CN110283288A - A kind of mass producible Heteroatom doping has cavity structure polymer nano-microspheres and preparation method thereof - Google Patents
A kind of mass producible Heteroatom doping has cavity structure polymer nano-microspheres and preparation method thereof Download PDFInfo
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- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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Abstract
The present invention discloses a kind of core-shell structure polymer nano-microspheres and preparation method thereof of Heteroatom doping；The method overcomes template complexity and is limited equal shortcomings, using mild reaction temperature (room temperature), with melamine, arylamine, aldehyde is raw material, 3, 5- diaminobenzoic acid or 2, in the presence of 4- diamino benzene sulfonic acid, in acetone water mixed system or pure acetone system, utilize the difference of reactant reaction rate, by aldehyde and general formula 3, 5- diaminobenzoic acid or 2, 4- diamino benzene sulfonic acid generates schiff bases, the nanosphere of cladding is made in arylamine with the schiff bases addition of generation again, the nanosphere of core-shell structure is obtained impregnating or washing by different solvents.The easy to operate of process of the present invention, mild condition, rapid reaction；Using the method prepare the size morphology controllable of resulting nanosphere product, epigranular, be uniformly dispersed, yield is big and Heteroatom doping uniformly, toughness of material enhances.It has a good application prospect.
Description
Technical field
The invention belongs to nanometer new material technology fields, and in particular to a kind of Heteroatom doping polymerize with cavity structure
Object nanosphere and preparation method thereof.
Background technique
Nanosphere with cavity structure is widely used in reality, and mainly include two kinds of structures: one is cores
Shell structure microballoon, another kind are hollow spheres.Nuclear shell structure nano microballoon refers to nanosphere by a closely related shell and one
The nano particle of a core composition.The composition of nucleocapsid can be organic matter, be also possible to inorganic matter, can also be biomass etc., by
This forms the nanoparticle of various different structure, and due to the diversity of core and shell composition, the nanometer for assigning core-shell structure is micro-
Ball multifrequency nature, such as optics, magnetism, electronics, mechanically and chemically property.And hollow sphere then has special hollow structure, inside
The features such as cavity is big.These with cavity structure nanosphere can be widely applied to battery, capacitor, sensor, drug delivery,
The numerous areas such as quantum dot, photonic crystal and catalysis.And the method for synthesizing nucleocapsid or hollow Nano carbon balls before relies primarily on
In template.Wherein hard template method is cumbersome, and low output limits its application, and hard template used need to be at NaOH or HF
Reason, template removal are difficult；Soft template method is restricted due to its limited obtainable template, and cumbersome, stream
Journey is long.
The high-energy density and high capacity of lithium-sulfur cell are just causing the extensive concern of people, the energy density of the battery of lithium sulphur
Five times or so of common lithium battery can be reached, be widely used background.Although lithium-sulfur cell has wide practical use, but electricity
There are problems for the anode in pond.Such as 1. the poorly conductive of sulphur causes battery specific capacity low, 2. sulphur exists during lithiumation
Study of Volume Expansion causes positive electrode to destroy, and 3. the diffusion of polysulfide causes capacity attenuation serious, the low (shuttle of coulombic efficiency
Effect).Nano particle with cavity has the advantage that 1. synthesis High-conductivity carbon shell, then mixes sulphur, can solve sulphur conduction
Property difference problem, 2. there is to alleviate volume expansion of sulphur during lithiumation in internal cavities, 3. Heteroatom doping
Shell can reduce the diffusion of polysulfide to reduce shuttle effect.These advantages can effectively solve existing for lithium-sulphur cell positive electrode
Problem.
Supercapacitor is as a kind of renewable green energy storage device, in new-energy automobile, electronics, the numerous areas such as national defence
It is widely used.Main problem existing for capacitance present device is that energy is low with power density, high production cost.Carbon material is mesh
It is preceding capacitor area it is most widely used be also most effective fruit electrode material.Mainly there is a graphene, carbon nanotube, active carbon,
And various nanostructured carbon materials.Carbon nanotube and graphene were used widely in capacitor area in recent years, but by
The limitation of its cost, is difficult to realize large-scale production.Solve that energy is low with power density there are many methods, effective method has adjusting
Pore structure, and doping hetero atom.The performance of capacitor can be significantly improved with micropore and mesoporous material, micropore is for storing up
Can, it is mesoporous that the channel of ion fast transfer can be provided.Hetero atom (such as N, O, S, B etc.) can change carbon material surface performance, from
And improve capacitor capacitance.The nanosphere with cavity structure that the present invention synthesizes can generate after calcining and activating is handled
Hierarchical porous structure has cavity structure nano carbon microsphere, and there are many hetero atoms to exist for obtained microballoon.Have in capacitor area and answers extensively
Use prospect.
The existing side that nitrogenous nanosphere is prepared from melamine or melamine and resorcinol mixture at present
Method, further nitrogenous nano carbon microsphere can be obtained in roasting.Specific method has water bath heating and hydro-thermal method.Water bath heating is made first
Standby prepolymer, i.e., the methylolated product of N-, referred to as prepolymer occur for melamine and formaldehyde, then prepolymer is further existed
Polycondensation under acid condition prepares melamine resin microballoon.Hydro-thermal method equally prepares prepolymer first, then in hydro-thermal item
Prepolymer polymerization is obtained into melamine resin microballoon under part；Need higher reaction temperature (70-300 DEG C) and longer
Reaction time (6-72h) and it is difficult to realize high-volume industrial application.It can high-volume under microballoon room temperature prepared by the present invention
Production, it is easy to accomplish industrial applications.
Summary of the invention
The purpose of the present invention is to provide a kind of no template, room temperature condition, rapid reactions and containing the tool of Heteroatom doping
There is the preparation method of cavity structure polymer nano-microspheres；This method is under agitation, using mild reaction temperature 10-
50 DEG C, with m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, 2,6-diaminopyridine, 1,5-diaminonaphthalene or 1,8- diaminonaphthalene and
Melamine is raw material, in ortho-aminobenzoic acid, p-aminobenzoic acid, gavaculine, metanilic acid, adjacent aminobenzene
Sulfonic acid, p-aminobenzene sulfonic acid, 3,5- diaminobenzoic acid or 2, in the presence of 4- diamino benzene sulfonic acid, in acetone and water mixed solution
It is different using reactant autoreactivity dynamics or in pure acetone system, a kind of nanosphere of cladding is formd, then use
Suitable solvent soaking or washing, selective removal internal component make internal formation cavity, and then form core-shell structure or sky
Core structure nanosphere.Resulting nanosphere primer size morphology controllable, epigranular, dispersion are prepared using the method
Even, yield is big and Heteroatom doping uniformly, toughness of material enhancing.
Specifically, the preparation method with cavity structure polymer nano-microspheres of Heteroatom doping of the present invention,
The following steps are included:
(1) under the conditions of 10-50 DEG C；By m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, 2,6- diamino-pyridine, 1,5- bis-
One or more of amino naphthalenes or 1,8- diaminonaphthalene；
With melamine；
With ortho-aminobenzoic acid, p-aminobenzoic acid, gavaculine, metanilic acid, orthanilic acid, right
One or more of aminobenzenesulfonic acid, 3,5- diaminobenzoic acid, 2,4- diamino benzene sulfonic acid are dissolved in solvent；
The solvent is selected from acetone, water methanol, ethyl alcohol, dimethyl sulfoxide, N-N- dimethylformamide, tetrahydrofuran, second
The mixing of one or more of glycol, normal propyl alcohol；
(2) ammonium hydroxide, sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate or carbon are added in Xiang Shangshu system
Potassium hydrogen phthalate solution, stirs evenly, regulation system pH value to 8-9；
(3) at room temperature, in Xiang Shangshu solution be added formaldehyde, glyoxal, malonaldehyde, butanedial, glutaraldehyde or oneself
Dialdehyde, it is stirred to react, obtains polymer nano-microspheres.
(4) by obtained nanosphere be put into methanol, ethyl alcohol, formaldehyde or formic acid and their mixed solution impregnate or
Washing just obtains the nanosphere with cavity structure.
Wherein, step (1) ortho-aminobenzoic acid, p-aminobenzoic acid, gavaculine, metanilic acid, adjacent ammonia
One or more of base benzene sulfonic acid, p-aminobenzene sulfonic acid, 3,5- diaminobenzoic acid or 2,4- diamino benzene sulfonic acid are in step
(1) concentration that solution is formed in is 0.002~1.0mol/L.M-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, 2,6- diamino pyrrole
One or more of pyridine, 1,5- diaminonaphthalene, 1,8- diaminonaphthalene or melamine form solution concentration in step (1)
0.002-1.0mol/L。
Wherein, step (1) temperature is 10-50 DEG C, preferably 25 DEG C of room temperature
Wherein, addition ammonium hydroxide, sodium bicarbonate described in step (2), sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate or
Potassium bicarbonate solution stirs evenly (about 0.5 hour) or forms clarification, clear solution, the time, about 1-6 was small by the way of being added dropwise
When；
It is added by the way of being added dropwise in above-mentioned steps (3) aldehyde, usage amount is aldehyde radical amount relative to arylamine 5-15
The aldehyde of times equivalent.
In above-mentioned steps (3), preferably under agitation, solution is become cloudy by clarification as time went on；Holding is stirred
It mixes polycondensation reaction 1~6 hour, product is centrifuged with 6000 revs/min, with different solvent soakings, forms cavity structure.Centrifugation
It afterwards dries 6 hours under the conditions of 100 DEG C of product, obtains uniform particle sizes, morphology controllable, good dispersion have cavity structure polymer nano
Meter Wei Qiu；
Further, in the above-mentioned technical solutions, it in step (3), is stirred to react 1~12 hour after aldehyde is added.
Method as discussed above of the present invention uses the basic materials such as melamine, arylamine and aldehyde for raw material, and reaction system is
Acetone and water are added the pH that ammonium hydroxide adjusts reaction, are conducive to the regulation to polymer nano-microspheres uniformity and pattern, amino aryl
The addition of fragrant race's derivative is conducive to the quick formation and pattern control of nanosphere.M-phenylene diamine (MPD), p-phenylenediamine, adjacent benzene in system
It is diamines, 2,6- diamino-pyridine, 1,5- diaminonaphthalene, 1,8- diaminonaphthalene, the concentration of melamine, ortho-aminobenzoic acid, right
Aminobenzoic acid, gavaculine, metanilic acid, orthanilic acid, p-aminobenzene sulfonic acid, 3,5- diaminobenzene first
Acid or 2,4- diamino benzene sulfonic acid, ammonia volume mutually restrict.Pass through amino aromatic derivant in change system and virtue
The molar ratio of amine, arylamine and the molar ratio of aldehyde, the concentration of arylamine, different ammonium hydroxide additional amounts, different reaction temperature (10-50
DEG C) it can all realize the regulation of thick, core the size of the partial size to polymer nano-microspheres, shell.
The present invention is described above to prepare what Heteroatom doping was obtained with cavity structure nanosphere using template-free method
The nitrogen of the polymer nano-microspheres of Heteroatom doping contains to measure 20-80wt%, and content is adjustable.100nm-1 μm of nanosphere diameter,
Uniform particle sizes, N, S hetero atom are evenly distributed, size adjustable, good dispersion.
The nitrogenous sulphur polymer nano-microspheres obtain nitrogenous sulphur charcoal nanosphere after roasting under inert gas atmosphere.Nanometer
100nm-1 μm of microsphere diameter, uniform particle sizes, hetero atom are evenly distributed, size adjustable, good dispersion.
It is cumbersome that the method for the present invention overcomes traditional hard template method to be prepared with cavity structure microballoon, severe reaction conditions,
The disadvantages of template removal is difficult.Overcome limitation and cumbersome, process of the soft template method by limited obtainable template
Long disadvantage, the new synthetic method that the present invention uses is easy to operate, Yi Fang great, easily realizes industrialization.
The present invention provides a kind of positive material for obtaining the above method there is cavity structure nanosphere to be used for lithium-sulfur cell
Material, solves the problems, such as that lithium-sulphur cell positive electrode exists.
The present invention provide it is a kind of the above method is obtained to be used for capacitor electrode material with cavity structure nano carbon microsphere, use
In solving capacitor energy and power density is low, the problems such as high production cost.
The present invention, the synthetic method of abandoning tradition hard template and soft template are anti-using reactant itself using template-free method
Answer the difference of dynamic performance, a step forms a kind of clad structure nanosphere, then with product shape inside simple extraction
At the method for cavity, many and diverse template process can avoid, so that the polymer nano-microspheres of synthesis nucleocapsid or hollow structure
Become simple, and can be mass-produced, provides more possibility for this application for having special construction nanosphere.
The utility model has the advantages that
1. the method for the invention uses completely new process route, can be produced at room temperature in mild operation temperature；It keeps away
70~100 DEG C or hydrothermal reaction condition relatively harsh used in traditional handicraft are exempted from；It is especially adapted for use at normal temperature
(15-25 DEG C) quickly carries out, and more conducively promotes and applies.
2. the present invention is departing from traditional hard template, the method for soft template, using the difference of two kinds of reactant reaction rates,
By simple extraction or washing operation, the polymer microballoon of core-shell structure can be obtained.
3. the simple process that the present invention uses, easy to operate, yield is big, can be according to use demand, by control system
It is the ratio of amino aromatic derivant and arylamine, the ratio of arylamine and aldehyde, the concentration of arylamine, different ammonium hydroxide additional amounts, different anti-
Temperature (10-50 DEG C) is answered to obtain the nanosphere of the core-shell structure of size and morphology controllable.
4. the method for the invention rapid reaction, step (3) has product generation within a few minutes being added dropwise after aldehyde,
Under agitation, solution is become cloudy by clarification as time went on, and product gradually increases, and until after reaction, is centrifuged
Take out polymer nano-microspheres.Being impregnated or being washed using specific solvent can just obtain with cavity structure nanometer polymer microballoon.
5. the hollow carbon sphere that the present invention synthesizes, by not same amount KOH and K2CO3It is activated (800 DEG C of 1h), then multiple with sulphur
It closes (sulfur content 50%-80%), by K2CO3Handle (K2CO3: sample=3:1 sulfur content~80%), electric discharge can reach for the first time
To 1176mAh g-1By recycling 100 times under the current density of 0.2C, battery is still able to maintain 670mAh g-1.At KOH
Electric discharge can reach 1172mAh g to reason (KOH: sample=1:1 sulfur content~80%) for the first time-1By under the current density of 0.2C
Circulation 180 times, battery is still able to maintain 602mAh g-1.KOH processing (KOH: sample=0.75:1 sulfur content~80%) is put for the first time
Electric energy reaches 1334mAh g-1By recycling 300 times under the current density of 1C, battery is still able to maintain 560mAhg-1。
Detailed description of the invention
Fig. 1: 3,5- diaminobenzoic acid is in the SEM figure that water is the nanosphere that solvent reacts under ambient temperature；
Fig. 2: 3,5- diaminobenzoic acid is in the SEM, TEM that acetone is the nanosphere that solvent reacts under ambient temperature
Figure；
Fig. 3: 3,5- diaminobenzoic acid is the nanosphere 0.4ml ammonia that solvent reacts in acetone under ambient temperature
The SEM of water schemes；
Fig. 4: 3,5- diaminobenzoic acid is that the nanosphere that solvent reacts changes 3,5- in acetone under ambient temperature
The amount SEM of diaminobenzoic acid schemes；
Fig. 5: 3,5- diaminobenzoic acid is that the nanosphere that solvent reacts is washed with ethyl alcohol in acetone under ambient temperature
Wash sample SEM figure；
Fig. 6: TEM of the 3,5- diaminobenzoic acid after acetone is solvent nanosphere ethanol washing under ambient temperature
Figure；
Fig. 7: 3,5- diaminobenzoic acid after acetone is solvent nanosphere ethanol washing between changing under ambient temperature
The amount SEM of phenylenediamine schemes；
Fig. 8: 3,5- diaminobenzoic acid after acetone is solvent nanosphere ethanol washing between changing under ambient temperature
Melamine amount SEM figure；
Fig. 9: 3,5- diaminobenzoic acid changes 3 after acetone is solvent nanosphere ethanol washing under ambient temperature,
The amount SEM of 5- diaminobenzoic acid schemes；
Figure 10: 3,5- diaminobenzoic acid changes ammonia after acetone is solvent nanosphere ethanol washing under ambient temperature
Water SEM figure；
Figure 11: 3,5- diaminobenzoic acid is the different acetone of solvent nanosphere in acetone water mixed liquid under ambient temperature
The SEM of water mixed solvent schemes；
Figure 12: 3,5- diaminobenzoic acid is washed for solvent nanosphere with straight alcohol in acetone water mixed liquid under ambient temperature
The TEM figure washed；
Figure 13: 3,5- diaminobenzoic acid is solvent nanosphere different solvents in acetone water mixed liquid under ambient temperature
The SEM of washing schemes；
Figure 14: 3,5- diaminobenzoic acid is washed for solvent nanosphere with methanol in acetone water mixed liquid under ambient temperature
TEM figure；
Figure 15: 3,5- diaminobenzoic acid is washed for solvent nanosphere with methanol in acetone water mixed liquid under ambient temperature
Various concentration SEM, TEM figure；
Figure 16: 3,5- diaminobenzoic acid is washed for solvent nanosphere with methanol in acetone water mixed liquid under ambient temperature
Different ammonia vol SEM, TEM figure；
Figure 17: 3,5- diaminobenzoic acid is washed for solvent nanosphere with methanol in acetone water mixed liquid under ambient temperature
Different melamine amount SEM figures；
Figure 18: 3,5- diaminobenzoic acid is washed for solvent nanosphere with methanol in acetone water mixed liquid under ambient temperature
Different m-phenylene diamine (MPD) amount SEM figures；
Figure 19: under ambient temperature 2,4- diamino benzene sulfonic acid in acetone solvent nanosphere with 20% ethanol washing SEM,
TEM figure；
Figure 20: 3,5- diaminobenzoic acid is washed for solvent nanosphere with methanol in acetone water mixed liquid under ambient temperature
TEM figure for 24 hours；
Figure 21: 3,5- diaminobenzoic acid is washed for solvent nanosphere with methanol in acetone water mixed liquid under ambient temperature
Charcoal ball SEM after calcining, TEM figure；
Figure 22: it is micro- for solvent nanometer in acetone water mixed liquid that 3,5- diaminobenzoic acid under ambient temperature six times greater is put in reaction
Charcoal ball SEM after ball washs calcining with formaldehyde, TEM figure；
Figure 23: 3,5- diaminobenzoic acid is solvent nanosphere sodium bicarbonate in acetone water mixed liquid under ambient temperature
Scheme instead of the SEM of ammonium hydroxide；
Figure 24: 3,5- diaminobenzoic acid is solvent nanosphere glutaraldehyde generation in acetone water mixed liquid under ambient temperature
For formaldehyde SEM figure；
Figure 25: K is used2CO3It is activated (K2CO3: sample=3:1 sulfur content~80%) battery is made into the electric current of 0.2C
It is recycled 100 times under density；
Figure 26: (KOH: sample=1:1 sulfur content~80%) is activated with KOH and is made into battery in the current density of 0.2C
Lower circulation 180 times；
Figure 27: it is close that electric current of the battery in 1C is made into KOH activation processing (KOH: sample=0.75:1 sulfur content~80%)
Degree lower circulation 300 times；
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
By 0.063g (0.0005mol) melamine, 0.054g (0.0005mol) m-phenylene diamine (MPD), 0.047g
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 50mL water in (0.0003mol) 3,5- dissolving diaminobenzoic acid, and 500rpm revolving speed stirs
The lower stirring of speed to solution is in brown suspension.2mL formalin is added, after about 40sec., liquid becomes muddy by clarification
It is turbid.Temperature is kept, 500rpm stirs 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carrying out Electronic Speculum sight
It examines, obtains polymer with nitrogen nanosphere nitrogen content about 30%.Partial size 116nm is as shown in Figure 1.
Embodiment 2
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 50mL acetone in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed is stirred under speed and stirred
It is in brown suspension to solution.2mL formalin is added, after about 3sec., liquid is become cloudy by clarifying.Keep temperature
Degree, 500rpm stir 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, contained
Nitrogen polymer nanosphere nitrogen content about 40%.Partial size 547nm is as shown in Figure 2.
Embodiment 3
By 0.126g (0.001mol) melamine, (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL acetone, ammonium hydroxide, 25 DEG C of temperature is added dropwise, it is in brown that 500rpm revolving speed, which stirs stirring to solution under speed,
Suspension.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.Keep temperature, 500rpm stirring
2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, obtain polymer with nitrogen nanometer
Microballoon nitrogen content about 40%.The amount (0.4mL) for changing ammonium hydroxide, shown in as shown in the figure 3.
Embodiment 4
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 3,5- diaminobenzoic acids
It is dissolved in 50mL acetone, 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, it is suspended in brown to solution that 500rpm revolving speed stirs stirring under speed
Liquid.2mL formalin is added, after about 3sec., liquid is become cloudy by clarifying.Temperature is kept, 500rpm stirs 2h.
After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, obtain polymer with nitrogen nanosphere
Nitrogen content about 40%.The amount (0.00060mol) for changing 3,5- diaminobenzoic acid is as shown in Figure 4.
Embodiment 5
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 50mL acetone in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed is stirred under speed and stirred
It is in brown suspension to solution.2mL formalin is added, after about 3sec., liquid is become cloudy by clarifying.Keep temperature
Degree, 500rpm stir 2h.After the reaction was completed, it is washed through centrifugation, with solvent, is dry, carried out Electronic Speculum observation, obtain polymer with nitrogen
Nanosphere nitrogen content about 40%.Shown in ethanol washing as shown in the figure 5.
Embodiment 6
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 50mL acetone in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed is stirred under speed and stirred
It is in brown suspension to solution.2mL formalin is added, after about 3sec., liquid is become cloudy by clarifying.Keep temperature
Degree, 500rpm stir 2h.After the reaction was completed, it is centrifuged, with ethanol washing, drying, carries out Electronic Speculum observation, obtain polymer with nitrogen
Nanosphere nitrogen content about 30%.As shown in Fig. 6 TEM picture.
Embodiment 7
By 0.126g (0.001mol) melamine, different amounts of m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- diamino
Yl benzoic acid is dissolved in 50mL acetone, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed stirs stirring to solution under speed and is in
Brown suspension.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.Keep temperature, 500rpm
Stir 2h.After the reaction was completed, it is centrifuged, with ethanol washing, drying, carries out Electronic Speculum observation, obtain polymer with nitrogen nanosphere
Nitrogen content about 50%.Shown in the amount (0.0025mol) as shown in the figure 7 for changing m-phenylene diamine (MPD).
Embodiment 8
By melamine, 0.126g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- diaminobenzoic acid
It is dissolved in 50mL acetone, 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, it is suspended in brown to solution that 500rpm revolving speed stirs stirring under speed
Liquid.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.Temperature is kept, 500rpm stirs 2h.
After the reaction was completed, it is centrifuged, with ethanol washing, drying, carries out Electronic Speculum observation, obtain polymer with nitrogen nanosphere nitrogen content about
50%.The amount (0.002mol) for changing melamine, shown in as shown in the figure 8.
Embodiment 9
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 3,5- diaminobenzoic acids
It is dissolved in 50mL acetone, 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, it is suspended in brown to solution that 500rpm revolving speed stirs stirring under speed
Liquid.2mL formalin is added, after about 3sec., liquid is become cloudy by clarifying.Temperature is kept, 500rpm stirs 2h.
After the reaction was completed, it is centrifuged, washed with straight alcohol solution, is dry, carried out Electronic Speculum observation, obtain polymer with nitrogen nanosphere nitrogen
Content about 40%.The amount (0.00015mol) of 3,5- diaminobenzoic acid is as shown in Figure 9.
Embodiment 10
By 0.126g (0.001mol) melamine, (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL acetone, ammonium hydroxide, 25 DEG C of temperature is added dropwise, it is in brown that 500rpm revolving speed, which stirs stirring to solution under speed,
Suspension.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.Keep temperature, 500rpm stirring
2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, obtain polymer with nitrogen nanometer
Microballoon nitrogen content about 40%.The amount (0.8ml) for changing ammonium hydroxide, shown in as shown in the figure 10.
Embodiment 11
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
3,5- dissolving diaminobenzoic acids are in water content difference acetone water mixed solvent, dropwise addition 0.2mL ammonium hydroxide, 25 DEG C of temperature,
It is in brown suspension that 500rpm revolving speed, which stirs stirring to solution under speed,.2mL formalin, after about 6sec., liquid is added
It is become cloudy by clarification.Temperature is kept, 500rpm stirs 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry,
Electronic Speculum observation is carried out, polymer with nitrogen nanosphere nitrogen content about 40% is obtained.The volume of acetone and the volume of water be (45mL,
5mL), as shown in figure 11.
Embodiment 12
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 35mL acetone, 5mL water in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed stirs speed
Lower stirring to solution is in brown suspension.2mL formalin is added, after about 6sec., liquid is become cloudy by clarifying.
Temperature is kept, 500rpm stirs 2h.After the reaction was completed, it is centrifuged, washs twice, dry, progress Electronic Speculum sight with straight alcohol solution
It examines, obtains polymer with nitrogen nanosphere nitrogen content about 40%.As shown in Figure 12 TEM.
Embodiment 13
By 0.126g (0.0005mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g
(0.0003mol) 3,5- dissolving diaminobenzoic acid is in 35mL acetone, 5mL water, dropwise addition 0.2mL ammonium hydroxide, 25 DEG C of temperature,
It is in brown suspension that 500rpm revolving speed, which stirs stirring to solution under speed,.2mL formalin, after about 5sec., liquid is added
It is become cloudy by clarification.Temperature is kept, 500rpm stirs 2h.After the reaction was completed, sample 1h is impregnated through centrifugation, with different solvents, is done
It is dry, Electronic Speculum observation is carried out, polymer with nitrogen nanosphere nitrogen content about 30% is obtained.The solvent of use has methanol SEM such as Figure 13
It is shown.
Embodiment 14
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 35mL acetone, 5mL water in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed stirs speed
Lower stirring to solution is in brown suspension.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.
Temperature is kept, 500rpm stirs 2h.After the reaction was completed, sample 1h, drying are impregnated through centrifugation, with methanol, carries out Electronic Speculum observation, obtains
To polymer with nitrogen nanosphere nitrogen content about 40%.TEM is as shown in figure 14.
Embodiment 15
By melamine 0.063g (0.0005mol) 0.126g (0.001mol), m-phenylene diamine (MPD) 0.054g (0.0005mol)
0.108g (0.001mol), 3,5- diaminobenzoic acid 0.0235g (0.00015mol) 0.047g (0.0003mol) are dissolved in
In 35mL acetone, 5mL water, 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, it is suspended in brown to solution that 500rpm revolving speed stirs stirring under speed
Liquid.2mL formalin is added, after about 3sec., liquid is become cloudy by clarifying.Temperature is kept, 500rpm stirs 2h.
After the reaction was completed, sample 30min, drying are impregnated through centrifugation, with methanol, carries out Electronic Speculum observation, it is micro- obtains polymer with nitrogen nanometer
Ball nitrogen content about 40%.Total reactant concentration (0.00115mol), (0.0023mol) SEM, TEM Figure 15.
Embodiment 16
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
Ammonium hydroxide, 25 DEG C of temperature is added dropwise in 35mL acetone, 5mL water in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed is stirred under speed and stirred
It is in brown suspension to solution.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.Keep temperature
Degree, 500rpm stir 2h.After the reaction was completed, sample 30min, drying are impregnated through centrifugation, with methanol, carries out Electronic Speculum observation, obtains
Polymer with nitrogen nanosphere nitrogen content all about 40%.Different amounts of ammonium hydroxide (0mL), (0.1mL), (0.4mL) is added as schemed
Shown in 16SEM, TEM.
Embodiment 17
By melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- diaminobenzoic acid
It is dissolved in 35mL acetone, in 5mL water, is added dropwise 0.2mL ammonium hydroxide, 25 DEG C of temperature, 500rpm revolving speed stirs under speed stirring to solution in palm fibre
Color suspension.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.Temperature is kept, 500rpm is stirred
Mix 2h.After the reaction was completed, sample 30min, drying are impregnated through centrifugation, with methanol, carries out Electronic Speculum observation, obtains polymer with nitrogen and receive
Meter Wei Qiu nitrogen content respectively may be about 25% and 45%.Change amount (0.00025mol), (0.0010mol) such as Figure 17 of melamine
It is shown.
Embodiment 18
By 0.126g (0.001mol) melamine, m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- diaminobenzoic acid
It is dissolved in 35mL acetone, in 5mL water, is added dropwise 0.2mL ammonium hydroxide, 25 DEG C of temperature, 500rpm revolving speed stirs under speed stirring to solution in palm fibre
Color suspension.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.Temperature is kept, 500rpm is stirred
Mix 2h.After the reaction was completed, sample 30min, drying are impregnated through centrifugation, with methanol, carries out Electronic Speculum observation, obtains polymer with nitrogen and receive
Meter Wei Qiu nitrogen content respectively about 40% and 25%.Change amount (0.00025mol), (0.0010mol) such as Figure 18 institute of m-phenylene diamine (MPD)
Show.
Embodiment 19
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.058g (0.0003mol)
2,4- diamino benzene sulfonic acids are dissolved in 50mL acetone, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed is stirred under speed and stirred
It is in brown suspension to solution.2mL formalin is added, after about 10sec., liquid is become cloudy by clarifying.Keep temperature
Degree, 500rpm stir 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, contained
Nitrogen polymer nanosphere nitrogen content about 40%.As shown in Figure 19 SEM, TEM.
Embodiment 20
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 35mL acetone, 5mL water in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed stirs speed
Lower stirring to solution is in brown suspension.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.
Temperature is kept, 500rpm stirs 2h.After the reaction was completed, through centrifugation, with methanol impregnate for 24 hours, it is dry, carry out Electronic Speculum observation, obtain
Polymer with nitrogen nanosphere nitrogen content about 40%.TEM is as shown in figure 20.
Embodiment 21
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 35mL acetone, 5mL water in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed stirs speed
Lower stirring to solution is in brown suspension.2mL formalin is added, after about 5sec., liquid is become cloudy by clarifying.
Temperature is kept, 500rpm stirs 2h.After the reaction was completed, 1h, drying are impregnated through centrifugation, with methanol, carries out Electronic Speculum observation, is contained
Nitrogen polymer nanosphere nitrogen content about 40%.Yellow shell structural nano charcoal ball nitrogen content about 20% is obtained by 800 DEG C of calcinings
SEM, TEM are as shown in figure 21.
Embodiment 22
By 0.756g (0.006mol) melamine, 0.648g (0.006mol) m-phenylene diamine (MPD), 0.282g (0.0018mol)
1.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 210mL acetone, 30mL water in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed stirs
The lower stirring of speed to solution is in brown suspension.12mL formalin is added, after about 5sec., liquid becomes muddy by clarification
It is turbid.Temperature is kept, 500rpm stirs 2h.After the reaction was completed, 1h, drying are impregnated through centrifugation, with formaldehyde, carries out Electronic Speculum observation, obtains
To polymer with nitrogen nanosphere nitrogen content about 30%.Hollow structure Nano carbon ball nitrogen content is obtained about by 700 DEG C of calcinings
20%SEM, TEM are as shown in figure 22.
Embodiment 23
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
3,5- dissolving diaminobenzoic acids are in 35mL acetone, 5mL water, addition 0.26g (0.003mol) sodium bicarbonate, 25 DEG C of temperature,
It is in brown suspension that 500rpm revolving speed, which stirs stirring to solution under speed,.2mL formalin, after about 5sec., liquid is added
It is become cloudy by clarification.Temperature is kept, 500rpm stirs 2h.After the reaction was completed, 1h, drying are impregnated through centrifugation, with formaldehyde, carries out electricity
Sem observation obtains polymer with nitrogen nanosphere nitrogen content about 40%.SEM is as shown in figure 23.
Embodiment 24
By 0.126g (0.001mol) melamine, 0.108g (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol)
0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise in 35mL acetone, 5mL water in 3,5- dissolving diaminobenzoic acids, and 500rpm revolving speed stirs speed
Lower stirring to solution is in brown suspension.2mL glutaraldehyde water solution is added, after about 5sec., liquid becomes muddy by clarification
It is turbid.Temperature is kept, 500rpm stirs 2h.After the reaction was completed, 1h, drying are impregnated through centrifugation, with formaldehyde, carries out Electronic Speculum observation, obtains
To polymer with nitrogen nanosphere nitrogen content about 40%.SEM is as shown in figure 24.
Embodiment 25
By 0.126g (0.001mol) melamine, (0.001mol) o-phenylenediamine, 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL acetone, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed is stirred under speed and stirred to solution
In brown suspension.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.Temperature is kept,
500rpm stirs 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, obtain nitrogenous
Polymer nano-microspheres nitrogen content about 40%.
Embodiment 26
By 0.126g (0.001mol) melamine, (0.001mol) p-phenylenediamine, 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL acetone, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed is stirred under speed and stirred to solution
In brown suspension.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.Temperature is kept,
500rpm stirs 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, obtain nitrogenous
Polymer nano-microspheres nitrogen content about 40%.
Embodiment 27
By 0.126g (0.001mol) melamine, (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL methanol, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed is stirred under speed and stirred to solution
In brown suspension.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.Temperature is kept,
500rpm stirs 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, obtain nitrogenous
Polymer nano-microspheres nitrogen content about 40%.
Embodiment 28
By 0.126g (0.001mol) melamine, (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL dimethyl sulfoxide, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed is stirred under speed and stirred
It is in brown suspension to solution.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.Keep temperature
Degree, 500rpm stir 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, contained
Nitrogen polymer nanosphere nitrogen content about 40%.
Embodiment 29
By 0.126g (0.001mol) melamine, (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL n,N-Dimethylformamide, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed stirs speed
Lower stirring to solution is in brown suspension.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.
Temperature is kept, 500rpm stirs 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carrying out Electronic Speculum observation,
Obtain polymer with nitrogen nanosphere nitrogen content about 40%.
Embodiment 30
By 0.126g (0.001mol) melamine, (0.001mol) m-phenylene diamine (MPD), 0.047g (0.0003mol) 3,5- bis-
Aminobenzoic acid is dissolved in 50mL ethyl alcohol, and 0.2mL ammonium hydroxide, 25 DEG C of temperature is added dropwise, and 500rpm revolving speed is stirred under speed and stirred to solution
In brown suspension.2mL formalin is added, after about 7sec., liquid is become cloudy by clarifying.Temperature is kept,
500rpm stirs 2h.After the reaction was completed, it is centrifuged, washed with 20% ethanol solution, is dry, carried out Electronic Speculum observation, obtain nitrogenous
Polymer nano-microspheres nitrogen content about 40%.
For any person skilled in the art, without departing from the scope of the technical proposal of the invention, all
Many possible changes and modifications are made to technical solution of the present invention using the technology contents of the disclosure above, or are revised as equivalent
The equivalent embodiment of variation.Therefore, anything that does not depart from the technical scheme of the invention, according to the technical essence of the invention to
Any simple modifications, equivalents, and modifications that upper embodiment is done should all still fall within the range of technical solution of the present invention protection
It is interior.
Claims (9)
1. a kind of preparation method with cavity structure polymer nano-microspheres of mass producible Heteroatom doping, including with
Lower step:
(1) under the conditions of 10-50 DEG C；By m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, 2,6- diamino-pyridine, 1,5- diamino
One or more of naphthalene or 1,8- diaminonaphthalene；
With melamine；
With ortho-aminobenzoic acid, p-aminobenzoic acid, gavaculine, metanilic acid, orthanilic acid, to amino
One or more of benzene sulfonic acid, 3,5- diaminobenzoic acid, 2,4- diamino benzene sulfonic acid are dissolved in solvent；
The solvent be selected from acetone, water methanol, ethyl alcohol, dimethyl sulfoxide, N-N- dimethylformamide, tetrahydrofuran, ethylene glycol,
The mixing of one or more of normal propyl alcohol；
(2) aqueous slkali is added in Xiang Shangshu system, stirs evenly, regulation system pH value to 8-9；The alkaline solution is selected from ammonia
One or more of water, sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate or potassium bicarbonate solution；
(3) formaldehyde, glyoxal, malonaldehyde, butanedial, glutaraldehyde or hexandial are added in Xiang Shangshu system, is stirred to react, obtains
Polymer nano-microspheres solution；
(4) obtained nanosphere is put into methanol, ethyl alcohol, formaldehyde or formic acid and their mixed solution and impregnates or washs
Just obtain the nanosphere with cavity structure.
2. preparation method according to claim 1, it is characterised in that: ortho-aminobenzoic acid, p-aminobenzoic acid, amino
Benzoic acid, metanilic acid, orthanilic acid, p-aminobenzene sulfonic acid, 3,5- diaminobenzoic acid or 2,4- diaminobenzene
The concentration that one or more of sulfonic acid forms solution in step (1) is 0.002~1.0mol/L.
3. preparation method according to claim 1, it is characterised in that: the step；M-phenylene diamine (MPD), p-phenylenediamine, adjacent benzene
One or more of diamines, 2,6- diamino-pyridine, 1,5- diaminonaphthalene, 1,8- diaminonaphthalene or melamine are in step
(1) it is 0.002-1.0mol/L that solution concentration is formed in.
4. preparation method according to claim 1, it is characterised in that: aldehyde is added by the way of being added dropwise, and aldehyde radical amount is opposite
In 5-15 times of equivalent of arylamine.
5. preparation method according to claim 1, it is characterised in that: addition alkaline solution described in step (2) is using drop
The mode added, mixing time are 1-6 hours.
6. preparation method according to claim 1, it is characterised in that: in step (3), be stirred to react 1~12 after aldehyde is added
Hour.
7. the Heteroatom doping that preparation method described in any one obtains according to claim 1~6 has cavity structure nanometer
Microballoon, microballoon nitrogen content are 20-80wt%, and 100nm-1 μm of microsphere diameter, uniform particle sizes, N, S hetero atom is evenly distributed.
8. Heteroatom doping as claimed in claim 7 has answering for positive electrode of the cavity structure nanosphere as lithium-sulfur cell
With.
9. Heteroatom doping as claimed in claim 7 has application of the cavity structure nanosphere as capacitor electrode material.
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