CN104843665A

CN104843665A - Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof

Info

Publication number: CN104843665A
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: 2015-08-19
Anticipated expiration: 2035-03-26
Also published as: CN104843665B

Abstract

The invention discovers and proposes a characteristic that interior species of phenolic resin are nonuniform in distribution in a polymerization process, and discloses a method for preparing a hollow carbon sphere by utilizing the characteristic of phenolic resin. The method comprises: (1) putting phenol into water or a solvent, adjusting the pH, then adding aldehyde and stirring at a certain temperature for a period of time; (2) adding a corrosive agent in a reaction system, stirring at a certain temperature, and selectively removing a part with a relatively low polymerization degree inside a polymer by utilizing a solubility difference of interior species for different solvents, to obtain an intermediate product, that is, a hollow sphere of phenolic resin polymer; and (3) calcining the intermediate product that is obtained in step (2) in an inertia or reducing atmosphere, naturally cooling to room temperature, and thus completing preparation of the hollow carbon sphere. The method is simple and practicable, and the prepared hollow carbon sphere is uniform in shape and controllable in dimension. Moreover, by utilizing a characteristic that the phenolic resin can be in-situ polymerized on surfaces of different nanometer particles, on one hand, a multi-layer hollow structure can be prepared in a multi-cladding and layer-by-layer corrosion manner, and on the other hand, the different nanometer particles can also be packaged in a cavity in an in-situ mode, so as to prepare a nuclear shell or egg yolk-nuclear structure. The prepared hollow carbon sphere has a potential application value in aspects of silicon-carbon negative electrode material, Li-S battery, supercapacitor, heavy metal ion adsorption, and the like.

Description

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

Technical field

The present invention relates to macromolecular material and inorganic nano material synthesis field, be specifically related to a kind of method utilizing phenolic resin and etching reagent to prepare individual layer and multi-layer hollow carbon ball nano material.

Background technology

Hollow carbon sphere is the special carbon material of a kind of structure, there is the character such as high-specific surface area, high porosity, excellent electroconductibility, chemical stability and thermostability, have important using value in fields such as catalysis, fractionation by adsorption, ion-exchange and electrochemical energy storages.Due to its distinctive cavity structure, can be used as the nanocages holding different sorts material, thus also can be used for the fields such as electrode materials, support of the catalyst, gas storage medium, lubricant, species adsorbs separation, drug sensor, drugrelease, artificial cell, be with a wide range of applications and receive a large amount of concerns.

At present, prepare hollow carbon sphere method various, mainly contain masterplate method, solvent-thermal method, chemical Vapor deposition process etc.Wherein report that more and comparatively ripe method is mainly template.With template synthesis carbon ball, the structure of carbon ball and size can be regulated and controled by the structure and yardstick controlling masterplate, therefore can prepare the hollow carbon sphere that various structures, yardstick are homogeneous in a large number.Chinese patent 200910055527.3 adopts SiO ₂as masterplate, then add furfuryl alcohol at SiO ₂surface aggregate, forms furfuryl alcohol coated Si O ₂nucleocapsid structure, remove masterplate and high-temperature burning process finally by NaOH solution, synthesize the hollow carbon sphere that yardstick is 80-300nm.But template step is comparatively loaded down with trivial details, comprise the step such as the combination of template and carbon base body and the removal of template.In addition, a large amount of solvents, acid or alkali such as hydrofluoric acid, sodium hydroxide etc. is also needed to remove masterplate.Therefore, develop a kind of simple and efficient method to prepare hollow carbon material tool and be of great significance.

Phenolic resin is a kind of widely used polymkeric substance, has good acid resistance, mechanical property, resistance toheat, is widely used in the industries such as anticorrosion engineering, tackiness agent, fire retardant material, grinding wheel manufacture.Phenolic resin at high temperature carries out carbonization, graphited carbon can be produced, there is good conductivity, the electrochemical device such as battery, electric capacity is also widely used, also have report based on masterplate legal system in the literature for the method for phenolic resin hollow ball, such as A.B.Fuertes, P.V.-Vig ó n, M.Sevilla, Chem.Commun.2012,48,6124-6126; X.Fang, S.Liu, J.Zang, C.Xu, M.S.Zheng, Q.F.Dong, D.Sun, N.Zheng, Nanoscale2013, the work such as 5,6908-6916..

The present invention finds and proposes a kind of method preparing phenolic resin individual layer and multi-layer hollow without the need to template in a large number.The method is simple to operate, reaction temperature and, by one-step synthesis reaction preparation scale homogeneous, the hollow carbon sphere of morphology controllable.By the regulation and control to polymer polymerizing degree, can also the yolk-shell of one-step synthesis interior solid outer hollow and the carbon spherical structure of overall complete mesoporous distribution.In addition, utilize phenolic resin in the coated character of variable grain surface in situ, one side can pass through repeatedly coated individual layer hollow ball and the mode of successively corroding prepares multi-layer hollow structure, on the other hand, also can load in cavity by different nano particles, preparation has the hollow carbon sphere matrix material of yolk-shell structure.Prepared hollow carbon sphere at silicon-carbon cathode electrode materials, Li-S battery, ultracapacitor, and all there is potential using value the aspect such as heavy metal ions in wastewater absorption.

Summary of the invention

Present invention finds the intrinsiccharacteristic of a kind of phenolic resin polymerization, and the preparation method of a kind of individual layer and multi-layer hollow carbon ball nano material is provided based on this.Find that phenolic resin is formed in the process of polymer globules in polymerization and there is the inside and outside inhomogenous characteristic of extent of polymerization, the component inside polymerization degree of bead is lower than the outer section of ball, and namely the outside of bead is than inner " solid ".By selecting suitable solvent (i.e. etching reagent), utilize the dissolubility difference of inside and outside composition, can by composition selective removal softer for inside, and the comparatively solid composition in outside is retained, thus form cavity structure.On this basis, by the regulation and control to polymer drops bulk polymerization degree, the yolk-shell of interior solid outer hollow and the carbon spherical structure of overall complete mesoporous distribution also can be synthesized further.On the other hand, utilize phenolic resin polyreaction in the coated feature of variable grain surface in situ, can by synthesized single polymer layer hollow ball or hollow carbon sphere as core, first at one or more layers phenolic resin polymkeric substance of its Surface coating, every layer of coated polymer layer is divided into inner soft composition and outside solid composition equally, therefore pass through repeatedly mode that is coated and that successively corrode and not only can synthesize two layers further, three layers or multiple layer polymer hollow ball and corresponding multilayer carbon hollow ball, utilize this principle, phenolic resin first can also be coated on the mode that various nano grain surface corrodes again is loaded in cavity by various nano particle in situ, form nucleocapsid structure (core-shell structure) or yolk-nuclear structure (yolk-shell structure).Fig. 1 is schematic diagram of the present invention.

The preparation method of the individual layer that the invention provides and multi-layer hollow carbon ball nano material, working method is simple, and reaction conditions is gentle, can by amplification test batch sintetics, be conducive to being applied in actual production.

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

Wherein method A comprises the steps:

A1) phenolic compound is placed in the mixed solvent that organic solvent or water and organic solvent form, fully dissolve, the pH value of regulator solution, the aqueous solution then adding aldehyde compound stirs for some time at a certain temperature;

A2) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain single polymer layer hollow ball, i.e. intermediate product II;

A3) by step a2) gained intermediate product II calcines, naturally cools to room temperature, obtain inside and be distributed with mesoporous individual layer hollow carbon sphere II.

Its external diameter is 300-350nm, internal diameter 240-260nm, wall thickness 30-50nm, and pore volume is 0.6-1.2cm ³/ g, specific surface area is 1400-1800m ²/ g.

Wherein method B comprises the steps:

B1) phenolic compound is placed in the mixed solvent that water, organic solvent or water and organic solvent form, abundant dissolving, the pH value of regulator solution, the aqueous solution then adding quaternary ammonium salt cationic surfactant and aldehyde compound successively stirs for some time at a certain temperature;

B2) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain intermediate product III;

B3) by step b2) gained intermediate product III calcines, naturally cools to room temperature, obtain inside and be distributed with mesoporous individual layer hollow carbon sphere III.

Its external diameter is 500-800nm, internal diameter 400-600nm, wall thickness 50-150nm, and pore volume is 0.6-0.9cm ³/ g, specific surface area is 1000-1300m ²/ g.

In aforesaid method A and method B, when the solubility of phenol and aldehyde is very high, at short notice because the interior polymeric speed of ball is accelerated, extent of polymerization is high, and the agent that can not be corroded again is corroded.When the solubility of phenol and aldehyde drops to a certain degree, can corrode at external sheath, therefore can utilize this method one-step synthesis inside that the yolk-shell hollow structure of novalac polymer solid sphere and carbon ball is housed.In addition, the solubility by adjusting phenol and aldehyde controls the carbon spherical structure of the overall complete mesoporous distribution of all right one-step synthesis of polymkeric substance degree of polymer drops.In addition, except above-mentioned pattern, by regulating phenol and the concentration of aldehyde or the concentration of quaternary ammonium salt cationic surfactant in method B, the carbon spherical structure of gained can be controlled as tubulose.

Utilize the growth pattern of phenolic resin uniqueness, caustic solution provided by the invention can be further used for preparing hollow carbon sphere that is double-deck and multilayer, described double-layer hollow carbon ball has following structure, the outer external diameter 300-350nm of one, internal diameter 220-250nm, wall thickness 40-60nm, internal layer external diameter 250-290nm, wall thickness 25-35nm; Its two internal layers external diameter 300-350nm, internal diameter 160-180nm, wall thickness 60-80nm, outer external diameter 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm; It three prepares double-layer hollow carbon ball, and its internal layer external diameter is 500-600nm, internal diameter 400-420nm, wall thickness 40-80nm, and outer external diameter is about 700-800nm, and internal diameter is about 600-660nm, wall thickness 20-70nm.Described multi-layer hollow carbon ball is that the structure possessing above-mentioned double-layer hollow carbon ball comprises the hollow carbon spheres such as the 3rd layer, the 4th layer, the 5th layer etc. 3 layers, 4 layers, 5 layers outward further.

Preparation method is C and method D.

Method C comprises the steps:

C1) a certain amount of phenolic compound is placed in the mixed solvent that organic solvent or water and organic solvent form, fully dissolve, the pH value of regulator solution, the aqueous solution then adding aldehyde compound stirs for some time at a certain temperature;

C2) in step c1) in again add a certain amount of phenolic compound, continue to stir, then repeat to add a certain amount of phenolic compound for n time, continue stirring, wherein n is selected from the natural number of 0 or 1,2,3 etc.;

C3) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain intermediate product V;

C4) by step c3) gained intermediate product V calcines, naturally cools 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 external diameter 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm.N=1,2, the natural number such as 3 time obtain 3 layers, 4 layers, 5 layers hollow carbon sphere.

Method D comprises the steps:

D1) a certain amount of phenolic compound is placed in the mixed solvent that water, organic solvent or water and organic solvent form, abundant dissolving, the pH value of regulator solution, then add the aqueous solution of quaternary ammonium salt type cationic surface active and aldehyde compound successively, stir for some time at a certain temperature;

D2) in steps d 1) in again add a certain amount of phenolic compound, continue to stir, then repeat to add a certain amount of phenolic compound for n time, continue stirring, wherein n is selected from the natural number of 0 or 1,2,3 etc.;

D3) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain intermediate product VI;

D4) by steps d 3) gained intermediate product VI calcines, naturally cools 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, and outer external diameter is about 700-800nm, and internal diameter is about 600-660nm, wall thickness 20-70nm.N=1,2, the natural number such as 3 time obtain 3 layers, 4 layers, 5 layers hollow carbon sphere.

Utilize phenolic resin to be applicable to the character of coated various particle, prepare hollow structure that is double-deck and multilayer by foregoing repeatedly coated mode of successively corroding again, and in the cavity of carbon ball, encapsulate various nanoparticle.

Therefore, the application provides a kind of hollow carbon sphere having nanoparticle of in-stiu coating in the cavities and preparation method thereof further, in the hollow carbon sphere of described in-stiu coating nano particle, nano particle is metal nanoparticle, oxide nano particles, sulfide nanoparticle, hydroxide nanoparticles, carbonate nano particle, vitriol nano particle, organic compound, high molecular polymer etc., and nanoparticle size is 10-800nm; Metal nanoparticle is preferably the nano particles such as Ag, Au, Pd, Pt, and oxide nano particles is preferably Fe ₂o ₃nano particle, ZnO nano particle, CuO nano particle etc., sulfide nanoparticle is preferably FeS nano particle, ZnS nano particle, CuS nano particle etc., and hydroxide nanoparticles is preferably Mg (OH) ₂nano particle, Cu (OH) ₂nano particles etc., carbonate nano particle is preferably MgCO ₃nano particle, CaCO ₃nano particles etc., vitriol nano particle is preferably BaSO ₄nano particle etc.;

Be specially method E and method F;

Method E: be a kind ofly packaged with the carbon ball of nanoparticle and the preparation method of multi-layer hollow carbon ball in the cavities, comprises the steps:

E1) nano particle and phenolic compound are placed in the mixed solvent that organic solvent or water and organic solvent form, ultrasonic abundant dispersion, the pH value of regulator solution, then the aqueous solution adding aldehyde compound stirs at a certain temperature, after this step reaction, for Surface coating has the nano particle of phenolic resin polymkeric substance in solution;

E2) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain the hollow sphere polymer being packaged with nano particle, called after intermediate product VIII;

E3) by step e2) gained intermediate product VIII calcines, naturally cools to room temperature, obtain the hollow carbon sphere final product VIII being packaged with nano particle.

When nano particle be method A, B, C, D prepare hollow carbon sphere time, then products therefrom is multilayer carbon hollow ball.

Method F: be a kind ofly packaged with the carbon ball of nanoparticle and the preparation method of multi-layer hollow carbon ball in the cavities, comprises the steps:

F1) nano particle and phenolic compound are placed in the mixed solvent that organic solvent or water and organic solvent form, ultrasonic abundant dispersion, the pH value of regulator solution, the aqueous solution then adding quaternary ammonium salt cationic surfactant and aldehyde compound successively stirs at a certain temperature;

F2) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain intermediate product IX;

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

Utilize some precious metal salt can be reduced by phenols or aldehyde compound, the particle of in-situ preparation metal nano, the method by fabricated in situ encapsulates nano particle in the cavities.In addition, the application also provides the method being prepared in cavity the carbon ball being packaged with metal nanoparticle by in-situ synthetic method, is specially method G and method H.

Method G: a kind of method being prepared in cavity the carbon ball being packaged with metal nanoparticle by in-situ synthetic method, is comprised the steps:

G1) precious metal salt and phenolic compound are placed in the mixed solvent that organic solvent or water and organic solvent form, abundant dissolving, the pH value of regulator solution, then the aqueous solution adding aldehyde compound stirs at a certain temperature, after this step reaction, for Surface coating has the nano particle of phenolic resin polymkeric substance in solution;

G2) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain intermediate product XI;

G3) by step g 2) gained intermediate product XI calcines, naturally cools to room temperature, obtain final product XI.

Method H: a kind of method being prepared in cavity the carbon ball being packaged with metal nanoparticle by in-situ synthetic method, is comprised the steps:

H1) precious metal salt and phenolic compound are placed in the mixed solvent that organic solvent or water and organic solvent form, abundant dissolving, the pH value of regulator solution, then the aqueous solution adding quaternary ammonium salt cationic surfactant and aldehyde compound successively stirs at a certain temperature, after this step reaction, for Surface coating has the nano particle of phenolic resin polymkeric substance in solution;

H2) add etching reagent, continue at a certain temperature to stir, collect the precipitation of gained, obtain intermediate product XII;

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

Utilizing the loose and porous structure of carbon material itself, and the physicochemical property of high-specific surface area, can realize encapsulating low melting point and the non-metal simple-substance that after melting, mobility is strong in described containing in the carbon ball of hollow structure.

In addition, the application is also provided in hollow structure further and is packaged with low melting point and the preparation method of the carbon ball of the non-metal simple-substance that after melting, mobility is strong, and described non-metal simple-substance is S or Se or P etc., is specially method M and method N.

Method M: be a kind ofly packaged with low melting point and the preparation method of the carbon ball of the non-metal simple-substance that after melting, mobility is strong in hollow structure, comprises the steps:

M1) hollow carbon sphere is prepared by either method in method A, B, C and D;

M2) by step m1) hollow carbon sphere of gained at room temperature mixes by a certain percentage with low melting point non-metal simple-substance;

M3) by step m2) sealing of the mixture of gained, calcine at a certain temperature, naturally cool to room temperature, obtain final product.

Method N: be a kind ofly packaged with low melting point and the preparation method of the carbon ball of the non-metal simple-substance that after melting, mobility is strong in hollow structure, comprises the steps:

N1) hollow carbon sphere is prepared by either method in method A, B, C and D;

N2) by step n1) hollow carbon sphere of gained and low melting point non-metal simple-substance are scattered in the solvent of low melting point non-metal simple-substance, fully stir under room temperature, and collecting precipitation;

N3) by step n2) seal after the mixture drying of gained, calcine at a certain temperature, naturally cool to room temperature, obtain final product.

Method O: the porous utilizing hollow carbon sphere, the features such as high-ratio surface sum good conductivity, the application provides a kind of preparation method of ultracapacitor, and it comprises the steps:

O1) by hollow carbon sphere material, carbon black, PVDF in mass ratio 85:10:5 mix, paste is modulated into NMP, coat on nickel foam collector, through 100 DEG C of drying and processings, roll, make after cut-parts the pole piece of diameter 12mm, select polyethylene porous membrane to be barrier film, by staggered relatively for two pole pieces, centre isolates with barrier film, after dripping 6mol/L KOH electrolytic solution, be packaged in button cell shell and be assembled into ultracapacitor; Wherein, described hollow carbon sphere is according to any one preparation in method A, B, C and D.

Method P: on the other hand, in the application of prepared hollow carbon sphere heavy metal ion in adsorption for disposing industrial effluent, also has larger potentiality.Therefore, the application provides a kind of method utilizing hollow carbon sphere process trade effluent, and it comprises following steps:

P1) the hollow carbon sphere material of certain mass is joined in the aqueous solution containing certain density heavy metal ion, use HNO ₃or the pH of NaOH regulator solution; After fully being stirred by suspension liquid or shaking for some time, collected by centrifugation supernatant liquor, measures heavy metal ion content remaining in clear liquid with inductively coupled plasma spectrometry immediately; Wherein, described hollow carbon sphere is according to any one preparation in method A, B, C and D.

Wherein, described step a1), b1), c), d1), e1), f1), g1), h1) in, phenolic compound is containing at least one in substituent phenol; Wherein, described substituting group is selected from least one in the alkoxyl group of the alkyl of C1-C5, amino, the aminoalkyl of C1-C5, hydroxyl, sulfydryl, nitro, sulfonic group, the carboxyl of C1-C5, halogen and C1-C5;

The described at least one be specifically selected from containing substituent phenol in methylphenol, dihydroxy-benzene, benzenetriol, amino-phenol and nitrophenols;

Wherein, described methylphenol is specially ortho-methyl phenol, m-methyl phenol or p-methyl phenol; Described dihydroxy-benzene is specially pyrocatechol, Resorcinol or Resorcinol; Described benzenetriol is specially pyrogaelol, oxyhydroquinone or Phloroglucinol; Described amino-phenol is specially Ortho-Aminophenol, Metha Amino Phenon or p-aminophenol; Described nitrophenols is specially the nitrophenols of ortho position, a position, para-orientation;

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

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

Described step a1), b1), c1), d1), e1), f1), g1), h1) in, pH scope is 5-11, regulates pH usable acid or alkali; Described acid is hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, citric acid, at least one in the acids such as xitix; Described alkali is ammoniacal liquor, quadrol, propylene diamine, triethylamine, 1-butylamine, 2-butylamine, sodium hydroxide, at least one in potassium hydroxide;

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

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

Described step a1), b1), c1), d1), e1), f1), g1) and h1) in, phenolic compound mass concentration is in a solvent 0.1-50mg/mL, is specially 0.83mg/mL, 1.67mg/mL, 3.3mg/mL;

Described step a1), b1), c1), d1), e1), f1), g1), h1) in, the mole dosage of phenolic compound and aldehyde compound, than being 0.05-30:0.05-30, is 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;

Described step b1), d1), f1), h1) in, the mole dosage of phenolic compound, aldehyde compound and cats product, than being 0.05-30:0.05-30:0.1-20, is specially 9:10:0.82;

Described step a1), b1), c1), d1), e1), f1), g1) and h1) in solvent be organic solvent, or the mixing solutions that water and organic solvent form;

Wherein, described organic solvent is specifically selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, ethylene glycol, glycerol, acetone, butanone, tetrahydrofuran (THF), at least one in DMF and N,N-dimethylacetamide;

In the described mixed solution be made up of water and organic solvent, the volume ratio of water and organic solvent is 0.5-50:1, is specially 2:1,1:1,1.5:1;

Described 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, nonmetal, metal oxide, nonmetal oxide, organic compound, mineral compound or high molecular polymer, and by method A, B, C, D, E, F, G, H intermediate product containing hollow structure synthesized by any one and the hollow carbon material after calcining thereof, be specifically selected from Ag, Au, Pd, Si, SnO ₂, TiO ₂, Fe ₂o ₃, Fe ₃o ₄, SiO ₂, polystyrene, phenolic resin, porous carbon materials, intermediate product I-XII, hollow carbon sphere I-III, any one in double-layer hollow carbon ball I-III;

Described step g 1) and h1) in, precious metal salt is Silver Nitrate, hydrochloro-auric acid, the acid of chlorine palladium, any one in Platinic chloride;

Described step b1), d1), f1) and h1) in, quaternary ammonium salt cationic surfactant is specifically selected from least one in alkyl trimethyl ammonium salt type cats product, dialkyl dimethyl ammonium salt type cats product and alkyl dimethyl benzyl ammonium salt type cats product;

Wherein, described alkyl trimethyl ammonium salt type cats product is specially octyl trimethyl brometo de amonio, octyltrimethylammonium chloride, eight alkyl trimethyl ammonium bromides, eight alkyl trimethyl ammonium chlorides, ten alkyl trimethyl ammonium bromides, decyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Cetyltrimethylammonium bromide or octadecyl trimethyl ammonium chloride etc., described dialkyl dimethyl ammonium salt type cats product is specially bisoctyl dimethyl ammonium bromide, two octyldimethyl ammonium chloride, two eight alkyl dimethyl brometo de amonios, two eight alkyl dimethyl ammonium chloride, didecyl Dimethy brometo de amonio, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two dodecyldimethylamine base brometo de amonio, two dodecyldimethylamine ammonium chloride, Varisoft 432PPG, DHAB, distearyl dimethyl ammonium chloride or DDA, described alkyl dimethyl benzyl ammonium salt type cats product is specially dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, myristyl benzyl dimethyl ammonium chloride, tetradecyl dimethyl benzyl ammonium, cetalkonium chloride, cetyl dimethyl benzyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride or octadecyl dimethyl benzyl brometo de amonio,

Described quaternary ammonium salt cationic surfactant mass concentration is in a solvent 3 × 10 ^-4~ 0.1mg/mL, is preferably specially 0.001mg/mL ~ 0.009mg/mL;

Described step a2), b2), c3), d3), e2), f2), g2) and h2) in, etching reagent is selected from alcohol, ketone, acid amides, furans, at least one in alkane or halohydrocarbon and their derivative thereof;

Wherein, described alcohol and the derivative of alcohols are specially methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, ethylene glycol or glycerol; Described ketone and derivative thereof are specially acetone, cyclopropanone, butanone, dimethyl diketone or methyl ethyl diketone; Described acid amides and derivative thereof are specially methane amide, ethanamide, propionic acid amide, butyramide, DMF, N,N-dimethylacetamide or N, N-dimethylpropionamide; Described Furan and its derivatives is specially tetrahydrofuran (THF); Described alkane hydrocarbons and their derivates is specially cyclohexane; Described halo hydrocarbons and their derivates is specially trichloromethane;

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

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

Described step c1) and d1) in whipping step in, the time is 0.01-1 hour, be preferably 20 minutes ~ 1 hour, be specially 0.5 hour;

Described step c2) and d2) in whipping step in, the time is 0.01-1 hour, be preferably 20 minutes ~ 1 hour, be specially 0.5 hour;

Described step a2), b2), c3), d3), e2), f2), g2) and h2) in, add volume and the step a1 of etching reagent), b1), d1), e1), f1), g1), h1) in the volume ratio of water or solvent be 0.1-100:1, be specially 0.7:1;

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

The atmosphere of calcining is inertia or reducing atmosphere, specifically be selected from nitrogen, argon gas, the gas mixture be made up of hydrogen and argon gas and the gas mixture that is made up of nitrogen and hydrogen any one, more specifically can for by volume ratio being the gas mixture that the hydrogen of 1 ~ 5:95 ~ 99 and argon gas form;

Described step m2), n2) in low melting point non-metal simple-substance be specially the powder of S or Se; The ratio of non-metal simple-substance powder shared by carbon ball and its total mass is 10 ~ 90%, is preferably 50-80%, is specially 50%, 60%, 70%;

Described step n2) in be specially dithiocarbonic anhydride containing the solvent of non-metal simple-substance; Churning time is 1-10h, is specially 4h;

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

Described step m3) and calcining step n3) in, temperature is 100-600 DEG C, specifically can be 155 DEG C, 300 DEG C, 400 DEG C, or points two sections calcine, such as first through 155 DEG C again through 300 DEG C, and first through 155 DEG C again through 400 DEG C, time is 1-30 hour, specifically can be 10 hours, temperature rise rate is 1-20 DEG C/min, specifically can be 5 DEG C/min;

The atmosphere of calcining is air, inertia or reducing atmosphere, specifically be selected from air, nitrogen, argon gas, the gas mixture be made up of hydrogen and argon gas and the gas mixture that is made up of nitrogen and hydrogen any one, more specifically can for by volume ratio being the gas mixture that the hydrogen of 1 ~ 5:95 ~ 99 and argon gas form.

Described step o1) and p1) in hollow carbon sphere material be the hollow carbon sphere prepared by either method in method A, B, C, D;

Described step p1) in heavy metal ion be Pb ²⁺, Cd ²⁺, Cu ²⁺, Hg ²⁺, As ⁵⁺, Cr ⁴⁺etc. one or more in harmful metal ion; The concentration of heavy metal ion is 1 ~ 100mg/L, is specially 10mg/L, 20mg/L, 30mg/L; The quality of hollow carbon sphere and the mass ratio of contained precious metal ion are 1 ~ 100:1, are preferably 1 ~ 10:1, are specially 5:1,6:1; PH scope is 2 ~ 10, is specially 5; Stirring or concussion time are 1 ~ 10 hour, are specially 4 hours; Stirring or shaking temperature is room temperature;

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

The preparation method of individual layer provided by the invention and multi-layer hollow carbon ball, simple to operate, low raw-material cost, the yardstick obtaining carbon ball is homogeneous, and the number of plies of carbon ball is controlled.Utilize this method not only can carry out original position encapsulation to various nano particle and prepare yolk-shell structure, and prepared material is at lithium ion battery negative material, in the fields such as the electrochemical devices such as Li-S battery and electrical condenser and heavy metal ions in wastewater absorption, all there is very large application prospect.

Accompanying drawing explanation

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

Fig. 2 schemes according to the TEM of the hollow carbon sphere prepared by embodiment A 1.

Fig. 3 schemes according to the TEM of the carbon ball of the mesoporous distribution of entirety prepared by embodiment A 2.

Fig. 4 is equipped with the TEM figure of the hollow yolk-shell structure of solid carbon ball according to the inside prepared by embodiment A 3.

Fig. 5 schemes according to the TEM of the hollow carbon sphere prepared by Embodiment B 1.

Fig. 6 schemes according to the TEM of the hollow carbon sphere prepared by Embodiment B 2.

Fig. 7 schemes according to the TEM of the hollow carbon pipe prepared by Embodiment B 3.

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

Fig. 9 schemes according to the TEM of the double-layer hollow carbon ball prepared by embodiment E 1.

Figure 10 schemes according to the TEM of the double-layer hollow carbon ball prepared by embodiment E 2.

Figure 11 schemes according to the TEM of the double-layer hollow carbon ball prepared by embodiment F 1.

Figure 12 schemes according to the TEM of the Si@void@C nucleocapsid structure prepared by embodiment F 2.

Figure 13 encloses charge-discharge performance figure according to the first charge-discharge curve and 100 of the Si@void@C sample prepared by embodiment F 2.。

Figure 14 is according to the SiO prepared by embodiment F 3 ₂the TEM figure of@void@C nucleocapsid structure.

Figure 15 is according to the SnO prepared by embodiment F 4 ₂the TEM figure of@void@C nucleocapsid structure.

Figure 16 schemes according to the TEM of the Ag@void@C2 nucleocapsid structure prepared by embodiment G1.

Figure 17 schemes according to the TEM of the Ag@void@C3 nucleocapsid structure 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 according to the first charge-discharge graphic representation of the S-C electrode materials prepared by embodiment M1 within the scope of 1-3V.

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

Figure 21 is adsorpting rate curve measured in embodiment P1.

Embodiment

Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.

Embodiment A 1, Application way A prepare hollow carbon sphere:

Take 0.1g 3-amino-phenol and be dissolved in 20ml H ₂in the mixing solutions that O and 10ml EtOH forms, add stirred at ambient temperature 1.3h after ammoniacal liquor and formaldehyde solution.

In reaction vessel, add 20ml acetone, continue to stir 30min under room temperature, by throw out collected by centrifugation, and with ethanol purge 2 times, gained precipitates the abundant dry 4h of loft drier being placed in 80 DEG C, obtains intermediate product II.

Dried intermediate product II is placed in the tube furnace being connected with hydrogen-argon-mixed (5/95 volume %), 900 DEG C are risen to from room temperature with the temperature rise rate of 5 DEG C/min, and 10h is calcined at 900 DEG C, naturally cool to the individual layer hollow carbon sphere II that room temperature obtains inner clean.

Finally obtain inside and be distributed with mesoporous individual layer hollow carbon sphere, its external diameter is 300-350nm, internal diameter 240-260nm, wall thickness 30-50nm, and pore volume is 0.9685cm ³/ g, specific surface area is 1504.06m ²/ g.

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

The carbon spherical structure of the overall complete mesoporous distribution of embodiment A 2, Application way A preparation:

Be with the difference of embodiment A 1:

Take 0.1g 3-amino-phenol in 16ml H ₂in the mixing solutions that O and 14ml EtOH forms, add stirred at ambient temperature 45min after ammoniacal liquor and formaldehyde solution.

Finally obtain overall distribution and have mesoporous carbon spherical structure, the diameter of ball is 280-360nm.

Fig. 3 is transmission electron microscope (TEM) figure of the mesoporous carbon spherical structure of overall distribution prepared by the present embodiment, can see that the yardstick of hollow carbon sphere is 300 ~ 350nm from figure.

The inner yolk-shell hollow structure that solid carbon ball is housed of embodiment A 3, Application way A preparation:

Be with the difference of embodiment A 1:

Take 0.4g 3-amino-phenol in 20ml H ₂in the mixing solutions that O and 10ml EtOH forms, add stirred at ambient temperature 1.3h after 0.1ml ammoniacal liquor and 0.4ml formaldehyde solution.

Finally obtain the hollow yolk-shell structure that solid carbon ball is equipped with in inside.The external diameter 470-520nm of gained hollow carbon sphere structure, interior solid spherical diameter 200-250nm.

Transmission electron microscope (TEM) figure of the hollow yolk-shell carbon ball material of solid carbon ball is equipped with in inside prepared by Fig. 4 the present embodiment, and 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 B 1, Application way B prepare hollow carbon sphere:

Take 0.1g 3-amino-phenol and be dissolved in 20ml H ₂in the mixing solutions that O and 10ml EtOH forms, then add 0.03g cetyl trimethylammonium bromide (CTAB) (0.082mmol).

Then add successively 0.1ml mass percentage concentration be 25% ammoniacal liquor (1.30mmol) and 0.1ml mass concentration be 37% formalin (1.34mmol), in stirred at ambient temperature 1.5h.In reaction vessel, add 20ml acetone, continue to stir 30min under room temperature, by throw out collected by centrifugation, and with ethanol purge 2 times, gained precipitates the abundant dry 4h of loft drier being placed in 80 DEG C, obtains intermediate product III.

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

Finally obtain inside and be distributed with mesoporous individual layer hollow carbon sphere, its external diameter is 500-800nm, internal diameter 400-600nm, wall thickness 50-150nm, and pore volume is 0.7611cm ³/ g, specific surface area is 1244.21m ²/ g.

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

Embodiment B 2, Application way B prepare hollow carbon sphere:

Be with the difference of Embodiment B 1:

Take 0.1g 3-amino-phenol and be dissolved in 50ml H ₂in the mixing solutions that O and 10ml EtOH forms.The individual layer hollow carbon sphere finally obtained, external diameter 50-60nm, internal diameter is about 30nm, wall thickness 10-20nm.

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

Embodiment B 3, Application way B prepare hollow carbon pipe:

Be with the difference of Embodiment B 1:

Take 0.1g 3-amino-phenol and be dissolved in 20ml H ₂in the mixing solutions that O and 2ml EtOH forms.

Finally obtain hollow carbon tubular construction, caliber is 25-50nm, and wall thickness is 10-20nm.

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

Embodiment C 1, Application way C prepare double-layer hollow carbon ball:

1) take 0.066g 3-amino-phenol (0.607mmol) and be dissolved in 14ml H ₂in the mixing solutions that O and 7ml EtOH forms, then add successively 0.1ml mass percentage concentration be 25% ammoniacal liquor (1.30mmol) and 0.1ml mass concentration be 37% formalin (2.68mmol), in stirred at ambient temperature 60 minutes.Separately 0.033g 3-amino-phenol (0.303mmol) is dissolved in 6ml H ₂in the mixing solutions that O and 3ml EtOH forms, add in solution above, continue reaction 40 minutes.In reaction vessel, add 22ml acetone, continue to stir 30min under room temperature, by throw out collected by centrifugation, and with ethanol purge 2 times, gained precipitates the abundant dry 4h of loft drier being placed in 80 DEG C, obtains intermediate product IV;

2) dried intermediate product II is placed in the tube furnace being connected with hydrogen-argon-mixed (5/95 volume %), rise to 900 DEG C with the temperature rise rate of 5 DEG C/min from room temperature, and calcine 10h at 900 DEG C, naturally cool to room temperature, obtain double-layer hollow carbon ball IV

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

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

1) take 0.1g3-amino-phenol (0.92mmol) and be dissolved in 20ml H ₂in the mixing solutions that O and 10ml EtOH forms, then add successively 0.03g cetyl trimethylammonium bromide (CTAB) (0.082mmol), 0.1ml mass percentage concentration be 25% ammoniacal liquor (1.30mmol) and 0.2ml mass concentration be 37% formalin (2.68mmol), in stirred at ambient temperature 40 minutes.Again add 0.1g3-amino-phenol (0.92mmol) in reaction system, continue stirring 40 minutes.In reaction vessel, add 22ml acetone, continue to stir 30min under room temperature, by throw out collected by centrifugation, and with ethanol purge 2 times, gained precipitates the abundant dry 4h of loft drier being placed in 80 DEG C, obtains intermediate product VI;

2) dried intermediate product IV is placed in the tube furnace being connected with hydrogen-argon-mixed (5/95 volume %), 900 DEG C are risen to from room temperature with the temperature rise rate of 5 DEG C/min, and 10h is calcined at 900 DEG C, naturally cool to room temperature and obtain double-layer hollow carbon ball VI, its internal layer external diameter is 500-600nm, internal diameter 400-420nm, wall thickness 40-80nm, outer external diameter is about 700-800nm, and internal diameter is about 600-660nm, wall thickness 20-70nm.

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

Embodiment E 1, Application way E prepare double-layer hollow carbon material:

Take 0.05g intermediate product II (synthesizing by the method for Embodiment B 1) and 0.1g 3-amino-phenol (0.92mmol) in 20ml H ₂in the mixing solutions that O and 10ml EtOH forms, ultrasonic disperse is even.

Add stirred at ambient temperature 1.3h after ammoniacal liquor and formaldehyde solution.

In reaction vessel, add 20ml acetone, continue to stir 30min under room temperature, by throw out collected by centrifugation, and with ethanol purge 2 times, gained precipitates the abundant dry 4h of loft drier being placed in 80 DEG C, obtains intermediate product VIII.

Dried intermediate product is placed in the tube furnace being connected with hydrogen-argon-mixed (5/95 volume %), rises to 900 DEG C with the temperature rise rate of 5 DEG C/min 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 prepared by the present embodiment.

Embodiment E 2, Application way E prepare double-layer hollow carbon material

Be with the difference of embodiment E 1:

Take 0.05g intermediate product I (synthesizing by the method for embodiment A 1) and 0.1g 3-amino-phenol (0.92mmol) in 20ml H ₂in the mixing solutions that O and 10ml EtOH forms, ultrasonic disperse is even.

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

Embodiment F 1, Application way F prepare double-layer hollow carbon material:

Take 0.05g intermediate product III (synthesizing by the method for Embodiment C 1) and 0.1g 3-amino-phenol (0.92mmol) in 20ml H ₂in the mixing solutions that O and 10ml EtOH forms, ultrasonic disperse is even.

Then add 0.03g cetyl trimethylammonium bromide (CTAB) (0.082mmol).

Then add successively 0.1ml mass percentage concentration be 25% ammoniacal liquor (1.30mmol) and 0.1ml mass concentration be 37% formalin (1.34mmol), in stirred at ambient temperature 1.5h.In reaction vessel, add 20ml acetone, continue to stir 30min under room temperature, by throw out collected by centrifugation, and with ethanol purge 2 times, gained precipitates the abundant dry 4h of loft drier being placed in 80 DEG C, obtains intermediate product IX.

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

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

Embodiment F 2, Application way F prepare Si@void@C nucleocapsid structure:

Take the Si powder (3.57mmol) that 0.1g granularity is 50-200nm, and add 1g (9.2mmol) 3-amino-phenol in the mixing solutions of 200ml water and 100ml ethanol, then add 0.3g cetyl trimethylammonium bromide (CTAB) (0.82mmol) successively, 1ml mass percentage concentration be 25% ammoniacal liquor (13mmol) and 1ml mass percentage concentration be 37% formaldehyde solution (13.4mmol).Finally obtain Si nano particle and be packaged in nucleocapsid structure in hollow carbon sphere, sample called after Si void C.

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

The prepared Si@void@C composite with nucleocapsid structure can be used as Li ionization cell negative pole, and its cavity can alleviate Si at Li ⁺embed and deviate from the enormousness that produces in process and expand, avoid generating SEI film and the capacity attenuation that causes because electrode materials and electrolytic solution directly contact.Prepared Si@void@C is selected to prepare cathode of lithium battery: according to Si@void@C: graphitized carbon black: polyvinylidene difluoride (PVDF) (PVDF)=40%:40%:20% (mass ratio) is prepared into electrode.Electrolytic solution component adopts EC:DMC:DEC=1:1:1,1M LiPF ₆as lithium salts.Metallic lithium is that positive pole is assembled into 2032 button cells, is 0.01-1V (vs Li in voltage range ⁺/ Li) in carry out constant current charge-discharge test.The electric current of discharge and recharge is 0.05C (210mA/g).

Figure 13 is first charge-discharge curve and the 100 circle charge-discharge performance figure of Si@void@C sample.As can be seen from the figure, Si@void@C sample is discharged first and is reached 1180mAh/g, and after 100 circle charge and discharge cycles, capacity is 1040mAh/g, and capability retention reaches 88.1%.

Embodiment F 3, Application way F prepare SiO ₂@void@C nucleocapsid structure:

According to the step of embodiment F 2, be with the difference of example I 2:

Take the SiO that 0.2g granularity is 200nm ₂(3.33mmol) powder, and add 1g (9.2mmol) 3-amino-phenol in mixing solutions.

Figure 14 is SiO prepared by the present embodiment ₂transmission electron microscope (TEM) figure of@void@C nucleocapsid sample.

Embodiment F 4, Application way F prepare SnO ₂@void@C nucleocapsid structure:

According to the step of embodiment F 3, be with the difference of embodiment F 3:

Taking 0.05g granularity is 30nm SnO ₂(0.332mmol) powder, and add 0.1g (0.909mmol) 3-amino-phenol in mixed solvent, finally obtain SnO ₂nano particle is packaged in the powdered material of the nucleocapsid structure in hollow carbon sphere, called after SnO ₂@void@C.

Figure 15 is SnO prepared by the present embodiment ₂transmission electron microscope (TEM) figure of@void@C nucleocapsid structure.

The prepared SnO with nucleocapsid structure ₂@void@C composite can be used as Li ionization cell negative pole, and its cavity can alleviate SnO ₂at Li ⁺embed and deviate from the enormousness that produces in process and expand, avoid generating SEI film and the capacity attenuation that causes because electrode materials and electrolytic solution directly contact.Select prepared SnO ₂@void@C prepares cathode of lithium battery: according to SnO ₂@void@C: graphitized carbon black: polyvinylidene difluoride (PVDF) (PVDF)=60%:20%:20% (mass ratio) is prepared into electrode.Electrolytic solution component adopts EC:DMC:DEC=1:1:1,1M LiPF ₆as lithium salts.Metallic lithium is that positive pole is assembled into 2032 button cells, can be 0.01-3V (vs Li in voltage range ⁺/ Li) in carry out 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

Be with the difference of embodiment A 1:

Take 0.02g AgNO ₃(0.118mmol) and 0.1g 3-amino-phenol (0.92mmol) in 20mlH ₂in the mixing solutions that O and 10ml EtOH forms, fully dissolve.Finally obtain the encapsulation of Ag nano particle and the nucleocapsid structure in hollow carbon sphere, called after Ag void C-2.

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

Embodiment H1, Application way H prepare Ag@void@C nucleocapsid structure:

Be with embodiment A 1 difference:

Take 0.02g AgNO ₃(0.118mmol) and 0.1g 3-amino-phenol (0.92mmol) in 20mlH ₂in the mixing solutions that O and 10ml EtOH forms, fully dissolve.Finally obtain the encapsulation of Ag nano particle and the nucleocapsid structure in hollow carbon sphere, called after Ag void C-3.

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

Embodiment M1, the Application way M application in Li-S positive electrode material to hollow carbon sphere material load S and hollow carbon sphere:

According to individual layer hollow carbon sphere I prepared by embodiment A 1.Take the fully grinding 20 ~ 30 minutes in agate mortar of 0.06g hollow carbon sphere I and 0.14g S powder; then the powder after grinding is loaded in the reaction vessel of sealing; and vacuumize, put into the tube furnace being connected with argon shield, rise to 155 DEG C with the temperature rise rate of 5 DEG C/min from room temperature; keep 10 hours; be warming up to 300 DEG C with the temperature rise rate of 5 DEG C/min again, and calcine 5h at 300 DEG C, naturally cool to room temperature; obtain the hollow carbon material of load S, called after S-C.

Figure 18 is TGA (thermogravimetric analysis) curve of the S-C matrix material of preparation, and as can be seen from the figure the charge capacity of S is 53.72%.

After loading S, hollow carbon sphere can be used as Li-S battery electrode material.Prepared S-C matrix material is selected to prepare lithium battery anode: according to S-C: graphitized carbon black: polyvinylidene difluoride (PVDF) (PVDF)=80%:10%:10% (mass ratio) is prepared into electrode.Metallic lithium is that negative pole is assembled into 2032 button cells, is 1-3V (vs Li in voltage range ⁺/ Li) in carry out constant current charge-discharge test.Electrolytic solution component adopts DOL:DME=1:1,1M LiTFSI as lithium salts.The electric current of discharge and recharge is 0.1C (~ 167mA/g).Figure 19 is the first charge-discharge curve of S-C electrode materials within the scope of 1-3V.As can be seen from the figure, the loading capacity first of S-C sample is 1000mAh/g, is potentially used as Li-S battery material.

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

According to individual layer hollow carbon sphere I prepared by embodiment A 1.Take 0.06g hollow carbon sphere I and 0.14g S powder is scattered in methanol solvate; fully stir under room temperature, collecting precipitation, load in the reaction vessel of sealing; and vacuumize; put into the tube furnace being connected with argon shield, rise to 155 DEG C with the temperature rise rate of 5 DEG C/min from room temperature, keep 10 hours; 300 DEG C are warming up to again with the temperature rise rate of 5 DEG C/min; and 5h is calcined at 300 DEG C, naturally cool to room temperature, obtain the hollow carbon material of load S.

Embodiment O1, the application of hollow carbon sphere material in ultracapacitor

By hollow carbon sphere material (synthesizing by Embodiment B 1), carbon black, PVDF in mass ratio 85:10:5 mix, paste is modulated into NMP, coat on nickel foam collector, through 100 DEG C of drying and processings, roll, make after cut-parts the pole piece of diameter 12mm, select polyethylene porous membrane to be barrier film, by staggered relatively for two pole pieces, centre isolates with barrier film, after dripping 6mol/L KOH electrolytic solution, be packaged in button cell shell and be assembled into ultracapacitor.Adopt electrochemical workstation, between operating voltage 0-1V, carry out performance test with 5,10,100mV/s, the specific discharge capacity of electrical condenser is respectively 144.8,140.7,106.2Fg ^-1, Figure 20 is the CV curve under prepared electrical condenser sweeps speed at three kinds.

The application in absorption heavy metal ions in wastewater of embodiment P1, hollow carbon sphere material

0.05g hollow carbon sphere material (synthesizing by Embodiment B 1) is joined 100ml and contains Pb ²⁺, Cd ²⁺, Cu ²⁺ionic concn is in the aqueous solution of 100mg/L, uses HNO ₃the pH value of solution is adjusted to 5.0.After mixed solution is at room temperature stirred 4 hours, with the membrane filtration of 0.15 μm, collect filtrate, use inductively coupled plasma spectrometry (Shimazu ICPE-9000) to measure heavy metal ion content remaining in clear liquid after different time immediately.Figure 21 is the adsorpting rate curve of different time, and as can be seen from the figure, adsorption process is very fast in initial 1h, and the adsorption equilibrium of three heavy metal species ions is set up after 1h.

Hollow carbon sphere prepared by visible the present invention at silicon-carbon cathode electrode materials, Li-S battery, ultracapacitor, and all there is potential using value the aspect such as heavy metal ion adsorbed.

Claims

1. an individual layer hollow carbon sphere, utilizes phenolic resin and etching reagent to prepare, and its external diameter is 300-350nm, internal diameter 240-260nm, wall thickness 30-50nm, and pore volume is 0.6-1.2cm ³/ g, specific surface area is 1400-1800m ²/ g.

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

Method A comprises the steps:

Method B comprises the steps:

In described method A and B, when the solubility of phenol and aldehyde is very high, at short notice because the interior polymeric speed of ball is accelerated, extent of polymerization is high, and the agent that can not be corroded again is corroded.When the solubility of phenol and aldehyde drops to a certain degree, can corrode at external sheath, therefore can utilize this method one-step synthesis inside that the yolk-shell hollow structure of novalac polymer solid sphere and carbon ball is housed.In addition, the solubility by adjusting phenol and aldehyde controls the carbon spherical structure of the overall mesoporous distribution of all right one-step synthesis of polymkeric substance degree of polymer drops.In addition, except above-mentioned pattern, by regulating phenol and the concentration of aldehyde or the concentration of quaternary ammonium salt cationic surfactant in method B, the carbon spherical structure of gained can be controlled as tubulose.

3. a bilayer or multi-layer hollow carbon ball and preparation method thereof, utilizes the sol-gel growth pattern of phenolic resin, is further used for preparing hollow carbon sphere that is double-deck or multilayer by caustic solution,

Described double-layer hollow carbon ball has following structure, the outer external diameter 300-350nm of one, internal diameter 220-250nm, wall thickness 40-60nm, internal layer external diameter 250-290nm, wall thickness 25-35nm; Its two internal layers external diameter 300-350nm, internal diameter 160-180nm, wall thickness 60-80nm, outer external diameter 420-450nm, internal diameter 380-400nm, wall thickness 20-30nm; It three prepares double-layer hollow carbon ball, and its internal layer external diameter is 500-600nm, internal diameter 400-420nm, wall thickness 40-80nm, and outer external diameter is about 700-800nm, and internal diameter is about 600-660nm, wall thickness 20-70nm.Described multi-layer hollow carbon ball is that the structure possessing above-mentioned double-layer hollow carbon ball comprises the hollow carbon spheres such as the 3rd layer, the 4th layer, the 5th layer etc. 3 layers, 4 layers, 5 layers outward further.

Described preparation method is C and method D;

Method C comprises the steps:

Method D comprises the steps:

4. the hollow carbon sphere and preparation method thereof of an in-stiu coating nano particle,

In the hollow carbon sphere of described in-stiu coating nano particle, nano particle is metal nanoparticle, oxide nano particles, sulfide nanoparticle, hydroxide nanoparticles, carbonate nano particle, vitriol nano particle, organic compound, high molecular polymer etc., and nanoparticle size is 10-800nm; Metal nanoparticle is preferably the nano particles such as Ag, Au, Pd, Pt, Si, and oxide nano particles is preferably Fe ₂o ₃nano particle, ZnO nano particle, CuO nano particle, SiO ₂nano particles etc., sulfide nanoparticle is preferably FeS nano particle, ZnS nano particle, CuS nano particle etc., and hydroxide nanoparticles is preferably Mg (OH) ₂nano particle, Cu (OH) ₂nano particles etc., carbonate nano particle is preferably MgCO ₃nano particle, CaCO ₃nano particles etc., vitriol nano particle is preferably BaSO ₄nano particle etc.;

Phenolic resin is utilized to be applicable to the character of coated various particle, hollow structure that is double-deck and multilayer is prepared by first coated mode of corroding again, and in the cavity of carbon ball, encapsulate various nanoparticle, preparation method is E and F, if when nano particle is the hollow carbon sphere of one of claim 1-3, obtain multi-layer hollow carbon ball; Some precious metal salt can be reduced by aldehyde compound, the particle of generated in-situ metal nano, utilizes the method for fabricated in situ to encapsulate nano particle in the cavities, and method is G and method H;

E3) by step e2) gained intermediate product VIII calcines, naturally cools to room temperature, obtain the hollow carbon sphere final product being packaged with nano particle.

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

G3) by step g 2) gained intermediate product XI calcines, naturally cools to room temperature, obtain final product.

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

5. one kind encapsulates low melting point and the preparation method of the carbon ball of the non-metal simple-substance that after melting, mobility is strong, described non-metal simple-substance is S or Se or P, utilize the loose and porous structure of carbon material itself, and the physicochemical property of high-ratio surface, can realize encapsulating low melting point and the non-metal simple-substance that after melting, mobility is strong in described containing in the carbon ball of hollow structure, preparation method is M and N;

M1) hollow carbon sphere is prepared by the hollow carbon sphere of claim 1 or Claims 2 or 3;

N1) hollow carbon sphere is prepared by the hollow carbon sphere of claim 1 or 2 or claim 3 or 4;

6. a preparation method for ultracapacitor, because hollow carbon sphere has porous, the features such as high-ratio surface sum good conductivity, can use it for the preparation of ultracapacitor, method comprises the steps:

The hollow carbon sphere material hollow carbon sphere of claim 1 or Claims 2 or 3 prepared, carbon black, PVDF in mass ratio 85:10:5 mix, paste is modulated into NMP, coat on nickel foam collector, through 100 DEG C of drying and processings, roll, make after cut-parts the pole piece of diameter 12mm, select polyethylene porous membrane to be barrier film, by staggered relatively for two pole pieces, centre isolates with barrier film, after dripping 6mol/L KOH electrolytic solution, be packaged in button cell shell and be assembled into ultracapacitor.

7. the method according to claim 2-4, it is characterized in that: described step a1), b1), c1), d1), e1), f1), g1), h1) in, phenolic compound is containing at least one in substituent phenol; Wherein, described substituting group is selected from least one in the alkoxyl group of the alkyl of C1-C5, amino, the aminoalkyl of C1-C5, hydroxyl, sulfydryl, nitro, sulfonic group, the carboxyl of C1-C5, halogen and C1-C5;

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

8. the method according to claim 2-4, is characterized in that: described step a1), b1), c1), d1), e1), f1), g1), h1) in, pH scope is 5-11, regulates pH usable acid or alkali; Described acid is hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, citric acid, at least one in the acids such as xitix; Described alkali is ammoniacal liquor, quadrol, propylene diamine, triethylamine, 1-butylamine, 2-butylamine, sodium hydroxide, at least one in potassium hydroxide;

In the described mixed solution be made up of water and organic solvent, the volume ratio of water and organic solvent is 0.5-50:1, is specially 2:1,1:1,1.5:1.

9. the method according to claim 2-4, it is characterized in that: described step e1) and f1) in, nano particle is water insoluble and organic solvent, yardstick is 1-500nm and at high temperature pattern keeps stable metal, nonmetal, metal oxide, nonmetal oxide, organic compound, mineral compound or high molecular polymer, and by method A, B, C, D, E, F, G, H intermediate product containing hollow structure synthesized by any one and the hollow carbon material after calcining thereof, specifically be selected from Ag, Au, Pd, Si, SnO ₂, TiO ₂, Fe ₂o ₃, Fe ₃o ₄, SiO ₂, polystyrene, phenolic resin, porous carbon materials, intermediate product I-XII, hollow carbon sphere I-III, any one in double-layer hollow carbon ball I-III;

Described quaternary ammonium salt cationic surfactant mass concentration is in a solvent 3 × 10 ^-4~ 0.1mg/mL, is preferably specially 0.001mg/mL ~ 0.009mg/mL.

Preferably, described step a2), b2), c3), d3), e2), f2), g2) and h2) in, etching reagent is selected from alcohol, ketone, acid amides, furans, at least one in alkane or halohydrocarbon and their derivative thereof;

The atmosphere of calcining is inertia or reducing atmosphere, specifically be selected from nitrogen, argon gas, the gas mixture be made up of hydrogen and argon gas and the gas mixture that is made up of nitrogen and hydrogen any one, more specifically can for by volume ratio being the gas mixture that the hydrogen of 1 ~ 5:95 ~ 99 and argon gas form.

10. the method according to claim 5-6, is characterized in that: described step m2), n2) in low melting point non-metal simple-substance be specially the powder of S or Se; The ratio of non-metal simple-substance powder shared by carbon ball and its total mass is 10 ~ 90%, is preferably 50-80%, is specially 50%, 60%, 70%;

Described step o1) and p1) in hollow carbon sphere material be the hollow carbon sphere prepared by either method in method B, C, E and F;