CN114775272B - Preparation method and application of metal and carbon coaxial fiber and macroscopic body thereof - Google Patents
Preparation method and application of metal and carbon coaxial fiber and macroscopic body thereof Download PDFInfo
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- CN114775272B CN114775272B CN202210301868.XA CN202210301868A CN114775272B CN 114775272 B CN114775272 B CN 114775272B CN 202210301868 A CN202210301868 A CN 202210301868A CN 114775272 B CN114775272 B CN 114775272B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 164
- 239000002184 metal Substances 0.000 title claims abstract description 164
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 120
- 239000000835 fiber Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 135
- 239000004917 carbon fiber Substances 0.000 claims abstract description 135
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 131
- 238000009713 electroplating Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000012159 carrier gas Substances 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 238000012983 electrochemical energy storage Methods 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 230000005284 excitation Effects 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001465 metallisation Methods 0.000 claims description 10
- 238000013016 damping Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000002923 metal particle Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 24
- 239000003990 capacitor Substances 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 11
- 238000005530 etching Methods 0.000 abstract description 2
- 238000003466 welding Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 50
- 239000011148 porous material Substances 0.000 description 26
- 229910018487 Ni—Cr Inorganic materials 0.000 description 8
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 8
- JBMRMLLHFBHFDV-UHFFFAOYSA-N [Ni].[Mn].[Zn] Chemical compound [Ni].[Mn].[Zn] JBMRMLLHFBHFDV-UHFFFAOYSA-N 0.000 description 6
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 5
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention provides a preparation method and application of metal and carbon coaxial fibers and macroscopic bodies thereof, and relates to the technical field of composite materials. The metal and carbon coaxial fiber has the structure that the metal is coated on the surface of the carbon fiber and is embedded into the main body of the carbon fiber to form a tightly combined phase; the invention also discloses a preparation method thereof by utilizing CO 2 Etching the surface of the carbon fiber precursor (or the woven macroscopic body) by using the medium to form the carbon fiber with holes; then, a continuous metal phase is formed in the holes and on the surface by electroplating or the like. The single metal and carbon coaxial fiber has the characteristics of tight interface combination, good conductivity and light density, and can be used as a high-strength and low-density wire; the macroscopic body of the metal and carbon coaxial fiber can be respectively used as a current collector of the positive electrode or the negative electrode of a lithium ion battery and a battery type capacitor according to metal types, and has the advantages of lighter weight than a pure metal current collector, higher strength than a pure carbon current collector and easiness in welding.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method and application of metal and carbon coaxial fibers and macroscopic bodies thereof.
Background
Both metal and carbon are conductors. Fibrous metallic materials, such as copper wire, aluminum wire is the most predominant transmission line material. However, metals generally have the disadvantage of having a high specific gravity and a high cost. For example, cross-river, cross-canyon metal cables often suffer from their own weight and require various support materials. Carbon fibers are among the super high strength materials, but are not sufficiently conductive for power transmission applications. Meanwhile, three-dimensional metal mesh materials and carbon woven macrostructures are also useful as current collector materials for lithium ion batteries. The drawbacks of three-dimensional metal mesh materials remain heavy, resulting in a device with low mass energy density. While is not easy to compact when the carbon woven macroscopic body is used for preparing the pole piece, so that the volume energy density of the device is low.
At present, a small number of reports exist, and nickel can be plated on the surface of carbon fiber to form a composite wire. There are also a number of reports of carbon nanotube-metal recombination. However, because the carbon fiber or carbon nanotube surface is relatively smooth, the adhesion between the metal and the carbon interface is not strong, limiting the performance and related applications.
Therefore, there is a need for a metal and carbon coaxial fiber that improves the bonding force between the metal and carbon fibers and a method for preparing the same.
Disclosure of Invention
In view of the above problems, the present invention provides a method for preparing metal and carbon coaxial fibers and macroscopic bodies thereof, and applications thereof, by preparing a carbon fiber with holes, and then depositing metal onto the carbon fiber with holes, the number of holes and the depth of holes of the carbon fiber with holes are controllable, and the purpose of improving the binding force between the metal and the carbon fiber and maintaining the strength is achieved.
To achieve the above object, the present invention protects a metal and carbon coaxial fiber, a metal and carbon coaxial fiber material single fiber structure and a macroscopic body structure;
the single fiber structure comprises metal and carbon fiber with holes, wherein the metal is coated on the surface of the carbon fiber and embedded into the holes of the carbon fiber to form a tightly combined phase;
the macroscopic body structure comprises a film macroscopic body woven by metal and carbon fibers, and carbon fiber woven nodes of the macroscopic body are completely covered by the metal.
Further, it is preferable that the diameter of the pores of the carbon fiber is 1 to 20nm.
Further, preferably, the number of holes of the maximum depth is 5% to 20% of the number of all holes; wherein the depth of the maximum depth hole is 1/4-1/2 of the diameter of the carbon fiber.
Further, preferably, the metal is one or more of copper, aluminum, manganese, nickel, chromium, titanium, magnesium, lithium, or zinc.
The invention also provides a preparation method of the metal and carbon coaxial fiber, which comprises the following steps of,
placing a carbon fiber precursor or a film-shaped macroscopic body woven by the carbon fiber precursor into a reactor, introducing water and/or carbon dioxide, and introducing carrier gas; wherein, the volume content of the carrier gas is 10-50%;
treating for 0.1 to 10 hours under the conditions that the temperature is 650 to 950 ℃ and the pressure is 0.1 to 2 MPa;
stopping heating the reactor, and stopping introducing water and/or carbon dioxide;
cooling to room temperature to obtain a carbon fiber product with holes;
carrying out metal deposition on the carbon fiber product with the holes to obtain a metal and carbon coaxial fiber product;
wherein,
the method comprises the steps of placing the carbon fiber product with holes in a magnetron sputtering device, forming metal vapor under the electric excitation of a metal target or metal particles, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5 to 3 hours of deposition treatment, closing the magnetron sputtering device, and cooling to obtain a metal and carbon coaxial fiber product;
the method comprises the steps of placing the carbon fiber product with holes in an evaporation device, forming metal vapor under the excitation of a metal target or metal particles at high temperature, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5 to 3 hours of deposition treatment, closing the magnetron sputtering device, and cooling to obtain a metal and carbon coaxial fiber product;
metal deposition is carried out on the carbon fiber product with holes by an electroplating method, and the method comprises the steps of placing the carbon fiber product with holes into metal-containing electrolyte of an electroplating bath of an electroplating device, and connecting electrodes; and (3) after the electroplating treatment is carried out for 0.5 to 5 hours, closing the electroplating device, and cooling to obtain the metal and carbon coaxial fiber product.
The invention also provides a preparation method of the macroscopic body of the metal and carbon coaxial fiber, which comprises the following steps of,
placing a film-shaped macroscopic body woven by a carbon fiber precursor in a reactor, introducing water and/or carbon dioxide, and introducing carrier gas; wherein, the volume content of the carrier gas is 10-50%;
treating for 0.1 to 10 hours under the conditions that the temperature is 650 to 950 ℃ and the pressure is 0.1 to 2 MPa;
stopping heating the reactor, and stopping introducing water and/or carbon dioxide;
cooling to room temperature to obtain a carbon fiber product with holes;
carrying out metal deposition on the carbon fiber product with the holes to obtain a metal and carbon coaxial fiber product;
wherein,
the method comprises the steps of placing the carbon fiber product with holes in a magnetron sputtering device, forming metal vapor under the electric excitation of a metal target or metal particles, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5 to 3 hours of deposition treatment, closing the magnetron sputtering device, and cooling to obtain a metal and carbon coaxial fiber product;
the method comprises the steps of placing the carbon fiber product with holes in an evaporation device, forming metal vapor under the excitation of a metal target or metal particles at high temperature, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5-3 hours of deposition treatment, closing the magnetron sputtering device, and cooling to obtain a macroscopic body of the metal and carbon coaxial fiber;
metal deposition is carried out on the carbon fiber product with holes by an electroplating method, and the method comprises the steps of placing the carbon fiber product with holes into metal-containing electrolyte of an electroplating bath of an electroplating device, and connecting electrodes; and (3) after the electroplating treatment is carried out for 0.5 to 5 hours, closing the electroplating device, and cooling to obtain the macroscopic body of the metal and carbon coaxial fiber.
Further, preferably, the carrier gas is N 2 、Ar、H 2 One of them.
Further, preferably, the material of the reactor is one of quartz, stainless steel, copper or nickel.
The invention also protects the application of the metal and carbon coaxial fiber in an electrochemical energy storage device.
The invention also protects the application of the metal and carbon coaxial fiber in damping materials.
The metal and carbon coaxial fiber and the macroscopic body of the metal and carbon coaxial fiber, as well as the preparation method and the application thereof, provided by the invention have the beneficial effects that:
1) The metal phase can be more uniform due to the addition of the combination interface of the metal and the carbon; compared with a structure with a simple surface bonding, the strength is improved by 5-40%, and the resistance is reduced by 5-30%.
2) Can replace pure metal wires under the application scene of small current, and reduce the mass by 20-50%.
3) When the metal foil is used for an electrochemical energy storage device (such as a current collector of a lithium ion battery, a lithium ion capacitor, a battery type capacitor or an electric double layer capacitor), the mass energy density is improved by 5-10% compared with the electrochemical energy storage device using a metal foil current collector. Compared with a lithium ion battery using a pure carbon current collector, the pole piece has 20-50% higher compressibility and 50-100% higher tensile strength.
4) As the specific surface area of the metal and carbon coaxial fiber macroscopic body is small, the electrochemical performance is stable, and compared with the braided macroscopic body such as a carbon nano tube, the active lithium phase influence on the lithium ion negative electrode is small, and the coulomb efficiency is 5% -10%.
Detailed Description
The present invention will be more specifically described with reference to the following examples. However, the protective scope of the invention is not limited to the examples below.
The invention discloses a metal and carbon coaxial fiber and a macroscopic body of the metal and carbon coaxial fiber as well as a preparation method and application thereof. The invention also discloses a preparation method thereof, which comprises the following steps of utilizing CO 2 ，H 2 Etching the surface of the carbon fiber precursor (or the woven macroscopic body) by the medium such as O to form holesCarbon fibers of (2); then, a continuous metal phase is formed in the holes and on the surface by electroplating or depositing. The single metal and carbon coaxial fiber has the characteristics of tight interface combination, good conductivity and light density, and can be used as a high-strength and low-density wire; the macroscopic body (such as a film shape) of the metal and carbon coaxial fiber can be respectively used as a current collector of a positive electrode or a negative electrode of a lithium ion battery, a lithium ion capacitor, an electric double layer capacitor and a battery type capacitor according to metal types, has the advantages of lighter weight than a pure metal current collector, higher strength than a pure carbon current collector and easiness in welding, and can improve the energy density of an electrochemical energy storage device. Can also be used as damping material.
Example 1
Placing commercial carbon fiber precursor into a reactor, introducing medium CO 2 The carrier gas is Ar, wherein the volume content of the carrier gas is 20%. The treatment was carried out at 650℃and at a pressure of 2MPa for 10 hours. Stopping the heating of the reactor and stopping the introduction of medium CO 2 . After cooling to room temperature, the resulting porous carbon fiber product was taken out.
It was found by observation that many pores of 1 to 20nm were formed on the surface of the obtained carbon fiber with pores, and the maximum depth of the pores was 1/2 of the diameter of the carbon fiber. The holes with the greatest depth account for 15% of the number of all holes. The specific surface area of the carbon fiber with holes is 1000m 2 /g。
Placing the carbon fiber product with the holes into an evaporation device; copper particles are excited at high temperature to form copper vapor, and the copper vapor is deposited on the surface and in the holes of the obtained carbon fiber with the holes. And (3) processing for 3 hours, closing the evaporation device, and cooling to obtain the bulk (combined) copper and carbon coaxial fiber product.
In the specific implementation process, when the metallized surface modification is performed on the carbon fiber product with holes, a deposition method, an electroplating method or an evaporation method may be used, so long as the purpose of combining the metal and the carbon coaxial fiber is achieved.
The obtained copper and carbon coaxial fiber product has macroscopic specific surface area of 20m 2 /g, metal content50%. The strength of the obtained (as-bonded) copper and carbon coaxial fiber product is improved by 5% -40% compared to copper and carbon coaxial fibers with only surface bonding (without bulk bonding). The bulk resistance of the copper and carbon coaxial fiber is reduced by 5 to 30 percent compared with that of the copper and carbon coaxial fiber which is only subjected to surface bonding (bulk bonding does not occur).
Example 2
Commercially available carbon fiber precursors were woven into a 200 μm thick film macroscopic body with a porosity of 70%.
Placing macroscopic body in quartz reactor, introducing 10% water and 90% CO 2 Is a mixture of H and carrier gas 2 The carrier volume content was 50%. The treatment was carried out at a temperature of 700℃and a pressure of 0.6MPa for 0.1 hour. Stopping the heating of the reactor and stopping introducing CO 2 And water. After cooling to room temperature, the obtained carbon fiber product with holes was taken out.
It was found by observation that on the obtained carbon fiber product of pores, there were many pores of 1 to 20nm on the surface of the carbon fiber, and the maximum depth of the pores could be up to 1/4 of the diameter of the carbon fiber. The holes with the greatest depth account for 5% of the number of all holes. The specific surface area of the carbon fiber with holes is 50m 2 /g。
And placing the obtained carbon fiber product with the holes in a magnetron sputtering device. And (3) forming aluminum vapor by the aluminum target under the electrical excitation, and depositing the aluminum vapor on the surface and in the holes of the obtained carbon fiber product with the holes. The magnetron sputtering device is turned off after 0.5 hour of treatment. After cooling, macroscopic bodies of (shedder-combined) metal and carbon coaxial fibers are obtained as final product.
By observing the obtained macroscopic body of (generator-bonded) metal and carbon coaxial fibers, it was found that the carbon fiber braid node of the macroscopic body of metal and carbon coaxial fibers was completely covered with metal. Macroscopic specific surface area of macroscopic body of metal and carbon coaxial fiber is 20m 2 And/g, the metal content is 10%.
The macroscopic body of the metal and carbon coaxial fiber can be used as a positive current collector of a lithium ion battery, a lithium ion capacitor and a battery type capacitor, and can be filled with various positive materials to form a composite pole piece; and positive and negative electrode current collectors used as double-layer capacitors can be filled with positive and negative electrode materials to form a composite pole piece. Macroscopic bodies of metal and carbon coaxial fibers can also be used as damping materials.
The composite electrode plate can be used as a positive electrode current collector of a lithium ion battery, a lithium ion capacitor and a battery type capacitor, and can be filled with various positive electrode materials to form a composite electrode plate. And positive and negative electrode current collectors used as double-layer capacitors can be filled with positive and negative electrode materials to form a composite pole piece. Compared with an electrochemical energy storage device (the cathode is the same or the anode and the cathode are the same) using an aluminum foil current collector, the mass energy density is improved by 2-8%. Compared with an electrochemical energy storage device (the cathode is the same or the anode and the cathode are the same) using a pure carbon current collector, the compressibility of the pole piece is 15-30% higher, and the tensile strength is 30-50% higher.
Example 3
Placing commercial carbon fiber precursor into a stainless steel reactor, introducing water, and carrying gas N 2 Wherein the carrier gas volume content is 10%. Treating at 750deg.C and 0.1MPa for 0.1 hr, stopping heating the reactor, and stopping introducing water. After cooling to room temperature, the resulting holed carbon fiber product was removed.
It was found by observation that the surface of the obtained carbon fiber with holes had many holes of 1 to 20nm, and the maximum depth of the holes could be 1/3 of the diameter of the carbon fiber. The holes with the greatest depth account for 5% of the number of all holes. The specific surface area of the carbon fiber with holes is 100m 2 /g。
Metal deposition is carried out by adopting an electroplating method, the obtained carbon fiber product with holes is placed in a metal-containing electrolyte (such as nickel sulfate solution) in an electroplating bath, and electrodes are uniformly connected for electroplating for 5 hours. Nickel and carbon coaxial fibers (of the generator phase combination) were obtained as final product.
The obtained nickel-carbon coaxial fiber after combination is observed to have macroscopic specific surface area of 2m 2 /g, metal content 48%.
The strength of the nickel and carbon coaxial fiber is 5-40% higher than that of the nickel and carbon coaxial fiber with only surface bonding (without bulk bonding). The bulk resistance of the nickel and carbon coaxial fiber is 5-30% lower than that of a nickel and carbon coaxial fiber with only surface bonding (no bulk bonding).
Example 4
Commercially available carbon fiber precursors were woven into a film-like macroscopic body with a thickness of 20 μm and a porosity of 50%.
The macroscopic body is placed in a copper reactor, 90% water and 10% CO are introduced 2 Is N as carrier gas 2 The carrier gas volume content was 30%. The treatment was carried out at 800℃and a pressure of 1.2MPa for 6 hours. Stopping the reactor from heating and stopping introducing CO 2 And water. After cooling to room temperature, the obtained carbon fiber product with holes was taken out.
It was found by observation that on the obtained carbon fiber product of pores, there were many pores of 1 to 20nm on the surface of the carbon fiber, and the maximum depth of the pores could be up to 1/2 of the diameter of the carbon fiber. The holes with the greatest depth account for 20% of the number of all holes. The specific surface area of the carbon fiber with holes is 1500m 2 /g。
Metal deposition is performed using electroplating. The resulting porous carbon fiber product was placed in a metal-containing electrolyte (e.g., copper sulfate solution) in a plating bath and uniformly connected to an electrode, and plated for 3 hours. Macroscopic bodies of metal-carbon coaxial fibers (combined with the generator body) are obtained as final products.
The macroscopic body of metal and carbon coaxial fibers obtained after the combination was observed to be completely covered with metal at the carbon fiber weave node of the macroscopic body of metal and carbon coaxial fibers. Macroscopic specific surface area of macroscopic body of metal and carbon coaxial fiber is 5m 2 /g, metal content 30%.
The macroscopic body of the metal and carbon coaxial fiber can be used as a negative current collector of a lithium ion battery, a lithium ion capacitor and a battery type capacitor. Can be filled with various cathode materials to form a composite pole piece. Compared with an electrochemical energy storage device (the positive electrode is the same) using a copper foil current collector, the quality energy density is improved by 10%. Compared with an electrochemical energy storage device (the positive electrode is the same) using a pure carbon current collector, the compressibility of the negative electrode plate is 50% higher, the tensile strength is 100% higher, and the coulombic efficiency is 10% higher. The macroscopic body can also be used as damping material.
Example 5
Placing commercial carbon fiber precursor into a stainless steel reactor, introducing CO 2 The carrier gas is N 2 The carrier gas volume content was 30%. The treatment was carried out at a temperature of 750℃and a pressure of 0.8MPa for 0.5 hours. Stopping the heating of the reactor and stopping the introduction of medium CO 2 . After cooling to room temperature, the obtained carbon fiber product with holes was taken out.
It was found by observation that on the obtained porous carbon fiber product, the surface of the carbon fiber had a plurality of pores of 1 to 20nm, the maximum depth of the pores was 1/3 of the diameter of the carbon fiber, and the pores having the maximum depth accounted for 15% of the number of all the pores, and the specific surface area of the porous carbon fiber was 200m 2 /g。
And (3) placing the obtained carbon fiber product with holes in a magnetron sputtering device, and forming aluminum-magnesium vapor under the electric excitation of an aluminum target and a magnesium target, and depositing the aluminum-magnesium vapor on the surfaces and in holes of the carbon fiber with holes. After 2 hours of treatment, the magnetron sputtering device is turned off, and after cooling, the (generator-combined) metal and carbon coaxial fiber is obtained as a final product.
The obtained bulk combined metal and carbon coaxial fiber was observed to have a macroscopic specific surface area of 12m 2 /g, metal content 25%.
The strength of the aluminum-magnesium and carbon coaxial fiber is 5% higher than that of an aluminum-magnesium and carbon coaxial fiber with only surface bonding (without bulk bonding). The bulk resistance of the aluminum magnesium and carbon coaxial fiber is 10% lower than that of an aluminum magnesium and carbon coaxial fiber with only surface bonding (without bulk bonding).
Example 6
Commercially available carbon fiber precursors were woven into a 50 μm thick film macroscopic body with a porosity of 70%.
Placing the macroscopic body in quartz reactor, introducing water, and carrier gas is N 2 The carrier gas volume content was 30%. The treatment was carried out at 650℃and a pressure of 0.1MPa for 0.1 hour. The reactor heating was stopped and the water feed was stopped. After cooling to room temperature, the resulting holed carbon fiber product was removed.
Through observation, it is found thatOn the obtained carbon fiber product with holes, a plurality of holes with the diameter of 1-20 nm are arranged on the surface of the carbon fiber, and the maximum depth of the holes can reach 1/3 of the diameter of the carbon fiber. The holes with the greatest depth account for 15% of the number of all holes. The specific surface area of the carbon fiber with holes is 80m 2 /g。
Placing the carbon fiber product with holes in a magnetron sputtering device, forming lithium vapor by a lithium target under the electric excitation, and depositing the lithium vapor on the surfaces and in holes of the carbon fiber with holes; and (3) processing for 0.5 hour, closing the magnetron sputtering device, and cooling to obtain a macroscopic body of the (combined with the generating body) lithium carbon coaxial fiber as a final product.
The macroscopic body of the obtained lithium carbon coaxial fiber was found to be completely covered with metal at the carbon fiber braid node of the macroscopic body of the lithium carbon coaxial fiber. The macroscopic specific surface area of the macroscopic body of the lithium carbon coaxial fiber is 10m 2 And/g, the metal content is 2%.
Since lithium can be directly used as the negative electrode material of a lithium battery, the macroscopic body of the lithium-carbon coaxial fiber can be directly used as the dual functions of a negative electrode plate and a current collector.
Example 7
Placing commercial carbon fiber precursor into a nickel reactor, introducing CO 2 The carrier gas was Ar and the volume content of the carrier gas was 30%. The treatment was carried out at 850℃and at a pressure of 1MPa for 5 hours. Stopping the reactor from heating and stopping introducing CO 2 . After cooling to room temperature, the resulting holed carbon fiber product was removed.
It was found by observation that on the obtained carbon fiber product of pores, there were many pores of 1 to 20nm on the surface of the carbon fiber, and the maximum depth of the pores could be up to 1/2 of the diameter of the carbon fiber. The holes with the greatest depth account for 18% of the number of all holes. The specific surface area of the carbon fiber with holes is 1200m 2 /g。
And (3) placing the carbon fiber product with the holes in a magnetron sputtering device, and forming nickel, zinc and manganese vapor on the surfaces and holes of the carbon fiber with the holes by electrically exciting a nickel target, a zinc target and a manganese target. After 3 hours of treatment, the relevant apparatus was shut down and after cooling, nickel zinc manganese and carbon coaxial fibers (combined with the generator) were obtained as final product.
The obtained nickel-zinc-manganese and carbon coaxial fiber is observed to find that the macroscopic specific surface area is 1-12 m 2 /g, metal content 25%.
The strength of the nickel zinc manganese and carbon coaxial fiber is 20% higher than that of the nickel zinc manganese and carbon coaxial fiber with only surface bonding (without bulk bonding). The bulk resistance of the nickel zinc manganese and carbon coaxial fiber is 20% lower than that of a nickel zinc manganese and carbon coaxial fiber with only surface bonding (no bulk bonding).
Example 8
Placing commercial carbon fiber precursor into a stainless steel reactor, introducing CO 2 The carrier gas is N 2 The carrier volume content was 10%. The treatment was carried out at 950℃and at a pressure of 0.5MPa for 3 hours. Stopping the reactor from heating and stopping introducing CO 2 . After cooling to room temperature, the obtained carbon fiber product with holes was taken out.
It was found by observation that on the obtained carbon fiber product of pores, there were many pores of 1 to 20nm on the surface of the carbon fiber, and the maximum depth of the pores could be up to 1/3 of the diameter of the carbon fiber. The holes with the greatest depth account for 8% of the number of all holes. The specific surface area of the carbon fiber with holes is 800m 2 /g。
The carbon fiber product with holes is placed in a metal-containing electrolyte (such as chromium sulfate solution) in a plating bath, and the electrodes are uniformly connected to perform plating for 0.5 hour. Nickel-chromium (combined with the generator) and carbon coaxial fibers were obtained as final product.
The obtained nickel-chromium and carbon coaxial fiber is observed to have a macroscopic specific surface area of 15m 2 /g, metal content 40%.
The strength of the chromium carbon coaxial fiber is 40% higher than that of the chromium carbon coaxial fiber with only surface bonding (without bulk bonding). The bulk resistance of the chromium carbon coaxial fiber is 5% lower than that of a chromium carbon coaxial fiber with only surface bonding (no bulk bonding).
Example 9
Commercially available carbon fiber precursors were woven into a film-like macroscopic body with a thickness of 2000 μm and a porosity of 90%.
Placing the macroscopic body in a stainless steel reactor, and introducing CO 2 The carrier gas is N 2 The carrier volume content was 10%. The treatment was carried out at 900℃and a pressure of 0.5MPa for 3 hours. Stopping the reactor from heating and stopping introducing CO 2 . After cooling to room temperature, the obtained carbon fiber product with holes was taken out.
It was found by observation that on the obtained carbon fiber product of pores, there were many pores of 1 to 20nm on the surface of the carbon fiber, and the maximum depth of the pores could be up to 1/3 of the diameter of the carbon fiber. The pores with the maximum depth account for 8% of the total number of pores, and the specific surface area of the carbon fiber with pores is 800m 2 /g。
The obtained porous carbon fiber product is placed in a metal-containing electrolyte (such as chromium sulfate and nickel sulfate solution) in an electroplating bath, and is uniformly connected with an electrode, and electroplating is carried out for 2 hours. Macroscopic bodies of nickel-chromium and carbon coaxial fibers (combined with the generator body) were obtained as final products.
The macroscopic body of nickel-chromium and carbon coaxial fibers obtained by observation was found to be completely covered with metal at the carbon fiber weave nodes. Its macroscopic specific surface area is 15m 2 /g, metal content 40%.
The strength of the nickel-chromium and carbon coaxial fiber is 40% higher than that of the nickel-chromium and carbon coaxial fiber with only surface bonding (without bulk bonding). The bulk resistance of the nickel-chromium and carbon coaxial fibers is 30% lower than that of a nickel-chromium and carbon coaxial fiber with only surface bonding (no bulk bonding). The macroscopic body can also be used as damping material.
In addition, a macroscopic body (membrane) woven of metal and carbon coaxial fiber material can act as a damping material in the performance context of the mechanical field.
According to the embodiment, the strength of the metal and carbon coaxial fiber provided by the invention is 5% -40% higher than that of the metal and carbon coaxial fiber with only surface bonding (without body bonding). The bulk resistance of the metal and carbon coaxial fiber is 5% -30% lower than that of the metal and carbon coaxial fiber with only surface bonding (without bulk bonding). When the metal is copper, the metal can be used as a negative electrode current collector of a lithium ion battery, a lithium ion capacitor or a battery type capacitor. Can be filled with various cathode materials to form a composite pole piece. Compared with an electrochemical energy storage device (the positive electrode is the same) using a metal foil current collector, the mass energy density is improved by 5% -10%. Compared with an electrochemical energy storage device (the positive electrode is the same) using a pure carbon current collector, the compressibility of the negative electrode plate is 20% -50%, the tensile strength is 50% -100% and the coulomb efficiency is 5% -10%. When the metal is aluminum, the metal can be used as a current collector of the positive electrode and the negative electrode of the double-layer capacitor. Can be filled with anode and cathode materials; when the metal is aluminum, the metal can be used as a positive electrode current collector of a lithium ion battery or a lithium ion capacitor or a battery type capacitor, and various positive electrode materials can be filled to form a composite pole piece. Compared with an electrochemical energy storage device (the cathode is the same or the anode and the cathode are the same) using a metal foil current collector, the mass energy density is improved by 2% -8%. Compared with an electrochemical energy storage device (the cathode is the same or the anode and the cathode are the same) using a pure carbon current collector, the compressibility of the pole piece is 15% -30% higher, and the tensile strength is 30% -50% higher. When the metal is lithium, the lithium can be directly used as a negative electrode material of a lithium battery, so that the coaxial macroscopic body of lithium and carbon is directly used as a negative electrode plate and a current collector.
In conclusion, the metal and carbon coaxial fiber provided by the invention can make the metal phase more uniform due to the addition of the metal and carbon phase combination interface. Compared with a structure with a simple surface bonding, the strength is improved by 5-40%, and the resistance is reduced by 5-30%. The metal and carbon coaxial fiber can replace a pure metal wire under the application scene of small current, so that the quality is reduced by 20-50%. When the lithium ion battery is used for an electrochemical energy storage device (such as a lithium ion battery, a lithium ion capacitor, a battery type capacitor or a current collector of an electric double layer capacitor), compared with the electrochemical energy storage device using a metal foil current collector, the mass energy density is improved by 5-10 percent, compared with a lithium ion battery using a pure carbon current collector, the pole piece compressibility is 20-50 percent higher, the tensile strength is 50-100 percent higher, and compared with a braided macroscopic body such as a carbon nano tube, the lithium ion battery has the technical effects that the active lithium of a lithium ion negative electrode has less influence and the coulomb efficiency is 5-10 percent higher due to the small specific surface area of a metal and carbon coaxial fiber macroscopic body.
Among the various laboratory supplies referred to herein, including but not limited to chemical reagents, instrumentation, etc., not specifically described are conventional laboratory supplies, which may be readily available in a variety of ways (e.g., purchased, self-prepared, etc.) prior to the date of this application.
While the invention has been described in detail in the foregoing general description, specific embodiments, and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications and improvements can be made without departing from the spirit of the invention, and are intended to be within the scope of the invention as claimed.
Claims (9)
1. A method for preparing metal and carbon coaxial fiber is characterized in that the method comprises the following steps of,
placing a carbon fiber precursor in a reactor, introducing water and/or carbon dioxide, and introducing carrier gas; wherein the volume content of the carrier gas is 10% -50%;
treating for 0.1 to 10 hours at the temperature of 650 to 950 ℃ and the pressure of 0.1 to 2 MPa;
stopping heating the reactor, and stopping introducing water and/or carbon dioxide;
cooling to room temperature to obtain a carbon fiber product with holes;
carrying out metal deposition on the carbon fiber product with the holes to obtain a metal and carbon coaxial fiber product;
wherein,
the method comprises the steps of placing the carbon fiber product with holes in a magnetron sputtering device, forming metal vapor by a metal target or metal particles under electric excitation, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5-3 hours of deposition treatment, closing the magnetron sputtering device, and cooling to obtain a metal and carbon coaxial fiber product;
the method comprises the steps of placing the carbon fiber product with holes in an evaporation device, forming metal vapor under the excitation of a metal target or metal particles at high temperature, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5-3 hours of deposition treatment, closing the evaporation device, and cooling to obtain a metal and carbon coaxial fiber product;
metal deposition is carried out on the carbon fiber product with holes by an electroplating method, and the method comprises the steps of placing the carbon fiber product with holes into metal-containing electrolyte of an electroplating bath of an electroplating device, and connecting electrodes; after electroplating for 0.5-5 hours, closing the electroplating device, and cooling to obtain a metal and carbon coaxial fiber product;
the metal and carbon coaxial fiber is applied to an electrochemical energy storage device or a damping material.
2. A method for preparing macroscopic bodies of metal and carbon coaxial fibers, characterized in that the method comprises,
placing a film-shaped macroscopic body woven by a carbon fiber precursor in a reactor, introducing water and/or carbon dioxide, and introducing carrier gas; wherein the volume content of the carrier gas is 10% -50%;
treating for 0.1 to 10 hours at the temperature of 650 to 950 ℃ and the pressure of 0.1 to 2 MPa;
stopping heating the reactor, and stopping introducing water and/or carbon dioxide;
cooling to room temperature to obtain a carbon fiber product with holes;
carrying out metal deposition on the carbon fiber product with the holes to obtain a metal and carbon coaxial fiber product;
wherein,
the method comprises the steps of placing the carbon fiber product with holes in a magnetron sputtering device, forming metal vapor by a metal target or metal particles under electric excitation, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5-3 hours of deposition treatment, closing the magnetron sputtering device, and cooling to obtain a metal and carbon coaxial fiber product;
the method comprises the steps of placing the carbon fiber product with holes in an evaporation device, forming metal vapor under the excitation of a metal target or metal particles at high temperature, and depositing the metal vapor on the surface and in the holes of the carbon fiber; after 0.5-3 hours of deposition treatment, closing the evaporation device, and cooling to obtain a macroscopic body of the metal and carbon coaxial fiber;
metal deposition is carried out on the carbon fiber product with holes by an electroplating method, and the method comprises the steps of placing the carbon fiber product with holes into metal-containing electrolyte of an electroplating bath of an electroplating device, and connecting electrodes; after electroplating for 0.5-5 hours, closing the electroplating device, and cooling to obtain a macroscopic body of the metal and carbon coaxial fiber;
macroscopic bodies of metal and carbon coaxial fibers are used in electrochemical energy storage devices or damping materials.
3. The method for preparing macroscopic body of coaxial fiber of metal and carbon according to claim 2, wherein the carrier gas is N 2 、Ar、H 2 One of them.
4. The method for preparing a macroscopic body of coaxial fiber of metal and carbon according to claim 2, wherein the material of the reactor is one of quartz, stainless steel, copper or nickel.
5. A metal and carbon coaxial fiber, characterized by being prepared by the method for preparing a metal and carbon coaxial fiber according to claim 1; the single fiber structure comprises metal and carbon fiber with holes, wherein the metal is coated on the surface of the carbon fiber and embedded into the holes of the carbon fiber to form a tightly combined phase.
6. A macroscopic body of metal and carbon coaxial fibers, characterized in that it is obtained by the preparation method of the macroscopic body of metal and carbon coaxial fibers of claim 2;
the macroscopic body structure of the metal and carbon coaxial fiber comprises a film macroscopic body woven by metal and carbon fiber, and the carbon fiber woven node of the macroscopic body is completely covered by the metal;
the macroscopic body of the metal and carbon coaxial fiber is applied to an electrochemical energy storage device or a damping material.
7. A macroscopic body of metal and carbon coaxial fibers as recited in claim 5 or 6,
the diameter of the holes of the carbon fibers is 1-20 nm.
8. A macroscopic body of metal and carbon coaxial fibers as recited in claim 5 or 6,
the number of the holes with the maximum depth accounts for 5% -20% of the number of all the holes; the depth of the maximum depth hole is 1/4-1/2 of the diameter of the carbon fiber.
9. A macroscopic body of metal and carbon coaxial fibers as recited in claim 5 or 6,
the metal is one or more of copper, aluminum, manganese, nickel, chromium, titanium, magnesium, lithium or zinc.
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