CN108219453A - 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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Abstract
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, is related to a kind of nanocomposite preparation method, includes the preparation of 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：Graphene containing intercalator is soaked in potassium hydroxide solution, 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 aniline and ammonium persulfate are added in, 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 method, more particularly to a kind of three-dimensional porous graphene/polyphenyl
The preparation method of amine composite material.
Background technology
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, ultracapacitor 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.At present, most super electrical part is main
It is the cheap carbon material based on electric double layer energy storage mechnism, realizes the possibility very little of high-energy density.The electrochemistry of homogenous material
Performance can not meet requirement of the today's society to ultracapacitor, 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 ultracapacitor.So
And since the interaction of pi-pi bond strong between graphene makes it easily assemble, the actual performance for leading to graphene is far low
In desired value.To solve this problem, lamella fold can be spaced by increase or prepare three-dimensional grapheme foam,
Sponge, hydrogel, aeroge etc. retain the excellent physicochemical properties of two-dimensional graphene, and be avoided that the production of agglomeration
It is raw.Electrically conductive polyaniline has higher energy density, 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 is with going doping that volume can be caused swollen
Swollen and contraction, leads to hydraulic performance decline, seriously limits its application.Three-dimensional grapheme is compound with polyaniline, on the one hand it can send out
The synergistic effect both waved, on the other hand can overcoming polyaniline again, composite material is in electric conductivity, stabilization in structure the defects of
Property and chemical property in terms of be improved, be gradually proved to be it is a kind of very have application value approach.
The Chinese patent application that notification number is CN105504277A " answer by a kind of highly ordered porous graphene/polyaniline
Condensation material and preparation method thereof ", which is used as soft template by introducing surfactant, makes graphene base body form orderly porous knot
Structure, during 1A/g, specific capacitance reaches 485 F/g.Chinese patent application " a kind of three-dimensional oxygen reduction that notification number is CN104559176A
The preparation method of graphite alkene/polyaniline composite material " 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 that graphene is built 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
" preparation method of porous graphene/polyaniline composite material " 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）It adopts
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 under 10 mV/s, obtains the three-dimensional stone with high specific surface
Black alkene/polyaniline nano-rod electrode material.Xu Jianjun（Perhaps strong monarch graphenes are prepared with polyaniline composite sponge and performance study
[D] Harbin:Harbin University of Science and Technology 2015）The graphene/polyaniline prepared using in-situ polymerization and freeze-drying
The specific capacitance of composite sponge is high and with three-dimensional porous reticular structure, with the increase of polyphenyl amine content, the ratio electricity of composite material
Hold also gradually increase, can reach 487 F/g, can be applied to ultracapacitor field.Luo Jian duckweeds et al.（The high such as Luo Jianping
Molecular material scientific and engineering, 2017,3 (03):84-88）Also it has been synthesized using in-situ polymerization and freeze-drying 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
Research [D] the Nanjing of performance:Nanjing Univ. of Posts and Telecommunications .2015）It is compound that three-dimensional grapheme/polyaniline is prepared using calcium carbonate as template
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, and 87 % are also kept after charge and discharge cycles 1000 times.
The three-dimensional porous grapheme/polyaniline composite material that above-mentioned published method is prepared uses soft or hard template more
The three-dimensional porous structure of graphene is built, 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 also exist and remove incomplete problem, so as to
Seriously affect the purity of composite material.In addition, some methods are difficult to effectively alleviate the agglomeration traits of graphene.Li et al. people（Li
L Y, etal. Nano Energy, 2016, 21:276-294）With aromatic amine（Including 1,2,4 triaminobenzene, 2,2 ' two
Aminobenzidine, 1,5 diaminonaphthalene, 1,8 diaminonaphthalene）High performance graphene-based super electric material is obtained as intercalator,
Wherein, with 1,2,4 triaminobenzene as the graphene chemical property that intercalator obtains best, series equivalent resistance RsFor
0.61 Ω, charge transmission resistance RctFor 1.83 Ω, under 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 built with reference to 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 been 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 conjunctions0.075 Ω is down to, electricity
Lotus transmission resistance RctBe down to 0.3 Ω, under equal-wattage density the energy density of composite material with compound preceding containing 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%, after being compared to 800 times of pure PANI cycles loss 30% compare, the electrochemical cycle stability of composite material
Also it is remarkably reinforced.
Invention content
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 activations obtain three-dimensional porous structure graphene, finally by aniline on three-dimensional porous graphene in-situ polymerization
Into 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, includes 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 is 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 preparation of three-dimensional porous graphene：The graphene containing intercalator of the step a is soaked in potassium hydroxide solution,
Priming reaction, reaction product are dried to obtain three-dimensional porous through pickling and deionized water washing under nitrogen or argon gas atmosphere after drying
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 are added in, under the conditions of ice salt bath, in-situ polymerization obtains three-dimensional porous graphene/polyphenyl
Amine composite material.
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, the graphite oxide of the step a
A concentration of 0.2 ~ 2 mg/ml of the alkene in mixed liquor；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
Spend is 500-800 mM/ls；A concentration of 4 ~ 12 mM/ls in mixed liquor of 1,2,4- triaminobenzene dihydrochloride,
A concentration of 50 ~ 100 mM/ls of hydrochloric acid solution；Hydrothermal temperature is 160 ~ 200 DEG C, and the reaction time is small for 12 ~ 48
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, and the drying 5 ~ 12 hours of 90 DEG C of baking oven is living
It is 400 ~ 800 DEG C to change temperature, and soak time is 1 ~ 5 hour；Pickling agents useful for same is one kind in 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, a concentration of 1 ~ 2 mol/L of acid solution；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.
Advantages of the present invention is with effect：
The present invention is progress KOH activation process, the three-dimensional porous structure graphene film of acquisition on the graphene containing intercalator
Layer is relatively thin, reunites without apparent so that the big specific surface area of graphene is released effectively.Further with polyaniline is compound prepares
Three-dimensional porous grapheme/polyaniline composite material be conducive to electrolyte come into full contact with ion, electron-transport, show
Good chemical property can be applied to the fields such as electrode material for super capacitor, energy storage material and Heat Conduction Material.
Description of the drawings
Fig. 1 is the SEM figures of the three-dimensional porous graphene in embodiment 1.
Specific embodiment
The invention will be further described in the following with reference to the drawings and specific embodiments.
Embodiment 1
A kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, includes the following steps：
Step a：It weighs sodium carbonate to be dissolved in deionized water, graphene oxide and sodium carbonate liquor is sufficiently mixed uniformly, it
After weigh 1,2,4 triaminobenzene dihydrochlorides and be dissolved in 80 mM/ls of hydrochloric acid solution, be ultrasonically treated 10 minutes, then will be mixed
The hydrochloric acid solution for having 1,2,4 triaminobenzene dihydrochlorides is added in graphene oxide/sodium carbonate mixture, and control is entire anti-
The concentration for answering graphene oxide in liquid, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides is respectively 0.8 mg/ml, 560
MM/l and 8.6 mM/ls, ultrasonic disperse 1 hour；The reaction solution is moved into ptfe autoclave later,
180 DEG C of hydro-thermal reactions 12 hours, after cooling, vacuum filtration is washed repeatedly with deionized water and absolute ethyl alcohol to neutrality, 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, standing 24 hours, 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 successively 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（The mass ratio of three-dimensional porous graphene and aniline is 1:
6）, under the conditions of ice salt bath, the hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate is slowly added dropwise into above-mentioned mixed liquor
Milliliter（The molar ratio of aniline and ammonium persulfate is 1:1）, controlling reaction temperature is at 0 ~ 5 DEG C, reaction 8 hours；It, will be heavy after reaction
Shallow lake is filtered, washed to neutrality, is dried at 60 DEG C, obtains three-dimensional porous grapheme/polyaniline composite material.
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, includes the following steps：
Step a：It weighs sodium carbonate to be dissolved in deionized water, graphene oxide and sodium carbonate liquor is sufficiently mixed uniformly, it
After weigh 1,2,4 triaminobenzene dihydrochlorides and be dissolved in 70 mM/ls of hydrochloric acid solution, be ultrasonically treated 10 minutes, then will be mixed
The hydrochloric acid solution for having 1,2,4 triaminobenzene dihydrochlorides is added in graphene oxide/sodium carbonate mixture, and control is entire anti-
The concentration for answering graphene oxide in liquid, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides is respectively 1 mg/ml, 700 millis
Mol/L and 10.7 mM/ls, ultrasonic disperse 1 hour；The reaction solution is moved into ptfe autoclave later,
180 DEG C of hydro-thermal reactions 12 hours, after cooling, vacuum filtration is washed repeatedly with deionized water and absolute ethyl alcohol to neutrality, 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, standing 24 hours, 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 successively 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（The mass ratio of three-dimensional porous graphene and aniline is 1:
6）, under the conditions of ice salt bath, the hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate is slowly added dropwise into above-mentioned mixed liquor
Milliliter（I.e. the molar ratio of aniline and ammonium persulfate is 1:1）, controlling reaction temperature is at 0 ~ 5 DEG C, reaction 8 hours；It, will after reaction
Precipitation 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, includes the following steps：
Step a：It weighs sodium carbonate to be dissolved in deionized water, graphene oxide and sodium carbonate liquor is sufficiently mixed uniformly, it
After weigh 1,2,4 triaminobenzene dihydrochlorides and be dissolved in 60 mM/ls of hydrochloric acid solution, be ultrasonically treated 10 minutes, then will be mixed
The hydrochloric acid solution for having 1,2,4 triaminobenzene dihydrochlorides is added in graphene oxide/sodium carbonate mixture, and control is entire anti-
The concentration for answering graphene oxide in liquid, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides is respectively 0.8 mg/ml, 560
MM/l and 8.6 mM/ls, ultrasonic disperse 1 hour；The reaction solution is moved into ptfe autoclave later,
180 DEG C of hydro-thermal reactions 24 hours, after cooling, vacuum filtration is washed repeatedly with deionized water and absolute ethyl alcohol to neutrality, 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, standing 24 hours, 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 successively 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（The mass ratio of three-dimensional porous graphene and aniline is 1:
6）, under the conditions of ice salt bath, the hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate is slowly added dropwise into above-mentioned mixed liquor
Milliliter（I.e. the molar ratio of aniline and ammonium persulfate is 1:1）, controlling reaction temperature is at 0 ~ 5 DEG C, reaction 8 hours；It, will after reaction
Precipitation 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, includes the following steps：
Step a：It weighs sodium carbonate to be dissolved in deionized water, graphene oxide and sodium carbonate liquor is sufficiently mixed uniformly, it
After weigh 1,2,4 triaminobenzene dihydrochlorides and be dissolved in 80 mM/ls of hydrochloric acid solution, be ultrasonically treated 10 minutes, then will be mixed
The hydrochloric acid solution for having 1,2,4 triaminobenzene dihydrochlorides is added in graphene oxide/sodium carbonate mixture, and control is entire anti-
The concentration for answering graphene oxide in liquid, sodium carbonate and 1,2,4 triaminobenzene dihydrochlorides is respectively 1 mg/ml, 700 millis
Mol/L and 10.7 mM/ls, ultrasonic disperse 1 hour；The reaction solution is moved into ptfe autoclave later,
180 DEG C of hydro-thermal reactions 24 hours, after cooling, vacuum filtration is washed repeatedly with deionized water and absolute ethyl alcohol to neutrality, 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, standing 24 hours, 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 successively 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（The mass ratio of three-dimensional porous graphene and aniline is 1:
6）, under the conditions of ice salt bath, the hydrochloric acid solution 100 of 1 mol/L dissolved with ammonium persulfate is slowly added dropwise into above-mentioned mixed liquor
Milliliter（I.e. the molar ratio of aniline and ammonium persulfate is 1:1）, controlling reaction temperature is at 0 ~ 5 DEG C, reaction 8 hours；It, will after reaction
Precipitation is filtered, washed to neutrality, is dried at 60 DEG C, is obtained three-dimensional porous grapheme/polyaniline composite material.
Claims (4)
1. a kind of preparation method of three-dimensional porous grapheme/polyaniline composite material, includes 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 is 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 preparation of three-dimensional porous graphene：The graphene containing intercalator of the step a is soaked in potassium hydroxide solution,
Priming reaction, reaction product are dried to obtain three-dimensional porous through pickling and deionized water washing under nitrogen or argon gas atmosphere after drying
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 are added in, under the conditions of ice salt bath, in-situ polymerization obtains three-dimensional porous graphene/polyphenyl
Amine composite material.
2. a kind of preparation method of three-dimensional porous grapheme/polyaniline composite material according to claim 1, feature exist
In：A concentration of 0.2 ~ 2 mg/ml of the graphene oxide of the step a in mixed liquor；Strong base-weak acid salt for carbonate,
Bicarbonate radical, acetate, phosphate radical, inferior sulfate radical, silicate, meta-aluminic acid root sodium salt or sylvite in any one, highly basic
A concentration of 500-800 mM/ls in mixed liquor of salt of weak acid；1,2,4- triaminobenzene dihydrochlorides are in mixed liquor
A concentration of 4 ~ 12 mM/ls, a concentration of 50 ~ 100 mM/ls of hydrochloric acid solution；Hydrothermal temperature is 160 ~ 200
DEG C, the reaction time is 12 ~ 48 hours.
3. a kind of preparation method of three-dimensional porous grapheme/polyaniline composite material according to claim 1, feature exist
In：The three-dimensional grapheme of the step b and the mass ratio of potassium hydroxide are 1：（0.5~15）Soaking time is 12 ~ 48 hours, is dried
The drying 5 ~ 12 hours of 90 DEG C of case, activation temperature are 400 ~ 800 DEG C, and soak time is 1 ~ 5 hour；Pickling agents useful for same is hydrochloric acid
Or one kind in acetic acid.
4. a kind of preparation method of three-dimensional porous grapheme/polyaniline composite material according to claim 1, feature exist
In：The acid solution of the step c is hydrochloric acid, any one in sulfuric acid, phosphoric acid, perchloric acid, and acid solution a concentration of 1 ~ 2 rubs
You/liter；The mass ratio of three-dimensional meso-hole graphene and aniline is（0.1~10）:1, the molar ratio of aniline and ammonium persulfate is（0.25~
4）:1；Cryosel is sodium chloride, any one in calcium chloride, sodium nitrate；Polymeric reaction temperature is 0 ~ 5 DEG C, and the reaction time is 2 ~ 12
Hour.
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Cited By (3)
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| CN110358137A (en) * | 2019-07-16 | 2019-10-22 | 沈阳大学 | A kind of porous network structure graphene/polyaniline composite xerogel preparation method |
| CN113345723A (en) * | 2021-04-30 | 2021-09-03 | 上海交通大学 | Porous graphene/polyaniline composite film and preparation method and application thereof |
| CN114171325A (en) * | 2021-11-17 | 2022-03-11 | 中北大学南通智能光机电研究院 | Preparation method of three-dimensional graphene/polyaniline loaded conductive fabric composite electrode material |
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| CN110358137A (en) * | 2019-07-16 | 2019-10-22 | 沈阳大学 | A kind of porous network structure graphene/polyaniline composite xerogel preparation method |
| CN110358137B (en) * | 2019-07-16 | 2022-03-04 | 沈阳大学 | Preparation method of graphene/polyaniline composite xerogel with porous network structure |
| CN113345723A (en) * | 2021-04-30 | 2021-09-03 | 上海交通大学 | Porous graphene/polyaniline composite film and preparation method and application thereof |
| CN114171325A (en) * | 2021-11-17 | 2022-03-11 | 中北大学南通智能光机电研究院 | Preparation method of three-dimensional graphene/polyaniline loaded conductive fabric composite electrode material |
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