CN105645403A - Preparation method of high-performance nitrogen-doped three-dimensional graphene - Google Patents
Preparation method of high-performance nitrogen-doped three-dimensional graphene Download PDFInfo
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Abstract
The invention relates to the technical field of synthesizing of graphene materials and provides a preparation method of nitrogen-doped graphene. The preparation method includes: using an improved Hummers method to prepare continuous large-piece graphene oxide; using a hydrothermal method to prepare the graphene oxide into graphene of a porous three-dimensional structure; ultrasonically dispersing the graphene of the porous three-dimensional structure into an acid solution with the pH being 1-5, adding aniline, well mixing, adding ammonium persulfate, well mixing, and transferring the obtained mixed liquid into a teflon container for hydrothermal reaction so as to obtain a porous three-dimensional graphene-polyaniline compound; performing high-temperature treatment under nitrogen protection to allow polyaniline to decompose out nitrogen sources so as to obtain the nitrogen-doped porous three-dimensional graphene. The method has the advantages that the nitrogen-doped graphene with high nitrogen content can be prepared, the structure of the three-dimensional graphene can be kept, the obtained nitrogen-doped porous three-dimensional graphene is good in electrochemical performance and quite suitable for being used for producing a super capacitor, and the method is convenient to operate and beneficial to industrial popularization.
Description
Technical field
The present invention relates to the synthesis technical field of grapheme material, particularly to the preparation method of a kind of high-performance nitrogen-doped graphene.
Background technology
Graphene is the bi-dimensional cellular shape network structure being made up of the monoatomic layer of carbon, is the primitive constituting other graphite materials. The basic structural unit of Graphene is benzene hexatomic ring, is current optimal two-dimension nano materials. Graphene is close to perfect material, but is extend its practical application in fields such as the energy, environment and biologies, it is necessary to the Graphene of two dimension is self-assembled into as three-dimensional graphene-structured. Such three dimensional structure, except some performances having Graphene itself, also has the feature of oneself uniqueness.
Three-dimensional grapheme is to be formed by the monoatomic layer stacking of carbon, has the electric conductivity more excellent than two-dimensional graphene, big specific surface area and loose structure. Unique three dimensional structure makes Graphene assembly have the character such as porous, pliability, lamination type, mass transfer performances. Although the surface of two-dimensional graphene can be higher, but it is susceptible to reunite, and three-dimensional netted Graphene stability is better, specific surface area is big and utilization rate is high, can increase the electrolyte wellability to electrode material, and improve the charge storage ability of electrode. Three-dimensional grapheme and composite thereof have the performance more superior than two-dimensional graphene material and broader practice in the energy, environment, catalysis etc. Based on this, we introduce nitrogen element in three-dimensional grapheme, utilize nitrogen to replace the carbon atom on Graphene, prepare N doping three-dimensional grapheme, it is possible to be greatly improved the energy-storage property of three-dimensional grapheme. At present, people mainly include following several direction for the research of the preparation method of N doping three-dimensional grapheme, including vapour deposition process, solvent-thermal method, heat treating process, plasma method etc. . Vapour deposition process can generate comparatively homogeneous large area film and the comparatively uniform nitrogen-doped graphene of doping, and controllability is better, but source of the gas and residual air generally have toxicity, and operating process is loaded down with trivial details, and equipment requirements is comparatively harsh, and yield is less, and production cost is high. Solvent-thermal method is easy to operate, mild condition, and safety is higher, and yield is big, is also at present for everybody a kind of most widely used method. But, the homogeneity of N doping is poor, and the controllability of doping rate is poor. Heat treating process is a kind of succinct, the method efficiently producing azepine Graphene, but the nitrogen content obtained is relatively low, and the handle control in temperature and response time is comparatively harsh.Plasma method is to equipment, and experiment condition has harsh requirement.
But the N doping limited amount on three-dimensional grapheme, this strongly limits the application of N doping three-dimensional grapheme at present. As can be seen here, preparing the higher N doping three-dimensional grapheme of nitrogen content is that art is badly in need of solving the technical problem that. The invention provides a kind of preparation method, it is possible to obtain the high performance N doping three-dimensional grapheme that nitrogen content is higher.
Summary of the invention
In view of prior art exists above-mentioned technical problem, the preparation method that the present invention proposes the higher N doping three-dimensional grapheme of a kind of nitrogen content, described preparation method, by first expanded graphite being peeled off into graphene oxide, simple hydro-thermal method is utilized to prepare three-dimensional grapheme, and oxidation three-dimensional grapheme-Polyaniline is prepared into aniline, the oxygen in three-dimensional grapheme is made to form chemical combination key with the nitrogen element in aniline, again three-dimensional grapheme-Polyaniline is at high temperature cracked, nitrogen element is then formed with carbon and is bonded, meanwhile, part skeleton function can also be played, at high temperature keep intact in the hole supporting three-dimensional grapheme, obtain the N doping three-dimensional grapheme structure of porous. the technical solution adopted in the present invention is specific as follows:
The present invention provide a kind of high-performance N doping porous three-dimensional Graphene and preparation method thereof, described method comprises the steps:
Step S1: use graphite to prepare graphene oxide;
Step S2: use graphene oxide to prepare three-dimensional grapheme hydrogel: to be 1��2mg:1ml according to mass volume ratio, add graphene oxide in deionized water, through supersound process, it is configured to graphene oxide water solution, then graphene oxide water solution is transferred in the container of politef, it is put into and carries out hydro-thermal reaction in a kettle., after cooling, obtain three-dimensional grapheme hydrogel;
Step S3: use three-dimensional grapheme hydrogel to prepare three-dimensional grapheme-polyaniline composite material: according to the amount of three-dimensional grapheme Yu acid solution mass volume ratio 1mg:20��50ml, described three-dimensional grapheme hydrogel is immersed in an acidic solution, it is the amount of 1:5��10 according to three-dimensional grapheme and aniline mass ratio, oxytropism solution instills quantitative aniline and stirs, allow aniline well in the microcellular structure of three-dimensional grapheme, then it is the amount of 5:3��5 by aniline and Ammonium persulfate. mass ratio, it is quantitatively adding Ammonium persulfate., and stir, again mixed liquor is transferred to polytetrafluoroethylcontainer container, it is put in reactor and continues hydro-thermal reaction, product sucking filtration is cleaned, three-dimensional grapheme-the polyaniline composite material dried is obtained through lyophilizing,
Step S4: use three-dimensional grapheme-polyaniline composite material to prepare N doping three-dimensional grapheme: under inert gas shielding; gained three-dimensional grapheme-Polyaniline is heated to 750��1000 DEG C; insulation 1��2h, cooled obtains high-performance N doping three-dimensional grapheme.
In further technical scheme, above-mentioned steps S1: use graphite to prepare graphene oxide; Improvement Hummers method can be adopted to prepare, concrete step includes: (1) is 5g:200ml according to mass volume ratio, expansible graphite is joined in the mixed liquor being made up of the concentrated sulphuric acid that volume ratio is 3:1 and concentrated nitric acid, and at room temperature stir preexpanding, use deionized water dilute reaction solution, collected by suction product also dries, and heats with microwave 1800W, and the microwave time, 40��60s made graphite expand completely;
(2) it is 5g:300ml by expanded graphite and concentrated sulphuric acid mass volume ratio, expanded graphite is added in concentrated sulphuric acid, again by expanded graphite: potassium peroxydisulfate: the amount that phosphorus pentoxide mass ratio is 5:4.2:6.2 is separately added into potassium peroxydisulfate and phosphorus pentoxide, 3��5h under stirring at 60��80 DEG C, react and used deionized water dilute reaction solution, again with deionized water wash sucking filtration and dry, obtain pre-oxidation graphite;
(3) it is 5g:200ml according to the mass volume ratio of preexpanding graphite Yu concentrated sulphuric acid, the pre-oxidation graphite that will be obtained by step (2) adds in concentrated sulphuric acid, it is then heated to 35��40 DEG C, stirring 1��2h carries out peeling off and intercalation, dilute with deionized water again, instilling 10ml volume fraction in diluent is the hydrogen peroxide of 3%, it is stirred continuously to solution appearance golden yellow, after standing, remove solution supernatant, leave golden yellow mixed liquor, with hydrochloric acid, deionized water is centrifugal treating respectively, obtain graphene oxide dispersion, last lyophilizing, obtain golden yellow solid oxide Graphene.
Above-mentioned graphite should choose expansible graphite, it is preferred to purity is the inflatable 300 order graphite of 99.7%. Above-mentioned concentrated sulphuric acid refers to the sulphuric acid that mass fraction is 98%; Above-mentioned concentrated nitric acid refers to the fuming nitric aicd that mass fraction is 65%.
In step (3), it is necessary to lentamente potassium permanganate is joined in the mixed solution of preexpanding graphite and concentrated sulphuric acid.
In above-mentioned steps S2, when carrying out described hydro-thermal reaction, reaction temperature is 140��180 DEG C, and the time is 8��12h. Meanwhile, the three-dimensional porous Graphene hydrogel obtained needs to clean two to three times with deionized water, and hydrogel should be immersed in aqueous solution, is sure not convection drying, otherwise destroys three-dimensional appearance.
In above-mentioned steps S3, the pH value of described acid flux material is 1��5, it is possible to be hydrochloric acid, sulphuric acid or perchloric acid etc.; Aniline solution should be slowly added to and need magnetic agitation 1-2h; When adding Ammonium persulfate., need first the Ammonium persulfate. of solid to be dissolved in above-mentioned acid solution, and stir 10��30min; , when again carrying out hydro-thermal reaction, reaction temperature is 120��160 DEG C, and the time is 10��12h.
Polyreaction is carried out, it is therefore an objective to using Ammonium persulfate. as initiator, causing aniline generation polyreaction, thus obtaining polyaniline by adding Ammonium persulfate.. Gained mixed liquor is put and reacts under hydrothermal conditions, be the polymerization in order to accelerate aniline. Aniline monomer, under the effect of Ammonium persulfate. derivant, is polymerized, and generates polyaniline, is grown in inside three-dimensional grapheme, obtains three-dimensional grapheme-polyaniline mixed liquor.
In above-mentioned steps S3, the three-dimensional grapheme-Polyaniline of gained is after filtering is washed, and lyophilizing 12��24h under freezer dryer, by moisture extraction under the three dimensional structure keeping Graphene.
In above-mentioned steps S4, it is: rise to 750��1000 DEG C with the heating rate of 5��10 DEG C/min, by the uniform velocity heating up, make polyaniline in three-dimensional grapheme thoroughly decompose by the heating condition of described graphene oxide-polyaniline mixture; The process of pyrolytic is except all right inert atmosphere such as helium, argon of nitrogen atmosphere; The condition of inert gas shielding is, is placed in high temperature resistant tube furnace by three-dimensional grapheme-polyaniline mixture, first by tube furnace evacuation, removes air, then passes into noble gas with the speed of 100��300ml/min, form oxygen-free environment. .
Being 5.4��10.8% according to the weight/mass percentage composition of nitrogen in N doping three-dimensional grapheme prepared by the preparation method of N doping three-dimensional grapheme of the present invention, nitrogen content reaches as high as 10.8%;The electric capacity of described N doping three-dimensional grapheme is 145��228C, and electric capacity is up to and reaches 228C.
Preparation method provided by the invention passes through step S1, first graphite oxide is peeled off into graphene oxide, by step S2, prepare into three-dimensional grapheme hydrogel, by step S3, three-dimensional grapheme and aniline prepare three-dimensional grapheme-polyaniline composite material, the functional group in three-dimensional grapheme is made to form chemical combination key with the nitrogen element in polyaniline, make it after Pintsch process by step S4, nitrogen element is then formed with carbon and is bonded, play the skeleton function of part, support the three-dimensional appearance of three-dimensional grapheme, N doping three-dimensional grapheme prepared by said method is made to have higher nitrogen content, and the weight/mass percentage composition of nitrogen reaches as high as 10.8%, three dimensional structure with porous. wherein, three-dimensional grapheme is prepared in oxidation three-dimensional grapheme-Polyaniline process with aniline, aniline monomer and Ammonium persulfate. are when hydro-thermal, and aniline polymerization generates polyaniline and is grown in endoporus and the lamella of three-dimensional grapheme, obtains three-dimensional grapheme-polyaniline composite material.
The N doping three-dimensional grapheme that the present invention prepares has loose structure and high nitrogen doped structure simultaneously, has both had structure and the performance characteristics of porous three-dimensional Graphene, and its specific surface area is up to 580m2/ g, BJH desorption accumulation internal surface of hole amasss 474.86 (m2/ g), present the structure of porous, there is again higher nitrogen content, the weight/mass percentage composition of nitrogen reaches as high as 10.8%, make the electric capacity of N doping three-dimensional grapheme prepared by the method up to 228C, there is the chemical property of excellence, be highly suitable as preparing the similar energy-storage travelling wave tubes such as ultracapacitor. And above-mentioned preparation method is simple, be conducive to industrialized production.
In more concrete technical scheme, the preparation method of nitrogen-doped graphene comprises the following steps:
The present invention provide a kind of high-performance N doping porous three-dimensional Graphene and preparation method thereof, described method comprises the steps:
Step S1: use graphite to prepare graphene oxide;
Using graphite to prepare graphene oxide can adopt improvement Hummers method to prepare, and concrete step includes:
(1) it is 5g:200ml according to mass volume ratio, expansible graphite is joined in the mixed liquor being made up of the concentrated sulphuric acid that volume ratio is 3:1 and concentrated nitric acid, and at room temperature stirring mixing 24h preexpanding, form mixed solution, mixed solution is diluted in 1L deionized water, and carry out 3 filtering and washing, collect product and dry, dry and obtain preexpanding graphite; Preexpanding graphite is carried out 1800w microwave heating, microwave time 40��60s, obtains complete expanded graphite;
(2) it is 5g:300ml by expanded graphite and concentrated sulphuric acid mass volume ratio, expanded graphite is added in concentrated sulphuric acid, again by expanded graphite: potassium peroxydisulfate: the amount that phosphorus pentoxide mass ratio is 5:4.2:6.2 is separately added into potassium peroxydisulfate and phosphorus pentoxide, stirring reaction 3��5h at 60��80 DEG C, again by product dilution to the deionized water of 2L, filtering and washing, final drying 1 day, obtain pre-oxidation graphite;
(3) it is 5g:200ml according to the mass volume ratio of preexpanding graphite Yu concentrated sulphuric acid, the pre-oxidation graphite that will be obtained by step (2) adds in concentrated sulphuric acid, potassium permanganate is added according to the amount that mass volume ratio is 5:15 of preexpanding graphite with potassium permanganate, it is then heated to 35��40 DEG C, insulation 30��60min, stirring 1��2h carries out peeling off and intercalation, then by product dilution to 2L deionized water, obtain reactant liquor, reactant liquor instills hydrogen peroxide that 10ml volume fraction is 3% while stirring, it is stirred continuously to solution appearance golden yellow, through standing 12h, remove supernatant, leave the golden yellow liquid in bottom, and use 1mol/L dilute hydrochloric acid and deionized water centrifugal treating successively, obtain large stretch of continuous oxidation graphene dispersing solution,Last lyophilizing 12��24h process obtains golden yellow graphene oxide solid.
In step (3), it is necessary to lentamente potassium permanganate is joined in the mixed solution of preexpanding graphite and concentrated sulphuric acid.
Step S2: use graphene oxide to prepare three-dimensional grapheme hydrogel; It is 1��2mg:1ml according to mass volume ratio, add graphene oxide in deionized water, supersound process 1��2h configures graphene oxide water solution, graphene oxide water solution is transferred in the container of politef, it is put in reactor and carries out hydro-thermal reaction, reaction temperature is 120��180 DEG C, and the time is 8��12h, obtains three-dimensional porous Graphene hydrogel;
Three-dimensional porous Graphene hydrogel obtained above needs to clean two to three times with deionized water, and hydrogel should be immersed in aqueous solution, is sure not convection drying, otherwise destroys three-dimensional appearance.
Step S3: use three-dimensional grapheme hydrogel to prepare three-dimensional grapheme-polyaniline composite material, according to the amount of three-dimensional grapheme Yu acid solution mass volume ratio 1mg:20��50ml, described three-dimensional grapheme hydrogel is immersed in the acid solution that PH is 1��5, it is the amount of 1:5��10 according to three-dimensional grapheme and aniline mass ratio, quantitative aniline is instilled at acid solution, magnetic agitation 1��2h, make aniline dispersed in an acidic solution, and enter in three-dimensional grapheme endoporus, then it is the amount of 5:3��5 by aniline and Ammonium persulfate. mass ratio, it is quantitatively adding Ammonium persulfate., continue stirring 10��30min, above-mentioned mixed liquor is transferred in the container of politef, it is placed in reactor and carries out hydro-thermal reaction, reaction temperature 120��160 DEG C, response time 8��12h. aniline monomer is under the effect of Ammonium persulfate. derivant, it is polymerized, generate polyaniline, it is grown in inside three-dimensional grapheme, obtains three-dimensional grapheme-polyaniline mixed liquor, by three-dimensional grapheme-polyaniline mixed liquor sucking filtration, unnecessary impurity is cleaned successively with ethanol and deionized water, adopt the way of lyophilizing, extract out at the premise decline moisture keeping graphene three-dimensional structure, finally give dry three-dimensional grapheme-polyaniline composite material.
Above-mentioned aniline is liquid, adds excessive and should be slowly added to and magnetic agitation 1��2h.
When adding Ammonium persulfate., need first the Ammonium persulfate. of solid to be dissolved to be then added in mixed liquor in an acidic solution, and stirring 10��30min.
Step S4: use three-dimensional grapheme-polyaniline composite material to prepare N doping three-dimensional grapheme. By described three-dimensional grapheme-polyaniline composite material under nitrogen protection, it is heated to 750��1000 DEG C with 5��10 DEG C/min of heating rate, and insulation reaction 1��2h, naturally cool to room temperature, obtain N doping three-dimensional grapheme.
In the particular embodiment, three-dimensional grapheme-polyaniline mixture is placed in high temperature resistant tube furnace, first by tube furnace evacuation, removes air, then pass into noble gas with the speed of 100��300ml/min, form oxygen-free environment.
The N doping three-dimensional grapheme there is advantages that 1, being prepared by the method for the invention has higher nitrogen content so that it is have high capacitance and excellent chemical property; 2, above-mentioned N doping three-dimensional grapheme has loose structure, has the features such as high-specific surface area, high BJH desorption accumulation internal surface of hole be long-pending; 3, the preparation method technique of N doping three-dimensional grapheme of the present invention is simple, it is simple to operation, is conducive to industrialized production.
Accompanying drawing explanation
Fig. 1 is the high power scanning electron microscope (SEM) photograph of the three-dimensional grapheme of embodiment 3;
Fig. 2 is the high power scanning electron microscope (SEM) photograph of the three-dimensional grapheme-polyaniline of embodiment 3;
Fig. 3 is the high power scanning electron microscope (SEM) photograph of the three-dimensional grapheme-polyaniline of embodiment 3;
Fig. 4 is the high power scanning electron microscope (SEM) photograph after the high-temperature process of the N doping three-dimensional grapheme of embodiment 3.
Detailed description of the invention
Mainly in combination with drawings and the specific embodiments, nitrogen-doped graphene and preparation method thereof is described in further detail below.
Embodiment 1
Preparing of the N doping three-dimensional grapheme of the present embodiment is as follows:
Step S1: use graphite to prepare graphene oxide; Adopting improvement Hummers method to prepare, concrete step includes:
(1) 5g300 order expansible graphite is taken, each addition 150ml concentrated sulphuric acid and 50ml fuming nitric aicd, at room temperature stirring 24h preexpanding, obtain the dilution of mixed liquor 1L deionized water, by dilute solution filtering and washing 3 times, collection product dries, then makes graphite expand completely with microwave 1800W heating 60s.
(2) taking the 5g graphite expanded and add 300ml concentrated sulphuric acid, 4.2g potassium peroxydisulfate, 6.2g phosphorus pentoxide, at 60 DEG C of stirring reaction 5h, have reacted by deionized water water washing sucking filtration, dry for one day, have obtained pre-oxidation graphite.
(3) 200ml concentrated sulphuric acid, 15g potassium permanganate are added what obtain with pre-oxidation graphite, at 40 DEG C, stir 1h carry out peeling off and intercalation, again with the dilution of 2L deionized water, instilling 10ml volume fraction in diluent is the hydrogen peroxide of 3%, it is stirred continuously to solution appearance golden yellow, stand 12h, remove solution supernatant, leave the golden yellow mixed liquor in bottom, centrifugal treating is being distinguished with hydrochloric acid, deionized water, obtaining graphene oxide dispersion, last lyophilizing 12��24h obtains golden yellow solid oxide Graphene.
Step S2: use graphene oxide to prepare three-dimensional grapheme hydrogel; Being that solid oxide Graphene is joined in deionized water by 1mg:1ml according to mass volume ratio, supersound process 1h configures graphene oxide water solution; Graphene oxide water solution being transferred in the container of politef, be put in reactor and carry out hydro-thermal reaction, reaction temperature is 120 DEG C, and the time is 12h, obtains three-dimensional grapheme hydrogel.
Step S3: use three-dimensional grapheme hydrogel to prepare three-dimensional grapheme-polyaniline composite material, three-dimensional grapheme hydrogel is added the hydrochloric acid solution of 1mol/L, according still further to three-dimensional grapheme and aniline mass ratio 1:5, quantitative aniline is added in three-dimensional grapheme acid solution, stirring 2h, Ammonium persulfate. is added with Ammonium persulfate. mass ratio 5:3 according still further to aniline, continue stirring 10min, transfer in the container of politef, it is placed on reactor interior edema thermal response, reaction temperature is 120 DEG C, time is 10h, there is polyreaction under these conditions in aniline monomer, it is grown in inside three-dimensional grapheme, by product sucking filtration after cooling, unnecessary impurity is cleaned successively with ethanol and deionized water, adopt the way of lyophilizing, obtain the three-dimensional grapheme-polyaniline composite material dried.
Step S4: use three-dimensional grapheme-polyaniline composite material to prepare N doping three-dimensional grapheme. Three-dimensional grapheme-polyaniline mixture is placed in nitrogen (passing into speed is 200ml/min) atmosphere, first evacuation removes air and is passing into nitrogen, then heat to 750 DEG C of insulation reaction 2h with the heating rate of 5 DEG C/min, naturally cool to room temperature, obtain N doping three-dimensional grapheme.
The weight/mass percentage composition of each element of N doping three-dimensional grapheme prepared by the present embodiment is in Table 1.The chemical property of N doping three-dimensional grapheme prepared by the present embodiment is in Table 2.
Embodiment 2
Preparing of the N doping three-dimensional grapheme of the present embodiment is as follows:
Step S1: use graphite to prepare graphene oxide; Adopting improvement Hummers method to prepare, concrete step includes:
(1) 5g300 order expansible graphite is taken, each addition 150ml concentrated sulphuric acid and 50ml fuming nitric aicd, at room temperature stirring 24h preexpanding, obtain the dilution of mixed liquor 1L deionized water, by dilute solution filtering and washing 3 times, collection product dries, then makes graphite expand completely with microwave 1800W heating 40s.
(2) taking the 5g graphite expanded and add 300ml concentrated sulphuric acid, 4.2g potassium peroxydisulfate, 6.2g phosphorus pentoxide stir 3h at 80 DEG C, have reacted by deionized water water washing sucking filtration, dry for one day, have collected pre-oxidation graphite.
(3) 200ml concentrated sulphuric acid, 15g potassium permanganate are added what obtain with pre-oxidation graphite, at 35 DEG C, stir 2h carry out peeling off and intercalation, again with the dilution of 2L deionized water, instilling 10ml volume fraction in diluent is the hydrogen peroxide of 3%, it is stirred continuously to solution appearance golden yellow, stand 12h, remove solution supernatant, leave the golden yellow mixed liquor in bottom, centrifugal treating is being distinguished with hydrochloric acid, deionized water, obtaining graphene oxide dispersion, last lyophilizing 12��24h obtains solid oxide Graphene.
Step S2: use graphene oxide to prepare three-dimensional grapheme hydrogel; Being that 1.5mg:1ml adds graphene oxide in deionized water according to mass volume ratio, supersound process 2h configures graphene oxide water solution; Graphene oxide water solution being transferred in the container of politef, be put in reactor and carry out hydro-thermal reaction, reaction temperature is 180 DEG C, and the time is 8h, obtains three-dimensional grapheme hydrogel.
Step S3: use three-dimensional grapheme hydrogel to prepare three-dimensional grapheme-polyaniline composite material, three-dimensional grapheme hydrogel is added the sulfuric acid solution of 1mol/L, according still further to three-dimensional grapheme and aniline mass ratio 1:8, quantitative aniline is added in three-dimensional grapheme acid solution, stirring 1h, Ammonium persulfate. is added with Ammonium persulfate. mass ratio 5:4 according still further to aniline, continue stirring 30min, transfer in the container of politef, it is placed on reactor interior edema thermal response, reaction temperature is 160 DEG C, time is 8h, there is polyreaction under these conditions in aniline monomer, it is grown in inside three-dimensional grapheme, by product sucking filtration after cooling, unnecessary impurity is cleaned successively with ethanol and deionized water, adopt the way of lyophilizing, obtain the three-dimensional grapheme-polyaniline composite material dried.
Step S4: use three-dimensional grapheme-polyaniline composite material to prepare N doping three-dimensional grapheme. Three-dimensional grapheme-polyaniline mixture is placed in argon (passing into speed is 200ml/min) atmosphere, first evacuation removes air and is passing into argon, then heat to 1000 DEG C of insulation reaction 1h with the heating rate of 10 DEG C/min, naturally cool to room temperature, obtain N doping three-dimensional grapheme.
The weight/mass percentage composition of each element of N doping three-dimensional grapheme prepared by the present embodiment is in Table 1. The chemical property of N doping three-dimensional grapheme prepared by the present embodiment is in Table 2.
Embodiment 3
Preparing of the N doping three-dimensional grapheme of the present embodiment is as follows:
Step S1: use graphite to prepare graphene oxide; Adopting improvement Hummers method to prepare, concrete step includes:
(1) 5g300 order expansible graphite is taken, each addition 150ml concentrated sulphuric acid and 50ml fuming nitric aicd, at room temperature stirring 24h preexpanding, obtain the dilution of mixed liquor 1L deionized water, by dilute solution filtering and washing 3 times, collection product dries, then makes graphite expand completely with microwave 1800W heating 40s.
(2) taking the 5g graphite expanded and add 300ml concentrated sulphuric acid, 4.2g potassium peroxydisulfate, 6.2g phosphorus pentoxide stir 5h at 80 DEG C, have reacted by deionized water water washing sucking filtration, dry for one day, have obtained pre-oxidation graphite.
(3) 200ml concentrated sulphuric acid, 15g potassium permanganate are added what obtain with pre-oxidation graphite, at 35 DEG C, stir 2h carry out peeling off and intercalation, again with the dilution of 2L deionized water, instilling 10ml volume fraction in diluent is the hydrogen peroxide of 3%, it is stirred continuously to solution appearance golden yellow, stand 12h, remove solution supernatant, leave the golden yellow mixed liquor in bottom, centrifugal treating is being distinguished with hydrochloric acid, deionized water, obtaining graphene oxide dispersion, last lyophilizing 12��24h obtains golden yellow solid oxide Graphene.
Step S2: use graphene oxide to prepare three-dimensional grapheme hydrogel; Being that 2mg:1ml adds graphene oxide in deionized water according to mass volume ratio, supersound process 1.5h configures graphene oxide water solution; Graphene oxide water solution being transferred in the container of politef, be put in reactor and carry out hydro-thermal reaction, reaction temperature is 180 DEG C, and the time is 12h, obtains three-dimensional grapheme hydrogel. Fig. 1 is shown in the microstructure of three-dimensional grapheme
Step S3: use three-dimensional grapheme hydrogel to prepare three-dimensional grapheme-polyaniline composite material, three-dimensional grapheme hydrogel is added the sulfuric acid solution of 1mol/L, according still further to three-dimensional grapheme and aniline mass ratio 1:10, quantitative aniline is added in three-dimensional grapheme acid solution, stirring 1h, Ammonium persulfate. is added with Ammonium persulfate. mass ratio 5:5 according still further to aniline, continue stirring 10min, transfer in the container of politef, it is placed on reactor interior edema thermal response, reaction temperature is 140 DEG C, time is 12h, there is polyreaction under these conditions in aniline monomer, it is grown in inside three-dimensional grapheme, by product sucking filtration after cooling, unnecessary impurity is cleaned successively with ethanol and deionized water, adopt the way of lyophilizing, obtain the three-dimensional grapheme-polyaniline composite material dried, Fig. 2 is shown in the microstructure of three-dimensional grapheme-polyaniline prepared by the present embodiment, Fig. 3.
Step S4: use three-dimensional grapheme-polyaniline composite material to prepare N doping three-dimensional grapheme. Three-dimensional grapheme-polyaniline mixture is placed in argon (passing into speed is 200ml/min) atmosphere, first evacuation removes air and is passing into argon, then heat to 800 DEG C of insulation reaction 2h with the heating rate of 5 DEG C/min, naturally cool to room temperature, obtain N doping three-dimensional grapheme.
The weight/mass percentage composition of each element of N doping three-dimensional grapheme prepared by the present embodiment is in Table 1. The chemical property of N doping three-dimensional grapheme prepared by the present embodiment is in Table 2, and Fig. 4 is shown in the microstructure of N doping three-dimensional grapheme prepared by the present embodiment.
Each element weight/mass percentage composition of the nitrogen-doped graphene of the preparation of table 1 embodiment 1��embodiment 3
| Carbon (%) | Nitrogen element (%) | Oxygen element (%) | |
| Embodiment 1 | 90.8 | 5.8 | 3.4 |
| Embodiment 2 | 89.4 | 7.7 | 2.9 |
| Embodiment 3 | 86.5 | 10.8 | 2.7 |
From table 1 it follows that the N doping three-dimensional grapheme of embodiment 1��embodiment 3 preparation is respectively provided with higher nitrogen content, the weight/mass percentage composition of nitrogen is at least 5.8%, reaches as high as 10.8%.
The chemical property of the nitrogen-doped graphene of the preparation of table 2 embodiment 1��embodiment 3.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Electric capacity (C) | 145 | 196 | 228 |
As can be seen from Table 2, the nitrogen-doped graphene of embodiment 1��embodiment 3 preparation is respectively provided with relatively high electrochemical performance, usual about the 100C of capacitance data of general N doping, and in the market, the nitrogen-doped graphene sold for Xian Feng nanometer of Nanjing, electric capacity only has about 66.Visible it is proposed that the more traditional nitrogen-doped graphene tool of the chemical property of a kind of N doping three-dimensional grapheme be significantly improved, the N doping three-dimensional grapheme electric capacity at least 145C that we prepare, be up to 256C.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention. It should be pointed out that, for the person of ordinary skill of the art, without departing from the inventive concept of the premise, it is also possible to making some deformation and improvement, these broadly fall into protection scope of the present invention. Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of a N doping three-dimensional grapheme, it is characterised in that specifically comprise the following steps that
Step S1: use graphite to prepare graphene oxide;
Step S2: use graphene oxide to prepare three-dimensional grapheme hydrogel: to be 1��2mg:1ml according to mass volume ratio, add graphene oxide in deionized water, through supersound process, it is configured to graphene oxide water solution, then graphene oxide water solution is transferred in the container of politef, it is put into and carries out hydro-thermal reaction in a kettle., after cooling, obtain three-dimensional grapheme hydrogel;
Step S3: use three-dimensional grapheme hydrogel to prepare three-dimensional grapheme-polyaniline composite material: according to the amount of three-dimensional grapheme Yu acid solution mass volume ratio 1mg:20��50ml, described three-dimensional grapheme hydrogel is immersed in an acidic solution, it is the amount of 1:5��10 according to three-dimensional grapheme and aniline mass ratio, oxytropism solution instills quantitative aniline and stirs, allow aniline well in the microcellular structure of three-dimensional grapheme, then it is the amount of 5:3��5 by aniline and Ammonium persulfate. mass ratio, it is quantitatively adding Ammonium persulfate., and stir, again mixed liquor is transferred to polytetrafluoroethylcontainer container, it is put in reactor and continues hydro-thermal reaction, product sucking filtration is cleaned, three-dimensional grapheme-the polyaniline composite material dried is obtained through lyophilizing,
Step S4: use three-dimensional grapheme-polyaniline composite material to prepare N doping three-dimensional grapheme: under inert gas shielding; gained three-dimensional grapheme-Polyaniline is heated to 750��1000 DEG C; insulation 1��2h, cooled obtains high-performance N doping three-dimensional grapheme.
2. N doping three-dimensional grapheme preparation method according to claim 1, it is characterised in that using the method that described graphite prepares graphene oxide to adopt and improve Hummers method, concrete step includes:
(1) it is 5g:200ml according to mass volume ratio, expansible graphite is joined in the mixed liquor being made up of the concentrated sulphuric acid that volume ratio is 3:1 and concentrated nitric acid, and at room temperature stir preexpanding, use deionized water dilute reaction solution, collected by suction product also dries, heating with microwave 1800W, the microwave time, 40��60s made graphite expand completely;
(2) it is 5g:300ml by expanded graphite and concentrated sulphuric acid mass volume ratio, expanded graphite is added in concentrated sulphuric acid, again by expanded graphite: potassium peroxydisulfate: the amount that phosphorus pentoxide mass ratio is 5:4.2:6.2 is separately added into potassium peroxydisulfate and phosphorus pentoxide, 3��5h under stirring at 60��80 DEG C, react and used deionized water dilute reaction solution, again with deionized water wash sucking filtration and dry, obtain pre-oxidation graphite;
(3) it is 5g:200ml according to the mass volume ratio of preexpanding graphite Yu concentrated sulphuric acid, the pre-oxidation graphite that will be obtained by step (2) adds in concentrated sulphuric acid, it is then heated to 35��40 DEG C, stirring 1��2h carries out peeling off and intercalation, dilute with deionized water again, instilling 10ml volume fraction in diluent is the hydrogen peroxide of 3%, it is stirred continuously to solution appearance golden yellow, after standing, remove solution supernatant, leave golden yellow mixed liquor, with hydrochloric acid, deionized water is centrifugal treating respectively, obtain graphene oxide dispersion, last lyophilizing, obtain golden yellow solid oxide Graphene.
3. the preparation method of N doping three-dimensional grapheme according to claim 1, it is characterised in that in above-mentioned steps S2, when carrying out described hydro-thermal reaction, reaction temperature is 140��180 DEG C, and the time is 8��12h.
4. the preparation method of N doping three-dimensional grapheme according to claim 1, it is characterised in that in above-mentioned steps S3, when again carrying out hydro-thermal reaction, reaction temperature is 120��160 DEG C, and the time is 10��12h.
5. the preparation method of nitrogen-doped graphene according to claim 1, it is characterised in that in above-mentioned steps S3, the pH value of described acid flux material is 1��5, is hydrochloric acid, sulphuric acid or perchloric acid; Aniline solution should be slowly added to and need magnetic agitation 1-2h; When adding Ammonium persulfate., need first the Ammonium persulfate. of solid to be dissolved in above-mentioned acid solution, and stir 10��30min.
6. N doping three-dimensional grapheme preparation method according to claim 1, it is characterized in that, in above-mentioned steps S3, the three-dimensional grapheme-Polyaniline of gained is after filtering is washed, lyophilizing 12��24h under freezer dryer, extracts out moisture under the three dimensional structure keeping Graphene.
7. the preparation method of N doping three-dimensional grapheme according to claim 1, it is characterised in that in above-mentioned steps S4, the heating condition of described graphene oxide-polyaniline mixture is: rise to 750��1000 DEG C with the heating rate of 5��10 DEG C/min.
8. the preparation method of N doping three-dimensional grapheme according to claim 1; it is characterized in that; in above-mentioned steps S4; the condition of inert gas shielding is; three-dimensional grapheme-polyaniline mixture is placed in high temperature resistant tube furnace, first by tube furnace evacuation, removes air; pass into noble gas with the speed of 100��300ml/min again, form oxygen-free environment.
9. N doping three-dimensional grapheme preparation method according to claim 1, it is characterised in that the nitrogen content mass percent in nitrogen-doped graphene is 5.3��10.8%.
10. N doping three-dimensional grapheme preparation method according to claim 1, it is characterised in that the electric capacity of N doping three-dimensional grapheme is 145��228C, and specific surface area is 580m2/ g, BJH desorption accumulation internal surface of hole amasss 474.86m2/ g, presents the structure of porous.
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| CN113270623A (en) * | 2021-06-10 | 2021-08-17 | 中国科学技术大学 | Microbial electrochemical system |
| CN113559913A (en) * | 2021-08-23 | 2021-10-29 | 湖南文理学院 | Nitrogen-coated graphene composite material with sandwich structure and preparation method and application thereof |
| CN115845805A (en) * | 2022-11-18 | 2023-03-28 | 哈尔滨工业大学（深圳） | Preparation method of nitrogen-doped Fe-BTC derived carbon-based material for activating peroxymonosulfate |
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