CN108219453B - A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material - Google Patents
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C08K2201/001—Conductive additives
Abstract
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, is related to a kind of nanocomposite preparation method, the preparation including the graphene containing intercalator: graphene oxide and strong base weak acid salting liquid are sufficiently mixed uniformly；1,2,4- triaminobenzene dihydrochloride is dissolved in hydrochloric acid solution, then hydrochloric acid solution is added in graphene oxide/sodium carbonate mixture, obtains the graphene containing intercalator；The preparation of three-dimensional porous graphene: the graphene containing intercalator is soaked in potassium hydroxide solution, and reaction product is dried to obtain three-dimensional porous graphene through pickling and deionized water washing；The preparation of three-dimensional porous grapheme/polyaniline composite material: by three-dimensional porous graphene dispersion in acid solution, and being added aniline and ammonium persulfate, and in-situ polymerization obtains three-dimensional porous grapheme/polyaniline composite material.The composite material chemical property is good, can be applied to the fields such as electrode material for super capacitor, energy storage material and Heat Conduction Material.
Description
Technical field
The present invention relates to a kind of nanocomposite preparation methods, more particularly to a kind of three-dimensional porous graphene/polyphenyl
The preparation method of amine composite material.
Background technique
As energy shortage is increasingly serious, key strategic skill of the high-efficiency energy-storage technology as support Renewable Energy Development
Art becomes research hotspot.Wherein, supercapacitor is concerned as a kind of novel energy storage apparatus, and electrode material is super
The key of capacitor technology of preparing is the big bottleneck for restricting electrochemical capacitance practical application.Currently, most super electrical part is main
The cheap carbon material based on electric double layer energy storage mechnism, realize high-energy density a possibility that very little.The electrochemistry of homogenous material
Performance can no longer meet requirement of the today's society to supercapacitor, and research object is by simple inorganic composite materials or organic
Composite material turns to inorganic-organic composite material.
The excellent physicochemical properties of two-dimensional graphene have established solid foundation for its application in supercapacitor.So
And since the interaction of pi-pi bond strong between graphene makes it be easy to happen aggregation, cause the actual performance of graphene far low
In desired value.To solve this problem, can by increase interval lamella fold or the three-dimensional grapheme foam of preparation,
Sponge, hydrogel, aeroge etc. retain the excellent physicochemical properties of two-dimensional graphene, and are avoided that the production of agglomeration
It is raw.Electrically conductive polyaniline energy density with higher, good thermal stability and chemical stability, and synthesis technology is simple,
Energy storage field has broad application prospects.But in long-term recycling, ion doping can cause volume swollen with doping is gone
Swollen and contraction, causes performance to decline, seriously limits its application.Three-dimensional grapheme is compound with polyaniline, on the one hand it can send out
The synergistic effect of the two is waved, on the other hand can overcome defect of the polyaniline in structure again, composite material is in electric conductivity, stabilization
Property and chemical property in terms of be improved, be gradually proved to be a kind of very with the approach of application value.
" a kind of highly ordered porous graphene/polyaniline is multiple for the Chinese patent application that notification number is CN105504277A
Condensation material and preparation method thereof " makes graphene base body form orderly porous knot by introducing surfactant as soft template
Structure, when 1A/g, specific capacitance reaches 485 F/g.Chinese patent application " a kind of three-dimensional oxygen reduction that notification number is CN104559176A
Graphite alkene/polyaniline composite material preparation method " by by graphene oxide and polyaniline In-situ reaction again through hydro-thermal also
Original obtains three-dimensional porous grapheme/polyaniline composite material.Chinese patent application " one kind three that notification number is CN105254877A
Tie up the preparation method of grapheme/polyaniline composite material " it is the three-dimensional structure of graphene to be constructed by poly furfuryl alcohol template, then pass through
Hydro-thermal method prepares three-dimensional porous grapheme/polyaniline composite material.Notification number is the Chinese patent application of CN104558597A
" porous graphene/polyaniline composite material preparation method " be by introducing carbonate deposition in graphene oxide solution,
Under alkaline condition through chemical hydrothermal reduction and after removing carbonate, in-situ polymerization obtains porous graphene/polyaniline composite material.
Zhao et al. (Zhao T, et al. Electrochimica Acta, 2017,230 (3): 342-349) is adopted
Three-dimensional foam graphene and polyaniline are compounded to form composite material with polymerization, be exactly graphene hydrogel surface solution according to
Secondary fabricated in situ polyaniline nano-rod, growth substrate of the three-dimensional graphene foam as polyaniline nano-rod, can increase compound
The specific surface area of material, highest specific capacitance value is 352 F/g at 10 mV/s, obtains the three-dimensional stone with high specific surface
Black alkene/polyaniline nano-rod electrode material.Xu Jianjun (Xu Jianjun graphene and the preparation of polyaniline composite sponge and performance study
The Harbin [D]: Harbin University of Science and Technology 2015) graphene/polyaniline prepared using in-situ polymerization and freeze-drying
The specific capacitance of composite sponge is high and has three-dimensional porous reticular structure, with the increase of polyphenyl amine content, the ratio electricity of composite material
Appearance is also gradually increased, and be can reach 487 F/g, be can be applied to supercapacitor field.Luo Jianping et al. (high such as Luo Jianping
Molecular material scientific and engineering, 2017,3 (03): 84-88) also synthesized using in-situ polymerization and freeze-drying it is three-dimensional more
Pore structure grapheme/polyaniline composite material, when current density is 0.5 A/g, the specific capacitance of composite material is 321.91 F/
G, than being higher by 81.53 F/g before reduction.Tang Wei (Tang Wei, the preparation of three-dimensional grapheme/polyaniline composite material and its electrochemistry
The Nanjing research [D] of performance: Nanjing Univ. of Posts and Telecommunications .2015) using calcium carbonate as template to prepare three-dimensional grapheme/polyaniline compound
Material has the pore structure being mutually communicated, and cyclical stability is high under low voltage condition；Three-dimensional porous stone is prepared using cross-linking method
Black alkene, polyaniline are grown in hole wall and the surface of three-dimensional porous graphene by in-situ polymerization, and cyclical stability is high, than electricity
Rong great.Wang et al. (Wang S, et al. Journal of Power Sources, 2015,299 (12): 347-
355) polyaniline is polymerize with three-dimensional grapheme using polystyrene microsphere as template, obtained composite material is in current density
Specific capacitance is up to 740 F/g under 0.5 A/g, also keeps 87 % after charge and discharge cycles 1000 times.
The three-dimensional porous grapheme/polyaniline composite material that above-mentioned published method is prepared mostly uses soft or hard template
The three-dimensional porous structure of graphene is constructed, these methods are undoubtedly plays graphene excellent properties very effective hands at present
Section, but since the removal of soft or hard template largely increases workload, while there is also the incomplete problems of removal, thus
Seriously affect the purity of composite material.In addition, some methods are difficult to that the agglomeration traits of graphene are effectively relieved.Li et al. people (Li
L Y, etal. Nano Energy, 2016,21:276-294) with aromatic amine (including 1,2,4 triaminobenzenes, 2,2 ' two
Aminobenzidine, 1,5 diaminonaphthalene, 1,8 diaminonaphthalene) it is used as intercalator to obtain high performance graphene-based super electric material,
Wherein, the graphene chemical property obtained with 1,2,4 triaminobenzene as intercalator is best, series equivalent resistance RsFor
0.61 Ω, charge transmit resistance RctFor 1.83 Ω, at 3.4 kW/kg of power density, energy density reaches 24.2 Wh/kg.
A kind of preparation method for three-dimensional porous grapheme/polyaniline composite material that present patent application proposes is proposed with Li LY
On the basis of the graphene that 1,2,4 triaminobenzene is obtained as intercalator, three-dimensional porous knot is constructed in conjunction with the method for chemical activation
Structure graphene, further promotes the specific surface area and Kong Rong of material, and three-dimensional porous structure has also provided for ion diffusive migration
Channel is imitated, and then improves the wellability of electrolyte and electrode material.It is further that three-dimensional porous graphene and aniline is poly- in situ
Three-dimensional porous grapheme/polyaniline composite material, the series equivalent resistance R of composite material are prepared in conjunctionsIt is down to 0.075 Ω, electricity
Lotus transmits resistance RctBe down to 0.3 Ω, under equal-wattage density the energy density of composite material and it is compound it is preceding contain intercalator 1,
The graphene of 2,4 triaminobenzenes is compared and improves 9%.Under the current density of 1 A/g, than electricity after 1000 charge and discharge cycles
Hold and keep 86%, loss 30% is compared after being compared to 800 circulations of pure PANI, the electrochemical cycle stability of composite material
Also it is remarkably reinforced.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, the party
Method obtains the graphene that limellar stripping is intact, reunites less by introducing 1,2,4 triaminobenzene of intercalator, by the stone containing intercalator
Black alkene through KOH chemical activation obtain three-dimensional porous structure graphene, finally by aniline on three-dimensional porous graphene in-situ polymerization
At polyaniline, three-dimensional porous grapheme/polyaniline composite material is obtained, the composite material chemical property is good.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, comprising the following steps:
A. the preparation of the graphene containing intercalator: graphene oxide and strong base weak acid salting liquid are sufficiently mixed uniformly,
A certain amount of 1,2,4- triaminobenzene dihydrochlorides are weighed later to be dissolved in hydrochloric acid solution, ultrasonic disperse is uniform, then will be mixed with 1,
The hydrochloric acid solution of 2,4- triaminobenzene dihydrochlorides is added in graphene oxide/sodium carbonate mixture, through hydrothermal reduction, is washed
It washs, obtain the graphene containing intercalator after vacuum freeze drying；
B. it is molten that the graphene containing intercalator of the step a preparation of three-dimensional porous graphene: is soaked in potassium hydroxide
In liquid, priming reaction, reaction product are dried to obtain three through pickling and deionized water washing under nitrogen or argon atmosphere after drying
Tie up porous graphene；
C. the preparation of three-dimensional porous grapheme/polyaniline composite material: by the three-dimensional porous graphene dispersion of the step b
In acid solution, and aniline and ammonium persulfate is added, under the condition of ice salt bath, in-situ polymerization obtain three-dimensional porous graphene/
Polyaniline composite material.
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, the graphite oxide of the step a
Concentration of the alkene in mixed liquor is 0.2 ~ 2 mg/ml；Strong base-weak acid salt is carbonate, bicarbonate radical, acetate, phosphoric acid
Root, inferior sulfate radical, silicate, meta-aluminic acid root sodium salt or sylvite in any one, strong base-weak acid salt is dense in mixed liquor
Degree is 500-800 mM/ls；Concentration of 1,2, the 4- triaminobenzene dihydrochloride in mixed liquor is 4 ~ 12 mM/ls,
The concentration of hydrochloric acid solution is 50 ~ 100 mM/ls；Hydrothermal temperature is 160 ~ 200 DEG C, and the reaction time is 12 ~ 48 small
When.
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, the three-dimensional graphite of the step b
The mass ratio of alkene and potassium hydroxide is 1:(0.5 ~ 15) soaking time is 12 ~ 48 hours, the drying 5 ~ 12 hours of 90 DEG C of baking oven, it is living
Changing temperature is 400 ~ 800 DEG C, and activation time is 1 ~ 5 hour；Pickling agents useful for same is one of hydrochloric acid or acetic acid.
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, the acid solution of the step c
For any one in hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, acid solution concentration is 1 ~ 2 mol/L；Three-dimensional meso-hole graphene with
The mass ratio of aniline is (0.1 ~ 10): 1, the molar ratio of aniline and ammonium persulfate is (0.25 ~ 4): 1；Cryosel is sodium chloride, chlorination
Any one in calcium, sodium nitrate；Polymeric reaction temperature is 0 ~ 5 DEG C, and the reaction time is 2 ~ 12 hours.
The advantages and effects of the present invention are:
The present invention is progress KOH activation processing, the three-dimensional porous structure graphite of acquisition on the graphene containing intercalator
Alkene lamella is relatively thin, reunites without obvious, so that the big specific surface area of graphene is released effectively.Further with the compound system of polyaniline
It is standby go out three-dimensional porous grapheme/polyaniline composite material be conducive to electrolyte come into full contact with ion, electron-transport, show
Good chemical property is shown, can be applied to the fields such as electrode material for super capacitor, energy storage material and Heat Conduction Material.
Detailed description of the invention
Fig. 1 is the SEM figure of the three-dimensional porous graphene in embodiment 1.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, comprising the following steps:
Step a: weighing sodium carbonate and be dissolved in deionized water, and graphene oxide and sodium carbonate liquor are sufficiently mixed
It is even, 1,2,4 triaminobenzene dihydrochlorides are weighed later and are dissolved in 80 mM/ls of hydrochloric acid solution, are ultrasonically treated 10 minutes,
The hydrochloric acid solution that 1,2,4 triaminobenzene dihydrochlorides will be mixed with again is added in graphene oxide/sodium carbonate mixture, control
The concentration of graphene oxide, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides is respectively 0.8 milligram/milli in entire reaction solution
It rises, 560 mM/ls and 8.6 mM/ls, ultrasonic disperse 1 hour；It is anti-that the reaction solution is moved into polytetrafluoroethylene (PTFE) later
Answer in kettle, 180 DEG C hydro-thermal reaction 12 hours, after cooling, vacuum filtration, washed repeatedly into deionized water and dehydrated alcohol
Property, vacuum freeze drying obtains the graphene containing intercalator after 24 hours.
Step b: the graphene containing intercalator that step a is obtained is soaked in potassium hydroxide solution (graphite containing intercalator
The mass ratio of alkene and potassium hydroxide is 1:7), ultrasonic disperse 1 hour, 24 hours are stood, the drying 12 hours of 90 DEG C of baking oven, later
In a nitrogen atmosphere in tube furnace 500 DEG C activate 5 hours, after cooling, the successive acetic acid solution and deionized water with 36%
To neutrality, vacuum freeze drying obtains three-dimensional porous graphene for washing.
Step c: aniline monomer is substantially soluble in 100 milliliters of the hydrochloric acid solution of 1 mol/L, then step b is obtained
Three-dimensional porous graphene be substantially soluble in the hydrochloric acid solution of the aniline (mass ratio of three-dimensional porous graphene and aniline be 1:
6) hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate, under the condition of ice salt bath, is slowly added dropwise in Xiang Shangshu mixed liquor
Milliliter (molar ratio of aniline and ammonium persulfate is 1:1), controls reaction temperature at 0 ~ 5 DEG C, reacts 8 hours；After reaction, it will sink
Shallow lake is filtered, washed to neutrality, is dried at 60 DEG C, and three-dimensional porous grapheme/polyaniline composite material is obtained.
According to the method described above, the three-dimensional porous graphene obtained after the graphene containing intercalator and KOH activation is carried out
SEM scanning electron microscope analysis, as shown in Figure 1, it can be clearly seen that graphene forms three-dimensional porous structure.
Embodiment 2
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, comprising the following steps:
Step a: weighing sodium carbonate and be dissolved in deionized water, and graphene oxide and sodium carbonate liquor are sufficiently mixed
It is even, 1,2,4 triaminobenzene dihydrochlorides are weighed later and are dissolved in 70 mM/ls of hydrochloric acid solution, are ultrasonically treated 10 minutes,
The hydrochloric acid solution that 1,2,4 triaminobenzene dihydrochlorides will be mixed with again is added in graphene oxide/sodium carbonate mixture, control
In entire reaction solution the concentration of graphene oxide, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides be respectively 1 mg/ml,
700 mM/ls and 10.7 mM/ls, ultrasonic disperse 1 hour；The reaction solution is moved into polytetrafluoroethyl-ne alkene reaction later
In kettle, 180 DEG C hydro-thermal reaction 12 hours, after cooling, vacuum filtration, washed repeatedly into deionized water and dehydrated alcohol
Property, vacuum freeze drying obtains the graphene containing intercalator after 24 hours.
Step b: the graphene containing intercalator that step a is obtained is soaked in potassium hydroxide solution (graphite containing intercalator
The mass ratio of alkene and potassium hydroxide is 1:7), ultrasonic disperse 1 hour, 24 hours are stood, the drying 12 hours of 90 DEG C of baking oven, later
In a nitrogen atmosphere in tube furnace 500 DEG C activate 5 hours, after cooling, the successive acetic acid solution and deionized water with 36%
To neutrality, vacuum freeze drying obtains three-dimensional porous graphene for washing.
Step c: aniline monomer is substantially soluble in 100 milliliters of the hydrochloric acid solution of 1 mol/L, then step b is obtained
Three-dimensional porous graphene be substantially soluble in the hydrochloric acid solution of the aniline (mass ratio of three-dimensional porous graphene and aniline be 1:
6) hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate, under the condition of ice salt bath, is slowly added dropwise in Xiang Shangshu mixed liquor
Milliliter (i.e. the molar ratio of aniline and ammonium persulfate is 1:1), controls reaction temperature at 0 ~ 5 DEG C, reacts 8 hours；It, will after reaction
Precipitating is filtered, washed to neutrality, is dried at 60 DEG C, is obtained three-dimensional porous grapheme/polyaniline composite material.
Embodiment 3
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, comprising the following steps:
Step a: weighing sodium carbonate and be dissolved in deionized water, and graphene oxide and sodium carbonate liquor are sufficiently mixed
It is even, 1,2,4 triaminobenzene dihydrochlorides are weighed later and are dissolved in 60 mM/ls of hydrochloric acid solution, are ultrasonically treated 10 minutes,
The hydrochloric acid solution that 1,2,4 triaminobenzene dihydrochlorides will be mixed with again is added in graphene oxide/sodium carbonate mixture, control
The concentration of graphene oxide, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides is respectively 0.8 milligram/milli in entire reaction solution
It rises, 560 mM/ls and 8.6 mM/ls, ultrasonic disperse 1 hour；It is anti-that the reaction solution is moved into polytetrafluoroethylene (PTFE) later
Answer in kettle, 180 DEG C hydro-thermal reaction 24 hours, after cooling, vacuum filtration, washed repeatedly into deionized water and dehydrated alcohol
Property, vacuum freeze drying obtains the graphene containing intercalator after 24 hours.
Step b: the graphene containing intercalator that step a is obtained is soaked in potassium hydroxide solution (graphite containing intercalator
The mass ratio of alkene and potassium hydroxide is 1:8), ultrasonic disperse 1 hour, 24 hours are stood, the drying 12 hours of 90 DEG C of baking oven, later
In a nitrogen atmosphere in tube furnace 500 DEG C activate 3 hours, after cooling, the successive acetic acid solution and deionized water with 36%
To neutrality, vacuum freeze drying obtains three-dimensional porous graphene for washing.
Step c: aniline monomer is substantially soluble in 100 milliliters of the hydrochloric acid solution of 1 mol/L, then step b is obtained
Three-dimensional porous graphene be substantially soluble in the hydrochloric acid solution of the aniline (mass ratio of three-dimensional porous graphene and aniline be 1:
6) hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate, under the condition of ice salt bath, is slowly added dropwise in Xiang Shangshu mixed liquor
Milliliter (i.e. the molar ratio of aniline and ammonium persulfate is 1:1), controls reaction temperature at 0 ~ 5 DEG C, reacts 8 hours；It, will after reaction
Precipitating is filtered, washed to neutrality, is dried at 60 DEG C, is obtained three-dimensional porous grapheme/polyaniline composite material.
Embodiment 4
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, comprising the following steps:
Step a: weighing sodium carbonate and be dissolved in deionized water, and graphene oxide and sodium carbonate liquor are sufficiently mixed
It is even, 1,2,4 triaminobenzene dihydrochlorides are weighed later and are dissolved in 80 mM/ls of hydrochloric acid solution, are ultrasonically treated 10 minutes,
The hydrochloric acid solution that 1,2,4 triaminobenzene dihydrochlorides will be mixed with again is added in graphene oxide/sodium carbonate mixture, control
In entire reaction solution the concentration of graphene oxide, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides be respectively 1 mg/ml,
700 mM/ls and 10.7 mM/ls, ultrasonic disperse 1 hour；The reaction solution is moved into polytetrafluoroethyl-ne alkene reaction later
In kettle, 180 DEG C hydro-thermal reaction 24 hours, after cooling, vacuum filtration, washed repeatedly into deionized water and dehydrated alcohol
Property, vacuum freeze drying obtains the graphene containing intercalator after 24 hours.
Step b: the graphene containing intercalator that step a is obtained is soaked in potassium hydroxide solution (graphite containing intercalator
The mass ratio of alkene and potassium hydroxide is 1:8), ultrasonic disperse 1 hour, 24 hours are stood, the drying 12 hours of 90 DEG C of baking oven, later
In a nitrogen atmosphere in tube furnace 500 DEG C activate 3 hours, after cooling, the successive acetic acid solution and deionized water with 36%
To neutrality, vacuum freeze drying obtains three-dimensional porous graphene for washing.
Step c: aniline monomer is substantially soluble in 100 milliliters of the hydrochloric acid solution of 1 mol/L, then step b is obtained
Three-dimensional porous graphene be substantially soluble in the hydrochloric acid solution of the aniline (mass ratio of three-dimensional porous graphene and aniline be 1:
6) hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate, under the condition of ice salt bath, is slowly added dropwise in Xiang Shangshu mixed liquor
Milliliter (i.e. the molar ratio of aniline and ammonium persulfate is 1:1), controls reaction temperature at 0 ~ 5 DEG C, reacts 8 hours；It, will after reaction
Precipitating is filtered, washed to neutrality, is dried at 60 DEG C, is obtained three-dimensional porous grapheme/polyaniline composite material.
Claims (1)
1. a kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, comprising the following steps:
A. the preparation of the graphene containing intercalator: graphene oxide and strong base weak acid salting liquid are sufficiently mixed uniformly, claimed later
A certain amount of 1,2,4- triaminobenzene dihydrochlorides are taken to be dissolved in hydrochloric acid solution, ultrasonic disperse is uniform, then will be mixed with 1,2,4- tri-
The hydrochloric acid solution of aminobenzene dihydrochloride is added in graphene oxide/sodium carbonate mixture, through hydrothermal reduction, washing, true
The graphene containing intercalator is obtained after vacuum freecing-dry；
B. the graphene containing intercalator of the step a preparation of three-dimensional porous graphene: is soaked in potassium hydroxide solution
In, priming reaction, reaction product are dried to obtain three-dimensional through pickling and deionized water washing under nitrogen or argon atmosphere after drying
Porous graphene；
C. the preparation of three-dimensional porous grapheme/polyaniline composite material: by the three-dimensional porous graphene dispersion of the step b in acid
In property solution, and aniline and ammonium persulfate is added, under the condition of ice salt bath, in-situ polymerization obtains three-dimensional porous graphene/polyphenyl
Amine composite material；
Concentration of the graphene oxide of the step a in mixed liquor is 0.2 ~ 2 mg/ml；The highly basic of the step a is weak
Hydrochlorate is in the sodium salt or sylvite of carbonate, bicarbonate radical, acetate, phosphate radical, inferior sulfate radical, silicate, meta-aluminic acid root
Any one, concentration of the strong base-weak acid salt in mixed liquor is 500-800 mM/ls；Tri- ammonia of 1,2,4- of the step a
Concentration of the base benzene dihydrochloride in mixed liquor is 4 ~ 12 mM/ls, the concentration of hydrochloric acid solution is 50 ~ 100 mMs/
It rises；The hydrothermal temperature of the step a is 160 ~ 200 DEG C, and the reaction time is 12 ~ 48 hours；The three-dimensional stone of the step b
The mass ratio of black alkene and potassium hydroxide is 1:(0.5 ~ 15) soaking time is 12 ~ 48 hours, the drying 5 ~ 12 hours of 90 DEG C of baking oven,
Activation temperature is 400 ~ 800 DEG C, and activation time is 1 ~ 5 hour；The step b pickling agents useful for same is in hydrochloric acid or acetic acid
It is a kind of；The acid solution of the step c is hydrochloric acid, sulfuric acid, phosphoric acid, any one in perchloric acid, and acid solution concentration is 1 ~ 2
Mol/L；The mass ratio of the three-dimensional porous graphene of the step c and aniline is (0.1 ~ 10): 1, aniline and ammonium persulfate
Molar ratio is (0.25 ~ 4): 1；The cryosel of the step c is sodium chloride, calcium chloride, any one in sodium nitrate；The step c
Polymeric reaction temperature be 0 ~ 5 DEG C, the reaction time be 2 ~ 12 hours.
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