CN104167302A - 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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- CN104167302A CN104167302A CN201410319594.2A CN201410319594A CN104167302A CN 104167302 A CN104167302 A CN 104167302A CN 201410319594 A CN201410319594 A CN 201410319594A CN 104167302 A CN104167302 A CN 104167302A
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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, belong to special appearance composite 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 area, and its conductivity, electrochemistry, thermal stability, mechanicalness are good, so Graphene is counted as a kind of electrode material of rationality.Owing to thering is stronger π-π active force between graphene sheet layer, graphene sheet layer is easily reunited, the grapheme material of preparing so actual, its specific area is far below the theoretical value of single-layer graphene;
The number of plies of grapheme material and specific area size all have important impact to the conductibility of the electro-chemical activity of material, electronics.For avoiding graphene sheet layer, reunite, increase the specific area of grapheme material, forefathers are compound by Graphene and other nano materials, for example: compound (the Z. P. Sun of Graphene and inorganic nano material, X. M. Lu, A Solid-State Reaction Route to Anchoring Ni (OH)
2nanoparticles 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. 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 MnO
2-Coated Carbon Nanotubes between Graphene Sheets as Supercapacitor Electrode, ACS Appl. Mater. Interfaces 2012,4,1058-1064.), compound (the L. W. Peng of Graphene and carbon nano-tube, Y. Feng, P. Lv, D. Lei, Y. 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 current density of 2 A/g, it is about 150 F/g than electric capacity, compound (the T. Qian of Graphene and polypyrrole medicine ball, C. F. Yu, 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 current density is 0.5 A/g, it is about 557 F/g than electric capacity, compound (the J. H. Liu of Graphene and polypyrrole pipe, 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.), when current density is 0.3A/g, it is 400 F/g than electric capacity, can effectively solve the agglomeration traits of Graphene.Really, have relatively high ratio electric capacity, but their production cost is higher as these composite materials of energy storage material, cyclical stability, high rate performance await improving.High-temperature heat treatment legal system high specific capacitance Graphene/melamine resin hollow ball hybrid supercapacitor material of having got everything ready, has not yet to see report.
Summary of the invention
The present invention utilizes high-temperature heat treatment legal system for Graphene/melamine resin Hollow Sphere Composites, and a kind of method of preparing the graphene-based hybrid supercapacitor material of special appearance is provided;
The present invention prepares Graphene/melamine resin Hollow Sphere Composites, and its preparation process comprises the steps:
A. under stirring condition, polyvinyl alcohol is dissolved in deionized water, makes the polyvinyl alcohol water solution that concentration is 2.0 ~ 12.0mg/mL;
B. under stirring condition, in the polyvinyl alcohol water solution of preparing, add weak acid to step a, regulator solution pH value is 2.0 ~ 6.0;
C. under stirring condition, melamine is mixed with formalin, melamine is 1:1.0 ~ 1:6.0 with the ratio of the amount of substance of formaldehyde, under uniform temperature, reacts 20min, obtains prepolymer melamine methylol;
D. under stirring condition, polyvinyl alcohol water solution is mixed with the resulting prepolymer melamine methylol of step c, be heated to uniform temperature, insulation, system to be mixed occurs after white opacity, start timing, and continue reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
E. the resulting milky white liquid of steps d is carried out to Separation of Solid and Liquid, solid, through alcohol wash, washing, is dried and obtains melamine resin white solid;
F. graphite oxide is dispersed in deionized water, ultrasonic a few hours, being made into concentration is the graphite oxide dispersion liquid of 1mg/mL;
G. melamine resin step e being obtained adds in deionized water, and ultrasonic a few hours, being made into concentration is the melamine resin dispersion liquid of 2.5mg/mL;
H. under stirring condition, the resulting graphite oxide dispersion liquid of step f is mixed with the resulting melamine resin dispersion liquid of step g, the mass ratio of graphite oxide and melamine resin is 1:10 ~ 9:1, continuous stirring a few hours, both is fully mixed;
I. by the resulting mixed solution of step h, freeze drying, obtains spongiform graphite oxide/melamine resin compound;
J. under Ar gas protection, with certain heating rate, by the resulting graphite oxide/melamine resin of step I compound carbonization at a certain temperature a few hours, naturally cool to room temperature, obtain black Graphene/melamine resin Hollow Sphere Composites;
Stir speed (S.S.) in described step a, b is 300 ~ 500r/min, and the mixing speed of step c, d is 200 ~ 300r/min, and the mixing speed of step h is 400 ~ 600r/min;
Polyvinyl alcohol concentration in described step a is 2.0 ~ 12.0mg/mL, and preferred concentration is 6.0mg/mL;
Weak acid in described step b is glacial acetic acid, and regulator solution pH value is 2.0 ~ 6.0, more preferably pH=4.5;
Melamine in described step c is 1:1.0 ~ 1:6.0 with the ratio of the amount of substance of formaldehyde, and preferred ratio is 1:3.3;
Reaction temperature in described step c is 40 ~ 80oC, and preferred temperature is 60oC;
Holding temperature in described steps d is 40 ~ 80oC, and preferred reaction temperature is 60oC;
Centrifugal rotational speed in described step e is 3000 ~ 10000r/min, and more excellent rotating speed is 6000r/min;
Baking temperature in described step e is 30 ~ 80oC, and more preferably temperature is 40oC;
Ultrasonic time in described step f is 1 ~ 6h, and more preferably ultrasonic time is 3h;
Ultrasonic time in described step g is 0.5 ~ 3h, and more preferably ultrasonic time is 1.5h;
Graphite oxide in described step h and the mass ratio of melamine resin are 1:10 ~ 9:1, and preferred ratio is 1:5;
Mixing time in described step h is 1 ~ 8h, and more preferably mixing time is 3h;
Heating rate in described step j is 0.5 ~ 5oC/min, and more preferably heating rate is 1oC/min;
Carburizing temperature in described step j is 400 ~ 900oC, and more preferably carburizing temperature is 600oC;
Carbonization time in described step j is 0.5 ~ 6h, and more preferably carbonization time is 1h;
With prior art, compare, the present invention has the following advantages:
(1) the present invention be take polyvinyl alcohol as dispersant, prepare monodispersed melamine resin medicine ball, after compound with graphite oxide, utilize high-temperature heat treatment method, synthesized first Graphene/melamine resin Hollow Sphere Composites, under the current density of 1A/g, discharge and recharge, than electric capacity, reach 625F/g, in electrode material for super capacitor field, there are many potential application prospects;
(2) technique of the present invention is simple, is applicable to large-scale industrial and produces.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) photo of the prepared Graphene/melamine resin Hollow Sphere Composites sample S-1 of embodiment 1;
Fig. 2 is transmission electron microscope (TEM) photo of the prepared Graphene/melamine resin Hollow Sphere Composites sample S-1 of embodiment 1;
Fig. 3 is the SEM photo of the Graphene/melamine resin composite sample S-2 of comparative example institute.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further elaborated, these embodiment just can not be considered as the restriction to the claims in the present invention content in order to set forth technical scheme of the present invention.Raw materials usedly in embodiment be conventional commercial product; Device therefor is conventional equipment; Method of testing is conventional method;
Bo Di chemical inc, polyvinyl alcohol Tianjin in embodiment is on sale;
Bo Di chemical inc, glacial acetic acid Tianjin is on sale;
Melamine Chemical Reagent Co., Ltd., Sinopharm Group is on sale;
Formalin Jinan Lu Kang chemical industry Co., Ltd is on sale;
The stereoscan photograph of the prepared sample of the present invention is to detect and obtain through Japanese Hitachi S-4800 field emission scanning electron microscope; Transmission electron microscope photo is to detect and obtain through Japanese JEM-1011 transmission electron microscope; Charge-discharge test is to detect and obtain through PARSTAT2263 electrochemical workstation.
embodiment 1
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.25g graphite oxide is dispersed in 250mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 1.25g melamine resin is added in 500mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 1:5, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 600oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Fig. 1 is the stereoscan photograph of Graphene/melamine resin Hollow Sphere Composites of preparing of the present embodiment; Fig. 2 is the transmission electron microscope photo of Graphene/melamine resin Hollow Sphere Composites of preparing of the present embodiment; The stereoscan photograph of prepared sample S-1 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 that the ball after melamine resin carbonization is covered by between graphene sheet layer, has formed a kind of tridimensional network, and melamine resin ball size is compared with homogeneous, and about diameter 500nm, graphene sheet layer has obvious fold; Melamine resin ball after carbonization is hollow as seen from Figure 2, and wall thickness is about 45nm left and right;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 625F/g.
embodiment 2
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.4g graphite oxide is dispersed in 400mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 0.8g melamine resin is added in 320mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 1:2, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 600oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 350F/g.
embodiment 3
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.46g graphite oxide is dispersed in 460mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 0.23g melamine resin is added in 92mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 2:1, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 600oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 300F/g.
embodiment 4
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.5g graphite oxide is dispersed in 500mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 0.1g melamine resin is added in 40mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 5:1, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 600oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 450F/g.
embodiment 5
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.5g graphite oxide is dispersed in 500mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 0.5g melamine resin is added in 200mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 1:1, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 600oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 400F/g.
embodiment 6
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.25g graphite oxide is dispersed in 250mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 1.25g melamine resin is added in 500mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 1:5, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 800oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 539F/g.
embodiment 7
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.25g graphite oxide is dispersed in 250mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 1.25g melamine resin is added in 500mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 1:5, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 700oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 580F/g.
embodiment 8
(1), under stirring condition, 0.54g polyvinyl alcohol is dissolved in 90mL deionized water;
(2), under stirring condition, in above-mentioned polyvinyl alcohol water solution, add glacial acetic acid, regulator solution pH=4.5;
(3) under stirring condition, 2.8g melamine is mixed with 5.946g formalin, be heated to 60oC, and continue reaction 20min, obtain prepolymer melamine methylol;
(4) under stirring condition, prepolymer melamine methylol solution is added in polyvinyl alcohol glacial acetic acid solution, and be incubated under 60oC, system to be mixed occurs after white opacity, starts timing, and continues stirring reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor;
(5) gained milky reactant liquor is carried out to Separation of Solid and Liquid, liquids recovery, standby.Solid is through alcohol wash, washing, and in 40oC air atmosphere, dry 24h, obtains melamine resin white solid, stand-by;
(6) 0.25g graphite oxide is dispersed in 250mL deionized water, ultrasonic 3h, obtaining concentration is the graphite oxide dispersion liquid of 1mg/mL;
(7) 1.25g melamine resin is added in 500mL deionized water, ultrasonic 1.5h, obtaining concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(8) under stirring condition, graphite oxide dispersion liquid is slowly added in melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 1:5, then continues to stir 3h, and both are fully mixed;
(9) graphite oxide and melamine resin mixed liquor are carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(10) graphite oxide/melamine resin compound is put into tube furnace, under Ar gas protection, with the heating rate of 1oC/min, is heated to 500oC, and is incubated 1h, after naturally cool to room temperature, obtain black objects product;
Graphene/melamine resin Hollow Sphere Composites prepared by the present embodiment is carried out charge-discharge test, under the current density condition of 1A/g, discharges and recharges, and than electric capacity, be 512F/g.
comparative example
This comparative example, in melamine resin ball preparation process, does not add polyvinyl alcohol, and all the other steps are with embodiment 1, and what obtain is Graphene/melamine resin composite material;
The SEM photo of Graphene/melamine resin composite material that Fig. 3 is prepared for this comparative example;
The stereoscan photograph of prepared sample S-2 is shown in Fig. 3;
As seen from Figure 3, sample S-2 does not form tridimensional network with graphene sheet layer after melamine resin carbonization, and composites is random pattern;
Graphene/melamine resin composite material prepared by this comparative example carries out charge-discharge test, at 1A/g, discharges and recharges under condition, and than electric capacity, be 480F/g.
Claims (9)
1. a preparation method for Graphene/melamine resin Hollow Sphere Composites, step is as follows:
(1) under stirring condition, in the deionized water that polyvinyl alcohol is dissolved in, make concentration and be 2.0 ~
12.0mg/mL polyvinyl alcohol water solution;
(2) under stirring condition, in polyvinyl alcohol water solution, add weak acid, regulator solution pH is 2.0 ~ 6.0, described weak acid is glacial acetic acid;
(3) under stirring condition, melamine is mixed with formalin, melamine is 1:1.0 ~ 1:6.0 with the ratio of the amount of substance of formaldehyde, under 60oC, reacts 20min, obtains prepolymer melamine methylol;
(4) under stirring condition, the polyvinyl alcohol glacial acetic acid aqueous solution is mixed with prepolymer melamine methylol, be incubated in 60oC, system to be mixed occurs after white opacity, starts timing, and continues reaction 6min, after put into 0oC ice bath, fast cooling, cessation reaction, obtains milky reactant liquor; Gained milky white liquid is carried out to Separation of Solid and Liquid, and solid, through washing, alcohol wash, obtains melamine resin white solid after being dried;
(5) graphite oxide is dispersed in deionized water, ultrasonic 1 ~ 6h, being made into concentration is the graphite oxide dispersion liquid of 1mg/mL; Melamine resin is added in deionized water, ultrasonic 0.5 ~ 3h, being made into concentration is the melamine resin dispersion liquid of 2.5mg/mL;
(6) under stirring condition, graphite oxide dispersion liquid to be mixed with melamine resin dispersion liquid, the mass ratio of graphite oxide and melamine resin is 1:10 ~ 9:1, continuous stirring 1 ~ 8h fully mixes both; Gained mixed solution is carried out to freeze drying, obtain spongiform graphite oxide/melamine resin compound;
(7) under Ar gas protection, the heating rate with 0.5 ~ 5oC/min, is warming up to 400 ~ 900oC, and 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/melamine resin Hollow Sphere Composites according to claim 1, is characterized in that, the concentration of the poly-vinyl alcohol solution described in step (1) is 2.0 ~ 12.0mg/mL, more preferably 6.0 mg/mL.
3. the preparation method of Graphene/melamine resin Hollow Sphere Composites according to claim 1, is characterized in that, described in step (2), adds glacial acetic acid, and the pH of regulator solution is 2.0 ~ 6.0, more preferably 4.5.
4. the preparation method of Graphene/melamine resin Hollow Sphere Composites according to claim 1, is characterized in that, the melamine described in step (3) is 1:1.0 ~ 1:6.0, more preferably 1:3.3 with the ratio of the amount of substance of formaldehyde; Described reacts 20min under 60oC.
5. the preparation method of Graphene/melamine resin Hollow Sphere Composites according to claim 1, is characterized in that, the system to be mixed described in step (4) occurs after white opacity, starts timing, and continues reaction 6min; The described 0oC ice bath of putting into, Quick stop reaction; Described mode of washing is alcohol wash after washing, and more preferably ethanol washes with water after washing 2 ~ 3 times 2 ~ 3 times; Described drying mode is in 30 ~ 80oC, dry 10 ~ 24h in air atmosphere.
6. the preparation method of Graphene/melamine resin Hollow Sphere Composites according to claim 1, is characterized in that, the graphite oxide dispersion liquid ultrasonic time described in step (5) is 1 ~ 6h, more preferably 3h; The concentration of described graphite oxide dispersion liquid is 1mg/mL; Described melamine resin dispersion liquid ultrasonic time is 0.5 ~ 3h h, more preferably 1.5h; The concentration of described melamine resin dispersion liquid is 2.5mg/mL.
7. the preparation method of Graphene/melamine resin Hollow Sphere Composites according to claim 1, is characterized in that, the mass ratio of the graphite oxide described in step (6) and melamine resin is 1:10 ~ 9:1, more preferably 1:5; Described graphite oxide and melamine resin mixed liquor, the time of being uniformly mixed is 1 ~ 8h, more preferably 3h; Described carries out freeze drying by graphite oxide and melamine resin mixed liquor, obtains spongiform graphite oxide/melamine resin compound.
8. the preparation method of Graphene/melamine resin Hollow Sphere Composites according to claim 1, is characterized in that, the heating rate described in step (7) is 0.5 ~ 5oC/min, more preferably 1oC/min; Described carburizing temperature is 400 ~ 900oC, more preferably 600oC; Described carbonization time is 0.5 ~ 6h, more preferably 1h.
9. the preparation method of Graphene/melamine resin Hollow Sphere Composites according to claim 1, it is characterized in that, stir speed (S.S.) described in step (1), (2) is 300 ~ 500r/min, mixing speed described in step (3), (4) is 200 ~ 300r/min, and the mixing speed described in step (6) is 400 ~ 600r/min.
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