CN104843665B

CN104843665B - A kind of individual layer and multi-layer hollow Nano carbon balls, preparation and its application

Info

Publication number: CN104843665B
Application number: CN201510137088.6A
Authority: CN
Inventors: 曹安民; 池子翔; 万立骏
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2015-03-26
Filing date: 2015-03-26
Publication date: 2017-07-21
Anticipated expiration: 2035-03-26
Also published as: CN104843665A

Abstract

The characteristic that phenolic resin has the heterogeneity distribution of internal species in the course of the polymerization process is proposed, a kind of this property of utilization phenolic resin is disclosed and prepares individual layer, the method for double-deck and multi-layer hollow carbon ball and its hollow carbon sphere prepared.In addition, using phenolic resin can different nano grain surface in-situ polymerizations property, on the one hand, multi-layer hollow structure can be prepared by way of repeatedly coating and successively corroding, on the other hand different nano particle in situ can also be packaged in cavity, so as to prepare nucleocapsid or yolk nuclear structure.Prepared hollow carbon sphere is in silicon-carbon cathode electrode material, Li S batteries, ultracapacitor, and it is heavy metal ion adsorbed in terms of have potential application value.

Description

A kind of individual layer and multi-layer hollow Nano carbon balls, preparation and its application

Technical field

The present invention relates to high polymer material and inorganic nano material synthesis field, and in particular to one kind using phenolic resin and The method that corrosive agent prepares individual layer and multi-layer hollow carbon ball nano material.

Background technology

Hollow carbon sphere is a kind of special carbon material of structure, with high-specific surface area, high porosity, excellent electric conductivity, The property such as chemical stability and heat endurance, has important in fields such as catalysis, adsorbing separation, ion exchange and electrochemical energy storages Application value., can be as accommodating the nanocages of variety classes material due to its distinctive cavity structure, thus can be additionally used in electrode Material, catalyst carrier, gas storage medium, lubricant, material adsorbing separation, drug sensor, drugrelease, artificial cell etc. are led Domain, is with a wide range of applications and by substantial amounts of concern.

At present, prepare hollow carbon sphere method various, mainly there is masterplate method, solvent-thermal method, chemical vapour deposition technique etc..Wherein Report is more and more ripe method is mainly template.Carbon ball is prepared with template, the structure and size of carbon ball can lead to The structure and yardstick for crossing control masterplate are regulated and controled, therefore can largely preparation structure is various, yardstick is homogeneous hollow carbon sphere.In State's patent 200910055527.3 uses SiO₂As masterplate, furfuryl alcohol is then added in SiO₂Surface aggregate, forms furfuryl alcohol cladding SiO₂Core shell structure, remove masterplate and high-temperature burning process finally by NaOH solution, synthesize yardstick for 80-300nm Hollow carbon sphere.But template step is relatively complicated, include combination and the step such as removal of template of template and carbon base body.This Outside, in addition it is also necessary to which substantial amounts of solvent, acid or alkali such as hydrofluoric acid, sodium hydroxide etc. remove masterplate.Therefore, develop a kind of easy to be fast Prompt method prepares hollow carbon material tool and is of great significance.

Phenolic resin is a kind of widely used polymer, with good acid resistance, mechanical property, heat resistance, It is widely used in the industries such as anticorrosion engineering, adhesive, fire proofing, grinding wheel manufacture.Phenolic resin carries out carbon at high temperature Change, graphited carbon can be produced, with good electric conductivity, widely should also have on the electrochemical devices such as battery, electric capacity With the method for preparing phenolic resin hollow ball based on masterplate method also has been reported that in the literature, such as A.B.Fuertes, P.V.- Vigón,M.Sevilla,Chem.Commun.2012,48,6124-6126；X.Fang,S.Liu,J.Zang,C.Xu, The work such as M.S.Zheng, Q.F.Dong, D.Sun, N.Zheng, Nanoscale2013,5,6908-6916..

Present invention discover that and proposing a kind of method that phenolic resin individual layer and multi-layer hollow are largely prepared without template. This method is simple to operate, and reaction is gentle, can be homogeneous by one-step synthesis reaction preparation scale, the hollow carbon sphere of morphology controllable.It is logical The regulation and control to polymer polymerizing degree are crossed, can be complete with the yolk-shell of one-step synthesis interior solid outer hollow and entirety The carbon ball structure of mesoporous distribution.In addition, the property coated using phenolic resin in variable grain surface in situ, on the one hand can lead to Cross repeatedly cladding individual layer hollow ball and the mode successively corroded prepares multi-layer hollow structure, on the other hand, can also will be different Nano particle is fitted into cavity, prepares the hollow carbon sphere composite with yolk-shell structure.Prepared hollow carbon sphere is in silicon Have in terms of Carbon anode electrode material, Li-S batteries, ultracapacitor, and heavy metal ions in wastewater absorption and potentially should With value.

The content of the invention

Present invention finds a kind of intrinsic characteristic of phenolic resin polymerization, and based on a kind of this individual layer of offer and multi-layer hollow The preparation method of carbon ball nano material.It was found that there is inside and outside polymerization journey during polymerization forms polymer globules in phenolic resin Inhomogenous characteristic is spent, the component inside degree of polymerization of bead is less than the outside than internal " solid " of the outer section of ball, i.e. bead. By selecting suitable solvent (i.e. corrosive agent), using the dissolubility difference of inside and outside composition, can by inside it is softer into Part selective removal, and outside more solid composition is retained, so as to form cavity structure.On this basis, by right The regulation and control of polymer drops bulk polymerization degree, the yolk-shell and entirety that can also further synthesize interior solid outer hollow is complete The carbon ball structure of mesoporous distribution.On the other hand, using phenolic resin polymerisation the characteristics of variable grain surface in situ is coated, Can be by synthesized single polymer layer hollow ball or hollow carbon sphere as core, first in one or more layers phenolic resin of its Surface coating Polymer, every layer of polymeric layer coated is equally divided into internal soft composition and outside solid composition, therefore by multiple Cladding and the mode successively corroded not only can further synthesize two layers, three layers or multiple layer polymer hollow ball and corresponding many Layer carbon hollow ball, utilizes this principle, additionally it is possible to which phenolic resin is first coated on to the mode general that various nano grain surfaces corrode again Various nano particle in situ are loaded in cavity, form core shell structure (core-shell structure) or yolk-nuclear structure (yolk-shell structure).Fig. 1 is schematic diagram of the invention.

The invention provides individual layer and multi-layer hollow carbon ball nano material preparation method, operating method is simple, reaction Mild condition, can by amplification test batch sintetics, be advantageously applied in actual production.

The preparation method of the hollow carbon sphere, is divided into method A and method B according to pattern and yardstick；

Wherein method A comprises the following steps：

A1 phenolic compound) is placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, fully dissolving is adjusted The pH value of solution is saved, the aqueous solution for then adding aldehyde compound stirs a period of time at a certain temperature；

A2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains single polymer layer hollow Ball, i.e. intermediate product II；

A3) by step a2) gained intermediate product II calcined, naturally cool to room temperature, obtain inside be distributed with it is mesoporous Individual layer hollow carbon sphere II.

Its external diameter is 300-350nm, internal diameter 240-260nm, and wall thickness 30-50nm, pore volume is 0.6-1.2cm³/ g, compares table Area is 1400-1800m²/g。

Wherein method B comprises the following steps：

B1) phenolic compound is placed in the in the mixed solvent of water, organic solvent or water and organic solvent composition, it is fully molten Solution, adjusts the pH value of solution, and the aqueous solution for then sequentially adding quaternary ammonium salt cationic surfactant and aldehyde compound exists A period of time is stirred at certain temperature；

B2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains intermediate product III；

B3) by step b2) gained intermediate product III calcined, naturally cool to room temperature, obtain inside be distributed with it is mesoporous Individual layer hollow carbon sphere III.

Its external diameter is 500-800nm, internal diameter 400-600nm, and wall thickness 50-150nm, pore volume is 0.6-0.9cm³/ g, than Surface area is 1000-1300m²/g。

In above method A and method B, when the solubility of phenol and aldehyde is very high, in a short time due to the interior polymeric speed of ball Degree is accelerated, and extent of polymerization is high, it is impossible to which the agent that is corroded again is corroded., can be in outer layer after the solubility of phenol and aldehyde drops to a certain degree Coat and corroded, thus using inside the method one-step synthesis equipped with novalac polymer medicine ball and carbon ball Yolk-shell hollow-core constructions.In addition, controlling the polymer degree of polymer drops can be with one by adjusting the solubility of phenol and aldehyde The carbon ball structure of the overall complete mesoporous distribution of step synthesis.In addition, in addition to above-mentioned pattern, by adjusting phenol and aldehyde in method B The concentration of concentration or quaternary ammonium salt cationic surfactant, can be tubulose by the carbon ball structure control of gained.

Using the unique growth pattern of phenolic resin, the caustic solution that the present invention is provided can be further used for preparing it is double-deck and The hollow carbon sphere of multilayer, the double-layer hollow carbon ball has following structure, one outer layer external diameter 300-350nm, internal diameter 220- 250nm, wall thickness 40-60nm, internal layer external diameter 250-290nm, wall thickness 25-35nm；Secondly internal layer external diameter 300-350nm, internal diameter 160-180nm, wall thickness 60-80nm, outer layer external diameter 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm；Thirdly being prepared into To double-layer hollow carbon ball, its internal layer external diameter is 500-600nm, internal diameter 400-420nm, wall thickness 40-80nm, outer layer external diameter about 700- 800nm, internal diameter about 600-660nm, wall thickness 20-70nm.The multi-layer hollow carbon ball is the knot for possessing above-mentioned double-layer hollow carbon ball The 3rd layer, the 4th layer, the 5th layer etc. of 3 layers, 4 layers, hollow carbon spheres such as 5 layers are further included outside structure.

Preparation method is C and method D.

Method C comprises the following steps：

C1 a certain amount of phenolic compound) is placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, filled Divide dissolving, adjust the pH value of solution, the aqueous solution for then adding aldehyde compound stirs a period of time at a certain temperature；

C2) in step c1) in add a certain amount of phenolic compound again, continue to stir, repeat n addition a certain amount of Phenolic compound, continue stir, wherein n be selected from 0 or 1,2,3 etc. natural number；

C3 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains intermediate product V；

C4) by step c3) gained intermediate product V calcined, naturally cool to room temperature, obtain double-layer hollow carbon ball V.

During n=0, gained double-layer hollow carbon ball, internal layer external diameter 300-350nm, internal diameter 160-180nm, wall thickness 60-80nm, Outer layer external diameter 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm.3 layers, 4 layers, 5 layers are obtained during the natural numbers such as n=1,2,3 Hollow carbon sphere.

Method D comprises the following steps：

D1) a certain amount of phenolic compound is placed in the in the mixed solvent of water, organic solvent or water and organic solvent composition, Fully dissolving, adjusts the pH value of solution, then sequentially adds the water-soluble of quaternary ammonium salt type cationic surface active and aldehyde compound Liquid, stirring at a certain temperature is for a period of time；

D2) in step d1) in add a certain amount of phenolic compound again, continue to stir, repeat n addition a certain amount of Phenolic compound, continue stir, wherein n be selected from 0 or 1,2,3 etc. natural number；

D3 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains intermediate product VI；

D4) by step d3) gained intermediate product VI calcined, naturally cool to room temperature, obtain double-layer hollow carbon ball VI.

During n=0, gained double-layer hollow carbon ball, its internal layer external diameter is 500-600nm, internal diameter 400-420nm, wall thickness 40- 80nm, outer layer external diameter about 700-800nm, internal diameter about 600-660nm, wall thickness 20-70nm.3 are obtained during the natural numbers such as n=1,2,3 Layer, 4 layers, 5 layers of hollow carbon sphere.

It is adapted to the property of the various particles of cladding using phenolic resin, is successively corroded again by foregoing multiple cladding Mode prepares the hollow-core construction of double-deck and multilayer, and encapsulates in the cavity of carbon ball various nano-particles.

Therefore, the application, which further provides for a kind of in-stiu coating in the cavities, hollow carbon sphere and its preparation of nano-particle Nano particle is metal nanoparticle, oxide nano particles, sulphur in method, the hollow carbon sphere of the in-stiu coating nano particle Compound nano particle, hydroxide nanoparticles, carbonate nano particle, sulfate nano particle, organic compound, macromolecule Polymer etc., nanoparticle size is 10-800nm；Metal nanoparticle is preferably the nano particles such as Ag, Au, Pd, Pt, oxidation Thing nano particle is preferably Fe₂O₃Nano particle, ZnO nano particle, CuO nano particles etc., sulfide nanoparticle is preferably FeS nano particles, ZnS nano particles, CuS nano particles etc., hydroxide nanoparticles are preferably Mg (OH)₂Nano particle, Cu(OH)₂Nano particle etc., carbonate nano particle is preferably MgCO₃Nano particle, CaCO₃Nano particle etc., sulfate nanometer Particle is preferably BaSO₄Nano particle etc.；

Specially method E and method F；

Method E：A kind of preparation method of the carbon ball for being packaged with nano-particle in the cavities and multi-layer hollow carbon ball, including Following steps：

E1 nano particle and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, Ultrasound is fully dispersed, adjusts the pH value of solution, and the aqueous solution for then adding aldehyde compound is stirred at a certain temperature, this step After reaction, there is the nano particle of phenolic resin polymer in solution for Surface coating；

E2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains being packaged with nano particle Hollow sphere polymer, be named as intermediate product VIII；

E3) by step e2) gained intermediate product VIII calcined, naturally cool to room temperature, obtain being packaged with nanometer The hollow carbon sphere final product VIII of grain.

When nano particle is the hollow carbon sphere that method A, B, C, D are prepared, then products therefrom is multilayer carbon hollow ball.

Method F：A kind of preparation method of the carbon ball for being packaged with nano-particle in the cavities and multi-layer hollow carbon ball, including Following steps：

F1 nano particle and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, Ultrasound is fully dispersed, adjusts the pH value of solution, then sequentially adds quaternary ammonium salt cationic surfactant and aldehyde compound The aqueous solution stir at a certain temperature；

F2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains intermediate product IX；

F3) by step f2) gained intermediate product IX calcined, naturally cool to room temperature, obtain final product IX.

It can be reduced using some precious metal salts by phenols or aldehyde compound, the particle of in-situ preparation metal nano can lead to The method for crossing fabricated in situ encapsulates nano particle in the cavities.In addition, the application is also provided prepares sky by in-situ synthetic method The method of the carbon ball of metal nanoparticle, specially method G and method H are packaged with chamber.

Method G：A kind of method that the carbon ball that metal nanoparticle is packaged with cavity is prepared by in-situ synthetic method, bag Include following steps：

G1 precious metal salt and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, Fully dissolving, adjusts the pH value of solution, and the aqueous solution for then adding aldehyde compound is stirred at a certain temperature, this step reaction Afterwards, there is the nano particle of phenolic resin polymer in solution for Surface coating；

G2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains intermediate product XI；

G3) by step g2) gained intermediate product XI calcined, naturally cool to room temperature, obtain final product XI.

Method H：A kind of method that the carbon ball that metal nanoparticle is packaged with cavity is prepared by in-situ synthetic method, bag Include following steps：

H1 precious metal salt and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, Fully dissolving, adjusts the pH value of solution, then sequentially adds the water of quaternary ammonium salt cationic surfactant and aldehyde compound Solution is stirred at a certain temperature, after this step reaction, there is the nano particle of phenolic resin polymer in solution for Surface coating；

H2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains intermediate product XII；

H3) by step h2) gained intermediate product XII calcined, naturally cool to room temperature, obtain final product XII.

Using the physicochemical properties of the loose and porous structure of carbon material in itself, and high-specific surface area, institute may be implemented in State and the strong non-metal simple-substance of mobility after low melting point and melting is encapsulated in the carbon ball containing hollow-core construction.

In addition, the application, which is further additionally provided in, is packaged with the strong non-gold of mobility after low melting point and melting in hollow-core construction Belong to the preparation method of the carbon ball of simple substance, the non-metal simple-substance is S or Se or P etc., specially method M and method N.

Method M：A kind of carbon ball that the strong non-metal simple-substance of mobility after low melting point and melting is packaged with hollow-core construction Preparation method, comprise the following steps：

M1) hollow carbon sphere is prepared by method A, B, any one of C and D；

M2) by step m1) obtained by hollow carbon sphere mixed by a certain percentage at room temperature with low melting point non-metal simple-substance It is even；

M3) by step m2) obtained by mixture sealing, calcine at a certain temperature, naturally cool to room temperature, obtain final Product.

Method N：A kind of carbon ball that the strong non-metal simple-substance of mobility after low melting point and melting is packaged with hollow-core construction Preparation method, comprise the following steps：

N1) hollow carbon sphere is prepared by method A, B, any one of C and D；

N2) by step n1) obtained by hollow carbon sphere and low melting point non-metal simple-substance be scattered in low melting point non-metal simple-substance In solvent, it is sufficiently stirred at room temperature, and collects precipitation；

N3) by step n2) obtained by mixture dry after seal, calcine at a certain temperature, naturally cool to room temperature, obtain To final product.

Method O：Using the porous of hollow carbon sphere, the features such as high-specific surface area and good conductivity, the application provides a kind of super The preparation method of level capacitor, it comprises the following steps：

O1) by hollow carbon sphere material, carbon black, PVDF in mass ratio 85:10:5 are mixed, and paste is modulated into NMP, are applied It is distributed in foamed nickel current collector, it is many from polyethylene through 100 DEG C of drying and processings, the pole piece for rolling, diameter 12mm being made after cut-parts Pore membrane is barrier film, and two pole pieces are staggered relatively, and centre is isolated with barrier film, is added dropwise after 6mol/L KOH electrolyte, is packaged in Ultracapacitor is assembled into button cell shell；Wherein, the hollow carbon sphere is prepared according to any in method A, B, C and D.

Method P：On the other hand, prepared hollow carbon sphere is in adsorption for disposing industrial effluent in the application of heavy metal ion, Also there are larger potentiality.Therefore, the application provides a kind of method that utilization hollow carbon sphere handles industrial wastewater, and it includes following step Suddenly：

P1) the hollow carbon sphere material of certain mass is added in the aqueous solution containing certain density heavy metal ion, Use HNO₃Or NaOH adjusts the pH of solution；Suspension is sufficiently stirred for or shaken after a period of time, supernatant is collected by centrifugation, immediately Heavy metal ion content remaining in clear liquid is determined with inductively coupled plasma spectrometry；Wherein, the hollow carbon sphere is according to side It is any in method A, B, C and D to prepare.

Wherein, the step a1), b1), c), d1), e1), f1), g1), h1) in, phenolic compound is contains substituent At least one of phenol；Wherein, the substituent is selected from C1-C5 alkyl, amino, C1-C5 aminoalkyl, hydroxyl, mercapto At least one of base, nitro, sulfonic group, C1-C5 carboxyl, halogen and C1-C5 alkoxy；

The phenol containing substituent is chosen in particular from methylphenol, benzenediol, benzenetriol, amino-phenol and nitrophenol At least one of；

Wherein, the methylphenol is specially ortho-methyl phenol, m-methyl phenol or p-methyl phenol；The benzenediol tool Body is catechol, resorcinol or hydroquinones；The benzenetriol be specially pyrogaelol, oxyhydroquinone or Benzenetriol；The amino-phenol is specially o-aminophenol, m-aminophenol or para-aminophenol；The nitrophenol is specially Ortho position, meta, the nitrophenol of contraposition substitution；

The step a1), b1), c1), d1), e1), f1), g1), h1) in, aldehyde compound be selected from formaldehyde, acetaldehyde, third At least one of aldehyde and glutaraldehyde；

Wherein the mass percentage concentration of the aqueous solution of aldehyde compound is 10-40%, specially 30-40%, is more specifically 37%；

The step a1), b1), c1), d1), e1), f1), g1), h1) in, pH scopes be 5-11, regulation pH usable acids or Alkali；Described acid is hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, citric acid, at least one of acid such as ascorbic acid； The alkali is ammoniacal liquor, ethylenediamine, propane diamine, triethylamine, 1- butylamine, 2- butylamine, sodium hydroxide, at least one in potassium hydroxide Kind；

Wherein, ammoniacal liquor mass percentage concentration is 25-28%, specially 25%；

The step a1), b1), c1), d1), e1), f1), g1), h1) in, the phenolic compound and the aldehydes The amount ratio of compound is 0.5-5, preferably 1:1.1.

The step a1), b1), c1), d1), e1), f1), g1) and h1) in, the quality of phenolic compound in a solvent is dense Spend for 0.1-50mg/mL, specially 0.83mg/mL, 1.67mg/mL, 3.3mg/mL；

The step a1), b1), c1), d1), e1), f1), g1), h1) in, phenolic compound and aldehyde compound rub Your amount ratio is 0.05-30：0.05-30, specially 1：3、0.65：13.4、0.7：13.4、9.09：13.4、9.09：13.4、 18：13.4、9：13.4、27：13.4、18：13.4、18：13.4、9：13.4；

The step b1), d1), f1), h1) in, phenolic compound, aldehyde compound and cationic surfactant rub Your amount ratio is 0.05-30：0.05-30：0.1-20, specially 9:10:0.82；

The step a1), b1), c1), d1), e1), f1), g1) and h1) in solvent be organic solvent, or water is with having The mixed solution of machine solvent composition；

Wherein, described organic solvent is chosen in particular from methanol, ethanol, propyl alcohol, isopropanol, butanol, ethylene glycol, glycerine, Acetone, butanone, tetrahydrofuran, at least one of DMF and DMA；

In the mixed liquor being made up of water and organic solvent, the volume ratio of water and organic solvent is 0.5-50：1, specifically For 2:1、1:1、1.5:1；

The step e1) and f1) in, nano particle is water insoluble and organic solvent, and yardstick is 1-500nm and in height The lower pattern of temperature keeps stable metal, nonmetallic, metal oxide, nonmetal oxide, organic compound, inorganic compound or High molecular polymer, and the intermediate product containing hollow-core construction as method A, B, C, D, E, F, G, H synthesized by any one And its hollow carbon material after calcining, it is chosen in particular from Ag, Au, Pd, Si, SnO₂, TiO₂, Fe₂O₃,Fe₃O₄, SiO₂, polystyrene, It is any one in phenolic resin, porous carbon materials, intermediate product I-XII, hollow carbon sphere I-III, double-layer hollow carbon ball I-III Kind；

The step g1) and h1) in, precious metal salt is silver nitrate, gold chloride, chlorine palladium acid, any one in chloroplatinic acid；

The step b1), d1), f1) and h1) in, quaternary ammonium salt cationic surfactant is chosen in particular from alkyl trimethyl Ammonium salt type cationic surfactant, dialkyl dimethyl ammonium salt type cationic surfactant and alkyl dimethyl benzyl ammonium salt At least one of type cationic surfactant；

Wherein, described alkyl trimethyl ammonium salt type cationic surfactant is specially octyl trimethyl ammonium bromide, pungent Base trimethyl ammonium chloride, eight alkyl trimethyl ammonium bromides, eight alkyl trimethyl ammonium chlorides, ten alkyl trimethyl ammonium bromides, ten alkane Base trimethyl ammonium chloride, DTAB, DTAC, tetradecyltrimethylammonium bromination Ammonium, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, octadecyl three Methyl bromide ammonium or OTAC etc.；Described dialkyl dimethyl ammonium salt type cationic surfactant tool Body is bisoctyl dimethyl ammonium bromide, double octyldimethyl ammonium chlorides, double eight alkyl dimethyls ammonium bromides, double eight alkyl dimethyls Ammonium chloride, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double ten Dialkyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double hexadecyl two Ammonio methacrylate, DHAB, dioctadecyl dimethyl ammonium chloride or double octadecyldimethyl bromines Change ammonium；Described alkyl dimethyl benzyl ammonium salt type cationic surfactant is specially dodecyl dimethyl Benzylmagnesium chloride Ammonium, dodecyl dimethyl benzyl ammonium bromide, myristyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl bromination Ammonium, cetalkonium chloride, cetyl dimethyl benzyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride Or octadecyl dimethyl benzyl ammonium bromide；

The mass concentration of described quaternary ammonium salt cationic surfactant in a solvent is 3 × 10^-4~0.1mg/mL, it is excellent Choosing is specially 0.001mg/mL~0.009mg/mL；

The step a2), b2), c3), d3), e2), f2), g2) and h2) in, corrosive agent be selected from alcohol, ketone, acid amides, furans, At least one of alkane or halogenated hydrocarbons and its their derivative；

Wherein, the derivative of described alcohol and alcohols is specially methanol, ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, Sec-butyl alcohol, the tert-butyl alcohol, ethylene glycol or glycerine；Described ketone and its derivative is specially acetone, cyclopropanone, butanone, diacetyl Or acetylacetone,2,4-pentanedione；Described acid amides and its derivative is specially formamide, acetamide, propionamide, butyramide, N, N- dimethyl methyls Acid amides, DMA or N, N- dimethylpropionamide；Described Furan and its derivatives are specially tetrahydrofuran；Institute State alkane hydrocarbons and their derivates specially thiacyclohexane；Described halo hydrocarbons and their derivates are specially chloroform；

The step a1), b1), c1), d1), e1), f1), g1), h1) in whipping step in, temperature be -15-180 DEG C, preferably 10~30 DEG C, specially room temperature, the time is 0.01-12 hours, preferably 1~5 hour, and specially 1.5 is small When；

The step a2), b2), c3), d3), e2), f2), g2) and h2) in whipping step in, temperature be -15-180 DEG C, preferably 30-100 DEG C, specially room temperature, the time is 0.01-12 hours, preferably 1~5 hour, and specially 0.5 is small When, 1 hour；

The step c1) and d1) in whipping step in, the time be 0.01-1 hours, preferably 20 minutes~1 hour, Specially 0.5 hour；

The step c2) and d2) in whipping step in, the time be 0.01-1 hours, preferably 20 minutes~1 hour, Specially 0.5 hour；

The step a2), b2), c3), d3), e2), f2), g2) and h2) in, add volume and the step a1 of corrosive agent), B1), d1), e1), f1), g1), h1) volume ratio of reclaimed water or solvent is 0.1-100:1, specially 0.7:1；

The step a3), b3), c4), d4), e3), f3), g3) and calcining step h3) in, temperature is 500-3000 DEG C, preferably 500-1000 DEG C, concretely 700 DEG C, 800 DEG C, 900 DEG C, the time be 1-30 hours, concretely 10 hours, Heating rate is 1-20 DEG C/min, concretely 5 DEG C/min；

The atmosphere of calcining is inertia or reducing atmosphere, is chosen in particular from nitrogen, argon gas, the gaseous mixture being made up of hydrogen and argon gas With any one in the gaseous mixture being made up of nitrogen and hydrogen, more specifically can be by volume ratio be 1~5:95~99 hydrogen The gaseous mixture constituted with argon gas；

The step m2), n2) in low melting point non-metal simple-substance be specially S or Se powder；Non-metal simple-substance powder exists Carbon ball is 10~90%, preferably 50-80%, specially 50%, 60%, 70% with ratio shared in its gross mass；

The step n2) in the solvent containing non-metal simple-substance be specially carbon disulfide；Mixing time is 1-10h, tool Body is 4h；

Mass concentration of the carbon ball in the solvent containing non-metal simple-substance is 10~1000mg/mL, is specially 100mg/mL；

The step m3) and calcining step n3) in, temperature is 100-600 DEG C, concretely 155 DEG C, 300 DEG C, 400 DEG C, or it is divided to two sections to be calcined, for example first pass through 155 DEG C and pass through 300 DEG C again, and 155 DEG C are first passed through again by 400 DEG C, when Between be 1-30 hour, concretely 10 hours, heating rate was 1-20 DEG C/min, concretely 5 DEG C/min；

The atmosphere of calcining be air, inertia or reducing atmosphere, be chosen in particular from air, nitrogen, argon gas, by hydrogen and argon gas group Into gaseous mixture and the gaseous mixture that is made up of nitrogen and hydrogen in any one, it by volume ratio is 1~5 that more specifically can be:95 The gaseous mixture of~99 hydrogen and argon gas composition.

The step o1) and p1) in hollow carbon sphere material be the B by method A, C, the sky that any one of D is prepared Heart carbon ball；

The step p1) in heavy metal ion be Pb²⁺, Cd²⁺, Cu²⁺, Hg²⁺, As⁵⁺, Cr⁴⁺Etc. harmful metal from One or more in son；The concentration of heavy metal ion is 1~100mg/L, specially 10mg/L, 20mg/L, 30mg/L；It is hollow The mass ratio of the quality of carbon ball and contained precious metal ion is 1~100：1, preferably 1~10：1, specially 5：1,6：1；PH models Enclose for 2~10, specially 5；Stirring or concussion time are 1~10 hour, specially 4 hours；Stirring or concussion temperature are room temperature；

The yardstick of the individual layer hollow carbon sphere be 30-1000nm, specially 50,180,300,500nm；The multi-layer hollow The number of plies of carbon ball is 2-10, is specially bilayer, three layers, four layers, five layers.

Individual layer and the preparation method of multi-layer hollow carbon ball that the present invention is provided, simple to operate, low raw-material cost obtain carbon The yardstick of ball is homogeneous, and the number of plies of carbon ball is controllable.Various nano particles can not only be carried out with encapsulation in situ using the method and prepare egg Huang-shell structure, and prepared material is in lithium ion battery negative material, the electrochemical device such as Li-S batteries and capacitor with And heavy metal ions in wastewater absorption etc. has very big application prospect in field.

Brief description of the drawings

Fig. 1 is individual layer and the schematic diagram of multi-layer hollow carbon ball preparation method in the present invention.

Fig. 2 is the TEM figures according to the hollow carbon sphere prepared by embodiment A1.

Fig. 3 is the TEM figures according to the carbon ball of the mesoporous distribution of entirety prepared by embodiment A2.

Fig. 4 schemes according to the TEM of hollow yolk-shell structures of the inside prepared by embodiment A3 equipped with solid carbon ball.

Fig. 5 is the TEM figures according to the hollow carbon sphere prepared by embodiment B1.

Fig. 6 is the TEM figures according to the hollow carbon sphere prepared by embodiment B2.

Fig. 7 is the TEM figures according to the hollow carbon pipe prepared by embodiment B3.

Fig. 8 is the TEM figures according to the double-layer hollow carbon ball prepared by embodiment D1.

Fig. 9 is the TEM figures according to the double-layer hollow carbon ball prepared by embodiment E1.

Figure 10 is the TEM figures according to the double-layer hollow carbon ball prepared by embodiment E2.

Figure 11 is the TEM figures according to the double-layer hollow carbon ball prepared by embodiment F1.

Figure 12 is the TEM figures according to the Si@void@C core shell structures prepared by embodiment F2.

Figure 13 is according to the first charge-discharge curve of the Si@void@C samples prepared by embodiment F2 and 100 circle discharge and recharges Cycle performance figure..

Figure 14 is according to the SiO prepared by embodiment F3₂The TEM figures of@void@C core shell structures.

Figure 15 is according to the SnO prepared by embodiment F4₂The TEM figures of@void@C core shell structures.

Figure 16 is the TEM figures according to the Ag@void@C2 core shell structures prepared by embodiment G1.

Figure 17 is the TEM figures according to the Ag@void@C3 core shell structures prepared by embodiment H1.

Figure 18 is TGA (thermogravimetric analysis) figure according to the S-C electrode materials prepared by embodiment M1.

Figure 19 is the first charge-discharge curve map in the range of 1-3V according to the S-C electrode materials prepared by embodiment M1.

Figure 20 is the CV curves according to the ultracapacitor prepared by embodiment O1.

Figure 21 is measured adsorpting rate curve in embodiment P1.

Embodiment

With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute It is conventional method unless otherwise instructed to state method.The raw material can be obtained from open commercial sources unless otherwise instructed.

Embodiment A1, Application way A prepare hollow carbon sphere：

Weigh 0.1g 3- amino-phenols and be dissolved in 20ml H₂O and 10ml EtOH composition mixed solution in, add ammoniacal liquor and 1.3h is stirred after formalin at room temperature.

20ml acetone is added into reaction vessel, continues to stir 30min at room temperature, sediment is collected by centrifugation, and use second Alcohol is cleaned 2 times, and gained precipitation, which is placed in 80 DEG C of drying box, fully dries 4h, obtains intermediate product II.

Dried intermediate product II is placed in and is connected with the tube furnace of hydrogen-argon-mixed (5/95 volume %), with 5 DEG C/ Min heating rate rises to 900 DEG C from room temperature, and calcines 10h at 900 DEG C, naturally cools to room temperature and obtains inner clean Individual layer hollow carbon sphere II.

Finally give it is internal be distributed with mesoporous individual layer hollow carbon sphere, its external diameter is 300-350nm, internal diameter 240-260nm, Wall thickness 30-50nm, pore volume is 0.9685cm³/ g, specific surface area is 1504.06m²/g.

Fig. 2 is transmission electron microscope (TEM) figure of hollow carbon sphere nano material manufactured in the present embodiment, can see hollow from figure The yardstick of carbon ball is 300~350nm, and cavity diameter is about 260nm.

Embodiment A2, Application way A prepare the carbon ball structure of overall complete mesoporous distribution：

It is with embodiment A1 difference：

0.1g 3- amino-phenols are weighed in 16ml H₂In the mixed solution of O and 14ml EtOH compositions, ammoniacal liquor and first are added 45min is stirred at room temperature after aldehyde solution.

Finally giving overall distribution has mesoporous carbon ball structure, a diameter of 280-360nm of ball.

Fig. 3 is transmission electron microscope (TEM) figure of the mesoporous carbon ball structure of overall distribution manufactured in the present embodiment, can be with from figure The yardstick for seeing hollow carbon sphere is 300~350nm.

Embodiment A3, Application way A prepare the internal yolk-shell hollow-core constructions that solid carbon ball is housed：

It is with embodiment A1 difference：

0.4g 3- amino-phenols are weighed in 20ml H₂In the mixed solution of O and 10ml EtOH compositions, 0.1ml ammonia is added 1.3h is stirred at room temperature after water and 0.4ml formalins.

Finally give the internal hollow yolk-shell structures that solid carbon ball is housed.The external diameter of gained hollow carbon sphere structure 470-520nm, interior solid bulb diameter 200-250nm.

The transmission electron microscope of hollow yolk-shell carbon ball material of Fig. 4 inside manufactured in the present embodiment equipped with solid carbon ball (TEM) figure, as can be seen from the figure the external diameter of ball is about 500nm, and the diameter of interior solid ball is about 230nm.

Embodiment B1, Application way B prepare hollow carbon sphere：

Weigh 0.1g 3- amino-phenols and be dissolved in 20ml H₂In the mixed solution of O and 10ml EtOH compositions, then add 0.03g cetyl trimethylammonium bromides (CTAB) (0.082mmol).

Then sequentially add 0.1ml mass percentage concentrations is for 25% ammoniacal liquor (1.30mmol) and 0.1ml mass concentrations 37% formalin (1.34mmol), stirs 1.5h at room temperature.Into reaction vessel add 20ml acetone, at room temperature after Continuous stirring 30min, sediment is collected by centrifugation, and is cleaned 2 times with ethanol, and gained precipitation is placed in fully dry in 80 DEG C of drying box Dry 4h, obtains intermediate product III.

Dried intermediate product I is placed in and is connected with the tube furnace of hydrogen-argon-mixed (5/95 volume %), with 5 DEG C/min Heating rate rise to 900 DEG C from room temperature, and calcine 10h at 900 DEG C, naturally cool to room temperature and obtain product I II.

Finally give it is internal be distributed with mesoporous individual layer hollow carbon sphere, its external diameter is 500-800nm, internal diameter 400-600nm, Wall thickness 50-150nm, pore volume is 0.7611cm³/ g, specific surface area is 1244.21m²/g.

Fig. 5 is transmission electron microscope (TEM) figure of hollow carbon sphere nano material manufactured in the present embodiment, can see hollow from figure The yardstick of carbon ball is 500~800nm, and cavity diameter is about 400~700nm.

Embodiment B2, Application way B prepare hollow carbon sphere：

It is with embodiment B1 difference：

Weigh 0.1g 3- amino-phenols and be dissolved in 50ml H₂In the mixed solution of O and 10ml EtOH compositions.Finally give Individual layer hollow carbon sphere, external diameter 50-60nm, internal diameter about 30nm, wall thickness 10-20nm.

Fig. 6 is transmission electron microscope (TEM) figure of hollow carbon sphere nano material manufactured in the present embodiment.

Embodiment B3, Application way B prepare hollow carbon pipe：

It is with embodiment B1 difference：

Weigh 0.1g 3- amino-phenols and be dissolved in 20ml H₂In the mixed solution of O and 2ml EtOH compositions.

Hollow carbon tubular construction is finally given, caliber is 25-50nm, and wall thickness is 10-20nm.

Fig. 7 is transmission electron microscope (TEM) figure of hollow carbon pipe nano material manufactured in the present embodiment, is as can be seen from the figure managed Footpath is about 30nm, and wall thickness is about 12nm.

Embodiment C1, Application way C prepare double-layer hollow carbon ball：

1) 0.066g 3- amino-phenols (0.607mmol) are weighed and are dissolved in 14ml H₂The mixing of O and 7ml EtOH compositions is molten In liquid, it is 37% then to sequentially add ammoniacal liquor (1.30mmol) that 0.1ml mass percentage concentrations are 25% and 0.1ml mass concentrations Formalin (2.68mmol), at room temperature stir 60 minutes.It is another that 0.033g 3- amino-phenols (0.303mmol) is molten In 6ml H₂In the mixed solution of O and 3ml EtOH compositions, add in solution above, continue to react 40 minutes.Hold to reaction 22ml acetone is added in device, continues to stir 30min at room temperature, sediment is collected by centrifugation, and is cleaned 2 times with ethanol, gained sinks Shallow lake, which is placed in 80 DEG C of drying box, fully dries 4h, obtains intermediate product IV；

2) dried intermediate product II is placed in and is connected with the tube furnace of hydrogen-argon-mixed (5/95 volume %), with 5 DEG C/ Min heating rate rises to 900 DEG C from room temperature, and calcines 10h at 900 DEG C, naturally cools to room temperature, obtains double-layer hollow carbon Ball IV,

Finally give double-layer hollow carbon ball, internal layer external diameter 300-350nm, internal diameter 160-180nm, wall thickness 60-80nm, outer layer External diameter 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm.

Embodiment D1, Application way D prepare double-layer hollow carbon ball：

1) 0.1g3- amino-phenols (0.92mmol) are weighed and are dissolved in 20ml H₂The mixed solution of O and 10ml EtOH compositions In, 0.03g cetyl trimethylammonium bromides (CTAB) (0.082mmol) are then sequentially added, 0.1ml mass percentage concentrations are 25% ammoniacal liquor (1.30mmol) and 0.2ml mass concentrations is 37% formalin (2.68mmol), is stirred at room temperature 40 minutes.0.1g3- amino-phenols (0.92mmol) are added again in reaction system, continue to stir 40 minutes.To reaction vessel Middle addition 22ml acetone, continues to stir 30min at room temperature, sediment is collected by centrifugation, and is cleaned 2 times with ethanol, gained precipitation It is placed in 80 DEG C of drying box and fully dries 4h, obtains intermediate product VI；

2) dried intermediate product IV is placed in and is connected with the tube furnace of hydrogen-argon-mixed (5/95 volume %), with 5 DEG C/ Min heating rate rises to 900 DEG C from room temperature, and calcines 10h at 900 DEG C, naturally cools to room temperature and obtains double-layer hollow carbon Ball VI, its internal layer external diameter is 500-600nm, internal diameter 400-420nm, wall thickness 40-80nm, outer layer external diameter about 700-800nm, internal diameter About 600-660nm, wall thickness 20-70nm.

Fig. 8 is transmission electron microscope (TEM) figure of double-layer hollow carbon nanomaterial manufactured in the present embodiment, can from figure Go out, hollow carbon sphere has double-layer epispores, and the yardstick of internal layer carbon ball is 500-600nm, and outer layer carbon ball yardstick is 700-800nm.

Embodiment E1, Application way E prepare double-layer hollow carbon material：

Weigh 0.05g intermediate products II (being synthesized by embodiment B1 method) and 0.1g 3- amino-phenols (0.92mmol) In 20ml H₂In the mixed solution of O and 10ml EtOH compositions, ultrasonic disperse is uniform.

1.3h is stirred at room temperature after adding ammoniacal liquor and formalin.

20ml acetone is added into reaction vessel, continues to stir 30min at room temperature, sediment is collected by centrifugation, and use second Alcohol is cleaned 2 times, and gained precipitation, which is placed in 80 DEG C of drying box, fully dries 4h, obtains intermediate product VIII.

Dried intermediate product is placed in and is connected with the tube furnace of hydrogen-argon-mixed (5/95 volume %), with 5 DEG C/min Heating rate rise to 900 DEG C from room temperature, and calcine 10h at 900 DEG C, naturally cool to room temperature and obtain product VIII.

Fig. 9 is transmission electron microscope (TEM) figure of double-layer hollow carbon nanomaterial manufactured in the present embodiment.

Embodiment E2, Application way E prepare double-layer hollow carbon material

It is with embodiment E1 difference：

Weigh 0.05g intermediate products I (by embodiment A1 method synthesize) and 0.1g 3- amino-phenols (0.92mmol) in 20ml H₂In the mixed solution of O and 10ml EtOH compositions, ultrasonic disperse is uniform.

Figure 10 is transmission electron microscope (TEM) figure of double-layer hollow carbon nanomaterial manufactured in the present embodiment.

Embodiment F1, Application way F prepare double-layer hollow carbon material：

Weigh 0.05g intermediate products III (being synthesized by embodiment C1 method) and 0.1g 3- amino-phenols (0.92mmol) In 20ml H₂In the mixed solution of O and 10ml EtOH compositions, ultrasonic disperse is uniform.

Then 0.03g cetyl trimethylammonium bromides (CTAB) (0.082mmol) are added.

Then sequentially add 0.1ml mass percentage concentrations is for 25% ammoniacal liquor (1.30mmol) and 0.1ml mass concentrations 37% formalin (1.34mmol), stirs 1.5h at room temperature.Into reaction vessel add 20ml acetone, at room temperature after Continuous stirring 30min, sediment is collected by centrifugation, and is cleaned 2 times with ethanol, and gained precipitation is placed in fully dry in 80 DEG C of drying box Dry 4h, obtains intermediate product IX.

Dried intermediate product IX is placed in and is connected with the tube furnace of hydrogen-argon-mixed (5/95 volume %), with 5 DEG C/ Min heating rate rises to 900 DEG C from room temperature, and calcines 10h at 900 DEG C, naturally cools to room temperature and obtains product I X.

Figure 11 is transmission electron microscope (TEM) figure of double-layer hollow carbon nanomaterial manufactured in the present embodiment.

Embodiment F2, Application way F prepare Si@void@C core shell structures：

Weigh 0.1g granularities be 50-200nm Si powder (3.57mmol), and add 1g (9.2mmol) 3- amino-phenols in In the mixed solution of 200ml water and 100ml ethanol, 0.3g cetyl trimethylammonium bromides (CTAB) are then sequentially added The ammoniacal liquor (13mmol) that (0.82mmol), 1ml mass percentage concentrations are 25% and the formaldehyde that 1ml mass percentage concentrations are 37% are molten Liquid (13.4mmol).The core shell structure that Si nano particles are packaged in hollow carbon sphere is finally given, sample is named as Si void C。

Figure 12 is transmission electron microscope (TEM) figure of the Si@void@C samples prepared in the present embodiment.

The prepared Si@void@C composites with core shell structure can be used as Li ion battery negative poles, and its cavity can Alleviate Si in Li⁺The enormousness expansion produced during embedded and abjection, it is to avoid because electrode material is directly contacted with electrolyte Generate capacity attenuation caused by SEI films.Cathode of lithium battery is prepared from prepared Si@void@C：According to Si@void@C： Conductive black：Kynoar (PVDF)=40%：40%：20% (mass ratio) is prepared into electrode.Electrolyte component uses EC： DMC：DEC=1:1:1,1M LiPF₆It is used as lithium salts.Lithium metal is that positive pole is assembled into 2032 button cells, is in voltage range 0.01-1V(vs Li⁺/ Li) interior progress constant current charge-discharge test.The electric current of discharge and recharge is 0.05C (210mA/g).

Figure 13 is the first charge-discharge curve and 100 circle charge-discharge performance figures of Si@void@C samples.Can be with from figure Find out, Si@void@C samples are discharged first reaches 1180mAh/g, capacity is 1040mAh/g after 100 circle charge and discharge cycles, Capability retention reaches 88.1%.

Embodiment F3, Application way F prepare SiO₂@void@C core shell structures：

The step of according to embodiment F2, it is with embodiment I2 difference：

Weigh the SiO that 0.2g granularities are 200nm₂(3.33mmol) powder, and add 1g (9.2mmol) 3- amino-phenols in In mixed solution.

Figure 14 is SiO manufactured in the present embodiment₂Transmission electron microscope (TEM) figure of@void@C nucleocapsid samples.

Embodiment F4, Application way F prepare SnO₂@void@C core shell structures：

The step of according to embodiment F3, it is with embodiment F3 difference：

0.05g granularities are weighed for 30nm SnO₂(0.332mmol) powder, and add 0.1g (0.909mmol) 3- aminobenzenes Phenol finally gives SnO in the mixed solvent₂Nano particle is packaged in the dusty material of the core shell structure in hollow carbon sphere, name For SnO₂@void@C。

Figure 15 is SnO manufactured in the present embodiment₂Transmission electron microscope (TEM) figure of@void@C core shell structures.

The prepared SnO with core shell structure₂@void@C composites can be used as Li ion battery negative poles, its cavity SnO can be alleviated₂In Li⁺The enormousness expansion produced during embedded and abjection, it is to avoid because electrode material directly connects with electrolyte Touch capacity attenuation caused by generation SEI films.From prepared SnO₂@void@C prepare cathode of lithium battery：According to SnO₂@ void@C：Conductive black：Kynoar (PVDF)=60%：20%：20% (mass ratio) is prepared into electrode.Electrolyte component Using EC：DMC：DEC=1:1:1,1M LiPF₆It is used as lithium salts.Lithium metal is that positive pole is assembled into 2032 button cells, can be in electricity Pressure scope is 0.01-3V (vs Li⁺/ Li) interior progress constant current charge-discharge test.The electric current of discharge and recharge can be 100-4000mA/ g。

Embodiment G1, Application way G prepare Ag@void@C

It is with embodiment A1 difference：

Weigh 0.02g AgNO₃(0.118mmol) and 0.1g 3- amino-phenols (0.92mmol) are in 20mlH₂O and 10ml In the mixed solution of EtOH compositions, fully dissolving.Finally give the encapsulation of Ag nano particles and the core shell structure in hollow carbon sphere, life Entitled Ag@void@C-2.

Figure 16 is transmission electron microscope (TEM) figure of the Ag@void@C-2 core shell structures prepared in the present embodiment

Embodiment H1, Application way H prepare Ag@void@C core shell structures：

It is with embodiment A1 differences：

Weigh 0.02g AgNO₃(0.118mmol) and 0.1g 3- amino-phenols (0.92mmol) are in 20mlH₂O and 10ml In the mixed solution of EtOH compositions, fully dissolving.Finally give the encapsulation of Ag nano particles and the core shell structure in hollow carbon sphere, life Entitled Ag@void@C-3.

Figure 17 is transmission electron microscope (TEM) figure of the Ag@void@C-3 core shell structures prepared in the present embodiment.

Embodiment M1, Application way M the answering in terms of Li-S positive electrodes to hollow carbon sphere material load S and hollow carbon sphere With：

The individual layer hollow carbon sphere I prepared according to embodiment A1.0.06g hollow carbon sphere I and 0.14g S powder is weighed to grind in agate It is fully ground 20~30 minutes, the powder after grinding is fitted into sealed reaction vessel in alms bowl then, and vacuumize, is put into logical Have in the tube furnace that argon gas is protected, 155 DEG C risen to from room temperature with 5 DEG C/min heating rate, kept for 10 hours, then with 5 DEG C/ Min heating rate is warming up to 300 DEG C, and calcines 5h at 300 DEG C, naturally cools to room temperature, obtains loading S hollow carbon materials Material, is named as S-C.

Figure 18 is TGA (thermogravimetric analysis) curve of the S-C composites prepared, and as can be seen from the figure S load capacity is 53.72%.

Load hollow carbon sphere after S and can be used as Li-S battery electrode materials.Lithium electricity is prepared from prepared S-C composites Pond positive pole：According to S-C：Conductive black：Kynoar (PVDF)=80%：10%：10% (mass ratio) is prepared into electrode.Gold Category lithium is that negative pole is assembled into 2032 button cells, is 1-3V (vs Li in voltage range⁺/ Li) interior progress constant current charge-discharge survey Examination.Electrolyte component uses DOL：DME=1:1,1M LiTFSI is used as lithium salts.The electric current of discharge and recharge is 0.1C (~167mA/ g).Figure 19 is first charge-discharge curve of the S-C electrode materials in the range of 1-3V.It can be seen that S-C samples are first Discharge capacity is 1000mAh/g, potential to be used as Li-S battery materials.

Embodiment N1, Application way N are to hollow carbon sphere material load S.

The individual layer hollow carbon sphere I prepared according to embodiment A1.Weigh 0.06g hollow carbon sphere I and 0.14g S powder and be scattered in first In alcoholic solvent, it is sufficiently stirred at room temperature, collects precipitation, be fitted into sealed reaction vessel, and vacuumize, is put into and is connected with argon gas guarantor In the tube furnace of shield, 155 DEG C are risen to from room temperature with 5 DEG C/min heating rate, is kept for 10 hours, then with 5 DEG C/min heating Speed is warming up to 300 DEG C, and calcines 5h at 300 DEG C, naturally cools to room temperature, obtains loading S hollow carbon material.

The application of embodiment O1, hollow carbon sphere material in terms of ultracapacitor

By hollow carbon sphere material (by embodiment B1 synthesis), carbon black, PVDF in mass ratio 85:10:5 are mixed, and use NMP Paste is modulated into, is coated in foamed nickel current collector, through 100 DEG C of drying and processings, the pole rolled, diameter 12mm is made after cut-parts Piece, is barrier film from polyethylene porous membrane, and two pole pieces are staggered relatively, and centre is isolated with barrier film, and 6mol/L KOH are added dropwise After electrolyte, it is packaged in button cell shell and is assembled into ultracapacitor.Using electrochemical workstation, operating voltage 0-1V it Between with 5,10,100mV/s carry out performance tests, the specific discharge capacity of capacitor is respectively 144.8,140.7,106.2Fg^-1, figure 20 be prepared capacitor in the three kinds of CV swept under speed curves.

The application of embodiment P1, hollow carbon sphere material in terms of heavy metal ions in wastewater is adsorbed

0.05g hollow carbon spheres material (being synthesized by embodiment B1) is added to 100ml and contains Pb²⁺, Cd²⁺, Cu²⁺Ion is dense During degree is the 100mg/L aqueous solution, HNO is used₃The pH value of solution is adjusted to 5.0.Mixed liquor is stirred at room temperature 4 hours Afterwards, with 0.15 μm of membrane filtration, filtrate is collected, immediately with inductively coupled plasma spectrometry (Shimazu ICPE-9000) Determine heavy metal ion content remaining in clear liquid after different time.Figure 21 is the adsorpting rate curve of different time, from figure As can be seen that adsorption process is very fast in initial 1h, the adsorption equilibrium of three heavy metal species ions is set up after 1h.

It can be seen that the hollow carbon sphere prepared by the present invention is in silicon-carbon cathode electrode material, and Li-S batteries, ultracapacitor, and There is potential application value in terms of heavy metal ion adsorbed.

Claims

1. a kind of individual layer hollow carbon sphere, is prepared using phenolic resin and corrosive agent, its external diameter is 300-350nm, internal diameter 240-260nm, wall thickness 30-50nm, pore volume is 0.6-1.2cm³/ g, specific surface area is 1400-1800m²/ g, its preparation method Selected from method A, comprise the following steps：

A1 phenolic compound) is placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, fully dissolving is adjusted molten The pH value of liquid, the aqueous solution for then adding aldehyde compound stirs a period of time at a certain temperature；

A2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection obtains single polymer layer hollow ball, i.e., Intermediate product II；

A3) by step a2) gained intermediate product II calcined, and naturally cools to room temperature, obtain internal mesoporous list being distributed with Layer hollow carbon sphere II；

The corrosive agent is selected from alcohol, ketone, acid amides, furans, alkane or at least one of halogenated hydrocarbons and its their derivative.

2. a kind of preparation method of individual layer hollow carbon sphere, is divided into method A and method B according to pattern and yardstick；

Method A comprises the following steps：

Its external diameter of the individual layer hollow carbon sphere II is 300-350nm, internal diameter 240-260nm, wall thickness 30-50nm, and pore volume is 0.6-1.2cm³/ g, specific surface area is 1400-1800m²/g；

Method B comprises the following steps：

B1) phenolic compound is placed in the in the mixed solvent of water, organic solvent or water and organic solvent composition, fully dissolving is adjusted The pH value of solution is saved, the aqueous solution of quaternary ammonium salt cationic surfactant and aldehyde compound is then sequentially added, certain At a temperature of stir a period of time；

B3) by step b2) gained intermediate product III calcined, and naturally cools to room temperature, obtain internal mesoporous list being distributed with Layer hollow carbon sphere III；

The corrosive agent is selected from alcohol, ketone, acid amides, furans, alkane or at least one of halogenated hydrocarbons and its their derivative

Its external diameter of the individual layer hollow carbon sphere III is 500-800nm, internal diameter 400-600nm, wall thickness 50-150nm, and pore volume is 0.6-0.9cm³/ g, specific surface area is 1000-1300m²/g。

3. a kind of double-layer hollow carbon ball, it is the sol-gel growth pattern using phenolic resin, further by caustic solution Prepare,

And the preparation method of the double-layer hollow carbon ball is selected from method C and method D,

Method C comprises the following steps：

C1 a certain amount of phenolic compound) is placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, it is fully molten Solution, adjusts the pH value of solution, and the aqueous solution for then adding aldehyde compound stirs a period of time at a certain temperature；

C2) in step c1) in add a certain amount of phenolic compound again, continue to stir；

C4) by step c3) gained intermediate product V calcined, naturally cool to room temperature, obtain double-layer hollow carbon ball V；

Wherein, outside gained double-layer hollow carbon ball V, internal layer external diameter 300-350nm, internal diameter 160-180nm, wall thickness 60-80nm, outer layer Footpath 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm；

Method D comprises the following steps：

D1) a certain amount of phenolic compound is placed in the in the mixed solvent of water, organic solvent or water and organic solvent composition, fully Dissolving, adjusts the pH value of solution, then sequentially adds the aqueous solution of quaternary ammonium salt type cationic surface active and aldehyde compound, A period of time is stirred at certain temperature；

D2) in step d1) in add a certain amount of phenolic compound again, continue to stir；

D4) by step d3) gained intermediate product VI calcined, naturally cool to room temperature, obtain double-layer hollow carbon ball VI；

The corrosive agent is selected from alcohol, ketone, acid amides, furans, alkane or at least one of halogenated hydrocarbons and its their derivative；

Wherein, gained double-layer hollow carbon ball VI, its internal layer external diameter is 500-600nm, and internal diameter is 400-420nm, and wall thickness is 40- 80nm, outer layer external diameter is 700-800nm, and internal diameter is 600-660nm, and wall thickness is 20-70nm.

4. a kind of preparation method of double-deck or multi-layer hollow carbon ball, the preparation method is method C or method D；

Method C comprises the following steps：

C2) in step c1) in add a certain amount of phenolic compound again, continue to stir, repeat n a certain amount of phenol of addition Class compound, continues to stir, wherein n is selected from 0 or 1,2,3 natural number；

C4) by step c3) gained intermediate product V calcined, naturally cool to room temperature, obtains bilayer, 3 layers, 4 layers or 5 layers Hollow carbon sphere V；

Wherein, during n=0, gained double-layer hollow carbon ball V, internal layer external diameter 300-350nm, internal diameter 160-180nm, wall thickness 60- 80nm, outer layer external diameter 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm；3 are respectively obtained during the natural number of n=1,2,3 Layer, 4 layers, 5 layers of hollow carbon sphere；

Method D comprises the following steps：

D2) in step d1) in add a certain amount of phenolic compound again, continue to stir, repeat n a certain amount of phenol of addition Class compound, continues to stir, wherein n is selected from 0 or 1,2,3 natural number；

D4) by step d3) gained intermediate product VI calcined, naturally cool to room temperature, obtain bilayer, 3 layers, 4 layers or 5 layers Hollow carbon sphere VI；

Wherein, during n=0, gained double-layer hollow carbon ball VI, its internal layer external diameter is 500-600nm, and internal diameter is 400-420nm, wall thickness For 40-80nm, outer layer external diameter is 700-800nm, and internal diameter is 600-660nm, and wall thickness is 20-70nm；The natural number of n=1,2,3 When obtain 3 layers, 4 layers or 5 layers hollow carbon sphere.

5. a kind of hollow carbon sphere of in-stiu coating nano particle,

Nano particle is metal nanoparticle, oxide nano particles, sulphur in the hollow carbon sphere of the in-stiu coating nano particle Compound nano particle, hydroxide nanoparticles, carbonate nano particle, sulfate nano particle, organic compound or high score Sub- polymer, nanoparticle size is 10-800nm；

Its preparation method is method E, method F, method G or method H, wherein, utilize phenolic resin to be adapted to the various particles of cladding Property, prepares the hollow-core construction of double-deck and multilayer, and encapsulated respectively in the cavity of carbon ball by way of first coating and corroding again Nano-particle is planted, corresponding preparation method is method E or method F, if also, hollow carbon sphere is the bilayer described in claim 3 During hollow carbon sphere, the double-layer hollow carbon ball of in-stiu coating nano particle is obtained, if hollow carbon sphere is claim 4 methods described system During for obtained multi-layer hollow carbon ball, the multi-layer hollow carbon ball of in-stiu coating nano particle is obtained；Can using some precious metal salts Reduced by aldehyde compound, in-situ preparation metal nanoparticle encapsulates nano particle in the cavities using the method for fabricated in situ, Corresponding method is method G or method H；

Method E：A kind of preparation method for the carbon ball for being packaged with nano-particle in the cavities, comprises the following steps：

E1 nano particle and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, ultrasound It is fully dispersed, the pH value of solution is adjusted, the aqueous solution of aldehyde compound is then added, stirs at a certain temperature, this step is anti- There is the nano particle of novalac polymer in Ying Hou, solution for Surface coating；

E2 corrosive agent) is added, continues to stir at a certain temperature, the precipitation obtained by collection, obtains being packaged with the poly- of nano particle Compound hollow ball, is named as intermediate product VIII；

E3) by step e2) gained intermediate product VIII calcined, naturally cool to room temperature, obtain being packaged with nano particle Hollow carbon sphere final product；

Method F：A kind of preparation method for the carbon ball for being packaged with nano-particle in the cavities, comprises the following steps：

F1 nano particle and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, ultrasound It is fully dispersed, the pH value of solution is adjusted, the water of quaternary ammonium salt cationic surfactant and aldehyde compound is then sequentially added Solution, is stirred at a certain temperature；

F3) by step f2) gained intermediate product IX calcined, naturally cool to room temperature, obtain final product；

Method G：A kind of method that the carbon ball that metal nanoparticle is packaged with cavity is prepared by in-situ synthetic method, including such as Lower step：

G1 precious metal salt and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, fully Dissolving, adjusts the pH value of solution, then adds the aqueous solution of aldehyde compound, stirs at a certain temperature, molten after this step reaction There is the nano particle of novalac polymer in liquid for Surface coating；

G3) by step g2) gained intermediate product XI calcined, naturally cool to room temperature, obtain final product；

Method H：A kind of method that the carbon ball that metal nanoparticle is packaged with cavity is prepared by in-situ synthetic method, including such as Lower step：

H1 precious metal salt and phenolic compound) are placed in the in the mixed solvent that organic solvent or water are constituted with organic solvent, fully Dissolving, adjusts the pH value of solution, then sequentially adds the aqueous solution of quaternary ammonium salt cationic surfactant and aldehyde compound Stir at a certain temperature, after this step reaction, there is the nano particle of novalac polymer in solution for Surface coating；

H3) by step h2) gained intermediate product XII calcined, naturally cool to room temperature, obtain final product；

6. the hollow carbon sphere of the in-stiu coating nano particle described in claim 5, wherein,

The metal nanoparticle is selected from Ag, Au, Pd, Pt, Si nano particle, and the oxide nano particles are selected from Fe₂O₃Nanometer Particle, ZnO nano particle, CuO nano particles, SiO₂Nano particle, the sulfide nanoparticle be selected from FeS nano particles, ZnS nano particles, CuS nano particles, the hydroxide nanoparticles are selected from Mg (OH)₂Nano particle, Cu (OH)₂Nanometer Grain, the carbonate nano particle is selected from MgCO₃Nano particle, CaCO₃Nano particle, the sulfate nano particle is selected from BaSO₄Nano particle.

7. a kind of preparation method of the hollow carbon sphere of in-stiu coating nano particle,

The preparation method is method E, method F, method G or method H, wherein, utilize phenolic resin to be adapted to the various particles of cladding Property, the hollow-core construction of double-deck and multilayer is prepared by way of first coating and corroding again, and encapsulated in the cavity of carbon ball Various nano-particles, corresponding preparation method is method E or method F, if also, hollow carbon sphere is double described in claim 3 During layer hollow carbon sphere, the double-layer hollow carbon ball of in-stiu coating nano particle is obtained, if hollow carbon sphere is claim 4 methods described During the multi-layer hollow carbon ball prepared, the multi-layer hollow carbon ball of in-stiu coating nano particle is obtained；Utilize some precious metal salts It can be reduced by aldehyde compound, in-situ preparation metal nanoparticle encapsulates nanometer in the cavities using the method for fabricated in situ Grain, corresponding method is method G or method H；

Method E：A kind of preparation method for the hollow carbon sphere for being packaged with nano-particle in the cavities, comprises the following steps：

Method F：A kind of preparation method for the hollow carbon sphere for being packaged with nano-particle in the cavities, comprises the following steps：

Method G：A kind of method that the hollow carbon sphere that metal nanoparticle is packaged with cavity is prepared by in-situ synthetic method, bag Include following steps：

Method H：A kind of method that the hollow carbon sphere that metal nanoparticle is packaged with cavity is prepared by in-situ synthetic method, bag Include following steps：

8. a kind of preparation method for encapsulating the carbon ball of the strong non-metal simple-substance of mobility after low melting point and melting, the nonmetallic list Matter is S or Se or P, using the physicochemical properties of the loose and porous structure of carbon material in itself, and high-ratio surface, be may be implemented in Encapsulate the strong non-metal simple-substance of mobility after low melting point and melting in carbon ball containing hollow-core construction, preparation method be method M or Method N；

Method M：A kind of system that the carbon ball of the strong non-metal simple-substance of mobility after low melting point and melting is packaged with hollow-core construction Preparation Method, comprises the following steps：

M1) method as described in claim 2 or 4 prepares hollow carbon sphere；

M2) by step m1) obtained by hollow carbon sphere be well mixed by a certain percentage at room temperature with low melting point non-metal simple-substance；

M3) by step m2) obtained by mixture sealing, calcine at a certain temperature, naturally cool to room temperature, finally produced Thing；

Method N：A kind of system that the carbon ball of the strong non-metal simple-substance of mobility after low melting point and melting is packaged with hollow-core construction Preparation Method, comprises the following steps：

N1) choose the hollow carbon sphere described in claim 1,3 or 5 or prepare hollow carbon by the method for claim 2,4 or 7 Ball；

N2) by step n1) obtained by hollow carbon sphere and low melting point non-metal simple-substance be scattered in the solvent of low melting point non-metal simple-substance In, it is sufficiently stirred at room temperature, and collect precipitation；

N3) by step n2) obtained by mixture dry after seal, calcine at a certain temperature, naturally cool to room temperature, obtain most End-product.

9. a kind of preparation method of ultracapacitor, because hollow carbon sphere has porous, the spy of high-specific surface area and good conductivity Point, thus the preparation of ultracapacitor is used it for, method comprises the following steps：

Hollow carbon sphere, the charcoal prepared by the hollow carbon sphere described in claim 1,3 or 5 or by the method for claim 2,4 or 7 Black, PVDF, in mass ratio 85:10:5 are mixed, and paste is modulated into NMP, are coated in foamed nickel current collector, through 100 DEG C Drying and processing, the pole piece for rolling, diameter 12mm being made after cut-parts, are barrier film from polyethylene porous membrane, are put two pole pieces are relative Put, centre is isolated with barrier film, be added dropwise after 6mol/L KOH electrolyte, be packaged in button cell shell and be assembled into super capacitor Device.

10. the method according to claim 2,4 or 7, it is characterised in that：

The step a1), b1), c1), d1), e1), f1), g1), h1) in, phenolic compound be the phenol containing substituent in At least one；Wherein, the substituent be selected from C1-C5 alkyl, amino, C1-C5 aminoalkyl, hydroxyl, sulfydryl, nitro, At least one of sulfonic group, C1-C5 carboxyl, halogen and C1-C5 alkoxy；

The step a1), b1), c1), d1), e1), f1), g1), h1) in, aldehyde compound be selected from formaldehyde, acetaldehyde, propionic aldehyde and At least one of glutaraldehyde；

Wherein the mass percentage concentration of the aqueous solution of aldehyde compound is 10-40%.

11. method according to claim 10, wherein the phenol containing substituent is chosen in particular from methylphenol, benzene two At least one of phenol, benzenetriol, amino-phenol and nitrophenol.

12. method according to claim 11, wherein, the methylphenol is ortho-methyl phenol, m-methyl phenol or right Methylphenol；The benzenediol is catechol, resorcinol or hydroquinones；The benzenetriol be pyrogaelol, 1, 2,4- benzenetriols or phloroglucin；The amino-phenol is o-aminophenol, m-aminophenol or para-aminophenol；The nitre Base phenol is ortho position, meta, the nitrophenol of contraposition substitution.

13. the method according to claim 2,4 or 7, it is characterised in that：

The step a1), b1), c1), d1), e1), f1), g1), h1) in, pH scopes be 5-11, regulation pH using acid or alkali； Described acid is hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, citric acid, at least one of ascorbic acid；The alkali is ammoniacal liquor, At least one of ethylenediamine, propane diamine, triethylamine, 1- butylamine, 2- butylamine, sodium hydroxide, potassium hydroxide；

The step a1), b1), c1), d1), e1), f1), g1), h1) in, the phenolic compound and the aldehyde compound Amount ratio be 0.5-5；

The step a1), b1), c1), d1), e1), f1), g1) and h1) in, the mass concentration of phenolic compound in a solvent is 0.1-50mg/mL；

The step a1), b1), c1), d1), e1), f1), g1), h1) in, phenolic compound and aldehyde compound mole with Amount is than being 0.05-30：0.05-30；

The step b1), d1), f1), h1) in, phenolic compound, aldehyde compound and cationic surfactant mole with Amount is than being 0.05-30：0.05-30：0.1-20；

The step a1), b1), c1), d1), e1), f1), g1) and h1) in solvent be organic solvent, or water with it is organic molten The mixed solution of agent composition；

Wherein, described organic solvent is selected from methanol, ethanol, propyl alcohol, isopropanol, butanol, ethylene glycol, glycerine, acetone, fourth Ketone, tetrahydrofuran, at least one of DMF and DMA；

In the mixed liquor being made up of water and organic solvent, the volume ratio of water and organic solvent is 0.5-50：1.

14. the method according to claim 2,4 or 7, it is characterised in that：

The step e1) and f1) in, nano particle is water insoluble and organic solvent, and yardstick is 1-500nm and at high temperature Pattern keeps stable metal, nonmetallic, metal oxide, nonmetal oxide, organic compound, inorganic compound or high score Sub- polymer, and as the intermediate product containing hollow-core construction synthesized by any one of method A, B, C, D, E, F, G, H and its Hollow carbon material after calcining, it is selected from Ag, Au, Pd, Si, SnO₂, TiO₂, Fe₂O₃,Fe₃O₄, SiO₂, polystyrene, phenolic aldehyde tree Any one in fat, porous carbon materials, intermediate product I-XII, hollow carbon sphere I-III, double-layer hollow carbon ball I-III；

The step b1), d1), f1) and h1) in, quaternary ammonium salt cationic surfactant be selected from alkyl trimethyl ammonium salt type sun Ionic surface active agent, dialkyl dimethyl ammonium salt type cationic surfactant and alkyl dimethyl benzyl ammonium salt type cation At least one of surfactant.

15. the method described in claim 14, wherein, described alkyl trimethyl ammonium salt type cationic surfactant is octyl group Trimethylammonium bromide, octyltrimethylammonium chloride, eight alkyl trimethyl ammonium bromides, eight alkyl trimethyl ammonium chlorides, ten alkyl three Methyl bromide ammonium, decyl trimethyl ammonium chloride, DTAB, DTAC, 14 Alkyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, cetyl trimethyl chlorination Ammonium, Cetyltrimethylammonium bromide or OTAC；Described dialkyl dimethyl ammonium salt type cation Surfactant is bisoctyl dimethyl ammonium bromide, double octyldimethyl ammonium chlorides, double eight alkyl dimethyls ammonium bromides, double eight alkane Base alkyl dimethyl ammonium chloride, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, double dodecyl dimethyl brominations Ammonium, double dodecyl dimethyl ammonium chlorides, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double ten Six alkyl dimethyl ammonium chlorides, DHAB, dioctadecyl dimethyl ammonium chloride or double octadecyls Ditallowdimethyl ammonium bromide；Described alkyl dimethyl benzyl ammonium salt type cationic surfactant is dodecyl dimethyl benzyl chloride Change ammonium, dodecyl dimethyl benzyl ammonium bromide, myristyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl bromination Ammonium, cetalkonium chloride, cetyl dimethyl benzyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride Or octadecyl dimethyl benzyl ammonium bromide.

16. the method according to claim 2,4 or 7,

The step a1), b1), c1), d1), e1), f1), g1), h1) in whipping step in, temperature be -15-180 DEG C, when Between be 0.01-12 hours；

The step a2), b2), c3), d3), e2), f2), g2) and h2) in whipping step in, temperature be -15-180 DEG C, when Between be 0.01-12 hours；

The step c1) and d1) in whipping step in, the time be 0.01-1 hours；

The step c2) and d2) in whipping step in, the time be 0.01-1 hours；

The step a2), b2), c3), d3), e2), f2), g2) and h2) in, add volume and the step a1 of corrosive agent), b1), D1), e1), f1), g1), h1) volume ratio of reclaimed water or solvent is 0.1-100:1；

The step a3), b3), c4), d4), e3), f3), g3) and calcining step h3) in, temperature is 500-3000 DEG C, when Between be 1-30 hour, heating rate be 1-20 DEG C/min；

The atmosphere of calcining is inertia or reducing atmosphere.

17. the method described in claim 16, wherein the atmosphere of the calcining is volume ratio 1~5:95~99 hydrogen and argon gas The gaseous mixture of composition.

18. method according to claim 8, it is characterised in that：

The step m2), n2) in low melting point non-metal simple-substance be S or Se powder；Non-metal simple-substance powder is in carbon ball and its Shared ratio is 10~90% in gross mass；

The step n2) in the solvent containing non-metal simple-substance be carbon disulfide；Mixing time is 1-10h；

Mass concentration of the carbon ball in the solvent containing non-metal simple-substance is 10~1000mg/mL；

The step m3) and calcining step n3) in, temperature is 100-600 DEG C, or is divided to two sections to be calcined；

The atmosphere of calcining is air, inertia or reducing atmosphere.