a carbon composite structure, A step of placing a precursor composition on a substrate, wherein the precursor composition is Pologen components, a supporting phase precursor component; Carbon components, Light-absorbing components, and Catalyst components A process comprising at least one of the following, Irradiate the precursor composition, A carbon composite multilayer structure having a substantially elongated profile, and Amorphous carbon matrix A step of forming at least one of the This provides a method for providing this.

[0127] Embodiment 2 provides the method of Embodiment 1, wherein the substrate comprises at least one of a metal and a polymer. Embodiment 3 provides the method of Embodiment 2, wherein the metal is at least one of aluminum, nickel, and copper.

[0128] Embodiment 4 provides one of the methods from Embodiments 1 to 3, wherein the substrate comprises a conductive material. Embodiment 5 provides one of the methods of Embodiments 1 to 4, wherein the substrate is substantially rod-shaped.

[0129] Embodiment 6 provides one of the methods of Embodiments 1 to 5, wherein the substrate comprises a metal foil. Embodiment 7 provides one of the methods of Embodiments 1 to 6, wherein the foil comprises at least one of aluminum, nickel, and copper.

[0130] Embodiment 8 provides one of the methods of Embodiments 1 to 7, wherein the substrate comprises the first polymer. Embodiment 9 provides the method of Embodiment 8, wherein the first polymer component is present in an amount of about 50% to about 100% by weight of the substrate.

[0131] Embodiment 10 provides the method of Embodiment 8, wherein the first polymer is present in an amount of about 90% to about 100% by weight of the substrate. Embodiment 11 provides one of the methods from Embodiments 1 to 10, wherein the pologen component is present in an amount of about 5% to about 50% by weight of the precursor composition.

[0132] Embodiment 12 provides one of the methods from Embodiments 1 to 11, wherein the pologen component is in the range of about 20% to about 40% by weight of the precursor composition. Embodiment 13 provides one of the methods of Embodiments 1 to 12, wherein the pologen component comprises a second polymer.

[0133] Embodiment 14 provides the method of Embodiment 13, wherein the second polymer is present in an amount ranging from about 1% to about 100% by weight of the pologen component. Embodiment 15 provides the method of Embodiment 13, wherein the second polymer component is in the proportion of about 90% to about 100% by weight of the pologen component.

[0134] Embodiment 16 provides the method of Embodiment 13, wherein at least one of the first polymer and the second polymer is a thermoplastic polymer, a thermosetting polymer, or a mixture thereof.

[0135] Embodiment 17 is a polymer in which at least one of the first polymer and the second polymer is a polyacetal, polyacrylic, polycarbonate, polystyrene, polyester, polyamide, polyamideimide, polyarylate, polyacrylate, polymethyl methacrylate, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl chloride, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketone, polybenzoxazole, polyoxadiazole, polybenzothiadinophenothiazine, polybenzothiazole, polypyradinoquinoxaline, polypyromellitoimide, polyquinoxaline, polybenzimidazole, polyoxyindole, polyoxoisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polypyrrolidine, polycarborane, polyoxabisic The present invention provides a method of Embodiment 13, which is selected from lononane, polydibenzofuran, polyphthalide, polyacetal, polyanhydride, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polysulfate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, polysiloxane, polyolefin, polyacrylamide, epoxy polymer, unsaturated polyester polymer, polyimide polymer, bismaleimide polymer, bismaleimide triazine polymer, cyanate ester polymer, vinyl polymer, benzoxazine polymer, benzocyclobutene polymer, acrylic, alkyd, phenol-formaldehyde polymer, novolac, resol, melamine-formaldehyde polymer, urea-formaldehyde polymer, hydroxymethylfuran, isocyanate, unsaturated polyesterimide, and mixtures thereof.

[0136] Embodiment 18 is a second polymer of poly(styrene-β-vinylpyridine), poly(styrene-β-butadiene), poly(styrene-β-isoprene), poly(styrene-β-methyl methacrylate), poly(styrene-β-alkenyl aromatic compound), poly(isoprene-β-ethylene oxide), poly(styrene-β-(ethylene-propylene)), poly(ethylene oxide-β-caprolactone), poly(butadiene-β-ethylene oxide), poly(styrene-β-butyl(meth)acrylate), poly(methyl methacrylate). The method of Embodiment 13 is provided, which is poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(styrene-b-trimethylsilylmethyl methacrylate), poly(methyl methacrylate-b-dimethylsiloxane), poly(methyl methacrylate-b-trimethylsilylmethyl methacrylate), or a mixture thereof.

[0137] Embodiment 19 provides the method of Embodiment 13, wherein the second polymer is a graft-block copolymer comprising two blocks, each block having a polymer backbone and different graft polymers covalently bonded to the polymer backbone.

[0138] Embodiment 20 provides the method of Embodiment 19, wherein the graft-block copolymer comprises (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide)).

[0139] Embodiment 21 provides one of the methods from Embodiments 1 to 20, wherein the carbon component is in the range of about 5% to about 50% by weight of the precursor composition. Embodiment 22 provides any one of Embodiments 1 to 21, wherein the carbon component is in the range of about 20% to about 40% by weight of the precursor composition.

[0140] Embodiment 23 is an embodiment in which the carbon component is substituted or unsubstituted (C1~C 40 ) Alkyl, (C1~C 40 ) Alkenil, (C1~C 40 ) Alkinyl, (C4~C 40 The present invention provides a method of embodiment 22, comprising at least one aryl and a mixture thereof.

[0141] Embodiment 24 provides the method of Embodiment 22, wherein the carbon component is in the gas phase, solid phase, or liquid phase. Embodiment 25 provides the method of Embodiment 22, wherein the carbon component comprises about 40% by weight of carbon to about 90% by weight of carbon.

[0142] Embodiment 26 provides any one of Embodiments 1 to 25, wherein the catalyst component is in the range of about 0.01% to about 50% by weight of the precursor composition. Embodiment 27 provides one of the methods from Embodiments 1 to 26, wherein the catalyst component is in the range of about 1% to about 15% by weight of the precursor composition.

[0143] Embodiment 28 provides any one of the methods of Embodiments 1 to 27, wherein at least one of the catalyst component and the light-absorbing component comprises at least one metal or metal oxide nanoparticle.

[0144] Embodiment 29 provides the method of Embodiment 28, wherein at least one metal or metal oxide nanoparticle constitutes about 50% to about 100% by weight of the catalyst component and the light-absorbing component. Embodiment 30 provides the method of Embodiment 28, wherein at least one metal or metal oxide nanoparticle constitutes about 90% to about 100% by weight of the catalyst component and the light-absorbing component.

[0145] Embodiment 31 provides the method of Embodiment 28, wherein the metal or metal oxide nanoparticles have a size ranging from about 1 to about 100 nanometers. Embodiment 32 provides the method of Embodiment 28, wherein the metal or metal oxide nanoparticles have a size ranging from about 1 to about 50 nanometers.

[0146] Embodiment 33 provides the method of Embodiment 28, wherein the metal or metal oxide nanoparticles comprise silicon, silicon carbide, iron, iron oxide, copper, nickel, palladium, platinum, ruthenium, rubidium, alloys thereof, or mixtures thereof.

[0147] Embodiment 34 is an iron oxide that is FeO, Fe2O3, Fe3O4, Fe4O6, Fe5O7, Fe 25 O 32 Fe 13 O 19 The present invention provides a method of embodiment 33, which is at least one of Fe2O3, (Fe(OH)2), and (Fe(OH)3).

[0148] Embodiment 35 provides one of the methods described in Embodiments 1 to 34, wherein the precursor composition is irradiated with electromagnetic radiation. Embodiment 36 provides one of the methods of Embodiments 1 to 35, wherein electromagnetic radiation is supplied from a xenon flash lamp.

[0149] Embodiment 37 provides one of the methods of Embodiments 1 to 36, wherein the individual layers of the carbon composite multilayer structure comprise at least one of nanowires, nanotubes, nanoribbons, amorphous carbon matrix, and metal or metal oxide nanoparticles.

[0150] Embodiment 38 provides the method of Embodiment 37, wherein at least one nanowire, nanotube, and nanoribbon has a width ranging from about 5 nanometers to about 500 nanometers.

[0151] Embodiment 39 provides the method of Embodiment 37, wherein at least one nanowire, nanotube, and nanoribbon has a width ranging from about 20 nanometers to about 50 nanometers.

[0152] Embodiment 40 provides one of the methods described in Embodiments 1 to 39, wherein individual layers of a carbon composite multilayer structure are in contact with at least one of a catalytic component and a light-absorbing component. Embodiment 41 provides one of the methods of Embodiments 1 to 40, wherein at least one of the carbon composite multilayer structure and amorphous carbon matrix is ​​part of the anode.

[0153] Embodiment 42 provides one of the methods from Embodiments 1 to 41, wherein the substrate is substantially free from decomposition during irradiation of the precursor composition. Embodiment 43 provides one of the methods from Embodiments 1 to 42, wherein the carbon composite structure comprises approximately 0.01% by weight to approximately 50% by weight of the composite.

[0154] Embodiment 44 provides one of the methods from Embodiments 1 to 43, wherein the support phase precursor comprises a metal alkoxide, a metal oxide, a polyoctahedral silsesquioxane, or a combination thereof.

[0155] Embodiment 45 is a precursor composition, supporting phase precursor, Light-absorbing components, and Carbon components The present invention provides one of the methods from Embodiments 1 to 44, wherein the carbon component is a phenol-formaldehyde resin.

[0156] Embodiment 46 is, Substrate, and Anode layer comprising a carbon composite structure placed on the substrate to form an electrode The present invention provides a battery comprising a carbon composite structure comprising at least one of nanowires, nanotubes, nanoribbons, amorphous carbon matrix, and metal or metal oxide nanoparticles.

[0157] Embodiment 47 provides the battery of Embodiment 46, wherein the battery is a lithium-ion battery. Embodiment 48 provides a battery according to any one of Embodiments 1 to 47, wherein the substrate comprises at least one of a metal and a polymer.

[0158] Embodiment 49 provides the battery of Embodiment 48, wherein the metal is at least one of aluminum, nickel, and copper. Embodiment 50 provides a battery according to any one of Embodiments 46 to 49, wherein the substrate comprises a conductive material.

[0159] Embodiment 51 provides a battery according to any one of Embodiments 46 to 50, wherein the base material is substantially rod-shaped. Embodiment 52 provides a battery according to any one of Embodiments 46 to 51, wherein the base material comprises a metal foil.

[0160] Embodiment 53 provides a battery according to any one of embodiments 46 to 52, wherein the foil comprises at least one of aluminum, nickel, and copper. Embodiment 54 provides a battery according to any one of embodiments 46 to 53, wherein the substrate comprises a first polymer.

[0161] Embodiment 55 provides the battery of Embodiment 54, wherein the first polymer component is present in an amount of about 50% to about 100% by weight of the substrate. Embodiment 56 provides the battery of Embodiment 54, wherein the first polymer is present in an amount of about 90% to about 100% by weight of the substrate.

[0162] Embodiment 57 provides the battery of Embodiment 56, wherein the first polymer is a thermoplastic polymer, a thermosetting polymer, or a mixture thereof. Embodiment 58 is a first polymer which is polyacetal, polyacrylic, polycarbonate, polystyrene, polyester, polyamide, polyamideimide, polyarylate, polyacrylate, polymethyl methacrylate, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl chloride, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketone, polybenzoxazole, polyoxadiazole, polybenzothiadinophenothiazine, polybenzothiazole, polypyradinoquinoxaline, polypyromellitoimide, polyquinoxaline, polybenzimidazole, polyoxyindole, polyoxoisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polypyrrolidine, polycarborane, polyoxabicyclononane, polydibenzo The present invention provides a battery of Embodiment 56, which is selected from furan, polyphthalides, polyacetals, polyanhydrides, polyvinyl ethers, polyvinyl thioethers, polyvinyl alcohols, polyvinyl ketones, polyvinyl phosphates, polyvinyl nitriles, polyvinyl esters, polysulfonates, polysulfides, polythioesters, polysulfones, polysulfonamides, polyureas, polyphosphazenes, polysilazanes, polysiloxanes, polyolefins, polyacrylamides, epoxy polymers, unsaturated polyester polymers, polyimide polymers, bismaleimide polymers, bismaleimide triazine polymers, cyanate ester polymers, vinyl polymers, benzoxazine polymers, benzocyclobutene polymers, acrylics, alkyds, phenol-formaldehyde polymers, novolacs, resols, melamine-formaldehyde polymers, urea-formaldehyde polymers, hydroxymethylfuran, isocyanates, unsaturated polyesterimides, and mixtures thereof.

[0163] Embodiment 59 provides a battery according to any one of embodiments 46 to 58, wherein the carbon composite structure comprises at least one of nanowires, nanotubes, and nanoribbons having a width ranging from about 5 nanometers to about 500 nanometers.

[0164] Embodiment 60 provides the battery of Embodiment 59, wherein at least one nanowire, nanotube, and nanoribbon has a width ranging from about 20 nanometers to about 50 nanometers.

[0165] Embodiment 61 provides a battery according to any one of Embodiments 46 to 60, wherein the metal or metal oxide nanoparticles comprise silicon, silicon carbide, iron, iron oxide, copper, nickel, palladium, platinum, ruthenium, rubidium, their alloys, or mixtures thereof.

[0166] Embodiment 62 provides a battery that comprises a plurality of chambers, one of the batteries from Embodiments 46 to 61. Embodiment 63 provides a battery according to any one of embodiments 46 to 62, wherein the carbon composite structure has a pattern formed from a plurality of protrusions extending from the substrate.

[0167] Embodiment 64 provides the battery of Embodiment 63, wherein the first width of the first individual protrusion in the x-direction is different from the second width of the second individual protrusion in the x-direction. Embodiment 65 provides the battery of Embodiment 63, wherein the width of the individual protrusions in the x-direction is in the range of approximately 900 nm to approximately 900 μm.

[0168] Embodiment 66 provides the battery of Embodiment 63, wherein the width of the individual protrusions in the x-direction is in the range of approximately 800 nm to approximately 10 μm. Embodiment 67 provides the battery of Embodiment 63, wherein the length in the y-direction of at least one of the first individual protrusions and the second individual protrusion is in the range of about 1.5 to about 20 times greater than the width.

[0169] Embodiment 67 provides the battery of Embodiment 63, wherein the distance between adjacent individual protrusions is in the range of approximately 2000 nm to approximately 500 μm. Embodiment 68 provides the battery of Embodiment 63, wherein the distance between adjacent individual protrusions is in the range of approximately 1600 nm to approximately 10 μm.

[0170] Embodiment 69 provides the battery of Embodiment 63, wherein the profiles of the individual protrusions are selected from the shapes of circles, ellipses, or polygons. Embodiment 70 provides the battery of Embodiment 69, wherein the polygonal shape is selected from triangles, squares, rectangles, pentagons, hexagons, heptagons, and octagons.

[0171] Embodiment 71 provides one of the batteries from Embodiments 46 to 70, further comprising a separator layer disposed on the anode layer. Embodiment 72 provides the battery of Embodiment 71, wherein the separator layer comprises at least one of microparticles, nanoparticles, and a binder.

[0172] Embodiment 73 provides the battery of Embodiment 72, wherein the microparticles are in the range of about 30% to about 100% by weight of the separator layer. Embodiment 74 provides the battery of Embodiment 72, wherein the microparticles are in the range of about 90% to about 100% by weight of the separator layer.

[0173] Embodiment 75 provides the battery of Embodiment 72, wherein the microparticles are selected from polymethylurea, melamine formaldehyde resin, lithium polyacrylate, polyamide, poly(lithium 2-acrylamido-2-methylpropanesulfonate), silicon dioxide (SiO2), aluminum oxide (Al2O3), boehmite (AlO(OH)), titanium dioxide (TiO2), zinc oxide (ZnO), potassium fluoride (KF), lithium fluoride (LiF), zeolite, and calcium carbonate (CaCO3).

[0174] Embodiment 76 provides the battery of Embodiment 72, wherein the nanoparticles are in the range of about 30% to about 100% by weight of the separator layer. Embodiment 77 provides the battery of Embodiment 72, wherein the nanoparticles are in the range of about 90% to about 100% by weight of the separator layer.

[0175] Embodiment 78 provides the battery of Embodiment 72, wherein the nanoparticles comprise particles selected from silicon dioxide (SiO2), aluminum oxide (Al2O3), boehmite (AlO(OH)), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), titanium dioxide (TiO2), zirconium oxide (ZrO2), tin dioxide (SnO2), zinc oxide (ZnO), potassium fluoride (KF), lithium fluoride (LiF), mesoporous aluminosilicate (Al2SiO5), mesoporous niobium-tantalum composite oxide, and mesoporous magnesium-tantalum composite oxide.

[0176] Embodiment 79 provides the battery of Embodiment 72, wherein the binder is in the range of about 10% to about 90% by weight of the separator layer. Embodiment 80 provides the battery of Embodiment 72, wherein the binder is in the range of about 30% to about 50% by weight of the separator layer.

[0177] Embodiment 81 provides a battery of Embodiment 72, wherein the binder is selected from polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylic acid, lithium polyacrylate, poly(methyl methacrylate), poly(butyl acrylate), ethyl hydroxyethyl cellulose, styrene-butadiene resin, carboxymethyl cellulose, polyimide, polyacrylonitrile, polyurethane, ethyl-vinyl acetate copolymer, and polyester.

[0178] Embodiment 75 provides one of the embodiments 46 to 74, further comprising a cathode layer disposed on a separator layer. Embodiment 76 provides the battery of Embodiment 75, wherein the cathode layer comprises lithium oxide.

[0179] Embodiment 77 provides the battery of Embodiment 76, wherein the lithium oxide is in the range of about 50% to about 100% by weight of the cathode layer. Embodiment 78 provides the battery of Embodiment 76, wherein the lithium oxide is in the range of about 90% to about 100% by weight of the cathode layer.

[0180] Embodiment 79 provides the battery of Embodiment 76, wherein the lithium oxide is a material selected from lithium metal oxide (LiCoO2), lithium nickel oxide (LiNiO2), lithium manganese oxide (LiMn2O4), and olivine-type lithium iron phosphate (LiFePO4).

[0181] Embodiment 80 is a method for forming a battery, A step of placing a precursor composition on a substrate, wherein the precursor composition is Pologen components, a supporting phase precursor component; Carbon components, Light-absorbing components, and Catalyst components A process comprising, A step of bringing a precursor composition into contact with a mold, wherein the mold is Multiple protrusions in contact with the precursor composition A process comprising, At least one of the steps of raising the temperature of the precursor composition to form an anode layer and irradiating the precursor composition to form an anode layer, A step of placing the separator layer on the anode layer, The process of forming a battery by arranging a conductor layer on the anode layer This provides a method for providing this.

[0182] Embodiment 81 provides the method of Embodiment 80, wherein the separator layer is placed on the precursor layer before the precursor layer is in contact with the mold, and the mold is in contact with the separator layer and the precursor composition.

[0183] Embodiment 82 provides the method of Embodiment 80 or 81, wherein the substrate comprises at least one of a metal and a polymer. Embodiment 83 provides the method of Embodiment 82, wherein the metal is at least one of aluminum, nickel, and copper.

[0184] Embodiment 84 provides one of the methods from Embodiments 80 to 83, wherein the substrate comprises a conductive material. Embodiment 85 provides one of the methods of Embodiments 80 to 84, wherein the substrate is substantially rod-shaped.

[0185] Embodiment 86 provides one of the methods of Embodiments 80 to 85, wherein the substrate comprises a metal foil. Embodiment 87 provides one of the methods of Embodiments 80 to 86, wherein the foil comprises at least one of aluminum, nickel, and copper.

[0186] Embodiment 88 provides one of the methods of Embodiments 80 to 87, wherein the substrate comprises the first polymer. Embodiment 89 provides the method of Embodiment 88, wherein the first polymer component is present in an amount of about 50% to about 100% by weight of the substrate.

[0187] Embodiment 90 provides the method of Embodiment 88, wherein the first polymer is present in an amount of about 90% to about 100% by weight of the substrate. Embodiment 91 provides any one of the methods of Embodiments 80 to 90, wherein the pologen component is in the range of about 5% to about 50% by weight of the precursor composition.

[0188] Embodiment 92 provides any one of the methods from Embodiments 80 to 91, wherein the pologen component is in the range of about 20% to about 40% by weight of the precursor composition. Embodiment 93 provides any one of the methods of Embodiments 80 to 92, wherein the pologen component comprises a second polymer.

[0189] Embodiment 94 provides the method of Embodiment 93, wherein the second polymer is present in an amount ranging from about 1% to about 100% by weight of the pologen component. Embodiment 95 provides the method of Embodiment 93, wherein the second polymer component is in the proportion of about 90% to about 100% by weight of the pologen component.

[0190] Embodiment 96 provides the method of Embodiment 93, wherein at least one of the first polymer and the second polymer is a thermoplastic polymer, a thermosetting polymer, or a mixture thereof.

[0191] Embodiment 97 is a polymer in which at least one of the first polymer and the second polymer is a polyacetal, polyacrylic, polycarbonate, polystyrene, polyester, polyamide, polyamideimide, polyarylate, polyacrylate, polymethyl methacrylate, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl chloride, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketone, polybenzoxazole, polyoxadiazole, polybenzothiadinophenothiazine, polybenzothiazole, polypyradinoquinoxaline, polypyromellitoimide, polyquinoxaline, polybenzimidazole, polyoxyindole, polyoxoisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polypyrrolidine, polycarborane, polyoxabisic The present invention provides a method of Embodiment 93, which is selected from lononane, polydibenzofuran, polyphthalide, polyacetal, polyanhydride, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polysulfate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, polysiloxane, polyolefin, polyacrylamide, epoxy polymer, unsaturated polyester polymer, polyimide polymer, bismaleimide polymer, bismaleimide triazine polymer, cyanate ester polymer, vinyl polymer, benzoxazine polymer, benzocyclobutene polymer, acrylic, alkyd, phenol-formaldehyde polymer, novolac, resol, melamine-formaldehyde polymer, urea-formaldehyde polymer, hydroxymethylfuran, isocyanate, unsaturated polyesterimide, and mixtures thereof.

[0192] Embodiment 98 is a second polymer of poly(styrene-β-vinylpyridine), poly(styrene-β-butadiene), poly(styrene-β-isoprene), poly(styrene-β-methyl methacrylate), poly(styrene-β-alkenyl aromatic compound), poly(isoprene-β-ethylene oxide), poly(styrene-β-(ethylene-propylene)), poly(ethylene oxide-β-caprolactone), poly(butadiene-β-ethylene oxide), poly(styrene-β-butyl(meth)acrylate), poly(methyl methacrylate). The method of Embodiment 93 is provided, which is poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(styrene-b-trimethylsilylmethyl methacrylate), poly(methyl methacrylate-b-dimethylsiloxane), poly(methyl methacrylate-b-trimethylsilylmethyl methacrylate), or a mixture thereof.

[0193] Embodiment 99 provides the method of Embodiment 93, wherein the second polymer is a graft-block copolymer comprising two blocks, each block having a polymer backbone and different graft polymers covalently bonded to the polymer backbone.

[0194] Embodiment 100 provides the method of Embodiment 99, wherein the graft-block copolymer comprises (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide)).

[0195] Embodiment 101 provides one of the methods of Embodiments 80 to 100, wherein the carbon component is in the range of about 5% to about 50% by weight of the precursor composition. Embodiment 102 provides one of the methods of Embodiments 80 to 100, wherein the carbon component is in the range of about 20% to about 40% by weight of the precursor composition.

[0196] Embodiment 103 is an embodiment in which the carbon components are substituted or unsubstituted C1-C 40 Alkyl, C1-C 40 Alkenyl, C1~C 40 The present invention provides a method according to embodiment 102, comprising at least one of alkynyl and a mixture thereof.

[0197] Embodiment 104 provides the method of Embodiment 102, wherein the carbon component is in the gas phase, solid phase, or liquid phase. Embodiment 105 provides the method of Embodiment 102, wherein the carbon component comprises about 40% by weight of carbon to about 90% by weight of carbon.

[0198] Embodiment 106 provides one of the methods from Embodiments 80 to 105, wherein the catalyst component is in the range of about 0.01% to about 50% by weight of the precursor composition. Embodiment 107 provides one of the methods from Embodiments 80 to 106, wherein the catalyst component is in the range of about 1% to about 15% by weight of the precursor composition.

[0199] Embodiment 108 provides one of the methods from Embodiments 80 to 107, wherein the catalyst component comprises at least one metal or metal oxide nanoparticle. Embodiment 109 provides the method of Embodiment 108, wherein at least one metal or metal oxide nanoparticles constitute about 50% to about 100% by weight of the catalyst component.

[0200] Embodiment 110 provides the method of Embodiment 108, wherein at least one metal or metal oxide nanoparticle constitutes about 90% to about 100% by weight of the catalyst component. Embodiment 111 provides the method of Embodiment 108, wherein the metal or metal oxide nanoparticles have a size ranging from about 1 to about 100 nanometers.

[0201] Embodiment 112 provides the method of Embodiment 108, wherein the metal or metal oxide nanoparticles have a size ranging from about 1 to about 50 nanometers. Embodiment 113 provides the method of Embodiment 108, wherein the metal or metal oxide nanoparticles comprise silicon, silicon carbide, iron, iron oxide, copper, nickel, palladium, platinum, ruthenium, rubidium, alloys thereof, or mixtures thereof.

[0202] Embodiment 114 is an example where iron oxide is FeO, Fe2O3, Fe3O4, Fe4O6, Fe5O7, Fe 25 O 32 Fe 13 O 19 The present invention provides a method of Embodiment 113, which is at least one of Fe2O3, (Fe(OH)2), and (Fe(OH)3).

[0203] Embodiment 115 provides one of the methods described in Embodiments 80 to 114, wherein the precursor composition is irradiated with electromagnetic radiation. Embodiment 116 provides one of the methods of Embodiments 80 to 115, wherein electromagnetic radiation is supplied from a xenon flash lamp.

[0204] Embodiment 117 provides one of the methods of Embodiments 80 to 116, wherein the carbon composite structure comprises at least one layer comprising at least one of nanowires, nanotubes, and nanoribbons.

[0205] Embodiment 118 provides the method of Embodiment 117, wherein at least one nanowire, nanotube, and nanoribbon has a width ranging from about 5 nanometers to about 500 nanometers.

[0206] Embodiment 119 provides the method of Embodiment 117, wherein at least one nanowire, nanotube, and nanoribbon has a width ranging from about 20 nanometers to about 50 nanometers.

[0207] Embodiment 120 provides one of the methods described in Embodiments 80 to 119, wherein the carbon composite structure is in contact with the catalyst component. Embodiment 121 provides one of the methods of Embodiments 80 to 120, wherein the carbon composite structure is part of the anode.

[0208] Embodiment 122 provides one of the methods from Embodiments 80 to 121, wherein the substrate is substantially free from decomposition during irradiation of the precursor composition. Embodiment 123 provides one of the methods from Embodiments 80 to 122, wherein the carbon composite structure comprises approximately 0.01% by weight to approximately 50% by weight of the composite.

[0209] Embodiment 124 provides one of the methods of Embodiments 80 to 123, wherein the mold is substantially transparent. Embodiment 125 is, A step of placing a precursor composition on a substrate, wherein the precursor composition Polymers that act to form pologens, light-absorbing components, supporting phase precursors, and solvents. A process comprising, A step of irradiating a precursor composition with electromagnetic radiation of a wavelength and intensity effective in decomposing the polymer and activating the support phase precursor, A process for forming a hierarchical structure on a substrate and This provides a method for providing this.

[0210] Embodiment 126 provides the method of Embodiment 125, wherein the substrate is transparent to electromagnetic radiation, and the electromagnetic radiation is absorbed mainly by a light-absorbing component. Embodiment 127 provides the method of Embodiment 125 or 126, wherein the substrate comprises a first polymer that is chemically different from the polymer used in the precursor composition, and the first polymer has a glass transition temperature, a high melting temperature, and a high decomposition temperature that are at least one higher than the glass transition temperature, melting temperature, and decomposition temperature of the polymer used in the precursor composition.

[0211] Embodiment 128 is a base material, 10 6 The present invention provides one of the embodiments 125 to 127, which is a flexible substrate having an elastic modulus of less than GPa. Embodiment 129 provides one of the methods from Embodiments 125 to 128, wherein the substrate is windable after the formation of a layered structure and is used in roll-to-roll processing.

[0212] Embodiment 130 is a first polymer and precursor composition in which the polymer used is a thermoplastic polymer, a thermosetting polymer, a blend of thermoplastic polymers, a blend of thermosetting polymers, and a blend of thermoplastic and thermosetting polymers, and includes polyacetal, polyacrylic, polycarbonate, polystyrene, polyester, polyamide, polyamide-imide, polyarylate, polyacrylate, polymethyl methacrylate, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl chloride, and Lysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketoneketone, polybenzoxazole, polyoxadiazole, polybenzothiadinophenothiazine, polybenzothiazole, polypyradinoquinoxaline, polypyromellitoimide, polyquinoxaline, polybenzimidazole, polyoxyindole, polyoxoisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, Litriazole, polypyrazole, polypyrrolidine, polycarborane, polyoxabicyclononane, polydibenzofuran, polyphthalide, polyacetal, polyanhydride, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl nitrile, polyvinyl ester, polysulfonate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, polysiloxane, polyolefin, polyacrylamide, epoxy polymer The present invention provides a method of Embodiment 127, which is selected from the group consisting of unsaturated polyester polymers, polyimide polymers, bismaleimide polymers, bismaleimide triazine polymers, cyanate ester polymers, vinyl polymers, benzoxazine polymers, benzocyclobutene polymers, acrylics, alkyds, phenol-formaldehyde polymers, novolacs, resols, melamine-formaldehyde polymers, urea-formaldehyde polymers, hydroxymethylfurans, isocyanates, unsaturated polyesterimides, or combinations thereof.

[0213] Embodiment 131 is a precursor composition in which the polymer used is a block copolymer, and includes poly(styrene-β-vinylpyridine), poly(styrene-β-butadiene), poly(styrene-β-isoprene), poly(styrene-β-methyl methacrylate), poly(styrene-β-alkenyl aromatic compound), poly(isoprene-β-ethylene oxide), poly(styrene-β-(ethylene-propylene)), poly(ethylene oxide-β-caprolactone), poly(butadiene-β-ethylene oxide), poly(styrene-β-butyl(meth)acrylate), and poly(methyl The present invention provides one of the methods described in Embodiments 125 to 130, selected from the group consisting of poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(styrene-b-trimethylsilylmethyl methacrylate), poly(methyl methacrylate-b-dimethylsiloxane), poly(methyl methacrylate-b-trimethylsilylmethyl methacrylate), or a combination thereof.

[0214] Embodiment 132 provides one of the methods from Embodiments 125 to 131, wherein the polymer used in the precursor composition is a graft-block copolymer comprising two blocks, each block having a polymer backbone and a different graft polymer covalently bonded to the polymer backbone.

[0215] Embodiment 133 provides the method of Embodiment 132, wherein the graft-block copolymer comprises (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide)).

[0216] Embodiment 134 provides one of the methods from Embodiments 125 to 133, wherein the light-absorbing component comprises light-absorbing and warming nanoparticles, and the nanoparticles are metal nanoparticles, carbonaceous nanoparticles, electrically conductive metal oxide nanoparticles, or a combination thereof.

[0217] Embodiment 135 provides the method of Embodiment 134, wherein the metal nanoparticles are selected from the group consisting of aluminum, copper, magnesium, chromium, tin, nickel, silver, iron, titanium, gold, platinum, palladium, or mixtures thereof, having a size of 1 to 100 nanometers, and the carbonaceous nanoparticles are selected from the group consisting of carbon nanotubes, graphene nanoparticles, carbon black, fullerenes, buckyballs, or combinations thereof.

[0218] Embodiment 136 provides any one of Embodiments 125 to 135, further comprising the step of drying the precursor composition by heating it to a temperature of 50 to 200°C.

[0219] Embodiment 137 provides one of the methods from Embodiments 125 to 136 for raising the temperature of a light-absorbing component to a temperature exceeding 300°C by irradiation. Embodiment 138 provides one of the methods from Embodiments 125 to 137, wherein the support phase precursor comprises a metal alkoxide, a metal oxide, a polyoctahedral silsesquioxane, or a combination thereof.

[0220] Embodiment 139 provides the method of Embodiment 138, wherein the support phase precursor is activated by heat and reacts to form a porous support phase. Embodiment 140 provides the method of Embodiment 138, wherein the support phase precursor is not a polymer.

[0221] Embodiment 141 is, Substrate, and The porous structure placed there The present invention provides an article comprising the above, wherein a porous structure is arranged over the entire area of ​​the base material exceeding 1 square meter.

[0222] Embodiment 142 provides the article of Embodiment 141, wherein the substrate on which the porous structure is arranged has an area of ​​more than 5 square meters. Embodiment 143 provides an article of Embodiment 141 or 142, wherein the substrate on which the porous structure is arranged has an area of ​​more than 10 square meters.

[0223] Embodiment 144 provides an article according to any one of Embodiments 141 to 143, wherein the porous structure has a hierarchical structure. Embodiment 145 provides an article of any one of Embodiments 141 to 144, wherein the porous structure comprises a metal oxide and / or a polyoctahedral silsesquioxane.

Claims

1. A method for forming a mesoporous graphite multilayer carbon composite structure, A step of placing a precursor composition on a substrate, wherein the substrate comprises a metal or a first polymer, and the precursor composition is The pologen component is a block copolymer, A carbon component containing phenol formaldehyde resin, glucose, cellulose, or 4-hydroxybenzoic acid, A process comprising: nanoparticles of metals or metal oxides, including aluminum, magnesium, chromium, tin, silver, titanium, gold, silicon, iron, iron oxide, copper, nickel, palladium, platinum, ruthenium, rubidium, their alloys, or mixtures thereof, which generate heat when they absorb light; or nanoparticles of silicon carbide, which generate heat when they absorb light. A method comprising the steps of irradiating the arranged precursor composition with a sub-millisecond light pulse to decompose the pologen component, convert the carbon component into a graphite material, and form a mesoporous graphite multilayer carbon composite structure.

2. The method according to claim 1, wherein the precursor composition is carbonized by the sub-millisecond light pulse.

3. The method according to claim 1, wherein the irradiation includes selective irradiation that produces a hierarchical structure having two or more different structural features.

4. The method according to claim 1, wherein the graphite material is generated during irradiation, and the precursor composition is directly converted into the mesoporous graphite multilayer carbon composite without the addition of another polymer or binder material.

5. The method according to claim 1, wherein the base material is metal.

6. The substrate comprises the first polymer, wherein the first polymer is polyacetal, polyacrylic, polycarbonate, polystyrene, polyester, polyamide, polyamide-imide, polyarylate, polyacrylate, polymethyl methacrylate, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl chloride, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketone, polybenzoxazole, polyoxadiazole, polybenzothiadinophenothiazine, polybenzothiazole, polypyradinoquinoxaline, polypyromellitoimide, polyquinoxaline, polybenzimidazole, polyoxyindole, polyoxoisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polypyrrolidine, polycarborane, polyoxabis The method according to claim 1, comprising chlorononane, polydibenzofuran, polyphthalide, polyacetal, polyanhydride, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polysulfate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, polysiloxane, polyolefin, polyacrylamide, epoxy polymer, unsaturated polyester polymer, polyimide polymer, bismaleimide polymer, bismaleimide triazine polymer, cyanate ester polymer, vinyl polymer, benzoxazine polymer, benzocyclobutene polymer, acrylic, alkyd, phenol-formaldehyde polymer, novolac, resol, melamine-formaldehyde polymer, urea-formaldehyde polymer, hydroxymethylfuran, isocyanate, unsaturated polyesterimide, and mixtures thereof.

7. The aforementioned block copolymers include poly(styrene-b-vinylpyridine), poly(styrene-b-butadiene), poly(styrene-b-isoprene), poly(styrene-b-methyl methacrylate), poly(styrene-b-alkenyl aromatic compound), poly(isoprene-b-ethylene oxide), poly(styrene-b-(ethylene-propylene)), poly(ethylene oxide-b-caprolactone), poly(butadiene-b-ethylene oxide), poly(styrene-b-t-butyl(meth)acrylate), and poly(methyl methacrylate). The method according to claim 1, wherein the material is thacrylate-b-t-butyl methacrylate, poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(styrene-b-trimethylsilylmethyl methacrylate), poly(methyl methacrylate-b-dimethylsiloxane), poly(methyl methacrylate-b-trimethylsilylmethyl methacrylate), or a mixture thereof.

8. The method according to claim 1, wherein the pologen component is in an amount of about 5 to about 50% by weight of the precursor composition, the nanoparticles of the metal or metal oxide are in an amount of about 0.01 to about 50% by weight of the precursor composition, and the carbon component is in an amount of about 5 to about 50% by weight of the precursor composition.

9. The method according to claim 1, wherein the mesoporous graphite multilayer carbon composite structure comprises at least one carbon composite having a width in the range of about 5 nanometers to about 500 nanometers, one or more of the following: nanowires, nanotubes, and nanoribbons.

10. The method according to claim 1, wherein the mesoporous graphite multilayer carbon composite structure comprises a pattern formed from a plurality of protrusions extending from the substrate.

11. The method according to claim 1, wherein the pologen component is in the range of about 20 to about 40% by weight of the precursor composition, and the block copolymer is in the range of about 90 to about 100% by weight of the pologen component.

12. The method according to claim 1, wherein the carbon component is a phenol-formaldehyde resin.

13. The method according to claim 1, wherein the pologen component is (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide)) brushblock copolymer.

14. The method according to claim 1, wherein the block copolymer comprises polystyrene and polyethylene oxide.

15. The method according to claim 1, wherein the nanoparticles of the metal or metal oxide are gold coated with 4-mercaptophenol or iron / iron oxide coated with 4-hydroxybenzoic acid.

16. A method for forming a mesoporous graphite-carbon composite structure, A step of placing a precursor composition on a substrate, wherein the substrate contains a metal, and the precursor composition is The porogen component is a polymer containing (polynorbornene-graft-poly(styrene))-block-(polynorbornene-graft-poly(ethylene oxide)), Phenolic formaldehyde resin and A process comprising: gold nanoparticles coated with 4-mercaptophenol and one or more iron / iron oxides coated with 4-hydroxybenzoic acid; A method comprising the steps of: irradiating the arranged precursor composition with a sub-millisecond light pulse to decompose the pologen component, convert the phenol-formaldehyde resin into a graphite material, and forming a mesoporous graphite-carbon composite structure.

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