OA21132A

OA21132A - Product for livestock feed based on Calcium Carbonate and Phosphorus minerals and its production process.

Info

Publication number: OA21132A
Application number: OA1202100518
Authority: OA
Inventors: FONGANG Gui Rodoph AWOUSSI
Original assignee: FONGANG Gui Rodoph AWOUSSI
Filing date: 2021-11-17
Publication date: 2024-02-02

Abstract

Procédé de fabrication de minéraux de carbonate de calcium et de phosphore à partir de roche magmatique volcanique enrichit au zinc, à la vitamine C et au phosphate provenant de la poudre d'os local calciné, par extraction de la roche, concassage et criblage primaire ensuite concassage et criblage secondaire pour obtenir une poudre fine de couleur grise sombre. Obtention d'une poudre de couleur grise claire par enrichissement au zinc, vitamine C et phosphate provenant de la poudre d'os local calciné. La poudre grise claire obtenue est ensuite conditionnée et livrée dans les entrepôts et magasins.
Process for manufacturing calcium carbonate and phosphorus minerals from volcanic magmatic rock enriched with zinc, vitamin C and phosphate from calcined local bone powder, by extraction of the rock, crushing and subsequent primary screening crushing and secondary screening to obtain a fine powder of dark gray color. Obtaining a light gray powder by enrichment with zinc, vitamin C and phosphate from local calcined bone powder. The light gray powder obtained is then packaged and delivered to warehouses and stores.

Description

Carbon-based composite material, préparation method therefor, and application thereof

TECHNIC AL FIELD

The invention belongs to the technical field of carbon material préparation, in particular to a carbon-based composite material and a préparation method thereof. The invention provides a technology for modifying the morphology and structure, the atomic, électron and ion transmission characteristics of the material surface. The carbon-based composite material prepared by the technology is used for applications comprising the battery and capacitor 15 électrodes, varions sensor électrodes, field émission électrodes, solar cell électrodes, electrolytic water hydrogen production électrodes, photocatalytic hydrogen production materials, catalysts and catalyst carriers, heat absorbing and dissipating materials, hydrogen storage materials, reinforcing materials.

BACKGROUND TECHNOLOGY

Carbon materials hâve three isomers, namely diamond, graphite and amorphous carbon. These kinds of carbon hâve different physical and Chemical properties and uses. Diamond is the hardest substance known in nature. Natural diamond contains 0.0025% - 0.2% nitrogen, with good thermal conductivity and semiconductor properties. (1) It has high température résistance, 25 good thermal stability and does not melt at 3600°C. (2) It has good thermal conductivity and conductivity, and the conductivity decreases with the increase of température. (3) It has good Chemical stability and résistance to acid, alkali and organic medium érosion, so it is used to manufacture électrodes, brushes, heat exchanger, coolers, etc. There are two kinds of graphite: natural graphite and artifïcial graphite. Amorphous carbon is the disordered arrangement of 30 carbon atoms or the grain size is too small. The amorphous carbon obtained by carbonization of coal, natural gas, oil or other organic matter at a high température of 400-1200°C is porous carbon material, carbon black and activated carbon. The main application fields of graphite are refractories, conductive materials, electrode materials, adsorption materials, friction materials, etc.

In 1991, lijima, an électron microscope expert at NEC in Japan, discovered hollow carbon fibers and carbon nanotubes. Carbon nanotubes, diamond, graphite and C60 are allotrope of carbon. Carbon nanotube is a spiral tubular structure rolled by hexagonal reticular graphene sheets. Its end can be either open or closed by pentagonal and hexagonal graphene sheets. 40 Single wall carbon nanotubes are composed of a layer of graphene sheets, which are hundreds of nanometers to several microns or even longer. Multi-walled carbon nanotubes are made of multi-layer graphene sheets. The gap between layers is about the same as that of graphite, about 0.343 nm, with a diameter of tens of nanometers and a length of more than a few microns. Carbon nanotube arrays are anisotropic in mechanical, thermal, optical and electrical properties, 45 so they are more suitable for some applications. It has been studied as the best thermal interface material for infrared detectors, capacitor électrodes, lithium battery électrodes, solar cell électrodes, various gas sensors, biosensors and high-power integrated circuit chips.

At présent, the electrode application of carbon materials needs to préparé slurry together with conductive agent and binder, and then apply the slurry to the current collector. After drying and rolling, the électrodes were producedfor batteries and capacitors, gas sensor électrodes, biosensor électrodes, etc. The prepared electrode has the following defects in practical application: (1) The use of binder will greatly reduce the effective surface area of electrode material, resulting in the réduction of effective capacity of electrode material. (2) The use of 10 binder will greatly reduce the electrical contact effect between electrode materials and current collector, and increase the working résistance of electrode. (3) At présent, the electrode materials and the current collector are combined together by adhesive. In this way, a large amount of heat will be generated in the process of charge and discharge, and the thermal shock caused by thermal expansion and cold contraction will cause the contact condition between the 15 electrode materials and the current collector to gradually deteriorate until the failure of the electrode. (4) The use of binder increases the thickness and weight of the electrode (The weight of electrode material, binder and conductive agent usually accounts for more than 30% of the weight of electrode.).

In order to solve the above inhérent defects of traditional électrodes, scientists began to study the integrated electrode combining the electrode material and current collector into one body. It can be seen from the current research results that the self-supporting binder free electrode has larger capacity, better cycle stability and rate characteristics than the traditional electrode. The binder free électrodes studied mainly include: (1) The carbon cloth based binder free electrode is a composite electrode that loads or deposits active substances such as Si and métal oxides on the carbon cloth, (2) Graphene/carbon nanotube based binder free electrode is a diaphragm electrode processed from graphene/carbon nanotube and Si or métal oxide, (3) Carbon nanotube array based binder free electrode (carbon nanotube array electrode) is prepared by depositing vertically oriented carbon nanotube arrays on conductive substrates such as copper and stainless Steel by CVD. Although the performance of these électrodes has been greatly improved, they still cannot meet the applications where the battery has higher requirements for energy density, cycling and rate performance such as energy storage, electric vehicles, electric aircraft and so on.

Scientists hâve encountered many unexpected problems when studying the application of carbon-based électrodes. These problems hâve not attracted the attention of scientists in ail fîelds of applied research. Solving these problems is of great significance to improve the performance, reliability and application potential of carbon fiber array.

(1) Bonding strength between carbon fiber array and substrate. We know that a necessary condition for the application of carbon fiber array is to grow carbon fiber array on conductive substrate. The bonding strength between carbon fiber and substrate détermines the reliability and service life of devices. Therefore, how to improve the bonding strength between carbon fiber array and substrate is the research focus and difficulty in this fîeld. At présent, the 45 préparation technology of métal catalysts is to coat nano métal catalysts such as copper, iron, cobalt and nickel on the substrate to grow carbon fibers on the métal catalysts by Chemical vapor déposition. There is no bonding between the carbon fibers in this carbon fiber array, and the bonding force between the carbon fibers and the substrate is also very weak. Therefore, the carbon fiber array is easy to fall off from the carbon fiber array and cause device failure. (2)

Carbon fiber lacks self-supporting abîlity. Another disadvantage of the carbon fiber array prepared by the above method is that the diameter of the carbon fiber in the array is too small, front a few nanometers to tens of nanometers, and each carbon fiber cannot be supported independently. The distance between carbon fibers is only a few nanometers to more than ten nanometers, and they collide or even wind each other to support each other. During the field émission, one carbon fiber tom offfrom the substrate may cause several carbon fibers lose support and fallen down. In other words, the field émission failure of carbon fiber array may be carried out in an accelerated way. When thetom off carbon fibersreach certain amount, the whole field émission device will fail completely. (3) Electrostatic shielding effect between carbon fibers. The research results of scientists on the field émission performance of carbon fiber arrays show that there is a strong electrostatic shielding effect with high-density carbon fiber arrays leading to poor the field émission performance of the array. More importantly, this shielding effect greatly reduces the effective spécifie surface area of carbon fiber array resulting in weak performance.

The main préparation technology of carbon fiber arrays is to préparé carbon nanotube arrays on quartz, glass and Silicon substrates by catalytic Chemical vapor déposition. The préparation of such large area carbon nanotube arrays is based on ion sputtering, vacuum coating and sol-gel method to deposit a catalyst or catalyst precursor on the substrate, and then deposit the aligned carbon nanotubes under certain conditions. With the in-depth study of carbon nanotube arrays, scientists began to study the préparation of carbon nanotube arrays with spécifie pattern. The fîrst method used to préparé the formatted array clusters is by using the porous template as catalyst template followed by Chemical vapor déposition. The frequently used porous template is anodized aluminum oxide. The catalyst is deposited into the pores of porous substrate followed by depositing the carbon nanotube array in the pores by Chemical vapor déposition. There is also a similar method called cover plate method. In this method, carbon nanotube array clusters are prepared by covering the parts that do not need to grow carbon nanotubes with a formatted cover plate. The characteristic of this method is that the catalyst precursor is coated on the substrate by sol-gel method, and then the coating is covered by a cover net, so that carbon nanotubes grow out of the gap of the cover net. Lithographie method has also been studied in recent years., The transition layer, catalyst layer and covering layer are deposited on the substrate by magnetron sputtering or vacuum évaporation, and then the catalyst format is engraved by laser engraving technology or ion beam grinding technology. Finally, the carbon nanotube array is grown by catalytic Chemical vapor déposition. The characteristic of this préparation method is that it is convenient to design and deposit formatted carbon nanotube array clusters according to needs. Another advantage is that the required formatted carbon nanotube array clusters can be prepared directly on the working substrate. A recent catalyst préparation technology is called dip pen nanolithography (DPN). The principle of this technology is to print the catalyst precursor directly on the substrate with the writable probe of atomic force microscope, and then grow carbon nanotube arrays (clusters) by Chemical vapor déposition. The advantage of this method is that the catalyst precursor can be directly printed on the substrate without template, vacuum conditions and complex déposition and etching process. More importantly, DPN technology can print the catalyst precursor at any required position very accurately. The printing dot diameter can be as small as 100 nm.

Lahiri et al directly deposited carbon nanotube arrays on copper substrate as binder free négative electrode of lithium-ion battery, as shown in Fig. 1. The electrode was prepared by depositing a layer of 20-25 nm Ti and Ni on a 50 micron thick copper foil, and then depositing carbon nanotube arrays by CVD at 500-900°C with H₂ + C₂H₂ mixture (1:2 ratio) as working gas. It can be seen from the figure that the deposited carbon nanotube arrays are intertwined with each other.

Tan et al. studied the in-situ déposition of nano array binder free électrodes on copper foil, copper mesh and copper braided mesh, as shown in Fig. 2. CuO nano array electrode (CNE) was prepared by heating and oxidizing the substrate in oxygen environment at 600°C/5h (Fig2. a). CuO/CNx nano array electrode (CCNE) was prepared by magnetron sputtering of CNE with graphite as target in N₂ environment (Fig2. b). Cu/CNx nano array electrode (CNNE) was prepared by reducing CCNE at 300°C/2h in hydrogen environment (Fig2. C).

Wang et al. deposited Si/CNT electrode on a 15.5mm diameter stainless Steel wafer, as shown in Fig. 3. The electrode was prepared by depositing Ή/tin layer on stainless Steel, foliowed by Ni catalyst layer. Using C₂H₂ as carbon source, CNT was deposited at 800°C. Then, a Si layer was deposited on the surface of CNT (SiH4 as Si source, 300°C).

SUMMARY OF THE INVENTON

The objectives of the invention include but are not limited to the foliowings:

1. The first objective of the invention is to modify the surface structure and morphology, the électron, atom and ion transmission characteristics, the electrical conductivity, the thermal conductivity, the gas adsorption and desorption and other physical and Chemical characteristics of the substrate material and hence préparé a carbon-based composite material with better physical and Chemical properties.

2. The second objective of the présent invention is to produce a carbon-based composite material for varions capacitors and battery électrodes

3. The third objective of the invention is to produce a carbon-based composite material embedded with lithium, sodium, potassium, rubidium, césium and béryllium, magnésium, calcium, strontium, barium éléments, for example C/LiC, C/K₂CO₃, C/MgCl₂, and use the prepared carbon-based materials for both positive and négative électrodes oflithium, sodium, potassium, rubidium, césium and béryllium, magnésium, calcium, strontium, barium ion battery and capacitor électrodes, and to enhance theelectrochemical property of the electrode.

4. The fourth objective of the invention is to préparé the composite material électrodes composed of carbon-based composite material and other compounds such as carbon/LiFePO₄, carbon/LiCl and carbon/LiCoO₂, and apply the produced carbon-based composite material as the positive and négative électrodes of hydrogen, lithium, sodium, potassium, rubidium, césium, magnésium, calcium, strontium, barium ion battery andas the electrode of capacitors,and improve the electrochemical performance of the électrodes.

5. The fifth objective of the invention is to produce carbon-based composite materials for applications as électrodes of electrolytic water hydrogen production, biosensors, gas sensors, infrared sensors and other sensors, solar cells, high-performance heat exchange devices, photocatalytic and electrolytic water hydrogen production materials, field émission and other applications.

6. The sixth objective of the invention is to improve the bonding strength, electrical contact and thermal conductivity of the electrode.

7. The seventh objective of the invention is to improve the effective spécifie surface area, capacity and sensitivity of the electrode.

8. The eighth objective ofthe invention is to reduce the thickness and weight ofthe electrode.

9. A ninth objective of the invention is to provide a carbon-based composite material as a catalyst and catalyst support and to improve its performance.

10. The tenth object of the invention is to préparé carbon-based composites material for high-performance beat exchange materials.

11. The eleventh obj ective of the invention is to préparé a carbon-based composite material for reinforcing and modifying the composites, such as carbon/CaCO₃ composite material.

12. The twelfth objective of the invention is to use the carbon-based composite material for absorbing and emitting the electromagnetic waves.

13. The thirteenth objective of the invention is to provide a carbon-based composite material for hydrogen storage materials such as carbon/Ni composites.

In order to achieve the above technical purposes, this disclosure provides a carbon-based composite material, which comprisesthe substrate, carbon film and structural carbon. The carbon film isbonded on the substrate surface and the structural carbon grows on the carbon film forming one body.

The substrate refers to ail materials that are solid at room température except organic matter. The substrate comprises, for example,métal, alloy, compound, non-metallic materials or non-metallic compound, such as copper, aluminum, nickel, iron, aluminum alloy, stainless Steel, alumina, zinc oxide, glass, Silicon, carbon, germanium, Silicon dioxide, Silicon Carbide, and the materials with surface coating such as copper nickel plating, aluminum silver plating, silver gold plating and anodized aluminum. The shape of the substrate is any shapes, comprisingone-dimensional, two-dimensional and three-dimensional structuressuch as particle, fiber, film, plate, block, solid, porous, interworking network and woven network structure. The surface area of the substrate is from 0.001 square nanometers to 1 billion square meters,

The carbon film contains the carbon element and one or more of other éléments. The content of catalyst alkali métal and alkaline earth métal éléments in the carbon film is 0.0000000000001 wt% - 99.9999wt% and the content of other éléments in the carbon film is 0.000000000000 lwt% 99.9999wt%. The thickness of the carbon film is 0.001 nm-1 mm. There is no binder between the carbon film and the substrate. The structural carbon contains the carbon and one or more of other éléments. The content of the catalyst alkali métal and alkaline earth métal éléments in the structural carbon is 0.000000000000 lwt% - 99.9999wt% andthe content of other éléments in the structural carbon is 0.000000000000 lwt% - 99.9999wt%.

The shape of structural carbon is not limited, comprising fiber, nanotubes and specialshapes such as spherical, hemispherical, flake, dendritic, spiral.

In addition, the substratecan be continuously or discontinuously covered by the carbon film and structural carbon by adjusting the coating position of the catalyst on the substrate. The area coated with the catalyst will be covered by the carbon film and structural carbon, while the area without coating the catalyst is not covered bythe carbon film and structural carbon or is covered by a different carbon material. By using thedisclosed method, the carbon-based composite material with a surface area of 0.001 square nm-1 billion square meters can be produced.

The first préparation method of carbon-based composite material according to the invention comprises the following steps:

(Al) The catalyst mixture is coated on the substrate surface followed by drying under required conditions.

(A2) The substrate loaded with the catalyst mixture is placed in a heating fumace with certain atmosphère followed by heating to a température of-50-1500°C and température holding of 0-1000 hours to décomposé, melt and mix the catalyst mixture and let the catalyst wet the substrate surface. This step is bénéficiai to the formation of carbon films and structural carbon with uniform thickness and high consistency of structure and morphology in the next step.

(A3) The fumace atmosphère is adjusted to replace the atmosphère in the step (A2) followed by adjusting the heating furnace to the reaction température of-50-1500°C. Then, the atmosphère in the heating fumace is adjusted as required followed by injecting the carbon containing organic matter into the heating fumace and température holding of 0-1000 hours. The carbon containing organic matter reacts under the action of catalyst to form the carbon film covering the substrate and structural carbon on the surface of carbon film. In some cases, the shape of the substrate can be changed after reaction. For example, the film like substrate is changed to powders and the large particle substrate is changed to smaller particle.

(A4) The fumace is tum off to let the fumace cool to -50-100°C to obtain the carbon-based composite material. During the cooling process, the fumace atmosphère is adjusted as needed to avoid side reactions.

The second préparation method of carbon-based composite according to the invention comprises the following steps:

(Bl) The catalyst mixture is coated on the substrate surface followed by drying and subsequently coating the carbon containing organic matter on the substrate to préparé the reactant. Or the catalyst mixture is mixed with the substrate, and then mixed with the carbon containing organic matter to préparé the reactant.

(B2) The reactant is placed in a heating furnace with certain atmosphère followed by heating the fumace to a température of -50-1500°C and température holding of 0-1000 hour to form the carbon film covering the substrate and structural carbon on the surface of the carbon fîlm.In some cases, the shape of the substrate can change after reaction. For example, the film like substrate is changed to powders and the large particle substrate is changed to smaller particle.

(B3) The fumace is tum off to cool the fumace to -50-100°C to obtain the carbon-based composite material. During the cooling process, the fumace atmosphère is adjusted as needed to avoid side reactions.

In the step (B 1 ), for the granular substrate, it is preferred to mix the catalyst mixture with the substrate and carbon containing organic matter to préparé the reactant. For the film, plate and block substrate, it is preferred to coat the catalyst mixture on the substrate surface followed by coating the carbon containing organic matter on the substrate to préparé the reactant.

In the preferred scheme, the atmosphère in the steps (A2), (A3) and (A4), and (B2) and (B3) is adjusted according to the actual reaction process. When the atmosphère required between adjacent steps is consistent, the adjustment of atmosphère in subséquent steps is omitted.

In the preferred scheme, the substrate to be coated in steps (Al) and (Bl) can be cleaned by various methods, such as Chemical cleaning and physical cleaning, so as to eliminate the influence of surface covering on the manufacturing process. The Chemical cleaning agent comprises éthanol, acetone, xylene, formaldéhyde, organic solvents, deionized water and surfactant. After cleaning, the substrate shall be dried under suitable conditions such as vacuum, various organic and inorganic gases, or mixed gases. Herein, the drying température is -50-1000°C, and the drying time is 0-1000 hours.Preferably further, the drying température is 50-700°C.

In the preferred scheme, in the steps (Al) and (Bl),the catalyst comprises one or more ofthe simple substances, organic compounds and inorganic compounds of ail alkali metals and + alkaline earth metals.These catalysts comprises, for example, Li, LiCl, L12CO3, LiOH, L1H2PO4, LiF, lithium acetate, lithium citrate, butyl lithium, phenyl lithium, lithium stéarate, lithium palmitate, NaCl, Na2CO₃ NaOH, NaF, sodium éthanol, sodium methoxide, sodium formate, sodium acetate, sodium citrate,KC1, K₂CO₃, KOH, KF, K₃PO₄, potassium oxalate, potassium hydrogen phthalate, RbCL, RbNO₃, rubidium acetate, rubidium oxalate CsCL, CS2CO3, CaCO₃, Ca(OH)2 CaCh, calcium gluconate, calcium lactate, calcium acetate, magnésium acetate, magnésium gluconate, MgCl₂, MgO, MgSO₄, SrCl₂, SrO, strontium gluconate, strontium acetate, barium acetate, barium citrate, BaCh, BaCO₃ and BaSO₄.

Preferably, the catalyst mixture in steps (Al) and (Bl) is a solution, suspension, paste or powder with uniform catalyst dispersion. The catalyst can be prepared into water-based, organic-based, waterand organicmixed solutions, suspensions or pastes, such as water-based, ethanol-based, acetone-based, or water/ethanol-based, acetone/ethanol-based solutions, suspensions or pastes. The mass fraction of catalyst in the catalyst mixture is usually 0.00000000 lwt% - 99.99wt%. Further, the additives, surfactant and thickeners can be added into the catalyst mixture as needed. The additivecomprisesall compounds, which are mainly used for controlling the structure and morphology ofthe structural carbon and producing the carbon-based composite/compound composite materials for hydrogen storage, catalyst and reinforcement and other functions,The additives can react with the catalyst.For example, an appropriate amount of additive FeCLis added to the catalyst LiH2PO₄ solution to préparé the carbon-based composite/LiFePO₄ composite material and the additive CoO is added to LiOH catalyst to produce carbon-based composite/LiCoO2 composite materials as the cathode materials of lithium-ion battery. The additives can also be mixed evenly with the catalyst without reacting with the catalyst. The additives are evenly distributed in the composite materials. For example, an appropriate amount of additive LiFePO₄ is added to the catalyst LiH₂PO₄ mixed solution to préparé the carbon-based composite/LiFePO₄ composite materials as the électrodes. The mass fraction of the additives in the mixture is usually 0.000000001% - 99.9999%. The additives include but are not limited to the exampleFeCh, Fe(OH)3, CuCh, ZnSÛ4, AI2O3, Fe2O3, T1O2 and Ζηθ2· At the reaction température of step (A2), the additivescan react with the catalyst to finally form the carbon-based composites/compound composites material.

Preferably, in the steps (Al) and (Bl), the catalyst mixture is coated on the substrate by spraying, dipping, wiping, scraping, brushing, drenching, wiping, roller coating, printing, and other methods. The coated substrate is then dried in any possible atmosphère, such as vacuum, air, oxygen, inert gas, hydrogen, ammonia, inorganic and organic gases and various mixed gases.Herein,the drying température is -50-700°C, and the drying time is 0-1000 hours. In the coating process, the spécifie pattern of catalyst coverage on the substrate surface can be obtained by porous template, mask and other methods.

Preferably, in the step (A2), the substrate coated with catalyst is placed in a closed heating fumace, and then the atmosphère in the heating furnace is adjusted. Then, the heating fumace is heated to a température of -50-1500°Cfollowed by température holding of 0-1000 hours. In order to avoid the occurrence of side reaction between the catalyst and air, the atmosphère in the heating fumace is adjusted according to the différence of substrate material and catalyst System. For example, if the substrate material is métal, the inert gas or organic gas or mixed gas atmosphère is used. If the substrate material is non-metallic, the inert gas, air, oxygen, organic gas or mixed gas atmosphère can be used.

Preferably, the carbon containing organic matter in steps (A3) and (Bl) includes but not limited to alcohols (such as methanol, éthanol, etc.), organic acids (such as formic acid, acetic acid, various saturated and unsaturated fatty acids, etc.), olefins, alkanes, alkynes, ketones (such as acetone, etc.), various carbonaceous gases (such as propane, methane, acetylene), sugars (such as starch, sucrose, etc.), various resins (such as phenolic resin) and mixtures of the above substances. In the step (A3), the atmosphère adjustment before the introduction of carbon containing organic matter is to eliminate the atmosphère in the previous step, and the atmosphère adjustment after the introduction of carbon containing organic matter is to avoid the side reactions or to make the gas in the atmosphère interact with carbon containing organic matter to form the carbon film and structural carbon. The heating method in the steps (A2), (A3) and (B2) comprisesany method that can be realized, including electric heating, combustion heating, optical radiation heating and electromagnetic heating.

Preferably, the atmosphère in the steps (A4) and (B3) can be adjusted to any atmosphère as needed, such as nitrogen, argon, hydrogen, or a mixture of two or more gases, such as argon/hydrogen, nitrogen/hydrogen, or methane, acetylene, propane, various organic and inorganic gases. As long as these atmosphères can avoid the side reactions in the cooling process.

Preferably, the carbon-based composite obtained in the step (A4) and (B3) can be post-treated as required such as heat treatment and coating binders.

COMPARED WITH THE PRIOR ART, THE INVENTION HAS THE FOLLOWING

BENEFICIAL EFFECTS

1. This disclosure can préparé the carbon-based composite comprising the substrate, carbon film and structural carbon, which arechemically bonded into one body. Hence, the strength of the bonding is higher, the electrical contact and beat exchange capacity is better and the property of the electrode is more stable.

2. The electrode prepared by this disclosureis lighter and thinner, simpler préparation and lower cost than the électrodes prepared by the prior art.

3. By adding the additive compounds into the catalyst, this disclosure can préparé thecomposite materials composed of the carbon-based composite materials and compound for applications comprising the electrode materials, hydrogen storage materials, catalyst material, and reinforcement materials.

4. This disclosure can préparé the carbon-based composite material comprising with Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba éléments as the électrodes

5. By changing the process parameters, such as the type and proportion of catalysts, the carbon-based composite materials with rich morphology of structural carbon can be prepared. However, the existing technology can only préparé single morphology, generally carbon fiber arrays with diameters ranging from several nanometers to several tens nanometers. The bonding force between single carbon fiber and substrate is weak.

6. This disclosure can préparé the positive and négative électrodes of batteries andcapacitor electrode, while the prior art can only préparé the positive or négative électrodes of batteries and capacitors.

7. This disclosure can modify the surface structure, morphological characteristics, conductive characteristics, thermal conductivity, gas adsorption and desorption characteristics, électron and ion transmission characteristics, absorption and émission of electromagnetic waves and other physical and Chemical characteristics of conductive and non-conductive substrates.

8. The electrode prepared by this disclosure avoids the electrostatic shielding effect due to the large space distance between the structural carbon. Therefore, the électrodes prepared by this disclosure hâve larger effective spécifie surface area, larger electrode capacity, faster reaction rate, greater photoelectric conversion efficiency and higher electrode sensitivity than the électrodes prepared by the prior art.

9. The carbon-based composite material prepared by this disclosure can be used as battery and capacitor électrodes, catalysts and catalyst carriers, varions sensors, field émission électrodes, solar cell électrodes, electrolytic water hydrogen production électrodes, photocatalytic hydrogen production materials, infrared detector électrodes, heat exchange materials, electromagnetic wave absorption and émission materials, etc. But the prior art can only produce the carbon materials with fewer applications.

10. This disclosure can greatly improve the hydrogen storage performance of the existing solid material and the mechanical properties of the interface between the solid material and the polymer.

DESCRIPTION OF ATTACHED DRAWINGS J

FIG . 1 illustrâtes a schematic description and scanning électron microscopy (SEM) photos of the carbon nanotube array deposited on Cu substrate using the existing technology.

FIG . 2 illustrâtes the SEM morphologies of the in-situ deposited carbon nanotube arrays on copper foil, copper mesh, copper braided mesh using existing technology as binder-free electrode.

FIG. 3 illustrâtes the schematic diagram and SEM morphologies of the Si/CNT electrode deposited on stainless Steel dise of 15.5 mm in diameter using existing technology.

FIG. 4 illustrâtes the schematic diagram of the carbon-based composite material produced in 10 accordance with this disclosure.

FIG. 5 illustrâtes the SEM morphologies of the carbon-based composite material produced in example 1 by using stainless Steel as substrate and K2CO3 as catalyst in accordance with this disclosure.(600 °C, 1 hour, acetylene) (a) magnification 2000, (b) magnification 10000, (c) magnification 50000

FIG. 6 illustrâtes the SEM morphologies of the carbon-based composite material producedin example 1 by using stainless Steel as substrate and NaiCOj as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnification 2000, (b) magnification 10000, (c) magnification 50000

FIG. 7 illustrâtes the SEM morphologies of the carbon-based composite material producedin 20 example 1 by using stainless Steel as substrate and L12CO3 as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnification 1000, (b) magnification 2000, (c) magnification 10000

FIG. 8 illustrâtes the SEM morphologies of the carbon-based composite material produced in example 1 by using stainless Steel as substrate and KF as catalyst in accordance with this 25 disclosure. (600°C, 1 hour, acetylene), (a) magnification 2000, (b) magnification 10000, (c) magnification 50000

FIG. 9 illustrâtes (a) TEM photos of carbon film and structural carbon formed into one body using K2CO3 catalyst and (b) TEM photos of carbon film and structural carbon formed into one body using Na2CÛ3 catalyst and (c) TEM photos of carbon film and structural carbon 30 formed into one body using Li2CO3 catalyst in accordance with this disclosure.

FIG. 10 illustrâtes the SEM photos of the carbon-based composite material produced in example 2 by using 8 um copper foil as substrate and Li2CO3 as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene)

FIG. 11 illustrâtes the SEM photos of the carbon-based composite material produced in 35 example 2 by using 8 um Cu foil as substrate and K2CO3 as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene)

FIG. 12 illustrâtes the SEM photos of the carbon-based composite material producedin example 2 by using 20um aluminium foil as substrate and K2CO3 as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene)

FIG. 13 illustrâtes the SEM photos of the carbon-based composite material producedin example 2 by using Si substrate and LÎ2CO3 catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene)

FIG. 14 illustrâtes the SEM photos of the carbon-based composite material produced in example 2 by using Silicon substrate and Li2CO3/Na2CO3/K₂CO3 (molar mass ratio 1:1:1) 45 catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnification 5000, (b) magnification 2000 TEM

FIG. 15 illustrâtes the SEM photos of the carbon-based composite material produced in example 3 by using stainless Steel as substrate and NaBr as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnification 20000, (b) magnification 50000

FIG. 16 illustrâtes the SEM photos of the carbon-based composite matériel producedin example 3 by using stainless Steel as substrate and L1H2PO4 as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnifïcation 20000, (b) magnifîcation 50000

FIG. 17 illustrâtes the SEM photos of the carbon-based composite produced in example 4 by using Silicon as substrate and Na2CO3/LiCl (molar mass ratio 1:2) as catalyst in accordance with this disclosure. (650°C, 1 hour, acetylene), (a) magnifîcation 20000, (b) magnifîcation 60000

FIG. 18 illustrâtes the SEM photos of the carbon-based composite material produced in example 5 by using Si as substrate and K₂CO3/Na2CO3 (molar mass ratio 1:1) as catalyst in accordance with this disclosure. (650°C, 1 hour, acetylene), (a) magnifîcation 3000, (b) magnifîcation 30000

FIG. 19 illustrâtes the SEM photos of the carbon-based composite material produced in example 6 by using Si as substrate and CH₃COONa as catalyst in accordance with this disclosure. (650°C, 1 hour, acetylene), (a) magnifîcation 10000, (b) magnifîcation 50000

FIG. 20 illustrâtes the SEM photos of the carbon-based composite material producedin example 6 by using Silicon as substrate and C6H₅O₇Na3.2H2O as catalyst in accordance with this disclosure. (650°C, 1 hour, acetylene), (a) magnifîcation 5000, (b) magnifîcation 30000

FIG. 21 illustrâtes the SEM photos of the carbon-based composite material producedin example 7 by using silica as substrate and KHCO3:NaHCO₃:Li2CO3=l:8:l (molar mass ratio) as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnifîcation 1000, (b) magnifîcation 5000

FIG. 22 illustrâtes the SEM photos of the carbon-based composite material producedin example 7 by using the silica as substrate and KHCO3:NaHCO3:Li₂CO3=8:l:l (molar mass ratio) as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnifîcation 5000, (b) magnifîcation 20000

FIG. 23 illustrâtes the SEM photos of the carbon-based composite material produced in example 7 by usingsilica as the substrate and KHCO3:NaHCO₃:Li2CO3=l:l:8 (molar mass d ratio) as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnifîcation 600, (b) magnifîcation 1000

FIG. 24 illustrâtes SEM photos of the carbon-based composite material produced in example 8 by using Si as substrate and KHCO3:NaHCO3:LÎ2CO3=l:8:l (molar mass ratio) as catalyst in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) magnifîcation 5000, (b) carbon film and structural carbon formed in one body

FIG. 25 illustrâtes SEM photos of the carbon-based composite material produced by using Si substrate and KHCO3:NaHCO3:Li2CO3=8:l:l (molar mass ratio) catalyst in example 8 in accordance with this disclosure (600°C, 1 hour, acetylene), (a) magnifîcation 2000, (b) magnifîcation 10000.

FIG. 26 illustrâtes the SEM photos of the carbon-based composite material produced by using Silicon substrate and KHCO3:NaHCO3:LiNO3=8:l:l (molar mass ratio) catalyst in example 9 in accordance with this disclosure (650°C, 2 hour, acetylene), (a) magnifîcation 500, (b) cross section view of structural carbon, (c) carbon film and structural carbon formed in one body, (d) carbon film and structural carbon formed in one body.

FIG. 27 illustrâtes the SEM photos of the carbon-based composite material produced by using Silicon substrate and KHCO3:NaHCO3:CsNO₃=8:l:l (molar mass ratio) catalyst in example 9 in accordance with this disclosure (650°C, 2 hour, acetylene), (a) magnifîcation 5000, (b) magnifîcation 30000.

FIG. 28 illustrâtes the SEM photos of the carbon-based composite material produced by using 8 um Cu foil as substrate and CaCh as catalyst in example 10 in accordance with this disclosure (600°C, 1 hour, acetylene), (a) magnifîcation 1000, (b) magnifîcation 3000.

FIG. 29 illustrâtes the SEM photos of the carbon-based composite material produced by using 8 um Cu foil and 50 um stainless-steel foil as the substrate and K2CO3 as catalyst in example 11 in accordance with this disclosure. (630°C, 1 hour, methane), (a) stainless Steel substrate, magnifîcation 10000, (b) stainless Steel substrate, magnifîcation 80000. (c) Cu substrate, magnifîcation 1000, (d) Cu substrate, magnifîcation 6000.

FIG. 30 illustrâtes the SEM photos of the carbon-based composite material produced by using the 8um copper foil and 50 um stainless Steel foil as substrates, and LiCl/Fe(NO₃)₃ and LiH2PO4/Fe(NO₃)₃ as catalysts in example 12 in accordance with this disclosure. (600°C, 1 hour, acetylene), (a) Cu substrate and LiCl/Fe(NO₃)₃ catalyst, magnifîcation 10000, (b) Cu substrate and LiCl/Fe(NO₃)₃ catalyst, magnifîcation 100000, (c) stainless Steel substrate and LiH2PO4/Fe(NO₃)₃ catalyst, magnifîcation 10000, (d) stainless Steel substrate and LiH2PO4/Fe(NO₃)₃ catalyst, magnifîcation 100000.

FIG. 31 illustrâtes the SEM photos of the carbon-based composite material produced by using8um copper foil as substrate and MgCl₂ as catalyst in example 13 in accordance with this disclosure. (550°C, 1 hour, acetylene), (a) magnifîcation 2000, (b) magnifîcation 5000 FIG. 32 illustrâtes the SEM photos of the carbon-based composite material produced in example 14 by using 20um nickel foil as the substrateand MgCl₂ as the catalyst in accordance with this disclosure. (530°C, 1 hour, toluene), (a) magnifîcation 10000, (b) magnifîcation 30000

FIG. 33 illustrâtes the SEM photos of the carbon-based composite material produced in example 15 by using 20umnickel foil as substrate, and MgCl₂/CaCl₂ (mass ratio 1:1) as catalystin accordance with this disclosure. (530°C, 1 hour, acetylene), (a) magnifîcation 5000, (b) magnifîcation 20000, (c) TEM, magnifîcation 4000, (d) TEM, magnifîcation 4000

FIG. 34 illustrâtes the SEM photos of the carbon-based composite material produced in example 16 by using 20um nickel foil as substrate, and Ba(NO₃)₃ as catalyst in accordance with this disclosure. (530°C, 1 hour, toluene), (a) magnifîcation 10000, (b) magnifîcation 30000

FIG. 35 illustrâtes the SEM photos of the carbon-based composite material produced in example 17 by using 8umcopper foil as substrate andBa(NO₃)₃/LiCl/FeCl₃ (mass molar ratio 1:10:0.1) as catalyst mixture and A1PO₄ as additive in accordance with this disclosure. (550°C, 1 hour, acetylene), (a) magnifîcation 5000, (b) magnifîcation 10000

FIG. 36 illustrâtes the SEM photos of the carbon-based composite material produced in example 18 by using graphite paper as substrate andBa(NO₃)₃/LiCl/FeCl₃ (mass molar ratio 1:10:0.1) as catalyst mixture in accordance with this disclosure. (550°C, 1 hour, acetylene), (a) magnifîcation 5000, (b) magnifîcation 10000

FIG. 37 illustrâtes the SEM photos of the carbon-based composite material producedin example 19 by using 8um copper foil as substrate andBa(NO₃)₃/LiCl/FeCl₃ (mass molar ratio 1:10:0.1) as catalyst mixture in accordance with this disclosure. (550°C, 1 hour, acetylene), (a) magnifîcation 10000, (b) magnifîcation 50000

FIG. 38 illustrâtes the SEM photos of the carbon-based composite material producedin example 20 by using titanium foil as substrate and LiCl as catalyst in accordance with this disclosure. (550°C, 1 hour, acetylene), (a) magnification 10000, (b) magnification 50000

FIG. 39 illustrâtes the SEM and TEM photos of the carbon-based composite material produced in example 21 by using CoO as substrate, LiCl/FeCl₃ as catalyst mixture in accordance with this disclosure. (600°C, 1 hour, polypropylene), (a) magnification 10000, (b) magnification 50000, (c)TEM magnification 8000, (d) TEM magnification 80000

FIG. 40 illustrâtes the SEM and TEM photos of the carbon-based composite material produced in example 22 by using AI2O3 as substrate, LiCl/FeCla as catalyst mixture in accordance with this disclosure. (600°C, 1 hour, vegetable oil), (a) magnification 2000, (b) magnification 10000, (c)TEM magnification 20000, (d) TEM magnification 250000 FIG. 41 illustrâtes the SEM photos of the carbon-based composite material producedin 15 example 23 by using AI2O3 as substrate andLiCl/CuC12/Ni(CH3COO)2as catalyst mixture in accordance with this disclosure. (500°C, 1 hour, acetylene)), (a) magnification 5000, (b) magnification 20000

FIG. 42 illustrâtes the SEM photos of the carbon-based composite material produced in example 24 by using CaCOs as substrate and catalyst in accordance with this disclosure. 20 (600°C, 1 hour, acetylene)), (a) magnification 2000, (b) magnification 50000

FIG. 43 illustrâtes the charge and discharge curves of the cell assembled by using (a) lithium foil and (b) composite material as the anodes and LiFePO₄ as the cathode.

DETAILED EXAMPLE DESCRITPTIONS

The examples described below aims to further explain the content of the invention, but not to limit the claim extent.

The examples described below aims to explain the method diversity of producing the carbon-based composite material in accordance with this disclosure.

The examples described below aims to show the morphological diversity of the carbon-based 30 composite material produced in accordance with this disclosure.

Examples described below aims to show the substrate, carbon film and structural carbon formed in one body of composite produced in accordance with this disclosure.

Examples described below aims to show the application of the carbon-based composite material produced in accordance with this disclosure as the anode of lithium-ion battery.

Example 1

The composite material is produced by the method as described below. 1 gram of K₂CO₃ and Li₂CO3 and KF were separately dissolved into 20 g deionized water with 1 % surfactant to préparé the catalyst solution. Then, the stainless-steel foil was coated by catalyst by spraying 40 followed by drying in an oven at 80 °C. The catalyst coated stainless Steel foil was then put into the tube fumace, followed by vacuuming the fumace and injecting the Ar gas. The fumace was then heated to 600 C at a rate of 10 °C/min, followed by température dwell for 30 min. Then, acetylene gas was inlet into the furnace at a flow rate of 100 ml/min, followed by température dwell at 600 °C for 1 hour. Then, the fumace was turn off followed by inletting the Ar gas into the fumace to let the fumace cool down at 10 °C/min to room température to get the composite materials. «

SEM (Jeol-6700) was used to examine the morphology of as fabricated composite material and the results are shown in FIG. 5. The composite material fabricated by using K2CO3 catalyst has a structural carbon of well aligned carbon nanotube array with a fiber diameter between 100 to 200 nm. The composite material fabricated by using NazCOa catalyst has a structural carbon of well aligned carbon nanotube array with a uniform fiber diameter of about 150 nm, as shown in FIG. 6. The composite material fabricated by using L12CO3 catalyst has a structural carbon of intertwined carbon nanotube with a fiber diameter and length of about 150 nm and 30 um, accordingly, as shown in FIG. 7. The composite material fabricated by using KF catalyst has a structural carbon of well aligned, but slightly bended and thin-top carbon nanotube array with a fiber diameter of about 100 nm, as shown in FIG. 8. The carbon film and structural carbon are scratched away from the substrate surface using razor blade, followed by examination using TEM. FIG. 9 shows clearly that the structural carbon is consisted of carbon nanotube, which is attached to the carbon film forming into one body.

Example 2

The carbon-based composite materials produced in this example and example 1 hâve the same structure, and the préparation method is as below.

g of K₂CO₃) and L12CO3 were dissolved into 20 g of deionized water to préparé the catalyst solution. Then, the catalyst solution was sprayed on 8 micron thick copper foil, 20 micron thick aluminum foil and Silicon wafer respectively, followed by drying them in a drying oven at 80°C. 0.3 g of K2CO3, 0.3 g of Li2CO3 and 0.3 g of Na2CÛ3 were dissolved into 20 g of deionized water to préparé the catalyst solution. Then, the catalyst solution was sprayed on the Silicon wafer, followed by drying in a drying oven. Subsequently, the dried copper foil, aluminum foil and Silicon wafer were placed in the tubular fumace, followed by vacuuming the tubular fumace and inletting argon gas, orderly. Then, the tubular fumace was heated from room température to 600°C at 10°C/min, and then the acetylene gas was introduced into the tubular fumace at 100 ml/min. After reacting at 600°C for 1 hour, the furnace was tum off and argon was introduced into the tubular fumace to let the tubular fumace cool to room température at 10°C/min to obtain copper substrate, aluminum substrate and Silicon substrate composite materials. The obtained samples were observed by jeol-6700 scanning électron microscope, then. As shown in FIG. 10, the structural carbon of copper substrate composite material prepared by L12CO3 catalyst is mainly spiral carbon fiber array with good orientation, and the fiber diameter is about 100 nm. FIG. 11 shows that the structural carbon of copper substrate composite material prepared by K2CO3 catalyst is mainly non-oriented and arbitrarily bent fibers with a fiber diameter of about 20 nm. The structural carbon of aluminum substrate composite material prepared by K2CO3 catalyst is carbon fibers with orientation and dispersed distribution, as shown in FIG. 12. The structural carbon of Silicon t substrate composite prepared by Li₂CO3 catalyst is intertwined slender carbon nanotubes with a fiber diameter of about 20 nm, as shown in FIG. 13. The structural carbon of the Silicon substrate composite materials prepared by LÎ2CO3/Na2CO3/K2CO3 mixed catalyst is a conical carbon nanotube with very good orientation, and the top diameter of the carbon nanotube is about 150 nm, as shown in FIG. 14.

Example 3

f g of sodium bromide (NaBr) and lithium dihydrogen phosphate (LiH₂PO4) were dissolved into 20 g of deionized water with 1 % surfactant to préparé the catalyst solution. The catalyst solution was then sprayed onto50 micron thick stainless-steel foil. The coated stainless-steel foil was dried in an 80°C drying oven followed by placing the sample in a tubular fumace. Then, the tubular fumace was vacuumed and injected argon. The tubular fumace was heated from room température to 650°C at 10°C/min followed by température holding of 30 minutes to ensure good contact and reaction between the catalyst and the substrate surface, so that, the thickness of the formed carbon film will be uniform, and the morphology of the formed structural carbon will be uniform. Then, the fumace température was reduced to 600°C, and the acetylene gas was introduced into the tubular fumace at 100 ml/min. After reacting at 600°C for 1 hour, argon was introduced into the tubular fumace, and the tubular fumace was cooled at 10°C/min to room température to obtain the carbon-based composite material. The morphology of composite material was observed by jeol-6700 scanning électron microscope, as shown in FIG. 15. It can be seen from the figure that the structural carbon of the composite material prepared by NaBr catalyst is a carbon nanotube array with an opening at the top, a uniform thickness and a fiber diameter of about 50 nm. The structural carbon of the composite material prepared by lithium dihydrogen phosphate (LiH₂PO₄) catalystconsists of a clustered carbon fiber array with uniform thickness and diameter of about 5 nm, as shown in FIG. 16.

Example 4

g of Na₂CO₃/LiCl (Na₂CO3:LiCl= 1:2 molar ratio) and an appropriate amount of distilled water were ground in a mortar into paste. Then, the paste catalyst is evenly coated on the Silicon wafer and dried in the drying oven. The Silicon wafer coated with catalyst was placed into the tubular fumace, followed by vacuuming the tubular fumace and injecting argon at a flow rate of 300 ml/min. Then, the furnace was heated to 650°C, followed by température dwell for 30 min. Then, acetylene was inlet into the fumace at the rate of 200 ml/min for 1 hour followed by cutting off acetylene and injecting argon to prevent oxidation of the example during coolingthe fumace to room température at 15°C/min. The prepared Silicon wafer substrate composites were observed by scanning électron microscope, as shown in FIG. 17.

Example 5

In this example, K₂CO3/Na₂CO3 (K₂CO3:Na₂CO3 =1:1, molar ratio) is used as catalyst. The catalyst and appropriate amount of water were ground into paste for use. Then, the paste catalyst was evenly smeared on the Silicon wafer followed by drying in the drying oven. The dried Silicon wafer was heated in the tubular fumace to 650°C in air atmosphère at a heating rate of 5 C/min followed bytemperature holding time of 100 minutes. Then, argon was inlet into the fumace at a flow rate of 300 ml/min for 10 minutes. Then, acetylene was inlet into fumace for 1 hour at a flow rate of 300 ml/min until the end of the reaction. Then, acetylene was eut off and argon was inlet into fumace as protective gas to prevent oxidization by air at a flow rate of 200 ml/min. When the fumace température was below 30°C, Ar gas was tum off

I and the sample was taken ont of the fumace. The morphology of composite material was observed with jeol-6700 scanning électron microscope. As shown in FIG. 18, the structural carbon consists of a curved carbon nanotube with an irregular conical structure at the bottom and a tube diameter of about 200 nm at the top.

Example 6

CH₃COONa (sodium acetate) and C6H5O7Nas-21^0 (sodium citrate) were ground into powder in a mortar. Then, appropriate amount of deionized water was added into the mortar followed by grinding the Chemicals into the paste. Then, the paste was applied evenly on the Silicon wafer followed by drying in an 80°C drying oven. After drying, the Silicon wafer was placed into the tubular fumace followed by heating to 650°C and température holding of 30 minutes. Then, the argon was inlet into the fumace at a flow rate of 300 ml/min for 10 minutes. Then, the argon was tum off followed by inletting acetylene gas at the rate of 300 ml/min for 1 hour for reaction. Then, the fumace was tumed off and the flow of acetylene was eut off. Then, argon was inlet into the furnace at a gas flow rate of 400 ml/min until the furnace température was below 30°C. The morphology of the composite material was observed by jeol-6700 scanning électron microscope. When sodium acetate is used as the catalyst, it can be seen that the structural carbon of the composite is a well oriented carbon nanotube array, which is evenly distributed, and the diameter of carbon nanotubes is about 100 nm, as shown in FIG. 19. When sodium citrate is used as the catalyst, as shown in FIG. 20, the structural carbon nanotubesof the composite are poorly oriented, and there is an emitting head on the top of the carbon nanotube. When the sample is enlarged to 30000 times, it can be seen that the carbon nanotubes is about 250 nm in diameter with rough top and burr shape. These burr like carbon structures may be caused by the residue of catalyst on the surface of carbon nanotubes.

Example 7

g of KHCOa/NaHCOa/LiiCOa^HCOaiNaHCOaiLiiCOa = 1:8:1 molar ratio), 1 g of KHCO3/NaHCO3/LÎ2CO3(KHCO3:NaHCO3:Li2CO3 = 8:1:1 molar ratio) and 1 g of KHCO3/NaHCO3/Li2CO3(KHCO3:NaHCO3:LÎ2CO3 = 1:1:8 molar ratio)were prepared. Then, an appropriate amount of waterwas added into the prepared Chemicals followed by grindinginto paste for use. Then, the paste was coatedontothe quartz followed by drying in an 80°Cdrying oven. Then, the dried quartz sheet was heated in a tubular fumace to 650°C at 5°C/min, followed by température holding of 120 minutes. Then, argon was inlet into the fumace at a flow rate of 300 ml/min for about 10 minutes. In this step, argon gas will take away the air in the tubular fumace. Then, the fumace température was reduced to 600°C followed by introducing acetylene into the fumace at the flow rate of 300 ml/min. After keeping the fumace température at 600°C for 2 hours, the acetylene gas was eut off followed by introducing argon as protective gas to prevent oxidization by air at the flow rate of 200 ml/min. The fumace wasthen cooled to about 30°C at a rate of 7°C/min. Finally, the argon was eut off and the sample was taken out. The morphology of composite material was observed with jeol-6700 scanning électron microscope. As shown in FIG. 21, the structural carbon of composite material prepared by catalyst with a KHCO3:NaHCO3:Li2CO3 = 1:8:1 is consisted of non-uniform carbon fibers with many small burr fibers on the surface of some carbon fibers. As shown in FIG. 22, the structural carbon of composite material prepared by the catalyst with a KHCO3:NaHCO3:LÎ2CO3 = 8:1:1 (molar ratio) catalyst System is like cabbage. As shown in FIG. 23, the structural carbon of composite material prepared by KHCO3:NaHCO3:Li2CO3 = 1:1:8 (molar ratio) catalyst System is like chrysanthemum coronarium. The research results show that the proportion of various éléments in the catalyst System will greatly affect the morphology of the structural carbon of carbon-based composite material.

Example 8

g of mixed catalyst KHCO3/NaHCO3/Li₂CO3 was preparedaccording to KHCO3:NaHCO3:Li2CO3 = 1:8:1 (molar ratio). 1g of mixed catalyst KHCO3/NaHCO3/Li₂CO3was prepared according to KHCO3:NaHCO3:Li2CO3 = 8:1:1 (molar ratio). Then, this catalyst mixture and an appropriate amount of water were ground into paste for use. Then, the paste was evenly coated on the Silicon wafer followed by drying in an 80°C drying oven. The dried Silicon wafer was heated in a tubular fumace to 650°C in air, with a heating rate of 5°C/min and a holding time of 120 minutes. Then, argon was inlet into the fumace at a flow rate of 300 ml/min for about 10 minutes. In this step, the air in the tubular fumace is fully discharged by argon. Then, the fumace température was reduced to 600°C followed by introducing acetylene to the fumace for 2 hours at a flow rate of 300 ml/min. After the reaction, the acetylene gas wascutoff, and then argon was introduced to tire fumace as a protective gas to prevent oxidization by air at a flow rate of 200 ml/min. The fumace was cooled to below 30°C at the rate of 7°C/min. Then, argon was tumed off and the example was taken out. The morphology of composite materialwas observed by jeol-6700 scanning électron microscope. As shown in FIG. 24, the structural carbon of composite material prepared with KHCO3:NaHCO3:LÎ2CO3 = 1:8:1 (molar ratio) catalyst System consists of conical carbon with good orientation and a small amount of carbon nanotubes. These structural carbon and carbon film form an integrated structure. As shown in FIG. 25, the structural carbon of composites prepared by KHCO3:NaHCO3:LÎ2CO3 = 8:1:1 (molar ratio) catalyst System has leek shape with good orientation.

Example 9

g of mixed catalyst with KHCO3:NaHCO₃:LiNO3 = 8:1:1 (molar ratio) and 1 g of mixed catalyst with KHCO3:NaHCO3:CsNO3 = 8:1:1 (molar ratio) were prepared. Then, these mixed catalysts were added an appropriate amount of water followed by grinding them into paste for use. The paste catalyst was evenly coated on the Silicon wafer followed by drying in an 80°C drying oven. Then, the dried Silicon wafer was placed in a tubular fumace followed by heating to 650°C at a heating rate of 5°C/min. After température holding for 100 minutes, argon was introduced into the fumace at a flow rate of 300 ml/min for 10 minutes. Then, acetylene was inlet into the fumace for 2 hours at a flow rate of 300 ml/min. After the reaction, the acetylene gas was tumed off and the argon was introduced at a flow rate of 200 ml/min as protective gas to prevent oxidation by air. When the fumace température was below 30°C, Ar gas was eut off and the sample was taken out. The morphology of composite material was observed by jeol-6700 scanning électron microscope. As shown in FIG. 26, the structural carbon of 10 composite material deposited with KHCO₃:NaHCO₃:LiNO₃ = 8:1:1 catalyst System is dendritic carbon tubes, which grow on the carbon film forming an integrated structure, and the thickness of the carbon film is about 800 nm. As shown in FIG. 27, the structural carbon of composite material prepared with KHCO₃:NaHCO₃:CsNO₃ = 8:1:1 (molar ratio) catalyst System is difficult to describe the shape in language. The great différence of the shape of the 15 two composites is due to the différence of one catalyst.

Example 10

2 g CaC12 was dissolved into 38 g of deionized water containing 0.1% surfactant TX-100 to préparé a catalyst mixture. Then, the 8 micron thick copper foil was evenly sprayed with the catalyst mixture followed by drying in a dry oven at 80°C for 20 minutes. Then, the sample was placed in a heating fumace followed by vacuuming the heating furnace and injecting acetylene gas. Then, the fumace was heated from room température to 600°C (heating time 45 25 minutes) followed by température holding of 1 hour. Finally, the power supply was tumed off to let the fumace cool naturally to 50°C, and then the sample was taken out. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 28. It can be seen from the figure that the structural carbon of the composite materialhasan irregular steep protrusion with a width of about 1 micron.

Example 11

g of K₂CO₃ was dissolved into 38 g of deionized water containing 0.1% surfactant TX-100 35 to préparé a catalyst solution. The catalyst solution was sprayed on 50 micron thick stainless-steel foil and 8 micron thick copper foil, respectively. The stainless-steel foil and copper foil were dried in a dry oven at 80°C for 20 minutes and then placed in a fumace. After vacuuming the fumace, methane gas was inlet into the fumace. Then, the fumace was heated from room température to 630°C (heating time 45 minutes) followed by température holding 40 of 1 hour. Then,the power supply was tum off to let the fumace cool naturally to 50°C, and thenthe sample was taken out. The morphology of the composite was observed by scanning électron microscope, and the results are shown in FIG. 29. It can be seen from FIGs 29a and 29b that the structural carbon deposited on stainless Steel is formed by relatively uniform 50 nm flakes and particles. It can be seen from FIGs 29c and 29d that the structural carbon 45 deposited on copper is formed by mutual bonding of strips about 500 nm wide growing in a spécifie direction.

Example 12

g of LiCl and 0.4 g of Fe(NO3)3 were dissolved into 38 g of deionized water to préparé LiCl/Fe(NO3)3 catalyst mixture. The mixture was then sprayed onto8 micron copper foil. 2 g of LiH₂PO4 and 0.4 g of Fe(NO3)3 were dissolved into 37.6 g of deionized water to préparé LiH₂PO4/Fe(NO3)3 catalyst mixture, which was sprayed onto 50 micron stainless Steel foil. Then, the above samples were dried in an 80°C drying oven for 20 minutes followed by placing the samples in a fumace. After vacuuming the fiimace, acetylene gas was inlet into fumace. Then, the fumace was heated to 600°C (heating time 45 minutes) followed by température holding of 1 hour. Then, the fumace was tum off to let it cool to 300°C followed by vacuumingthe fumace. When the fumace température was 30°C, the example was taken out for examination. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 30. It can be seen from FIGs 30a and 30b that the structural carbon of composite deposited by LiCl/Fe(NO₃)3 catalyst System consists of a curved carbon fiber with a diameter of about 50 nm, which is intertwined and bonded with t each other. It can be seen from FIGs 30c and 30d that the carbon structure of composites deposited by LiH2PO4/Fe(NO3)3 catalyst System is consisted of particles with a diameter of about 20 nm which are bonded together forming the main carbon structure with few carbon fibers of about 10 nm in diameter.

Example 13

g of MgCl₂ was dissolved into 38 g of deionized water to préparé a catalyst mixture. The 8 micron thick copper foil was evenly sprayed with the catalyst mixture followed by drying in a dry oven at 80°C for 20 minutes. Then, the sample was placed in the fumace, followed by vacuuming the fumace and injecting acetylene gas. The furnace was heated from room température to 500°C (heating time 45 minutes) and the température was hold for 1 hour. Then the power was tum off to let the fumace cool naturally. When the température of the fumace was 300°C, the fumace was vacuumed and then cooled continually to 30°C. The sample was then taken out of the fumace. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 31. It can be seen from the figure that the structural carbon of the prepared composite material is mainly composed of better oriented and regular conical structure mixed with a small amount of fibrous carbon.

Example 14

g of MgCl₂ was dissolved into 38 g of deionized water to préparé a catalyst mixture. The 20 micron thick nickel foil washed with acetone was evenly sprayed with the catalyst mixture and dried in a dry oven at 80°C for 20 minutes. Then the sample was placed in the heating fumace followed by vacuuming the fumace and injecting toluene solution. Then, the furnace was heated to 530°C (heating time 45 minutes) followed by température holding of 1 hour. Then, the fumace was tum off to let the fumace cool naturally. When the température of the heating fumace was 300 C, the fumace was vacuumed. When the fumace température was 30 C, the sample was taken out. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 32. It can be seen from the figure that the structural carbon of the prepared composite materialconsists of mainly intertwined carbon fibers with a diameter of about 50 nm and a small amount of special-shaped carbon.

Example 15

g of MgCl₂ and 1 g of CaCl₂ were dissolved into 38 g of deionized water to préparé a catalyst mixture. The 20 micron thick nickel foil washed with acetone was evenly sprayed with the catalyst mixture followed by drying in vacuum oven at 80°C for 20 minutes. Then the sample was placed in the heating fumace, followed by vacuuming and injecting acetylene gas. Then the fumace was heated from room température to 530°C (heating time 45 minutes) followed by température holding of 1 hour. Then the fumace was turn off to let the furnace cool naturally. When the température of the heating fumace was 300°C, the fumace wasvacuumed.When the fumace température was 30°C, the sample was taken out. The morphology of the sample was observed by scanning électron microscope, and the results are shown in Fig. 33. As can be seen from Fig. 33 (a) and (b), the structural carbon of the prepared composite is mainly linear and helical fibers with a diameter of about 100 nm. The electrode was scraped off the copper foil with a blade, and then observed with transmission électron microscope. It can be seen that the structural carbon is connected together through carbon film, as shown in Fig. 33 (c) and (d).

Example 16

g of Ba(NO₃)₃ was dissolved into 38 g of deionized water to préparé a catalyst mixture. The 20 micron thick nickel foil washed with acetone was evenly sprayed with the catalyst mixture and dried in a vacuum oven at 80°C for 20 minutes. Then, the sample was placed in the heating fumace followed by vacuuming the heating fumace and injecting toluene liquid. Then the fumace was heated from room température to 530°C (heating time 45 minutes) followed by température holding for 1 hour. Then the fumace was tum off to let the furnace cool naturally. When the température of the heating fumace was 300°C, the fumace was vacuumed. When the fumace température was 30°C, the sample was taken out. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 34. It can be seen from the figure that the structural carbon of the prepared composites consists of a small amount of granular carbon and fibers with a diameter of 30 to 100 nm.

Example 17

g ofBa(NO₃)₃, 20 g of LiCl and 0.2 g of FeC13 and 77.8 g of deionized water were mixed to préparé a mixed catalyst solution. 1 g of aluminum phosphate powder was dispersed in 10 g of mixed catalyst solution to préparé a mixed catalyst suspension of catalyst and solid additives. The copper foil was evenly sprayed with mixed catalyst suspension and dried in at 80°C vacuum drying oven for 20 minutes. Then, the copper foil was placed in the heating furnace followed by vacuuming and in letting acetylene gas. Then, the heating fumace was heated &om room température to 550°CfolIowed by température holding of 1 hour. Then, the fumace was tum off to cool the heating furnace to 300°C. Then, the fumace was vacuumed.When the fumace température was 30°C, the sample was taken out.The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 35. It can be seen from the figure that the structural carbon is consisted of mainly short fibrous protrusions and the aluminum phosphate powder that is adhered and wound together by long carbon fibers. The diameter of carbon fiber is 200 nm to 500 nm. This structure ensures the surface conductivity of aluminum phosphate powder and good electrical contact between aluminum phosphate and copper substrate composite.

Example 18

g of Ba(NO₃)₃, 20 of g LiCl and 0.2 g of FeCl₃ and 77.8 g of deionized water containing 1 wt% of surfactant TX-100 were mixed to préparé a mixed catalyst solution. The graphite paper was evenly sprayed with a thin layer of mixed catalyst solution followed by drying in an80°C vacuum oven for 20 minutes. Then, the samples were put into the fumace followed by vacuuming and in letting acetylene gas. Then, the fumace was heated to 550°Cfollowed by température holding for 1 hour. Then the fumace was tum off to let the fumace cool naturally. When the fumace température was 300°C, the heating fumace was vacuumed. When the fumace was 30 °C, the samples were taken out. The morphology of the sample was observed by scanning eléctron microscope, and the results are shown in FIG. 36. It can be seen from the figure that the structural carbon consists of carbon fibers with a diameter of about 20 nm, which are intertwined with each other.

Example 19

g of Ba(NO₃)₃, 20 g of LiCl, 0.2 g of FeCl₃ and 77.8 g of deionized water were mixed to préparé a mixed catalyst solution. The copper foil was evenly sprayed with mixed catalyst solution and dried in an 80°C vacuum drying oven for 20 minutes. Then, the copper foil was placed in the heating fumace followed by vacuuming the heating furnace before passing acetylene gas. The heating fumace was heated from room température to 550°C with a température dwell of 1 hour. Then, the furnace was tum off to let it cool naturally. When the température of the heating fumace is 300°C, the fumace was vacuumed. When the furnace température was 30°C, the samples were taken out. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 37. It can be seen from the figure that the structural carbon consists of a dead tree pile carbon fiber with a diameter of about 1 micron, which is evenly distributed in the intertwined carbon fibers with a diameter of about 20 nm.

Example 20

g of LiCl was dissolved into 98 g of deionized water to préparé a 2wt% catalyst solution. The 100 micron thick titanium foil was evenly sprayed with catalyst solution followed by drying in a 100°C drying oven for 10 minutes. The samples were then put into the heating fumace followed by vacuuming and inlettingacetylene gas.The fumace was then heated to 550°C with a température dwell of 1 hour. Then, the fumace was turn off followed by vacuuming the fumace at 300°C. When the fumace was cooled to 30°C, the sample was taken out. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 38. It can be seen from the figure that the structural carbon consists of granular carbon and very short carbon fïbers.

Example 21

g of LiCl and 0.2 g of FeC13 were dissolved into 38 g of deionized water to préparé the composite catalyst solution. Then, 5 g of CoO powder and 1 g of composite catalyst solution were evenly mixed and dried in a 100°C drying oven for 20 minutes followed by grinding with an appropriate number of polypropylene particles to préparé the reaction precursor. Then, the reaction precursor was put into the heating fumace followed by vacuuming and introducing nitrogen. The heating fumace was then heated to 600°C with a température dwell of 1 hour. The fumace was then tum off followed by vacuuming at 300°C. When the température of the heating fumace was 30°C, the samples were taken out. The morphology of the sample was observed by scanning électron microscope, and the results are shown in FIG. 39. It can be seen from the figure that there are short fibers of about 20 nm in diameter deposited on the surface of CoO particles. The carbon film and structural carbon on the surface of CoOsubstrate can be seen by transmission électron microscope. The thickness of the carbon film is about 20 nm, andthe structural carbon consists of short carbon nanotube and anisotropic carbon, as shown in FIG. 39 (c) and (d). The experimental results also show that the electrical conductivity between prepared CoO substrate composite materials is very good.

Example 22

The carbon-based composite materials produced in this example and example 1 hâve the same structure, and the préparation method is as below. * g of LiCl and 0.2 g of FeCl₃ were dissolved into 38 g of deionized water to préparé the composite catalyst solution. Then, 5 g of A1₂O₃ powder and 1 g of composite catalyst solution were evenly mixed and dried in a 100°C drying oven for 20 minutes. The dried material was ground into powder followed by mixing with an appropriate amount of unsaturated fatty acid. Then, the sample was put into the fumace followed by vacuuming and inletting nitrogen. Then, the fumace was heated to 600°C followed by température holding of 1 hour. Then, the fumace was tum off followed by vacuuming the fumace at 300°C. When the furnace température was 30 °C, the sample was taken out. The morphology of the sample was observed by scanning électron microscope. The results are shown in FIG. 40 (a) and (b). The structural carbon of particulate was deposited on A1₂O₃ particles. The samples were observed by transmission électron microscope as shown in FIG. 40 (c) and (d).The thickness of carbon film on the surface of A1₂O₃ particles is about 15 nm, and the structural carbon consists of irregular protrusions and tubes. The experimental results also show that the prepared A1₂O₃ substrate composite material hâve good electrical conductivity.

Example 23

g of LiCl, 0.2 g of CuCL and 0.2 g of nickel acetate were dissolved into 38 g of deionized water to préparé the composite catalyst solution. Then, 5 g of AI2O3 powder and 1 g of composite catalyst solution were evenly mixed and dried in a 100°C drying oven for 60 minutes. The dried material was ground into powder for use. Then, the samples were put into the heating fumace followed by heating the fumace to 500°C. Then, the fumace was vacuumed followed by inletting acetylene. The-fumace température was kept at 500°C for 1 hour followed by tuming off the fumace. When the furnace was cooled to 30°C, the sample was taken out. The morphology of the sample was observed by scanning électron microscope. The results are shown in FIG. 41 (a) and (b). The surface of AI2O3 particles is covered with intertwined carbon fïbers with a diameter of about 100 nm, and the carbon fibers grow from the carbon film on the surface of AI2O3. AI2O3 powder was white before reaction and tum grey black after reaction, indicating that the powder surface is coated with a layer of carbon film.

Example 24

In this experiment, the catalyst was prepared by precursor method. Fumaric acid and calcium hydroxide were mixed and stirred at a molar ratio of 1:1. The obtained solution was dried in a drying oven at 60°C to obtain a white powder. The powder was ground to obtain a catalyst precursor. Then, the catalyst precursor was calcined in air atmosphère at 700°C for 1 hour to obtain CaCO₃ catalyst. Then, nitrogen was inlet into the tubular fumace to clean off the air in the tubular fumace to prevent explosion. The fumace was cooled to the déposition température of 600°C, followed by cutting off nitrogen and inletting acetylene for vacuumed 1 hour. After the reaction, the fumace was tum off followed by cutting off the acetylene gas and inletting a small amount of hydrogen as protective gas to prevent the déposition products from being oxidized by air. When the heating fumace température was 80°C, the sample was taken out. The sample was then observed with scanning électron microscope, and the resuit is as shown in FIG. 42. It can be seen from the figure that carbon fibers with a diameter of about 50 nm grow on the surface of CaCÜ3, and the carbon fibers are intertwined with each other.

Example 25

The electrochemical performance of the prepared composite material as the electrode of lithium-ion battery was tested as follows. The composite materialproduced by using 8um copper foil as substrate and LiCl as catalyst was eut into a 14 mm diameter dise. LiFePO₄powder, conductive graphite and PVDF were prepared into slurry at 85:5:10 mass ratio, and then the slurry was coated on the aluminum foil, followed by vacuum drying at 150°C for 8 hours to obtain LiFePO₄ positive electrode sheet. The button cells (2025) were assembled in argon (H₂O, O₂< 1 ppm) glove boxby using LiFePO₄ as cathode, copper substrate composite material and lithium métal as anodes and PP film (Celgard 2400) as separator and 1 m LiPF6 (EC/ DMC = 1:1) as electrolyte. The constant current charge and discharge performances of button cell were tested with constant current charge and discharge tester (Wuhan Land charge discharge tester). The test conditions are 2-4.2 v and current 50 mA/g. The test results are shown in FIG 43. The experimental results show that the prepared copper substrate composite material as anode has very good electrochemical properties.

Claims

1. A carbon-based composite material, which characteristics is that the carbon-based composite material comprises the substrate, carbon film and structural carbon; the carbon film is bonded to the substrate surface and the structural carbon grows on the carbon film forming one body.

2. The carbon-based composite material according to claim 1, which is characterized in that the substrate comprises ail the solid material at room température except organic matter; the shape of the substrate is not limited, comprising particle, fiber, film, plate, block, solid, hollow, porous, interworking hole, porous net and woven net; the surface area of the substrate ranges from 0.001 square nanometers to 1 billion square meters.

3. The carbon-based composite material according to claim 1, which is characterized in that the carbon film comprises carbon element; 0.000000000000 lwt%- 99.9999wt%of alkali and/or alkali earth éléments, 0.000000000000lwt% - 99.9999wt% of other éléments; the thickness of the carbon film is O.OOlnm-lmm; the carbon film is continuous or discontinuous covering the substrate.

4. The carbon-based composite material according to claim 1, which is characterized in that the structural carbon comprises carbon element, 0.0000000000001 wt% - 99.9999wt%of alkali and/or alkali earth éléments, 0.000000000000 lwt% - 99.9999wt%of other éléments; the structural carbon comprises the carbon containing material with arbitrary shape including regular and irregular fiber, nanotube, flake and special-shaped.

5. A préparation method of carbon-based composite material according to any one of daims 1-4, which is characterized in that it comprises the following steps:

(Al) the catalyst mixture is coated on the substrate surface foliowed by drying under required conditions;

(A 2) the substrate loaded with catalyst mixture is placed in a heating furnace with certain atmosphère, followed by heating the heating furnace to a température of -50-1500°C foliowed by the température holding of 0-1000 hours to let the catalyst mixture décomposé, melt, mix and wet the substrate surface;

(A 3) the atmosphère in the heating furnace is adjusted to replace the atmosphère in the step (A2), followed by adjusting the heating furnace to a reaction température of -50-1500°C and adjusting the atmosphère in the heating furnace according to the need, then the carbon containing organic matter is inlet into the heating furnace followed by température holding of 0-1000 hours; wherein the carbon containing mater react with catalyst forming the carbon film and the structural carbon on the substrate surface;

(A4) the heating furnace is tum off to cool the furnace to -50-100°C to obtain the carbon-based composite material; wherein the furnace atmosphère is adjusted as needed to avoid the side reaction during the cooling process.

in the step (A2)„ (A3) and (A4), the atmosphère is adjusted as needed; if the atmosphère needed between adjacent step is the same, the adjustment is omitted;

or includes the following steps:

(Bl ) the catalyst mixture is coated on the substrate surface followed by drying and coating the carbon containing organic matter to préparé the reaction precursor; or the catalyst mixture is mixed with the substrate followed by mixing with carbon containing organic matter to préparé the reaction precursor;

(B2 ) the reaction precursor is heated in a heating fumace with required atmosphère to a température of -50-1500°C followed by température holding of 0-1000 hours;

(B3 ) the heating fumace is tum off to let the fumace cool to -50-100°C to obtain carbon-based composite material; wherein the furnace atmosphère is adjusted as needed to avoid the side reaction during the cooling process.

m;SteK(BL),ior_fpartiçnlate substrate, it is.particulanappropriate.to^mix the. catalyst; mixture; substrate and carbon containing organic matter to préparé the precursor; while for film; plate « *........ «JL y «to » and ibulki substrate; « itiissparticular appropnateîtœcoatethewatalÿst «mixture : andicarbon ^rtv ^J '' 'y χί' î<S.--’ <’if . “x — lwO.XXX 4 / ' ίν::ϊ:ΐϊΐ;;ΐϊ;^ Ύ' ^:,i/' 'ν'·. .-: J:.-J., i contamingî orgamcimatter onto · the substrateTo; préparéethe: precursor; -jγ;y..; , > - ; ' - ^--- ; - « 4^ «««»«,. / ih ste&(B2)farid;(B3);fËê&tmo^phere isâ^üstê^^ betweensthe adjacent stefeiTs the same, the atmospherëXadjustmehtis”bmittëdl ri

6. The préparation method of carbon-based composite material according to claim 5, which is characterized in that the substrate to be coated in steps (Al) and (Bl) is cleaned by various methods followed by drying under appropriate conditions; herein the drying température is -50-1000°C, and the drying time is 0-1000 hours; the catalyst mixture is coated on the substrate by any realizable methods including spraying, dipping, wiping, scraping, brushing, drenching, wiping, roller coating, printing, printing followed by drying in any suitable atmosphère; the catalyst in steps (Al) and (Bl) comprises one or more of the simple substances, organic compounds and inorganic compounds of ail alkali metals and alkaline earth metals.

7. The préparation method of carbon-based composite materials according to claim 6, which is characterized in that the catalyst mixture comprises uniformly dispersed solution, suspension, paste or powder comprising one or more kinds of catalysts; wherein the catalyst content is usually 0.00000001wt%-99wt%.

8. The préparation method of carbon-based composite material according to claim 7, which is characterized in that the catalyst mixture comprises the additive, surfactant and thickeners as needed; the additive comprises ail compounds and is used for applications comprising morphology control of structural carbon and production of the carbon-based-composite/compound composite; the mass fraction of additive, surfactant and thickener in the catalyst mixture is both 0-99%; the carbon containing organic matter in steps (A3) and (B 1 )comprises ail the carbon containing organic matter, comprising alcohols, organic acids, alkenes, alkanes, alkynes, ketones, various carbonaceous gases, sugars, various resins and mixtures of the above substances.

9. The carbon-based composite material produced according to any one of daims 5-8 is used for applications comprising the electrode materials of capacitor and battery.