Super-structured glassy carbon material and applications thereof

Abstract

The application belongs to the technical field of material preparation, and particularly relates to a superstructure glass carbon material and application thereof. The application first provides a porous support structure, wherein the porous support structure has a stable structure with uniform distribution of anisotropic stress; the porous support structure takes a three-period minimal surface cell as a minimum repeating unit; the three-period minimal surface cell comprises a diamond or diamond-like structure; and a material constituting the porous support structure is a high polymer. Further, the superstructure glass carbon material can be obtained by pyrolysis of the porous support structure. The application designs a porous structure with uniform stress and mechanical stability, and develops a high-strength glass carbon material with precise controllable shape and size, which has good application prospect in multiple fields.

Description

[0001] Priority Application

[0002] This application claims priority to Chinese Invention Patent Application No. CN2024114799352, filed on October 22, 2024, entitled “A Superstructure Glass Carbon and Its Preparation Method and Application,” which is incorporated by reference in its entirety. TECHNICAL FIELD

[0003] The present application belongs to the technical field of material preparation, and specifically relates to a superstructure glass carbon material and its application. BACKGROUND

[0004] Glass carbon is a kind of amorphous carbon, which usually has good mechanical properties, electrical conductivity, biocompatibility and chemical stability, and has important application value in the fields of biological medicine, energy, aerospace, etc. At present, the preparation method of glass carbon is usually to pyrolyze the high molecular precursor under vacuum or inert gas at high temperature, and the pyrolysis process will cause a large volume shrinkage, which is easy to cause deformation, foaming, breaking, cracking and other problems, which seriously limits the development and application of glass carbon materials.

[0005] The existing preparation and application of glass carbon are severely limited by the process, mainly including uncontrolled shrinkage, uneven shape and structure, and micro defects during sintering. That is, it is difficult to prepare glass carbon materials with both mechanical properties and specific shape design by using the existing technology.

[0006] Patent No. CN116143519A discloses a preparation method of large-size medical glass carbon block material, but the raw material required by this process is nano diamond, which is expensive. At the same time, this process is complex and requires high temperature and high pressure. Patent No. CN116495720A discloses a reticular glass carbon and its preparation method, but the three-dimensional reticular structure glass carbon prepared by this method has the problem of insufficient mechanical properties, which is difficult to meet the needs of many practical applications.

[0007] At present, the research on high-performance structural glass carbon is still in its infancy, and with the development of energy, aerospace, biological medicine and other fields, the demand for high-strength glass carbon materials with precise shape and size control is becoming more and more urgent. The mechanical properties of existing porous glass carbon materials are low, and it is difficult to precisely control the shape and size. With the increase of size, the mechanical properties of glass carbon materials will be greatly reduced, and the control of shape and size will be further increased. Therefore, it is necessary to propose improved methods and strategies to address the above problems in the existing technology, in order to develop high-performance porous glass carbon materials, and to promote the application of glass carbon materials in many fields. SUMMARY

[0008] In view of the above, the purpose of the present application is to provide an ultra-structured glass carbon material with an innovative structure, a preparation method and applications thereof, so as to alleviate or partially alleviate the deficiencies in the prior art in the field.

[0009] In one aspect, the present application provides a scaffold structure.

[0010] A porous scaffold structure having a stable structure with uniform distribution of anisotropic stress; the porous scaffold structure takes a three-period minimal surface cell as the smallest repeating unit; the three-period minimal surface cell includes a diamond or diamond-like structure; the material constituting the porous scaffold structure is a high molecular polymer.

[0011] Further, the three-period minimal surface includes the following numerical model characteristics:

[0012] (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z) = 0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0013] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0014] Or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))-(cos(2x)+cos(2y)+cos(2z))=0.3.

[0015] Further, the high molecular polymer includes a high molecular polymer with a high carbon content.

[0016] As a preferred embodiment, the high-carbon-content high-molecular polymer comprises one or more materials selected from the group consisting of furan resin, furfuryl alcohol resin, furfural resin, phenol resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyether ether ketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene dichloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylsulfone, polyethylene naphthalate, polyaniline, polyacetylene, poly-p-phenylene, polyphthalazinone, polyphenylene acetylene, polylactide, polychloroprene, cyano polyacrylate, polynaphthalene acetylene, parylene, polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinyl acetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polytrifluorochloroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly-p-phenylene sulfone, polyphenylene, polybenzoxazole, polypiperidine, polyvinyl acetal, polybenzothiazole, and polyvinyl pyrrolidone.

[0017] Another aspect of the present application also provides a super-structure glass carbon.

[0018] A super-structure glass carbon obtained by pyrolysis of the above porous scaffold structure and then scaling down by equal proportions; the pyrolysis conditions include vacuum high-temperature pyrolysis or high-temperature atmospheric pressure pyrolysis under inert atmosphere.

[0019] As a preferred embodiment, the vacuum high-temperature pyrolysis or the high-temperature atmospheric pressure pyrolysis can first be warmed from room temperature to 250°C, then warmed to 350°C, incubated for a period of time, then warmed to 700-3000°C at a rate of 1 degree per 2 minutes, and then naturally cooled.

[0020] A super-structure glass carbon having a stable structure with uniform distribution of anisotropic stress; the super-structure glass carbon has a three-period minimal surface cell as the smallest repeating unit; the three-period minimal surface cell comprises a diamond or diamond-like structure.

[0021] Further, the surface average curvature of the three-period minimal surface structure ranges from -0.135 to 0.137.

[0022] As a preferred embodiment, the surface average curvature of the three-period minimal surface structure is 0.

[0023] Further, the three-period minimal surface comprises the following numerical model characteristics:

[0024] (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z) = 0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0025] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0026] or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x)) -(cos(2x)+cos(2y)+cos(2z))=0.3.

[0027] Further, the superstructure glass carbon is obtained by pyrolysis of a polymer scaffold with the same structural unit in a proportionally reduced carbonization; the pyrolysis conditions include vacuum high-temperature pyrolysis or inert atmosphere high-temperature pyrolysis under normal pressure.

[0028] The "same structural unit" refers to the polymer scaffold also having a stable structure with uniform distribution of anisotropic stress; and a cell of a three-period minimal surface is also used as a minimum repeating unit; the cell of the three-period minimal surface includes a diamond or diamond-like structure.

[0029] As a preferred embodiment, the vacuum high-temperature pyrolysis or the high-temperature pyrolysis under normal pressure can be first heated from room temperature to 250°C, then heated to 350°C, kept for a period of time, then heated to 700-3000°C at a rate of 1 degree per 2 minutes, and then naturally cooled.

[0030] In some preferred embodiments, the porous scaffold structure or the superstructure glass carbon has a uniform porous structure, the porous structure has a pore wall thickness of less than 3 mm and a porosity of greater than 50%, but is not limited.

[0031] In other embodiments, the porous scaffold structure or the superstructure glass carbon has a non-uniform porous structure.

[0032] Another aspect of the present application also provides the use of the superstructure glass carbon described above.

[0033] The superstructure glassy carbon is applied to prepare large-size materials, and the large-size materials have a size from millimeter level to decimeter level; preferably, the large-size materials have a size including millimeter level, centimeter level or decimeter level.

[0034] Further, the large-size materials include large-size glassy carbon materials and composite materials of large-size glassy carbon and other materials; the other materials include metal materials, polymer materials, ceramic materials, glass materials or semiconductor materials.

[0035] In some preferred embodiments, the large-size glassy carbon has a size greater than 5 cm, but is not limited.

[0036] The superstructure glassy carbon is applied to prepare micro-complex structure materials, and the micro-complex structure materials have a size from nanometer level to millimeter level; preferably, the micro-complex structure materials have a size including nanometer level, micrometer level or millimeter level.

[0037] Further, the micro-complex structure materials have a precision from nanometer level to micrometer level. The "precision" is the minimum line width of a scaffold structure printed by using a 3D printing method.

[0038] The superstructure glassy carbon is applied to prepare energy materials.

[0039] The application can also provide a preparation method of the superstructure glassy carbon.

[0040] S01: design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, and the three-dimensional digital model includes

[0041] (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z) = 0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0042] (3) sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0043] or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x)) –(cos(2x)+cos(2y)+cos(2z))=0.3;

[0044] S02: 3D printing the three-dimensional digital model designed and constructed in S01 as a template, the material used in the 3D printing including a high polymer, obtaining a high polymer support;

[0045] S03: pyrolyzing (inert atmosphere protection) the high polymer support obtained in S02 at high temperature and normal pressure, obtaining the super-structure glass carbon.

[0046] Further, the bond angle of the three-dimensional digital model is 109.5°.

[0047] Further, the high polymer used in S02 comprises one or more materials selected from the group consisting of furan resin, furfuryl alcohol resin, furfural resin, phenol formaldehyde resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyether ether ketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylsulfone, polyethylene naphthalate, polyaniline, polyacetylene, poly-p-phenylene, polyphthalimide, polyphenylene acetylene, polylactide, polychloroprene, cyano polyacrylate, polynaphthalene acetylene, parylene, polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinyl acetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polytrifluorochloroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly-p-phenylene sulfone, polyphenylene, polybenzoxazole, poly-piperidine, polyvinyl acetal, polybenzothiazole and polyvinyl pyrrolidone.

[0048] Further, S03 is heated at normal pressure in an inert gas, the inert gas comprising one or more gases selected from the group consisting of nitrogen, argon, helium and neon.

[0049] Further, the 3D printing used in S02 comprises liquid crystal display printing technology, digital light processing printing technology, two-photon printing technology, extrusion printing technology or powder laser sintering printing technology.

[0050] The support can be prepared by direct or indirect 3D printing.

[0051] Direct printing is to print a specific structure directly by using 3D printing technology.

[0052] Indirect printing is to print a mold first, and then indirectly prepare a specific structure by using a mold guide, the specific operation being as follows:

[0053] S01: design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model comprising

[0054] (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z) = 0、(2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0、

[0055] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0056] Or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x)) -(cos(2x)+cos(2y)+cos(2z))=0.3;

[0057] S02: construct a solid model with the same length, width and height as the three-dimensional digital model, subtract the structure of the three-dimensional digital model in the solid model to obtain a guide model, and print the guide model using 3D printing technology;

[0058] S03: fill the guide model with a high polymer material, then burn the guide model at high temperature to obtain a scaffold structure made of a high polymer;

[0059] S04: further pyrolyze the scaffold structure to obtain the superstructure glass carbon.

[0060] Beneficial technical effects:

[0061] The present application aims to solve the contradiction between the shape, size and mechanical properties of glass carbon materials, and by designing a stress-uniform structure, a superstructure glass carbon with consideration of mechanical-shape design is prepared, which is specifically as follows.

[0062] (1) The present application uses a three-period minimal surface lattice superstructure design, and utilizes the excellent stress-uniform distribution behavior of the lattice structure during pyrolysis shrinkage to prepare a superstructure glass carbon with large size, controllable pyrolysis deformation, uniform structure and few micro defects.

[0063] (2) The present application adopts the existing 3D printing technology, and does not make many changes to the preparation and pyrolysis process of the existing glass carbon support, and does not need the assistance of special process, but only through the unique three-period minimal surface lattice design. Therefore, the production process of the superstructure glass carbon material is simple, and mass production is easy to realize.

[0064] (3) The superstructure glass carbon prepared by the present application can be further prepared into large-size products (from millimeter to decimeter), and can be prepared into complex micro products (from nanometer to micrometer), and has excellent mechanical properties, low density, low resistance, high temperature resistance, corrosion resistance and other characteristics, and can be well applied in the fields of energy, aerospace, biomedicine and even artistic decoration.

[0065] (4) The superstructure glass carbon prepared by the present application can be modularized and split, realize assembly type design, and can be modularly assembled with other metals, polymer materials and other materials to form a composite material. BRIEF DESCRIPTION OF DRAWINGS

[0066] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiment or prior art description. In all the drawings, similar elements or parts are generally identified by similar reference signs. In the drawings, each element or part is not necessarily drawn according to the actual proportion. Obviously, the drawings described below are some embodiments of the present application, and those skilled in the art can obtain other drawings according to these drawings without creative labor.

[0067] Figure 1 The three-period minimal surface lattice structure (support structure) model diagram provided for one of the embodiments of the present application;

[0068] Figure 2 The structure schematic diagram of the three-period minimal surface lattice structure in XYZ three directions provided for one of the embodiments of the present application;

[0069] Figure 3 The actual picture of the centimeter-level superstructure glass carbon prepared for one of the embodiments of the present application;

[0070] Figure 4 The thermal shrinkage performance verification diagram of the ordinary structure glass carbon prepared for one of the comparative embodiments of the present application;

[0071] Figure 5 The verification diagram of the equal proportional shrinkage ability of the different size superstructure carbon prepared by the method of the present application (A is the equal proportional shrinkage of the glass carbon of different sizes after high temperature pyrolysis under the same condition, and B is the shrinkage rate of the glass carbon of different sizes in different directions).

[0072] Figure 6 Schematic diagram of large defects and deformation of glass carbon scaffold prepared by common method and common structure (A is common scaffold structure glass carbon, B is common regular octahedral structure glass carbon, C is SEM image of defects of common scaffold structure glass carbon, D is SEM image of defects of common regular octahedral structure glass carbon);

[0073] Figure 7 Scanning electron microscope image for microdefect characterization of different glass carbon materials (A is superstructure glass carbon of the application, B is common structure glass carbon, and the scale is 200 μm);

[0074] Figure 8 Microstructure and defect analysis of large size superstructure carbon (A is high resolution TEM image of superstructure glass carbon, the scale is 5 nm and 2 nm, B is cross-section SEM image and cross-section TEM image of superstructure glass carbon, the scale is 50 μm and 100 nm);

[0075] Figure 9 Result graph of maximum compressive strength of different glass carbon materials;

[0076] Figure 10 Verification of superstructure glass carbon of the application with excellent mechanical properties;

[0077] Figure 11 Stress distribution graph of finite element analysis of three-period minimal surface lattice structure proposed by the application;

[0078] Figure 12 Finite element analysis of other structures (A is finite element analysis of common scaffold structure, B is finite element analysis of common regular octahedral structure);

[0079] Figure 13 Schematic diagram of complex modeling of micro size superstructure glass carbon prepared by the application (the scale is 2 μm and 5 μm);

[0080] Figure 14 Maximum compressive strength and maximum strain result of micro size glass carbon prepared by the application (the scale is 1 μm);

[0081] Figure 15 Elastic test result of micro size glass carbon prepared by the application (the scale is 1 μm);

[0082] Figure 16 TEM image of micro size superstructure carbon (the scale is 5 nm);

[0083] Figure 17 Schematic diagram of complex modeling of large size superstructure glass carbon prepared by the application (the scale is 1 cm);

[0084] Figure 18 Modularized partition design effect drawing of superstructure glass carbon module prepared by the present application;

[0085] Figure 19 Schematic diagram of coating PEEK coating on the surface of superstructure glass carbon. DETAILED DESCRIPTION

[0086] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0087] In this document, "and / or" includes any and all combinations of one or more of the associated items.

[0088] In this document, "multiple" means two or more, that is, it includes two, three, four, five, etc.

[0089] In this specification, the term "about" typically means + / - 5% of the stated value, more typically + / - 4% of the stated value, more typically + / - 3% of the stated value, more typically + / - 2% of the stated value, even more typically + / - 1% of the stated value, even more typically + / - 0.5% of the stated value.

[0090] In this specification, certain embodiments can be disclosed in one format in terms of a range. It is to be understood that such a "range" description is merely for the convenience and brevity and should not be construed as a rigid limitation on the scope of the disclosed range. Therefore, the description of the range should be considered to have specifically disclosed all possible sub-ranges and individual numerical values within the range. For example, the description of the range 1-6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within the range, such as 1, 2, 3, 4, 5, and 6. The above rule applies regardless of the breadth of the range.

[0091] Glossary:

[0092] The "uniform distribution of stress in all directions" described in the present application refers to the fact that the static stress analysis results of the X, Y, and Z directions of the three-period minimal surface lattice structure of the present application all show uniform static stress distribution.

[0093] The "superstructure" of the present application refers to a structure that simultaneously satisfies the three-period minimal surface and the stable structure of diamond or diamond-like stress uniformity.

[0094] The "diamond-like structure" of the present application refers to a variant with a tetrahedral structure similar to diamond, which includes slight changes in bond angles or side lengths.

[0095] The "isometric scaling" of the present application refers to the same or nearly the same shrinkage rate in all directions of the three-period minimal surface structure during the pyrolysis process.

[0096] Example 1:

[0097] This embodiment provides a method for preparing a superstructure glass carbon material, which comprises the following steps: first, designing a three-period minimal surface lattice superstructure, and then using 3D printing technology to prepare.

[0098] The three-period minimal surface (TPMS) of the present application is a kind of minimal surface with crystal structure, which periodically (along X, Y, Z axis) constructs a smooth and fully connected porous structure in three-dimensional space, with an average curvature range of -0.135 ~ 0.137 and an optimal average curvature of 0.

[0099] This embodiment provides four three-dimensional digital models of three-period minimal surface lattice structures, namely D-type, G-type, CY-type and IWP-type.

[0100] The specific preparation process includes the following steps.

[0101] Step one: using 3D modeling software to design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model equation (hereinafter referred to as "equation") involved is as follows.

[0102] (1) D-type:

[0103] Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0

[0104] (2) G-type:

[0105] cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0

[0106] (3) CY-type:

[0107] sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0108] (4) IWP type:

[0109] 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))-(cos(2x) + cos(2y)+cos(2z))=0.3

[0110] The embodiment preferably is D type. A three-period minimal surface lattice model (scaffold structure model) designed according to the D type equation is shown in Figure 1 . Further, the structural schematic diagram of the three-period minimal surface lattice model in X, Y and Z directions is shown in Figure 2 .

[0111] Step two: using a carbon-rich high polymer as a printing material, and specifically using epoxy resin as the material, a high polymer scaffold, also known as a superstructure scaffold, is printed by digital light processing printing technology (light curing printing).

[0112] Step three: using a muffle furnace, a tube furnace, a hot isostatic pressing sintering furnace and the like, the superstructure scaffold prepared in step two is heated under the protection of inert gas argon at normal pressure, specifically, first heated from room temperature to 250°C for 60 minutes, then heated to 350°C for 100 minutes, kept for 120 minutes, then heated by 1 degree per 2 minutes, heated to 700-3000°C, and then naturally cooled, and the superstructure scaffold is proportionally reduced to prepare a superstructure glass carbon material. The superstructure glass carbon prepared in the embodiment has a porous structure, a specification size of more than 5 cm, a porous structure hole wall thickness of less than 3 mm, and a porosity of more than 50%. The centimeter-level superstructure glass carbon prepared in the embodiment is shown in Figure 3 .

[0113] It can be understood that the present application can also use one or more materials of furan resin, furfuryl alcohol resin, furfural resin, phenolic resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyether ether ketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylsulfone, polyethylene naphthalate, polyaniline, polyacetylene, poly-p-phenylene, polyphthalimide, polyphenylene acetylene, polylactide, polychloroprene, cyano polyacrylate, polynaphthalene acetylene, p-xylene, polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinyl acetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polytrifluorochloroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly-p-phenylene sulfone, polyphenylene, polybenzoxazole, poly-piperidine, polyvinyl acetal, polybenzothiazole or polyvinyl pyrrolidone as the 3D printing material.

[0114] It can be understood that the present application can also use liquid crystal display printing technology, two-photon printing technology, extrusion printing technology, powder laser sintering printing and other 3D printing technologies.

[0115] It can be understood that the present application can also use inert gases such as nitrogen, helium or neon or combinations thereof as the protective gas.

[0116] Example 2

[0117] The performance verification of the superstructure glass carbon material prepared in Example 1 is provided.

[0118] 2.1 Shrinkage determination

[0119] The superstructure glass carbon prepared in Example 1 was subjected to shrinkage determination, and the results showed that the superstructure glass carbon prepared in Example 1 did not appear uneven shrinkage and stress concentration.

[0120] Control experiment: The ordinary structure glass carbon precursor was first heated from room temperature to 250℃ for 60 minutes, then heated to 350℃ for 100 minutes, and then kept for 120 minutes, and then heated to 700-3000℃ at a rate of 2 minutes per degree, and then naturally cooled. Then the shrinkage determination was carried out, and the results showed that there was obvious uneven shrinkage and stress concentration, as shown in Figure 4 .

[0121] 2.2 Proportional shrinkage verification

[0122] Different sizes of superstructure glass carbon were prepared by the method of Example 1, and then the uniform shrinkage detection experiment of the glass carbon scaffold was carried out, and the results are as followsFigure 5 As shown in the figure. Figure 5 As can be seen in A, after high temperature pyrolysis under the same conditions, the glass carbon of different sizes are all reduced in equal proportion, and their shapes are not changed. Figure 5 B shows the shrinkage rate of glass carbon of different sizes in different directions.

[0123] The ordinary glass carbon prepared in the control experiment 2.1 was observed in appearance and micro-morphology, and the results are shown in Figure 6 As shown in the figure. Figure 6 It can be seen that the ordinary glass carbon prepared by the method other than the present application has obvious deformation and larger defects after shrinking.

[0124] 2.3 Microstructure observation

[0125] The apparent micro-defects of the superstructure glass carbon prepared in Example 1 and the ordinary structure glass carbon prepared in the control experiment 2.1 were analyzed by scanning electron microscopy, as shown in Figure 7 Obvious surface cracks were observed on the ordinary structure glass carbon, while similar defects were not found on the superstructure glass carbon prepared in Example 1, as shown in Figure 8 The figure shows that the superstructure glass carbon prepared in the present application has no defects above micron level.

[0126] 2.4 Mechanical property verification

[0127] The superstructure glass carbon prepared in Example 1 and the ordinary structure glass carbon prepared in the control experiment 2.1 were subjected to compression test, and the specific steps were as follows.

[0128] Glass carbon material samples of 1cm × 1cm × 1cm were prepared, and the maximum compression strength of the samples was tested by a universal mechanical compressor. The displacement rate of the beam of the compressor was set to 1mm / min, and the maximum load was recorded until the sample was destroyed. The ratio of the maximum load to the stress area was the maximum compression strength.

[0129] The experimental results are shown in Figure 9 The maximum compression strength of the superstructure glass carbon material sample prepared in Example 1 was 186 MPa; and the maximum compression strength of the ordinary structure glass carbon material sample was only 17.59 MPa.

[0130] Further verification showed that the superstructure glass carbon material prepared in Example 1 had excellent mechanical properties, and only 0.1g could bear the weight of 100kg, as shown in Figure 10 .

[0131] Example 3

[0132] This example provides another preparation method of superstructure glass carbon material, as follows.

[0133] Example 1

[0134] Step one: design and build a three-dimensional digital model with a three-period minimal surface lattice structure by using 3D modeling software, which involves the following three-dimensional digital model equation (hereinafter referred to as "equation").

[0135] (1) D type:

[0136] Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0

[0137] (2) G type:

[0138] cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0

[0139] (3) CY type:

[0140] sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0141] (4) IWP type:

[0142] 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3

[0143] The D type is preferred in this example.

[0144] Step two: use a carbon-rich high polymer as the printing material, and in this example, furfuryl alcohol resin is used as the material, and a high polymer scaffold, also known as a superstructure scaffold, is printed by two-photon printing technology.

[0145] Step three: use a muffle furnace, a tube furnace, a hot isostatic pressing sintering furnace, etc. to heat the superstructure scaffold prepared in step two under the protection of inert gas argon at normal pressure, specifically, first heat from room temperature to 250°C for 70 minutes, then heat to 350°C for 80 minutes, keep warm for 100 minutes, then heat up by 1 degree every 3 minutes, heat to 700-3000°C, then naturally cool down, and obtain a superstructure glass carbon material.

[0146] Example 2

[0147] Step one: adopt 3D modeling software to design and build a three-dimensional digital model with three-period minimal surface lattice structure, and the D type is preferred in this example.

[0148] Step two: take carbon-rich high polymer as printing material, and adopt acrylic resin as material in this example. The high polymer support, also known as superstructure support, is printed by extrusion printing technology.

[0149] Step three: adopt muffle furnace, tube furnace, hot isostatic pressing sintering furnace and other equipment to heat the superstructure support prepared in step two under the protection of inert gas argon at normal pressure. Specifically, it is heated from room temperature to 255℃ for 100 minutes, then heated to 360℃ for 100 minutes, kept for 80 minutes, then heated by 1 degree per 5 minutes, heated to 700-3000℃, and then naturally cooled to prepare superstructure glass carbon material.

[0150] Example 3

[0151] Step one: adopt 3D modeling software to design and build a three-dimensional digital model with three-period minimal surface lattice structure, and the D type is preferred in this example.

[0152] Step two: take carbon-rich high polymer as printing material, and adopt polyurethane as material in this example. The high polymer support, also known as superstructure support, is printed by powder laser sintering printing technology.

[0153] Step three: adopt muffle furnace, tube furnace, hot isostatic pressing sintering furnace and other equipment to heat the superstructure support prepared in step two under the protection of inert gas argon at normal pressure. Specifically, it is heated from room temperature to 255℃ for 100 minutes, then heated to 360℃ for 100 minutes, kept for 80 minutes, then heated by 1 degree per 5 minutes, heated to 700-3000℃, and then naturally cooled to prepare superstructure glass carbon material.

[0154] It should be noted that the above embodiments are only examples, and the final sintering of superstructure glass carbon material is used as the standard, not as a limitation.

[0155] Example 4

[0156] Further explanation of the four three-period minimal surface models involved in Example 1 is provided.

[0157] The four three-period minimal surface models are all based on the definition of three-period minimal surface, and their common point is that they all have structural periodic repetition in three dimensions, and the average curvature range is -0.135 ~ 0.137.

[0158] More intuitively, the average curvature of each point on the surface is 0.

[0159] Further, the structure with zero curvature has isotropic uniform stress distribution.

[0160] Therefore, the glassy carbon prepared based on the three-dimensional digital model of the four triply periodic minimal surface equations provided in Example 1 has the characteristics of large size and superstructure.

[0161] The finite element simulation of the triply periodic minimal surface structure of the D-type equation is performed using the software ABAQUS, as shown in Figure 11 During the simulation, the pre-processing is performed using HyperMesh, and the solution is performed using ABAQUS. The pre-processing includes geometry processing and removal of some very small features that do not affect the calculation results. Then, the mesh is generated using a mesh size of 0.4 mm, and the second-order tetrahedral element is used. The total number of elements is 400,814, and the number of nodes is 617,725. The material is set as an elastic-plastic material, with a density of 1.1 g / cm³, a Young's modulus of 11 GPa, and a Poisson's ratio of 0.4. One end of the structure is completely fixed, and a compression strain of 5% is applied in three different lattice directions (X, Y, Z). The stress distribution under compression strain in different directions is calculated. The results show that when the strain is applied in each direction, the overall model has uniform stress distribution, and there is no stress concentration phenomenon. In addition, Figure 11 As can be seen from the lower right graph, the triply periodic minimal surface lattice structure is scaled down by an equal proportion after pyrolysis to form a superstructure glassy carbon.

[0162] Comparing the finite element analysis of other structures, it can be seen that stress concentration phenomenon can occur in other structures, as shown in Figure 12 .

[0163] Example 5

[0164] The superstructure glassy carbon provided by the present application can also be prepared as other materials, and this embodiment only shows some examples thereof.

[0165] In some embodiments, the superstructure glassy carbon provided by the present application can be prepared as a micro-complex structure (micro-size) material, and the specifications of the micro-complex structure material include nanoscale or micrometer scale.

[0166] Specifically:

[0167] S01: designing and constructing a three-dimensional digital model with a triply periodic minimal surface lattice structure, the three-dimensional digital model comprising

[0168] (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z) = 0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0169] (3) sin(x)sin(y)sin(z) + sin(2x)sin(y) + sin(2y)sin(z) + sin(2z)sin(x) - cos(x)cos(y)cos(z) + sin(2x)cos(z) + cos(x)sin(2y) + cos(y)sin(2z) = 0

[0170] or (4) 2(cos(x)cos(y) + cos(y)cos(z) + cos(z)cos(x)) - (cos(2x) + cos(2y) + cos(2z)) = 0.3.

[0171] S02: using the three-dimensional digital model designed in S01 as a template for two-photon printing, using materials including high molecular polymers to obtain a high molecular polymer scaffold;

[0172] S03: sintering the high molecular polymer scaffold obtained in S02 under vacuum or normal pressure inert gas to obtain a micro-sized superstructure glass carbon, and the sintering temperature conditions are similar to those in Example 1, and further preparing a specific shape, see Figure 13 .

[0173] Further test the mechanical properties and elasticity of the micro-sized superstructure glass carbon, see Figure 14 and Figure 15 , the results show that the maximum compressive strength of the micro-sized glass carbon is 7.23 GPa, and the maximum strain is 66%; and has super-high elastic deformation recovery ability, and the maximum elastic recovery strain is 25%.

[0174] Further characterize the micro-sized superstructure glass carbon material, see Figure 16 , a large number of curled graphene sheet structures can be seen in the TEM image, indicating that the mechanical properties are enhanced.

[0175] In some embodiments, the superstructure glass carbon proposed by the present application can also be prepared as a large-sized complex structure material, using light-cured printing, see Figure 17 .

[0176] In some embodiments, the superstructure glass carbon proposed by the present application can also be designed for modular segmentation, see Figure 18 .

[0177] In some embodiments, the superstructure glass carbon proposed by the present application can also be compounded with high molecular materials. For example, a PEEK coating layer is coated on the surface of the superstructure glass carbon, see Figure 19 . The figure shows a coating layer prepared from a 1% concentration of PEEK dispersion liquid and a coating layer prepared from a 2% concentration of PEEK dispersion liquid.

[0178] It has to be noted that, as used herein, the terms "includes" and / or "contains", or any other tautological variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements is not limited to those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. An element proceeded by "comprises a... " does not, without further constraints, exclude the presence of additional identical elements in the process, method, article, or apparatus that comprises the element.

[0179] The embodiments of the present application described above are only illustrative and not restrictive, and the above-described specific embodiments are only illustrative and not restrictive, and a person of ordinary skill in the art can make many forms under the inspiration of the present application without departing from the purpose of the present application and the scope of protection of the claims, which are all within the protection of the present application.

Claims

1. An ultrastuctured glassy carbon, characterized in that, The superstructure glass carbon has a stable structure with uniform distribution of anisotropic stress; the superstructure glass carbon takes a three-period minimal surface cell as a minimum repeating unit; the three-period minimal surface cell includes a diamond or diamond-like structure; a surface average curvature of the three-period minimal surface structure ranges from -0.135 to 0.137; the superstructure glass carbon is obtained by pyrolysis and equal-proportion reduction and carbonization of a high-molecular polymer support with the same structure unit; the three-period minimal surface includes the following numerical model characteristics: (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z) = 0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0, (3) sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0 or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x)) –(cos(2x)+cos(2y)+cos(2z))=0.

3. The pyrolysis conditions include vacuum high-temperature pyrolysis or high-temperature normal-pressure pyrolysis under an inert atmosphere. The high-molecular polymer includes a high-molecular polymer with a high carbon content.

2. The ultrastuctured glassy carbon of claim 1, wherein The high-molecular polymer with a high carbon content includes one or more materials selected from the group consisting of furan resin, furfuryl alcohol resin, furfural resin, phenol formaldehyde resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyether ether ketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylsulfone, polyethylene naphthalate, polyaniline, polyacetylene, poly-p-phenylene, polyphthalimide, polyphenylene acetylene, polylactide, polychloroprene, cyano polyacrylate, polynaphthalene acetylene, parylene, polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinyl acetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polytrifluorochloroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly-p-phenylene sulfone, polyphenylene, polybenzoxazole, poly-piperidine, polyvinyl acetal, polybenzothiazole and polyvinyl pyrrolidone.

3. The ultrastuctured glassy carbon of claim 1, wherein ​ 4. The ultrastuctured glassy carbon of claim 3, wherein ​ 5. Use of the super-structured glassy carbon according to any one of claims 1 to 4 for the production of large-sized materials, characterized in that, The large-size material has a size from millimeter to decimeter; or, the use of the superstructure glassy carbon according to any one of claims 1-4 in the preparation of micro-structured materials, characterized in that the micro-structured material has a size from nanometer to millimeter.

6. The use according to claim 5, wherein the compound is ###0002### The large-size material includes large-size glassy carbon material and composite material of large-size glassy carbon and other materials; the other materials include metal material, polymer material, ceramic material, glass material or semiconductor material.

7. The use of the superstructure glassy carbon according to any one of claims 1-4 in the preparation of energy materials.

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