CN109052374A - A kind of method that heteropoly acid catalysis quickly prepares graphene aerogel - Google Patents
A kind of method that heteropoly acid catalysis quickly prepares graphene aerogel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of method that heteropoly acid catalysis quickly prepares graphene aerogel, the method are as follows: phosphorus molybdenum acid solution and fragrant amine aqueous solution are uniformly mixed, mixed liquor is obtained, then graphene oxide dispersion is added in the mixed liquor, stands, obtains graphene hydrogel；Precooling will be carried out after gained graphene hydrogel with water soaking and washing, is freeze-dried later, obtains the graphene aerogel；This method preparation process is simple, easily operated, time-consuming short, it consumes energy low, raw materials used from a wealth of sources, price is less expensive, can be mass-produced different size graphite alkene aerogel block bodies, and graphene aerogel obtained shows excellent properties in terms of electrode of super capacitor.
Description
(1) technical field
The present invention relates to a kind of methods that heteropoly acid catalysis quickly prepares graphene aerogel.
(2) background technique
Graphene aerogel has caused very big attention as a kind of novel three-dimensional material, mainly by graphite flake
The interlaced connected composition on three-dimensional space.Graphene aerogel has the small (1~50mg/cm of density3), porosity height (>
50%) the features such as, large specific surface area, mechanical property is good, and electric conductivity is good and chemical stabilization.It can be used as clean energy resource storage such as
The electrode material of hydrogen, the dielectric material of natural gas and power storage such as supercapacitor, in heterogeneous catalysis, sewage treatment and biography
Equally also there is important application prospect in the fields such as sensor.
Graphene aerogel is generally prepared by graphene hydrogel by technologies such as frozen drying or supercritical dryings
Obtain, and its properity, manufacturing cycle and cost influenced by graphene hydrogel it is very big.The preparation of graphene hydrogel
Method is by many articles and patent report mistake, generally hydro-thermal method.However there is the problems such as time-consuming long, energy consumption is high in hydro-thermal method,
Rapid scale production requirement is not met.Such as Song Xi is bright etc. reports a kind of " three-dimensional structure in patent CN1068428246A
Graphene aerogel compound and its preparation method and application ", uses hydro-thermal method to prepare, but (12~18 is small long for its time-consuming
When), consume energy high (120~180 DEG C), and need to generally synthesize at high temperature under high pressure, be not suitable for large area production, can not actually answer
With.Disclosed in CN106422995A such as Liu Chen sun again " a kind of graphene aerogel and its hybrid composite material and its
Preparation method and application ", uses more mild oil bath heating method (70~100 DEG C), but oil bath repeatedly is needed to be up to 18
Hour, equally exist the high problem of long duration of energy consumption.Therefore the new method for preparing graphene hydrogel of one kind is developed to overcome
The shortcomings that above method, just seems very significant and competitiveness.
Heteropoly acid (abbreviation POMs) is by hetero atom (such as P, Si, Fe, Co) and metallic atom (such as Mo, W, V, Nb, Ta
Deng) by the oxygen-containing polyacid of one kind of oxygen atom ligand composition, stability is preferable, have stronger acid and oxidation-reduction quality,
It is provided simultaneously with higher catalytic activity, can be used as alkylating aromatic hydrocarbon and dealkylation, esterification, dehydration/combination reaction, oxygen
Change reduction reaction and open loop, condensation, addition and etherification reaction etc., is a kind of novel green catalyst.
(3) summary of the invention
It is simple and environmentally-friendly, low in cost that the purpose of the present invention is to provide a kind of processes, quickly prepares stone at room temperature
The method of black alkene aeroge.Compared with other congenic methods, the time of graphene aerogel is prepared very using the method for the present invention
Short (usually within 1 minute).
The method of the present invention selects a kind of suitable heteropoly acid (phosphomolybdic acid is most common heteropoly acid), aromatic amine (to benzene two
Amine, 2,6-diaminopyridine, melamine or 2,6- diaminopurine) and graphene oxide generation polymerization reaction, to make oxygen
Graphite alkene lamella Quick cross-linking together, obtains stable three-dimensional space net structure graphene aerogel.Wherein, heteropoly acid
Cause aromatic amine (p-phenylenediamine, 2,6- diamino-pyridine, melamine or 2,6-diaminopurine) hair as green catalyst
Raw polymerization reaction, forms polymer.After graphene oxide is added, heteropoly acid be used as again bronsted acid catalyst promote aromatic amine with
Amidation process occurs for graphene oxide, thus graphene oxide layer is crosslinked together, form graded porous structure.The party
Method prepares simple process, easily operated, time-consuming short, consumes energy low, raw materials used from a wealth of sources, price is less expensive, can give birth on a large scale
Different size graphite alkene aerogel block bodies are produced, and graphene aerogel obtained is shown in terms of electrode of super capacitor
Excellent properties.
Technical scheme is as follows:
A kind of method that heteropoly acid catalysis quickly prepares graphene aerogel, the method are as follows:
(1) phosphomolybdic acid is soluble in water, it is configured to the phosphorus molybdenum of 0.01~0.05mmol/mL (preferably 0.0125mmol/mL)
Acid solution；Aromatic amine is soluble in water, it is configured to the fragrant amine aqueous solution of 0.1~0.5mmol/mL (preferably 0.125mmol/mL)；
Phosphorus molybdenum acid solution and fragrant amine aqueous solution are uniformly mixed, mixed liquor is obtained, then by the oxidation of 1~6mg/mL (preferably 5mg/mL)
Graphene dispersing solution is added in the mixed liquor, is stood (1~60min), is obtained graphene hydrogel；
The operation temperature of step (1) is usually room temperature (20~30 DEG C)；
The phosphorus molybdenum acid solution, fragrant amine aqueous solution, graphene oxide dispersion volume ratio be 1:1~6:1~6, preferably
1:1:1.5；
The aromatic amine is p-phenylenediamine, 2,6- diamino-pyridine, melamine or 2,6-diaminopurine；
(2) graphene hydrogel with water soaking and washing (remove unreacted substance) obtained by step (1) is carried out afterwards pre-
It freezes (- 10~-50 DEG C), is freeze-dried (- 50 DEG C, < 10Pa) later, obtains the graphene aerogel.
In the present invention, the preferred deionized water of the water.
The phosphomolybdic acid is solid crystals shape, molecular formula H3PMo12O40·xH2O, wherein x=1~20, commercially available to obtain
?.
The graphene oxide dispersion can be commercially available by conventional route, or improves hummer legal system according to following
It is standby to obtain, the specific steps are as follows:
85wt% phosphoric acid, 98wt% sulfuric acid are uniformly mixed, at 0 DEG C, crystalline flake graphite is added, stirs 40min, is subsequently added into
Potassium permanganate is warming up to 35 DEG C of stirring 30min, then raises temperature to 50 DEG C of stirring 12h, backward reaction system in sequentially add ice
Water, 30wt%H2O2, mixed liquor is obtained, the sedimentation of 10wt%HCl aqueous solution is added in gained mixed liquor, is centrifuged, washing obtains
Gained graphene oxide is added in water by graphene oxide, the ultrasonic disperse 2h at frequency 30kW, obtains dispersion liquid, sampling warp
(- 50 DEG C, < 10Pa) of freeze-drying quantitative, and then gained dispersion liquid is configured to the graphene oxide dispersion of 1~6mg/mL；
The volume ratio of the 85wt% phosphoric acid and 98wt% sulfuric acid is 1:9；
The mass ratio of the crystalline flake graphite and potassium permanganate is 1:6；
The volumetric usage of the 98wt% sulfuric acid is calculated as 120mL/g with the quality of crystalline flake graphite.
Graphene aerogel produced by the present invention can be used as the electrode material of supercapacitor.
The preparation method of graphene aerogel of the present invention has the technical effect that:
(1) present invention provides a kind of method that heteropoly acid catalysis quickly prepares graphene aerogel at room temperature.
(2) under phosphomolybdic acid acidic environment, introducing aromatic amine (p-phenylenediamine, 2,6-diaminopyridine, melamine or 2,
6- diaminopurine), it can be catalyzed and cause aromatic amine generation polymerization reaction；Phosphomolybdic acid promotes graphene oxide as catalyst simultaneously
Amidation process occurs between aromatic amine, graphene oxide layer is promoted to be cross-linked with each other together.
(3) graphene aerogel prepared have apparent three-dimensional porous reticular structure and certain mechanical strength and
Biggish specific surface area.
(4) in terms of the graphene aerogel prepared is applied to supercapacitor, excellent performance is shown.
(5) graphene hydrogel techniques mild condition (at room temperature) is prepared, easy to operate, time-consuming short, consume energy low, original used
Expect it is from a wealth of sources, it is safe and efficient.
(4) Detailed description of the invention
Fig. 1 is 1 sample surfaces scanning electron microscope diagram of embodiment；
Fig. 2 is 1 sample constant current charge-discharge test map of embodiment；
Fig. 3 is 2 sample surfaces scanning electron microscope diagram of embodiment；
Fig. 4 is 2 sample constant current charge-discharge test map of embodiment；
Fig. 5 is 3 sample surfaces scanning electron microscope diagram of embodiment；
Fig. 6 is 3 sample constant current charge-discharge test map of embodiment；
Fig. 7 is 4 sample surfaces scanning electron microscope diagram of embodiment；
Fig. 8 is 4 sample constant current charge-discharge test map of embodiment.
(5) specific embodiment
Below by specific embodiment, the invention will be further described, is not limited in protection scope of the present invention
This.
In following each embodiments, commercial oxidation graphene solution is can be used in used graphene oxide dispersion, or
Person is prepared according to following hummer method of improving, the specific steps are as follows:
20mL phosphoric acid (85wt%) and the 180mL concentrated sulfuric acid (98wt%) are stirred, 1.5g scale is added at 0 DEG C
Graphite (Aladdin chemical reagent Co., Ltd) simultaneously stirs 40 minutes.Being subsequently added into 9g potassium permanganate, (Aladdin chemical reagent has
Limit company), and be warming up to 35 DEG C and stir 30 minutes, it is then warming up to 50 DEG C of stirring 12h again.It is slowly added to after reaction
200mL ice water, and 12mL 30wt%H is added2O2(solution colour becomes golden yellow), obtains mixed liquor.In gained mixed liquor
Isometric 10wt%HCl aqueous solution sedimentation (repeating sedimentation 3 times) is added, then washing centrifugation is until pH value > 4, the oxygen that will be obtained
Graphite alkene is added in water, in frequency 30kW ultrasonic disperse 2h, after sampling is freeze-dried quantitatively under the conditions of -50 DEG C, < 10Pa,
And then it is configured to 5mg/mL graphene oxide dispersion.
Embodiment 1
(1) 0.05g, 0.025mmol phosphomolybdic acid yellow crystals (Mike's woods biochemical technology Co., Ltd) are dissolved in first
In 2mL deionized water, yellow clear solution is formed, solution A is denoted as；
(2) by 0.027g, 0.25mmol p-phenylenediamine powder (Mike's woods biochemical technology Co., Ltd) be dissolved in 2mL go from
Red clear solution is formed in sub- water, is denoted as solution B.
(3) the two is uniformly stirred, obtains suspension, suspension is transferred to 10mL glass after 30kW ultrasound 1min
In bottle.
(4) in the graphene oxide dispersion liquid-transfering gun implantation glass bottle for being 5mg/mL by 3mL concentration, after standing 1min
Graphene hydrogel can be obtained.
(5) first pre- at -30 DEG C by obtained graphene hydrogel after deionized water impregnates removal unreacting substance
Freezing, then at -50 DEG C, is freeze-dried 12h under < 10Pa pressure environment, obtains graphene aerogel.
The Analysis of Surface Topography of sample is observed using II type field emission scanning electron microscope of HitachiS-4700, result
As shown in Figure 1, display obtains three-dimensional porous structure.
(6) obtained graphene aerogel is added into acetylene black and Kynoar, according to mass ratio 7.5:1.5:1 ratio
Example, obtains electrode of super capacitor by blade coating mode after grinding sample preparation.In Shanghai Chen Hua Co., Ltd electrochemical operation
To embodiment sample in electrolyte (1M H on standing2SO4, similarly hereinafter) in carry out electrochemical property test.Test result shows super
Capacitor is up to 770F/g in the electrode specific capacitance that charging and discharging currents density is 1A/g, as a result as shown in Figure 2.
Embodiment 2
(1) 0.05g, 0.025mmol phosphomolybdic acid crystal (Mike's woods biochemical technology Co., Ltd) are dissolved in 2mL first
In ionized water, yellow clear solution is formed, solution A is denoted as；
(2) 0.027g, 0.25mmol 2,6- diamino-pyridine powder (Mike's woods biochemical technology Co., Ltd) are dissolved in
Red clear solution is formed in 2mL deionized water, is denoted as solution B.
(3) the two is uniformly stirred, obtains suspension, suspension is transferred to 10mL after the 30kW ultrasound 1min time
In vial.
(4) in the graphene oxide dispersion liquid-transfering gun implantation glass bottle for being 5mg/mL by 3mL concentration, after standing 1min
Graphene hydrogel can be obtained.
(5) first pre- at -30 DEG C by obtained graphene hydrogel after deionized water impregnates removal unreacting substance
Freezing, then at -50 DEG C, is freeze-dried 12h under < 10Pa pressure environment, obtains graphene aerogel.The Analysis of Surface Topography of sample
Observed using II type field emission scanning electron microscope of HitachiS-4700, result as shown in figure 3, display obtain it is three-dimensional porous
Structure.
(6) obtained graphene aerogel is added into acetylene black and Kynoar, according to mass ratio 7.5:1.5:1 ratio
Obtain electrode of super capacitor.Electrochemical property test is carried out in the electrolytic solution to embodiment sample on electrochemical workstation.
Test result shows that supercapacitor is up to 570F/g in the electrode specific capacitance that charging and discharging currents density is 1A/g, as a result such as Fig. 4
It is shown.
Embodiment 3
(1) 0.05g, 0.025mmol phosphomolybdic acid crystal (Mike's woods biochemical technology Co., Ltd) are dissolved in 2mL first
In ionized water, yellow clear solution is formed, solution A is denoted as；
(2) by 0.036g, 0.25mmol melamine powder (Mike's woods biochemical technology Co., Ltd) be dissolved in 2mL go from
Red clear solution is formed in sub- water, is denoted as solution B.
(3) the two is uniformly stirred, obtains suspension, suspension is transferred to 10mL glass after 30kW ultrasound 1min
In bottle.
(4) in the graphene oxide dispersion liquid-transfering gun implantation glass bottle for being 5mg/mL by 3mL concentration, after standing 1min
Graphene hydrogel can be obtained.
(5) first pre- at -30 DEG C by obtained graphene hydrogel after deionized water impregnates removal unreacting substance
Freezing, then at -50 DEG C, is freeze-dried 12h under < 10Pa pressure environment, obtains graphene aerogel.The Analysis of Surface Topography of sample
Observed using II type field emission scanning electron microscope of HitachiS-4700, result as shown in figure 5, display obtain it is three-dimensional porous
Structure.
(6) obtained graphene aerogel is added into acetylene black and Kynoar, according to mass ratio 7.5:1.5:1 ratio
Obtain electrode of super capacitor.Electrochemical property test is carried out in the electrolytic solution to embodiment sample on electrochemical workstation.
Test result shows that supercapacitor is up to 591F/g in the electrode specific capacitance that charging and discharging currents density is 1A/g, as a result such as Fig. 6
It is shown.
Embodiment 4
(1) 0.05g, 0.025mmol phosphomolybdic acid crystal (Mike's woods biochemical technology Co., Ltd) are dissolved in 2mL first
In ionized water, yellow clear solution is formed, solution A is denoted as；
(2) 0.036g, 0.25mmol 2,6-diaminopurine powder (Mike's woods biochemical technology Co., Ltd) are dissolved in
Red clear solution is formed in 2mL deionized water, is denoted as solution B.
(3) the two is uniformly stirred, obtains suspension, suspension is transferred to 10mL glass after 30kW ultrasound 1min
In bottle.
(4) in the graphene oxide dispersion liquid-transfering gun implantation glass bottle for being 5mg/mL by 3mL concentration, after standing 1min
Graphene hydrogel can be obtained.
(5) first pre- at -30 DEG C by obtained graphene hydrogel after deionized water impregnates removal unreacting substance
Freezing, then at -50 DEG C, is freeze-dried 12h under < 10Pa pressure environment, obtains graphene aerogel.The Analysis of Surface Topography of sample
Observed using II type field emission scanning electron microscope of HitachiS-4700, result as shown in fig. 7, display obtain it is three-dimensional porous
Structure.
(6) obtained graphene aerogel is added into acetylene black and Kynoar, according to mass ratio 7.5:1.5:1 ratio
Obtain electrode of super capacitor.Electrochemical property test is carried out in the electrolytic solution to embodiment sample on electrochemical workstation.
Test result shows that supercapacitor is up to 513F/g in the electrode specific capacitance that charging and discharging currents density is 1A/g, as a result such as Fig. 8
It is shown.
Comparative example 1
A kind of graphite oxide aerogel, preparation method and application CN 102910625A
(1) taking 5mL concentration is the graphene oxide water solution of 15mg/mL, and 0.4mL 0.5mol/L is added under stirring condition
Sodium hydroxide solution, adjust pH be 8, then thereto be added 0.4mL30mg/L La (OH)3Solution, ultrasonic disperse obtain molten
Liquid 1；
(2) gluconic acid lactone of 100mg is added into solution 1, ultrasonic disperse obtains solution 2, by solution 2 at 20 DEG C
It stands for 24 hours to get having arrived uniform graphene oxide hydrogel；
(3) it is added ethyl alcohol in graphene oxide hydrogel, pours out ethyl alcohol after impregnating 6h, repeatedly after 5 times, aoxidized
Graphene alcogel.The supercritical carbon dioxide drying instrument produced with u s company is dry for 24 hours, supercritical carbon dioxide drying
Critical-temperature is 31.05 DEG C, critical pressure 7.38Pa, has obtained the graphite oxide aerogel of La crosslinking.
(4) obtained graphite oxide aerogel is used as electrode of super capacitor, steps are as follows: by graphite oxide
After alkene aeroge is ground with mortar, according to aeroge, acetylene and PVDF (Kynoar, as binder) mass ratio=
87:10:3 prepares resulting mixture and grinds in mortar, is pressed in Ni film until forming uniform high viscosity solution, is placed in 120 DEG C
It is 6 hours dry, it is then assembled into electrode system, Ni film is used as working electrode, Pt electrode to electrode.Electrolyte is 5mg/
The solution of LKOH.The tests such as all electro-chemical test cyclic voltammetrics and constant current charge-discharge are in work Shanghai Chen Hua company at electricity production
It is carried out in chem workstation, obtained aeroge specific capacitance value is 120F/g.
Under comparison, the graphene aerogel method of the present invention for preparing has advantage as follows:
(1) present invention using heteropoly acid as bronsted acid catalyst, simple agitation at room temperature, without controlling pH value,
Graphene aerogel can be prepared in the extremely short time (usual 1min).
(2) graphene aerogel of preparation of the present invention can be obtained by graphene hydrogel by the method being freeze-dried
, need not move through ethyl alcohol exchange and supercritical CO2It is dry, and excellent three-dimensional porous reticular structure is kept, and have one
Fixed mechanical strength, simplifies technique.
(3) comparative example is compared, the graphene aerogel of preparation of the present invention specific capacitance value with higher 500~
770F/g。
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of method that heteropoly acid catalysis quickly prepares graphene aerogel, which is characterized in that the method are as follows:
(1) phosphomolybdic acid is soluble in water, it is configured to the phosphorus molybdenum acid solution of 0.01~0.05mmol/mL；Aromatic amine is soluble in water,
It is configured to the fragrant amine aqueous solution of 0.1~0.5mmol/mL；Phosphorus molybdenum acid solution and fragrant amine aqueous solution are uniformly mixed, mixed
The graphene oxide dispersion of 1~6mg/mL is then added in the mixed liquor by liquid, is stood, is obtained graphene hydrogel；
The phosphorus molybdenum acid solution, fragrant amine aqueous solution, graphene oxide dispersion volume ratio be 1:1~6:1~6；
The aromatic amine is p-phenylenediamine, 2,6- diamino-pyridine, melamine or 2,6-diaminopurine；
(2) precooling will be carried out after graphene hydrogel with water soaking and washing obtained by step (1), is freeze-dried later, obtains institute
State graphene aerogel.
2. the method as described in claim 1, which is characterized in that the operation temperature of step (1) is room temperature.
3. the method as described in claim 1, which is characterized in that in step (1), the time of the standing is 1~60min.
4. the method as described in claim 1, which is characterized in that in step (2), the temperature of the precooling is -10~-50
℃。
5. the method as described in claim 1, which is characterized in that in step (2), the condition of the freeze-drying are as follows: temperature -50
DEG C, pressure < 10Pa.
6. the method as described in claim 1, which is characterized in that the graphene oxide dispersion is prepared as follows
It arrives:
85wt% phosphoric acid, 98wt% sulfuric acid are uniformly mixed, at 0 DEG C, crystalline flake graphite is added, stirs 40min, is subsequently added into Gao Meng
Sour potassium is warming up to 35 DEG C of stirring 30min, then raises temperature to 50 DEG C of stirring 12h, backward reaction system in sequentially add ice water,
30wt%H2O2, mixed liquor is obtained, the sedimentation of 10wt%HCl aqueous solution is added in gained mixed liquor, is centrifuged, washing is aoxidized
Gained graphene oxide is added in water by graphene, the ultrasonic disperse 2h at frequency 30kW, obtains dispersion liquid, is sampled chilled
Drying is quantitative, and then gained dispersion liquid is configured to the graphene oxide dispersion of 1~6mg/mL；
The volume ratio of the 85wt% phosphoric acid and 98wt% sulfuric acid is 1:9；
The mass ratio of the crystalline flake graphite and potassium permanganate is 1:6；
The volumetric usage of the 98wt% sulfuric acid is calculated as 120mL/g with the quality of crystalline flake graphite.
7. graphene aerogel made from method as described in claim 1.
8. application of the graphene aerogel as claimed in claim 7 as the electrode material of supercapacitor.
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|---|---|---|---|---|
| CN113526494A (en) * | 2021-06-28 | 2021-10-22 | 合肥国轩高科动力能源有限公司 | Method for preparing graphene hydrogel |
| CN113526494B (en) * | 2021-06-28 | 2023-09-08 | 合肥国轩高科动力能源有限公司 | Method for preparing graphene hydrogel |
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