CN104167302B - Preparation method for grapheme/melamine resin hollow ball composite material - Google Patents
Preparation method for grapheme/melamine resin hollow ball composite material Download PDFInfo
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- CN104167302B CN104167302B CN201410319594.2A CN201410319594A CN104167302B CN 104167302 B CN104167302 B CN 104167302B CN 201410319594 A CN201410319594 A CN 201410319594A CN 104167302 B CN104167302 B CN 104167302B
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- melamine resin
- graphite oxide
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- hollow sphere
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Abstract
The invention relates to a preparation method for grapheme/ a melamine resin hollow ball composite material, comprising steps of dissolving ethanol in deionized water and adding glacial acetic acid and adjusting pH value to 2.0-6.0, (2) mixing melamine and formaldehyde solution, wherein the ratio of the quantities of two materials is 1:1.0-6.0, reacting at around 600 DEG for 20 min to obtain a prepolymer, (3) mixing polyvinyl alcohol glacial acetic acid aqueous solution with prepolymer and preserving at 600 DEG, when the system appears white turbidity, starting the timer and continuing the reaction for 6 min, ending the reaction quickly, performing liquid-solid separation on the obtained reaction liquid, cleaning and drying to obtain white melamine resin balls, (4) dispersing the graphite oxide and the melamine resin in the deionized water and stirring for 1-8h to make sure the two materials are fully mixed, wherein the ratio between two materials is 1:10-9:1, (5) freezing and drying the mixed liquid to obtain sponginess composite which is put in the Ar gas, carbonized for 0.5-5h, and naturally cooled to atmosphere temperature to obtain the black products. The preparation method disclosed by the invention is simple, and can produce the product which is unique in appearance and excellent in capacitive performance.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene/melamine resin Hollow Sphere Composites, belongs to special appearance and answers
Condensation material preparing technical field.
Background technology
Graphene is a kind of material with carbon element of sequential 2 D, and it not only has larger specific surface area, and its electric conductivity, electricity
Chemical, heat stability, mechanicalness are excellent, therefore Graphene is counted as a kind of electrode material of rationality.Due to graphene film
There is stronger π-π active forces between layer, make graphene sheet layer be susceptible to reunite, so the Graphene material actually prepared
Material, theoretical value of its specific surface area far below single-layer graphene；
The number of plies and specific area size of grapheme material has important to the electro-chemical activity of material, the conductivity of electronics
Affect.To avoid graphene sheet layer from reuniting, increase the specific surface area of grapheme material, forefathers are by Graphene and other nano materials
It is compound, for example：Graphene is combined with inorganic nano material（Z. P. Sun, X. M. Lu, A Solid-State
Reaction Route to Anchoring Ni(OH)2 Nanoparticles on Reduced Graphene Oxide
Sheets for Supercapacitors, Ind. Eng. Chem. Res. 2012, 51, 9973-9979. Y. L.
Chen, Z. A. Hu, Y. Q. Chang, H. W. Wang, Z. Y. Zhang, Y. Y. Yang, H. Y. Wu,
Zinc Oxide/Reduced Graphene Oxide Composites and Electrochemical Capacitance
Enhanced by Homogeneous Incorporation of Reduced Graphene Oxide Sheets in
Zinc Oxide Matrix, J. Phys. Chem. C 2011, 115, 2563-2571. Z. B. Lei, F. H.
Shi, L. Lu, Incorporation of MnO2-Coated Carbon Nanotubes between Graphene
Sheets as Supercapacitor Electrode, ACS Appl. Mater. Interfaces 2012, 4,
1058-1064.）；Graphene (L. W. Peng, Y. Y. Feng, P. Lv, D. Lei, Y. compound with CNT
T. Shen, Y. Li, W. Feng, Transparent, Conductive, and Flexible Multiwalled
Carbon Nanotube/Graphene Hybrid Electrodes with Two Three-Dimensional
Microstructures, J. Phys. Chem. C 2012,116,4970-4978.), under the electric current density of 2 A/g,
Its specific capacitance is about 150 F/g；Graphene is combined with polypyrrole medicine ball（T. Qian, C. F. Yu, S. S. Wu, J.
Shen, A Facilely Prepared Polypyrrole–Reduced Graphene Oxide Composite with a
Crumpled Surface for High Performance Supercapacitor Electrodes, J. Mater.
Chem. A 2013, 1, 6539-6542.）, when electric current density is 0.5 A/g, its specific capacitance is about 557 F/g；Graphene with
Polypyrrole pipe is combined（J. H. Liu, J. W. An, Y. X. Ma, M. L. Li, R. B. Ma, Synthesis of
a Graphene-Polypyrrole Nanotube Composite and Its Application in
Supercapacitor Electrode, J. Electrochem. Soc. 2012, 159 (6), A828-A833.）, electricity
When current density is 0.3A/g, its specific capacitance is 400 F/g, can be with the agglomeration traits of effectively solving Graphene.Really, as energy storage
Material these composites have of a relatively high specific capacitance, but their production cost is higher, cyclical stability, forthright again
Can await improving.High-temperature heat treatment legal system is got everything ready high specific capacitance Graphene/melamine resin hollow ball hybrid supercapacitor
Material, has not yet to see report.
The content of the invention
The present invention prepares Graphene/melamine resin Hollow Sphere Composites using high-temperature heat treatment method, there is provided one kind system
The method of the graphene-based hybrid supercapacitor material of standby special appearance；
The present invention prepares Graphene/melamine resin Hollow Sphere Composites, and its preparation process comprises the steps：
A. under agitation, polyvinyl alcohol is dissolved in deionized water, concentration is obtained for the poly- of 2.0 ~ 12.0mg/mL
Vinyl alcohol aqueous solution；
B. under agitation, weak acid is added in the polyvinyl alcohol water solution prepared to step a, adjusting solution ph is
2.0~6.0；
C. under agitation, tripolycyanamide is mixed homogeneously with formalin, the amount of the material of tripolycyanamide and formaldehyde
Ratio be 1:1.0~1:6.0,20min is reacted under uniform temperature, obtain prepolymer melamine methylol；
D. under agitation, polyvinyl alcohol water solution is mixed with the prepolymer melamine methylol obtained by step c
Close uniform, be heated to uniform temperature, be incubated, system to be mixed occurs after white opacity, start timing, and continue to react 6min,
After be put in 0 C ice baths, fast cooling, terminating reaction obtains milky reactant liquor；
E. the milky white liquid obtained by step d is carried out into solid-liquid separation, solid Jing alcohol is washed, washed, and is dried to obtain melamine
Resin white solid；
F. graphite oxide is disperseed in deionized water, ultrasonic a few hours, is made into the graphite oxide point that concentration is 1mg/mL
Dispersion liquid；
G. the melamine resin for step e being obtained is added in deionized water, ultrasonic a few hours, is made into concentration for 2.5mg/mL's
Melamine resin dispersion liquid；
H. under agitation, by the melamine resin point obtained by the graphite oxide dispersion obtained by step f and step g
Dispersion liquid mixes, and graphite oxide is 1 with the mass ratio of melamine resin:10~9:1, continuous stirring a few hours, it is sufficiently mixed both
Uniformly；
I. by the mixed solution obtained by step h, lyophilization, obtain spongiform graphite oxide/melamine resin and be combined
Thing；
J. under Ar gas shieldeds, with certain heating rate, by the graphite oxide obtained by step i/melamine resin complex
It is carbonized a few hours at a certain temperature, naturally cools to room temperature, obtains black Graphene/melamine resin Hollow Sphere Composites；
Stir speed (S.S.) in step a, b is 300 ~ 500r/min, and the mixing speed of step c, d is 200 ~ 300r/
Min, the mixing speed of step h is 400 ~ 600r/min；
Polyvinyl alcohol concentration in step a is 2.0 ~ 12.0mg/mL, and preferred concentration is 6.0mg/mL；
Weak acid in step b is glacial acetic acid, and it is 2.0 ~ 6.0 to adjust solution ph, more preferably pH=4.5；
Tripolycyanamide in step c is 1 with the ratio of the amount of the material of formaldehyde:1.0~1:6.0, preferred ratio is
1:3.3；
Reaction temperature in step c is 40 ~ 80 C, and preferred temperature is 60 C；
Holding temperature in step d is 40 ~ 80 C, and preferred reaction temperature is 60 C；
Centrifugal rotational speed in step e is 3000 ~ 10000r/min, and more excellent rotating speed is 6000r/min；
Baking temperature in step e is 30 ~ 80 C, and more preferably temperature is 40 C；
Ultrasonic time in step f is 1 ~ 6h, and more preferably ultrasonic time is 3h；
Ultrasonic time in step g is 0.5 ~ 3h, and more preferably ultrasonic time is 1.5h；
Graphite oxide in step h is 1 with the mass ratio of melamine resin:10~9:1, preferred ratio is 1:
5；
Mixing time in step h is 1 ~ 8h, and more preferably mixing time is 3h；
Heating rate in step j is 0.5 ~ 5 C/min, and more preferably heating rate is 1 C/min；
Carburizing temperature in step j is 400 ~ 900 C, and more preferably carburizing temperature is 600 C；
Carbonization time in step j is 0.5 ~ 6h, and more preferably carbonization time is 1h；
Compare with prior art, the present invention has advantages below：
（1）The present invention prepares monodispersed melamine resin medicine ball with polyvinyl alcohol as dispersant, multiple with graphite oxide
After conjunction, using high-temperature heat treatment method, Graphene/melamine resin Hollow Sphere Composites are synthesized first, it is close in the electric current of 1A/g
The lower discharge and recharge of degree, specific capacitance reaches 625F/g, has many potential application prospects in electrode material for super capacitor field；
（2）Present invention process is simple, is adapted to scale industrial production.
Description of the drawings
Fig. 1 is the scanning electron microscope of the Graphene/melamine resin Hollow Sphere Composites sample S-1 prepared by embodiment 1
（SEM）Photo；
Fig. 2 is the transmission electron microscope of the Graphene/melamine resin Hollow Sphere Composites sample S-1 prepared by embodiment 1
（TEM）Photo；
Fig. 3 for comparative example institute Graphene/melamine resin composite sample S-2 SEM photograph.
Specific embodiment
Technical scheme is further elaborated with reference to specific embodiment, these embodiments are intended merely to explain
State technical scheme and the restriction to the claims in the present invention content can not be considered as.It is raw materials used in embodiment to be often
Rule commercial products；Device therefor is conventional equipment；Method of testing is conventional method；
Polyvinyl alcohol Tianjin Bo Di chemical inc in embodiment is on sale；
Glacial acetic acid Tianjin Bo Di chemical inc is on sale；
Tripolycyanamide Chemical Reagent Co., Ltd., Sinopharm Group is on sale；
Formalin Jinan Lu Kang chemical industry company limited is on sale；
The stereoscan photograph of prepared sample of the invention is that Jing Japan Hitachi S-4800 Flied emissions scanning electron shows
Micro mirror detection is obtained；Transmission electron microscope photo is that the detection of Jing Japan JEM-1011 transmission electron microscopes is obtained；Charge-discharge test is
The detection of Jing PARSTAT2263 electrochemical workstations is obtained.
Embodiment 1
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.25g graphite oxides are dispersed in 250mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）1.25g melamine resins are added in 500mL deionized waters, ultrasonic 1.5h, obtain concentration for the close of 2.5mg/mL
Polyimide resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 1:5, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 600 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Fig. 1 is the stereoscan photograph of Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites；Fig. 2 is
The transmission electron microscope photo of Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites；The scanning of prepared sample S-1
Electromicroscopic photograph is shown in Fig. 1；The transmission electron microscope photo of prepared sample S-1 is shown in Fig. 2；
As seen from Figure 1, sample S-1 is covered by between graphene sheet layer for the ball after melamine resin carbonization, defines one
Tridimensional network is planted, melamine resin ball size is more uniform, and diameter about 500nm or so, graphene sheet layer has obvious fold；
Melamine resin ball after being carbonized as seen from Figure 2 is hollow, and wall thickness is about 45nm or so；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 625F/g.
Embodiment 2
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.4g graphite oxides are dispersed in 400mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）0.8g melamine resins are added in 320mL deionized waters, ultrasonic 1.5h, obtain concentration for the close of 2.5mg/mL
Polyimide resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 1:2, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 600 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 350F/g.
Embodiment 3
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.46g graphite oxides are dispersed in 460mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）0.23g melamine resins are added in 92mL deionized waters, ultrasonic 1.5h, obtain concentration for the close of 2.5mg/mL
Polyimide resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 2:1, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 600 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 300F/g.
Embodiment 4
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.5g graphite oxides are dispersed in 500mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）0.1g melamine resins are added in 40mL deionized waters, ultrasonic 1.5h, obtain the melamine that concentration is 2.5mg/mL
Resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 5:1, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 600 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 450F/g.
Embodiment 5
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.5g graphite oxides are dispersed in 500mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）0.5g melamine resins are added in 200mL deionized waters, ultrasonic 1.5h, obtain concentration for the close of 2.5mg/mL
Polyimide resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 1:1, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 600 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 400F/g.
Embodiment 6
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.25g graphite oxides are dispersed in 250mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）1.25g melamine resins are added in 500mL deionized waters, ultrasonic 1.5h, obtain concentration for the close of 2.5mg/mL
Polyimide resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 1:5, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 800 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 539F/g.
Embodiment 7
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.25g graphite oxides are dispersed in 250mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）1.25g melamine resins are added in 500mL deionized waters, ultrasonic 1.5h, obtain concentration for the close of 2.5mg/mL
Polyimide resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 1:5, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 700 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 580F/g.
Embodiment 8
（1）Under agitation, 0.54g polyvinyl alcohol is dissolved in 90mL deionized waters；
（2）Under agitation, glacial acetic acid is added in above-mentioned polyvinyl alcohol water solution, pH value of solution=4.5 are adjusted；
（3）Under agitation, 2.8g tripolycyanamide is mixed homogeneously with 5.946g formalins, is heated to 60 C, and
Continue to react 20min, obtain prepolymer melamine methylol；
（4）Under agitation, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and
Be incubated under 60 C, system to be mixed occurs after white opacity, start timing, and continue stirring reaction 6min, after be put into 0 C ice
In bath, fast cooling, terminating reaction obtains milky reactant liquor；
（5）Gained milky reactant liquor is carried out into solid-liquid separation, it is liquids recovery, standby.Solid Jing alcohol is washed, washed, in 40
24h is dried in C air atmospheres, melamine resin white solid is obtained, it is stand-by；
（6）0.25g graphite oxides are dispersed in 250mL deionized waters, ultrasonic 3h, obtain the oxidation that concentration is 1mg/mL
Graphite dispersing solution；
（7）1.25g melamine resins are added in 500mL deionized waters, ultrasonic 1.5h, obtain concentration for the close of 2.5mg/mL
Polyimide resin dispersion liquid；
（8）Under agitation, graphite oxide dispersion is slowly added in melamine resin dispersion liquid, graphite oxide with it is close
The mass ratio of polyimide resin is 1:5, it is further continued for stirring 3h, both is sufficiently mixed uniformly；
（9）Graphite oxide and melamine resin mixed liquor are carried out into lyophilization, spongiform graphite oxide/melamine tree is obtained
Fat complexes；
（10）Graphite oxide/melamine resin complex is put in tube furnace, under Ar gas shieldeds, with the liter of 1 C/min
Warm speed is heated to 500 C, and is incubated 1h, after naturally cool to room temperature, obtain black objects product；
Charge-discharge test is carried out to Graphene manufactured in the present embodiment/melamine resin Hollow Sphere Composites, 1A/g's
Discharge and recharge under current density condition, specific capacitance is 512F/g.
Comparative example
In melamine resin ball preparation process, not Polyvinyl alcohol, remaining step is obtained this comparative example with embodiment 1
It is Graphene/melamine resin composite；
Fig. 3 is the SEM photograph of Graphene/melamine resin composite prepared by this comparative example；
The stereoscan photograph of prepared sample S-2 is shown in Fig. 3；
As seen from Figure 3, sample S-2 is with graphene sheet layer not form tridimensional network after melamine resin carbonization, and multiple
The generally random pattern of condensation material；
Charge-discharge test is carried out to Graphene/melamine resin composite prepared by this comparative example, in 1A/g discharge and recharge bars
Under part, specific capacitance is 480F/g.
Claims (9)
1. a kind of preparation method of Graphene/melamine resin Hollow Sphere Composites, step is as follows：
（1）Under agitation, polyvinyl alcohol is dissolved in deionized water, poly- second of the concentration for 2.0 ~ 12.0mg/mL is obtained
Enol aqueous solution；
（2）Under agitation, weak acid is added in polyvinyl alcohol water solution, it is 2.0 ~ 6.0 to adjust pH value of solution, and the weak acid is
Glacial acetic acid；
（3）Under agitation, tripolycyanamide is mixed homogeneously with formalin, the ratio of the amount of the material of tripolycyanamide and formaldehyde
For 1:1.0~1:6.0,20min is reacted under 60 C, obtain prepolymer melamine methylol；
（4）Under agitation, polyvinyl alcohol glacial acetic acid aqueous solution is mixed homogeneously with prepolymer melamine methylol, is incubated
In 60 C, system to be mixed occurs after white opacity, start timing, and continue react 6min, after be put in 0 C ice baths, quickly
Cooling, terminating reaction obtains milky reactant liquor；Gained milky white liquid is carried out into solid-liquid separation, solid Jing washings, alcohol are washed, done
Melamine resin white solid is obtained final product after dry；
（5）Graphite oxide is disperseed in deionized water, 1 ~ 6h of ultrasound, be made into the graphite oxide dispersion that concentration is 1mg/mL；
Melamine resin is added in deionized water, 0.5 ~ 3h of ultrasound, be made into the melamine resin dispersion liquid that concentration is 2.5mg/mL；
（6）Under agitation, graphite oxide dispersion is mixed with melamine resin dispersion liquid, graphite oxide and melamine resin
Mass ratio is 1:10~9:1,1 ~ 8h of continuous stirring, make both be sufficiently mixed uniformly；Gained mixed solution is carried out into freezing dry
It is dry, obtain spongiform graphite oxide/melamine resin complex；
（7）Under Ar gas shieldeds, with the heating rate of 0.5 ~ 5 C/min, 400 ~ 900 C are warming up to, carbonization time is 0.5 ~ 6h,
After naturally cool to room temperature, obtain black Graphene/melamine resin Hollow Sphere Composites.
2. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（1）Described in poly-vinyl alcohol solution concentration be 6.0mg/mL.
3. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（2）Described in addition glacial acetic acid, adjust solution pH be 4.5.
4. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（3）Described in the ratio of amount of material of tripolycyanamide and formaldehyde be 1:3.3.
5. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（4）Described in mode of washing wash 2 ~ 3 times for ethanol after wash 2 ~ 3 times with water；The drying mode be in 30 ~ 80 C,
10 ~ 24h is dried in air atmosphere.
6. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（5）Described in graphite oxide dispersion ultrasonic time be 3h；Described melamine resin dispersion liquid ultrasonic time is 1.5h.
7. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（6）Described in the mass ratio of graphite oxide and melamine resin be 1:5；Described graphite oxide mixes with melamine resin
Liquid, stirring incorporation time is 3h.
8. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（7）Described in heating rate be 1 C/min；Described carburizing temperature is 600 C；Described carbonization time is 1h.
9. the preparation method of Graphene according to claim 1/melamine resin Hollow Sphere Composites, it is characterised in that
Step（1）、（2）Described in stir speed (S.S.) be 300 ~ 500r/min, step（3）、（4）Described in mixing speed be 200 ~
300r/min, step（6）Described in mixing speed be 400 ~ 600r/min.
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