CN106744849B - The method that polybenzimidazoles (PBI) class macromolecule prepares three-dimensional grapheme - Google Patents

The method that polybenzimidazoles (PBI) class macromolecule prepares three-dimensional grapheme Download PDF

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CN106744849B
CN106744849B CN201611236542.4A CN201611236542A CN106744849B CN 106744849 B CN106744849 B CN 106744849B CN 201611236542 A CN201611236542 A CN 201611236542A CN 106744849 B CN106744849 B CN 106744849B
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pbi
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doped graphene
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李忠芳
战明明
王素文
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Shandong University of Technology
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Abstract

The present invention is a kind of method for preparing three-dimensional grapheme, it is carbon source and nitrogen source with the mPBI in polybenzimidazoles (PBI), it is template with nano silica, iron oxide, iron hydroxide and magnesium oxide particle, uneven finish is in nano grain surface after PBI dissolution, benzimidazole ring in its macromolecule is regularly arranged in template surface, pyrolysis, goes template to obtain three-dimensional nitrogen-doped graphene.It is required that: mPB viscosity average molecular weigh 3 ~ 50,000；The mass ratio that template partial size is both 5 ~ 50nm is 3:1 ~ 1:3；Pyrolysis temperature is 700 ~ 1100 DEG C, is pyrolyzed 2 ~ 3h, is washed 3 times with dilute hydrochloric acid (or hydrofluoric acid), and deionized water is washed 3 times.Catalyst is precipitated for oxygen reduction catalyst, oxygen in the three-dimensional nitrogen-doped graphene of preparation, for fields such as fuel cell, metal-air battery, electrolysis, it can also be used to supercapacitor, lithium ion battery and sensor field.

Description

The method that polybenzimidazoles (PBI) class macromolecule prepares three-dimensional grapheme
Technical field
Belong to field of nano material preparation, is urged for the fuel cell in clean energy resource field, the cathode of metal-air battery Agent, electrolysis water catalyst, the fields such as electrode material for super capacitor and electrochemical sensor.
Background technique
Graphene is a kind of novel carbon two-dimension nano materials, as single layer of carbon atom it is tightly packed made of bi-dimensional cellular shape Structure.With unique optics, calorifics, electronics and mechanical performance (Allen M J, et al. Chem Rev (chemistry comment), 2010,110:132).But graphene often reunites because being interacted by π-π, is piled into graphite-structure, causes to compare table Area reduces, and the performance of various aspects is greatly reduced, to lose the superiority and inferiority performance of graphene.And three-dimensional grapheme is not only able to maintain The characteristic of graphene, and the porous mass-transfer efficiency that reactant and product can be improved formed.Therefore three-dimensional grapheme catalysis, The fields such as sensor, environmental protection and energy storage have important application value, and cause extensive concern (the DongX et al. of people ACS Applied material Interface (American Chemical Society-interface application material), 2012,4:3129).By right The research of grapheme material it is found that nitrogen-doping graphene, the cloud density on the adjacent carbon of nitrogen occurs Change, so that the carbon atom around nitrogen-atoms has part positive charge, is conducive to the adsorption activation of oxygen, to improve catalysis oxygen The activity and durability of gas reduction.
There are many method for preparing three-dimensional nitrogen-doped graphene: macromolecule that can be nitrogenous by using melamine resin etc. Materials pyrolysis；Graphene oxide is restored in the small-molecule substance of ammonia or nitrogen atom；Or nitrogenous high molecular material is used, As polyaniline (PANI) (Wu G, et al. Science (science), 2011,332:443), polypyrrole (PPy) (Li H, Yang F. J Mater Chem A (materials chemistry magazine), 2013,1:3446) it is used as forerunner's body method to prepare N doping Carbon material or nitrogen-doped graphene material.People often use the pyrolysis such as phenolic resin, pollopas and melamine resin to prepare Carbon material.
As nitrogen containing polymer material, polybenzimidazoles (PBI) imidazole ring structure high with nitrogen content.Benzimidazole ring The phenomenon that being the stiffening ring of armaticity, accumulation aggregation is easy to appear in polymer molecule, its accumulation aggregation in order to prevent can be with Some groups are added in PBI molecule, it is enable to improve its molecular flexibility.The study found that containing on imidazole ring in PBI molecule If imidazoles nitrogen, which carries out coordination with metal ion (such as Cu, Mn, Fe, Ru, Ti, Mo and Os), can prepare catalyst, catalyst is urged Change the redox reaction of organic compound, catalytic activity and stability preferably (Cameron C G, et al. J Phys Chem B, ((U.S.) Acta PhySico-Chimica Sinica B) 2001,105:8838).D Archivio is to porous PBI resin material The redox reaction that metallic ion coordination prepares catalyst organic compound is studied (D Archivio, et Al. Chem-A Eur J, (European The Chemicals) 2000,6 (5): 794) its catalytic performance is excellent.The synthetic method of PBI 5 kinds can be divided into: tetramine and dintrile, tetramine and diester, tetramine and diacid, tetramine and diamides, tetramine and dialdehyde, wherein virtue Fragrant tetramine and reacting for aromatic diacid are the most frequently used.The structural formula of mPBI are as follows:
The invention be using the polybenzimidazoles (PBI) of armaticity as provide carbon and nitrogen raw material, be with nano particle Hard mould agent, soluble PBI covering with paint to template surface, rigid benzimidazole ring are regularly arranged in template surface, Pyrolysis prepares nitrogenous carbon material under inert gas argon gas shielded.Template agent removing is removed with diluted acid, generates nano-pore.It is former by changing The ratio of material and hard template controls the size of template particles to control aperture, porosity and the graphite of the nitrogenous carbon material of synthesis The parameters such as the number of plies of alkene finally obtain ideal multi-layer three-dimension nitrogen-doped graphene.
Compared with the high molecular materials such as phenolic resin, pollopas, melamine resin, PBI the difference is that it Rigid benzimidazole ring containing armaticity, and the nitrogen content on imidazole ring is more abundant.Therefore high temperature pyrolysis PBI is available The carbon material of the N doping of high nitrogen-containing, and the regularly arranged side of the aromatic rings by introducing suitable template or control molecule To the grapheme material of available multilayer N doping respectively after pyrolysis.Nitrogen is prepared with materials such as polyaniline and polypyrroles to mix Miscellaneous graphene is compared, and PBI can dissolve, and is easy to cover with paint, lacquer, colour wash, etc. on template surface, and polyaniline, polypyrrole etc. are insoluble, can not be with mould Plate agent mixing.
Summary of the invention
The present invention has invented and a kind of mPBI has been used to prepare three-dimensional nitrogen-doped graphene as nitrogen source and utilization of carbon source template Method.MPBI is since solubility is better than ABPBI, so the two can choose the slightly larger polymer of the degree of polymerization, its advantage is that Its caking property can be more preferable, more abundant in nano grain surface covering with paint, since the benzimidazole molecule of the rigidity of the Solarium lycopersicoide can To be regularly arranged in template nano-material surface, by being pyrolyzed under inert gas protection, nitrogen is obtained after removing template agent removing Adulterate carbon material.It is required that PBI be it is soluble, in molecule rich in nitrogen imidazole ring and end ammonia, benzimidazole ring is rigid Property armaticity ring, pyrolysis when easily formed nitrogen-doped graphene structure.Its aperture, porosity, specific surface area and N doping stone The number of plies etc. of black alkene has PBI and nano template dosage, the factors such as partial size of template to determine.Mixed according to different quality ratio, Argon gas is protected in lower high temperature furnace and is pyrolyzed 2 ~ 3h, goes template that three-dimensional nitrogen-doped graphene can be obtained with dilute hydrochloric acid (or hydrofluoric acid). The material is applied to the oxygen reduction catalyst of fuel cell and metal air battery cathodes, and catalyst and load is precipitated in electrolysis water oxygen Body, supercapacitor, the fields such as electrolysis, sensor material.
The high molecular materials such as PBI and the above phenolic resin, pollopas and melamine resin difference is: PBI molecule Middle benzimidazole ring belongs to the stiffening ring of armaticity, contains imidazoles nitrogen in molecule on imidazole ring, belongs to the aroma type high score of rich nitrogen Sub- polymer.Therefore, it is pyrolyzed the carbon material of available N doping, if the plane of the aromatic rings of control molecule is according to one Direction arrangement, is pyrolyzed the graphene-structured of available N doping.With the high scores such as polyaniline, poly- (o-phenylenediamine), polypyrrole Unlike sub- material: PBI class macromolecule is soluble in the organic solvents such as DMAc, DMSO, is easily sufficiently mixed with template, It covers with paint, lacquer, colour wash, etc. on template surface, split-phase does not have fine due to its solubility when preparing 3D nitrogen-doped graphene nano material Operability.However, the high molecular materials such as polyaniline compound, polypyrrole are insoluble, template surface can not be covered with paint, lacquer, colour wash, etc., it can not be with mould Plate agent is blended.
Viscosity average molecular weigh being soluble between 30,000~50,000 that PBI can be prepared with solid phase method or liquid phase method DMAc, DMF, DMSO, in N-Methyl pyrrolidone equal solvent.Molecular weight is too big, and the solubility property of PBI is deteriorated；Molecular weight is too small Its viscosity is too small, cannot coated die plate agent well.
The method of the preparation of the graphene of three-dimensional N doping are as follows: prepare degree of polymerization PBI appropriate first, PBI is dissolved in Solution is formed in solvent, be added into solution it is suitable, partial size be 5 ~ 50 nm nanoparticle template agent do template, stirring makes It is sufficiently mixed uniformly.Under stiring, it heats, steams solvent at leisure and done to close, is transferred in vacuum oven at 60 ~ 120 DEG C Drying.It is finely ground in mortar, it is laid in porcelain boat bottom, is put into electric tube furnace, under protection of argon gas, at 700~1100 DEG C, It is pyrolyzed 2 ~ 3h.It is cooled to room temperature, takes out to furnace temperature, repeatedly washing is filtered with removing template agent removing with dilute hydrochloric acid (or hydrofluoric acid), is used Deionized water is cleaned, and product is dried to obtain.
In the present invention, template can be a variety of nano-scale oxides or hydroxide particles.Three-dimensional can be prepared Nitrogen-doped graphene, the partial size and additional amount of template are crucial: the partial size of template determines the aperture of the carbon material of preparation； The additional amount of template determines the number of plies and performance of the graphene of preparation, and additional amount is very little, can only obtain porous carbon materials, adds Enter excessively, the obtained three-dimensional grapheme number of plies is very little, after removing template agent removing, is easy to collapse, it is broken to can only obtain broken graphene Piece.The granularity of template has a certain impact to the amount that template is added, and granularity is small, and surface area is big, the template needed The amount of agent is just few；, whereas if granularity is big, the amount of the template needed is just more.The dosage of template are as follows: PBI and template Mass ratio be 3:1~1:3；Ratio variation is related with the granularity of template.Granularity is from 5 ~ 50 nm.In inert gas shielding Lower pyrolysis, pyrolysis temperature are as follows: 700~1100 DEG C；Dilute hydrochloric acid (or hydrofluoric acid) is used in washing, after repeatedly template agent removing is removed in washing, is used Deionized water, which is washed to neutrality, dries.
The graphene characterizing method of three-dimensional N doping are as follows: aperture, porosity, Kong Rong and specific surface area nitrogen adsorption instrument (BET), the Morphology analysis of product scanning electron microscope (SEM) and projection electron microscope (TEM), graphene number of plies It can be characterized by high power transmission electron microscope (HRTEM) and Raman spectrum.Degree of graphitization, the graphene-structured of product It can be characterized with X-ray powder diffraction (XRD), Raman spectrum with the number of plies.The element of product forms, and valence state can be penetrated with X- Photoelectron spectra (XPS) is characterized, and is reacted with rotating disk electrode (r.d.e) (RDE) come the catalytic oxidation-reduction of test product (ORR) the capacitive property test of performance, water electrolysis oxygen evolution reaction (EOR), evolving hydrogen reaction (EHR) and product can use circulation volt Peace (CV), linear volt-ampere (LSV), Tafel curve and charge-discharge performance are tested.Durability test of the product as catalyst CV, LSV and chronoa mperometric plot (i-t) can be used.The catalytic performance of product finally needs to assemble metal-air battery, hydrogen-oxygen Fuel cell, the electrolytic cell of electrolysis water, supercapacitor and sensor test its performance.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 700~1100 DEG C.The too low PBI of temperature cannot be pyrolyzed completely, be obtained The electric conductivity of product is poor；After pyrolysis temperature reaches optimum temperature, then to increase pyrolysis temperature its performance constant, still, indifferent gas When insufficient oxidation reaction can occur for body protection, so pyrolysis temperature is unsuitable excessively high.
Specific embodiment
The preparation of [embodiment 1] mPBI: polyphosphoric acids is added in the three-necked flask equipped with electric stirring and nitrogen protection (PPA) (100g), the lower 160 DEG C of stirrings 1h of nitrogen protection is to remove extra moisture and air.By DABz (4g, 18.7 Mmol) and M-phthalic acid (3.1g, 18.7 mmol) is uniformly mixed, and is slowly added in three-necked flask.Control nitrogen Flow velocity prevents DABz to be oxidized, while reaction temperature being promoted to 200 DEG C and continues to keep the temperature, is stirred to react 5-8h.With reaction The increase of time, polymerization system gradually become sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to largely It reels off raw silk from cocoons in deionized water, cleans, drying, crush, to remove polyphosphoric acids and unreacted reactant, i.e., deionized water is repeatedly washed MPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
[embodiment 2] Solid phase synthesis mPBI: by DABz (4g, 18.7 mmol) and 4,4 '-diphenyl ether diformazans Sour (4.83g, 18.7 mmol) are uniformly mixed in being fully ground in mortar, be transferred to nitrogen protection, blender three In mouth flask.Lead to nitrogen 15min to drain the air in flask.N2Protection, under stirring, 225 DEG C of oil bath heating keep 3h.It is cold But it takes out afterwards, finely ground, N2Under protection, heating in electric furnace is warming up to 270-275 DEG C, keeps 3h.It is cooled to room temperature, product is taken Out, finely ground to get mPBI is arrived, with the molecular weight of determination of ubbelohde viscometer mPBI.
[embodiment 3] uses the SiO of partial size 30nm2It is mixed for template with mPBI, with mPBI and SiO2Template mass ratio is For 1:1: in the beaker of 250mL, ten thousand) the mPBI(viscosity average molecular weigh 3 ~ 5 of 1g is added to be made with 20mL DMAc, heating, stirring It is dissolved, and is slowly added into 1g SiO under stiring2Partial size is that the nano particle of 30nm makes it be uniformly dispersed.Obtained thick liquid Body is heated to be concentrated under stiring and closely be done, and dry at 100 DEG C in vacuum oven, solid is finely ground in mortar, is transferred to porcelain In boat, under protection of argon gas, 900 DEG C of pyrolysis 2-3h, are down to room temperature to furnace temperature in high-temperature electric resistance furnace, take out, finely ground, obtain black Pulverulent solids are transferred in 250mL conical flask, and the hydrofluoric acid of 70mL is added, and heating, stirring for 24 hours, filter, and use hydrogen fluorine in this way Acid elution three times, be washed to neutrality, be dried to obtain black powder solid product 0.71g.BET test shows its pore-size distribution For 30nm, specific surface area is 948.6 m2 g-1, the product that SEM test shows is porous carbon materials, and TEM and HRTEM divide Analysis shows that product is three-dimensional grapheme structure carbon material, and aperture 30nm, graphene, which is drawn a bow to the full back, is shown to be 2 ~ 4 layers of graphene.XRD Show that product is 2 ~ 4 layers of graphene-structured with Raman spectrum test；XPS analysis shows that product nitrogen content is 6.4%, and nitrogen For pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping.Under its 0.1mol/LKOH Catalytic oxidation-reduction performance, oxygen initial reduction current potential are 0.96V vs RHE, and electron transfer number 3.97, durability is good；Magnesium Air cell performance is up to 98 mW/cm2.It is 580.2 mW/cm for its peak power of hydrogen-oxygen fuel cell2, the sulfuric acid of 0.5mol/L It is 1.55V vs RHE that take-off potential, which is precipitated, in oxygen in solution, and limiting current density reaches 110mA/cm2.Supercapacitor is than electricity Holding is 338F g-1, be recycled 10000 times still holding capacitor value 97%.
[embodiment 4] as described in Example 3, other conditions are identical, and only the quality of mPBI and silica becomes 2: 1, it is similarly obtained the solid powder of black.BET test shows that its pore-size distribution is still 30nm, but its specific surface area is then reduced to 703 m2 g-1, SEM and TEM test show its it is internal be porous structure carbon material, surface is multi-layer graphene structure, XRD and Raman data show 7 ~ 8 layers of the number of plies of its graphene.XPS data are similar with the product of embodiment 3.Its 0.1mol/ Catalytic oxidation-reduction performance under LKOH, oxygen initial reduction current potential are 0.87V vs RHE, and electron transfer number 3.63, durability is good It is good；Magnesium air battery performance reaches 77mW/cm2.It is 279mW/cm for its peak power of hydrogen-oxygen fuel cell2, the sulfuric acid of 0.5mol/L It is 1.58V vs RHE that take-off potential, which is precipitated, in oxygen in solution, and limiting current density reaches 40mA/cm2.Supercapacitor specific capacitance For 227F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 5] as described in Example 3, other conditions are identical, and only the quality of mPBI and silica becomes 1: 2, it is similarly obtained the solid powder of black.BET test shows 10 ~ 30nm of its pore size distribution range, but its specific surface area then drops For 847 m2 g-1, SEM and TEM test show its it is internal be porous structure carbon material, surface is multi-layer graphene structure, XRD and Raman data show 7 ~ 8 layers of the number of plies of its graphene.XPS data are similar with the product of embodiment 3.Its 0.1mol/ Catalytic oxidation-reduction performance under LKOH, oxygen initial reduction current potential are 0.87V vs RHE, and electron transfer number 3.63, durability is good It is good；Magnesium air battery performance reaches 77mW/cm2.It is 279mW/cm for its peak power of hydrogen-oxygen fuel cell2, the sulfuric acid of 0.5mol/L It is 1.58V vs RHE that take-off potential, which is precipitated, in oxygen in solution, and limiting current density reaches 40mA/cm2.Supercapacitor specific capacitance For 247 F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 6] as described in Example 3, other conditions are identical, and only pyrolysis temperature is 700 DEG C, the product of preparation Similar with embodiment 3, only electric conductivity is poor, and catalytic performance is also poorer.Other conditions are identical, and pyrolysis temperature is 1100 DEG C, Product various aspects of performance is similar than embodiment 3.
[embodiment 7] as described in Example 3, other conditions are identical, are only 5nm SiO with partial size2Particle does template Agent, at this moment, since the partial size of template becomes smaller, surface area increases, and the dosage of mPBI increases, then the quality of mPBI and template Than being changed to as 3:1, obtained product is similar to Example 3, and only for its pore-size distribution in 5 ~ 10nm, specific surface area is 1698 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.93V vs under 0.1mol/LKOH RHE, electron transfer number 3.95, durability is good；Magnesium air battery performance reaches 95mW/cm2.For its peak of hydrogen-oxygen fuel cell Power is 571.6mW/cm2, it is 1.54V vs RHE, carrying current that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L Density reaches 120 mA/cm2.Supercapacitor specific capacitance is 445F g-1, it is recycled 10000 still holding capacitor values 96%。
[embodiment 8] as described in Example 3, other conditions are identical, are only 50nm SiO with partial size2Particle does mould Plate agent, at this moment since the partial size of template increases, surface area reduces, and the dosage of mPBI is reduced, then the matter of mPBI and template Amount ratio is changed to as 1:3, and obtained product is similar to Example 3, and only for its pore-size distribution in 50nm, specific surface area is 765 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.89V vs under 0.1mol/LKOH RHE, electron transfer number 3.96, durability is good；Magnesium air battery performance reaches 89mW/cm2.For its peak of hydrogen-oxygen fuel cell Power is 468mW/cm2, it is 1.54V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and carrying current is close Degree reaches 80 mA/cm2.Supercapacitor specific capacitance is 248F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 9] uses Fe2O3Or iron hydroxide nano particle is template, partial size is 30 nanometers.Other experiment conditions are same Embodiment 3.The mass ratio of mPBI and template is 1:1.Its result is similar to Example 3.Product is three-dimensional grapheme structural carbon Material, aperture 30nm, 1088.3 m2 g-1, it is 2 ~ 4 layers of graphene.Nitrogen content is 7.7%, and nitrogen is pyridine type nitrogen and pyrroles Type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping.Catalytic oxidation-reduction performance, oxygen under its 0.1mol/LKOH Gas initial reduction current potential is 0.95V vs RHE, and electron transfer number 3.96, durability is good；Magnesium air battery performance reaches 106mW/cm2.It is 573.5mW/cm for its peak power of hydrogen-oxygen fuel cell2, starting is precipitated in oxygen in the sulfuric acid solution of 0.5mol/L Current potential is 1.56V vs RHE, and limiting current density reaches 120mA/cm2.Supercapacitor specific capacitance is 468F g-1, can follow The 96% of the still holding capacitor value of ring 10000 times.Iron oxide and iron hydroxide template dilute hydrochloric acid removing template, due to receiving The iron ion on rice grain surface can generate coordinate bond with the nitrogen-atoms in mPBI molecule, can play the role of fixed nitrogen, make three The nitrogen content for tieing up nitrogen-doped graphene is higher.The case where template of other partial sizes is as template is similar with above embodiments.
[embodiment 10] uses MgO template, and partial size is 30 nanometers.Other experiment conditions are the same as embodiment 3.MPBI and template The mass ratio of agent is 1:1.Its result is similar to Example 3.Aperture is 30nm, 1074.9 m2 g-1, it is 2 ~ 4 layers of graphene.Nitrogen Content is 6.6%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping. Catalytic oxidation-reduction performance under its 0.1mol/LKOH, oxygen initial reduction current potential are 0.94V vs RHE, and electron transfer number is 3.91, durability is good；Magnesium air battery performance reaches 92mW/cm2.It is 465.7mW/ for its peak power of hydrogen-oxygen fuel cell cm2, it is 1.53V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches 110mA/ cm2.Supercapacitor specific capacitance is 337F g-1, be recycled 10000 times still holding capacitor value 96%.Magnesium oxide template can be with It is removed with dilute hydrochloric acid.
[embodiment 11] is also similar to the above embodiments with the structure of other templates.Template preparation of different shapes Three-dimensional nitrogen-doped graphene the case where it is similar with above embodiments, the pattern in the hole only seen from pattern is different, but It is that performance is similar with above embodiments.

Claims (3)

1. the method for preparing three-dimensional nitrogen-doped graphene with polybenzimidazoles (PBI) class macromolecule, it is characterised in that: such virtue The polybenzimidazoles molecule of the rigidity of fragrance can be regularly arranged on the surface of template nano particle, under protection of argon gas, Pyrolysis, the method for removing template agent removing prepare three-dimensional nitrogen-doped graphene；PBI be it is soluble, macromolecular chain is by armaticity Rigid benzimidazole composition, and contain imidazole ring and Amino End Group rich in nitrogen, the lower pyrolysis of argon gas protection, easy shape in molecule At nitrogen-doped graphene structure, pore-creating is played the role of in decarboxylation when the carboxyl in molecule is pyrolyzed；Nano template is SiO2, oxidation Magnesium, iron oxide or iron hydroxide, partial size is in 5~50nm；PBI and the mass ratio of nano template are 2:1~1:2；Hybrid mode Are as follows: PBI solution is mixed with nano particle, after being uniformly mixed, is stirred lower heating and is steamed solvent to closely doing, vacuum drying is ground Carefully；In high temperature furnace, under argon gas protection, at 700~1000 DEG C, it is pyrolyzed 2~3 hours, after cooling, takes out, with dilute hydrogen fluorine Acid or dilute hydrochloric acid washing are to go template agent removing to obtain three-dimensional nitrogen-doped graphene.
2. the method according to claim 1 for preparing three-dimensional nitrogen-doped graphene with polybenzimidazoles (PBI) class macromolecule, Its PBI is poly- [2,2 '-(phenyl) -5,5 '-bibenzimidaz sigmales] (mPBI) or poly- [4,4 '-(diphenyl ether bases) -5,5 ' - Bibenzimidaz sigmale] (oPBI), it is characterised in that: polymer viscosity average molecular weigh can be dissolved in dimethylacetamide between 3~50,000 Amine (DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, any one in dimethylbenzene In solvent, since the solubility property of mPBI or oPBI is better than poly- (2,5 benzimidazole) (ABPBI), so their degree of polymerization is wanted It is bigger than ABPBI.
3. the method according to claim 1 for preparing three-dimensional nitrogen-doped graphene with polybenzimidazoles (PBI) class macromolecule, It is characterized by: it is a nanometer ball-type, cube, multiedge cylinder, cylindric or cuboid that nano template, which is grain shape,.
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