CN117263174B - Sulfonic acid graphene electrode material and synthesis method thereof - Google Patents
Sulfonic acid graphene electrode material and synthesis method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title claims abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 12
- 239000003990 capacitor Substances 0.000 abstract description 8
- 238000009825 accumulation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- 239000011147 inorganic material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 7
- -1 1, 2-dimethyl-3-hydroxyethyl imidazole bis (trifluoromethanesulfonyl) imide salt Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 125000004434 sulfur atom Chemical group 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXVWUVUOXFZVLQ-UHFFFAOYSA-N CC1=CC=C(C=C1)S(=O)(=O)O.CN1C(N(C=C1)CCO)C Chemical compound CC1=CC=C(C=C1)S(=O)(=O)O.CN1C(N(C=C1)CCO)C VXVWUVUOXFZVLQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
The invention discloses a sulfonic acid graphene electrode material and a synthesis method thereof, belonging to the field of inorganic materials and electrode synthesis. (1) Mixing chlorinated graphene, sulfite and solvent ultrasonically, and reacting at 80-153 ℃; (2) Acidifying, filtering, washing, and drying a filter cake to obtain the graphene sulfonate. According to the method, sulfonic acid is introduced into graphene sheets to avoid excessive accumulation of the sheets, so that the defects of small specific surface area and the like of graphene are overcome, the synthesized sulfonic acid graphene has good quality, and the specific surface area of the sulfonic acid graphene reaches more than 600 square meters per gram. The sulfonic acid group is introduced into the graphene, so that the variety of the graphene is widened, and the electrode material of the super capacitor prepared from the sulfonic acid graphene has good electrochemical performance, can be used as a carrier of a medicament and the like, and has good application prospect.
Description
Technical Field
The application relates to the field of supercapacitor electrode materials, in particular to a sulfonic acid graphene electrode material and a synthesis method thereof.
Background
With the rapid development of energy economy in the world, the problems of climate change, environmental pollution, energy shortage and the like are increasingly severe, and the construction of new energy automobiles and electrochemical energy storage industries is greatly supported while the strategy of adjusting energy structures, controlling atmospheric pollution and the like is implemented in China, so that the industries are rapidly developed. Meanwhile, the new energy automobile requires a power supply to have high energy density and high power density at the same time so as to meet the power requirement of the electric automobile in normal operation and the high-current and high-power requirement in starting, climbing and emergency stopping.
Supercapacitors are a widely used electrochemical energy storage device. The super capacitor is close to the battery in terms of the use conditions such as volume, cost, working mode, service life and the like, and can be well complemented with the battery in terms of the electrical properties such as power density, energy density, self-discharge rate, cycle life and the like. In particular, the high-power rapid discharge is possible, which is a remarkable characteristic.
The graphene material is low in price and simple to synthesize, and is an attractive energy storage material. The graphene has a large conjugated structure, a rich microstructure and a large specific surface area, and is strong in modifiable property. It has the characteristics of rich pores, excellent physical and chemical stability, adjustable pore diameter, low heat conduction and the like, thereby attracting the extensive attention of researchers
The comparative document CN108335917A discloses a preparation method of a carbon nanofiber load-carrying ordered reduced graphene oxide electrode material, graphene oxide is modified by using ionic liquid, and the ionic liquid adopts a plurality of sulfonates such as 1, 2-dimethyl-3-hydroxyethyl imidazole p-methylbenzenesulfonate, 1, 2-dimethyl-3-hydroxyethyl imidazole bis (trifluoromethanesulfonyl) imide salt, 1, 2-dimethyl-3-hydroxyethyl imidazole hexafluorophosphate and the like, so as to modify the graphene oxide, and belongs to doping modification reactions. The graphene oxide is subjected to surface modification by reactive groups of ionic liquid, such as carboxyl, sulfonic acid group, amino or hydroxyl. The sulfur of the control document is not directly linked to the lamellae, and is linked by atoms such as oxygen. The method is characterized in that a substitution reaction is carried out between a carbon-chlorine bond of the chlorinated graphene and a sulfite (hydrogen) salt to generate sulfonate or sulfonic acid (-SO 3 OH), sulfur of a sulfonic acid group (sulfonate) is directly connected with a lamellar, the sulfonic acid group is directly connected with the graphene lamellar, the sulfonic acid structure is stable, and the sulfonic acid group is not easy to remove after being reacted with other substances.
The synthesis of the graphene electrode material has the defects of small yield, harsh synthesis conditions, difficult synthesis, low processing capacity and the like by integrating various documents and related patents. Sulfonic acid modified graphene has few reports, and in the reports, sulfonic acid groups are indirectly connected to graphene sheets and have bridging groups. Such as through the diazonium salt of an aryl sulfonic acid, to the graphene sheets, with aryl bridging between the sulfonic acid groups and the sheets. The application is to react chlorinated graphene with sulfite, and sulfonic acid groups are directly connected to graphene sheets. And sulfonic acid groups are introduced into graphene to improve capacitor capacity and stability.
Disclosure of Invention
The invention aims to solve the problem of improving the capacity performance of graphene so as to improve the capacity of a super capacitor for storing charges. The sulfonic acid groups are introduced into the graphene to improve the binding capacity of the graphene and charges and increase the stability.
The invention provides a synthetic method of a sulfonic acid graphene electrode material, which comprises the following steps:
(1) Mixing chlorinated graphene, sulfite and a solvent, ultrasonically mixing, and reacting at a certain temperature and time; the preparation method of the chlorinated graphene comprises the following steps: firstly, adding graphene into a sodium hypochlorite solution, and regulating the graphene to be neutral or acidic by hydrochloric acid; secondly, carrying out illumination reaction for 36-72h at the constant temperature of 20-60 ℃ in a sealing way; and thirdly, filtering, washing and drying the film to obtain the chlorinated graphene.
(2) Acidifying, filtering, washing, and drying a filter cake to obtain the sulfonic acid graphene electrode material;
the solvent is one or more of N, N-dimethylformamide, 1, 4-epoxy hexacyclic ring or acetonitrile; the sulfite is one or two of sodium sulfite, potassium sulfite, sodium bisulfite or potassium bisulfite.
Further, the mass ratio of the sulfite to the chlorinated graphene is 1-4:1.
in the step (1), the reaction temperature is 80-153 ℃ and the reaction time is 6-24 hours.
The invention provides a sulfonic acid graphene electrode material, which is prepared by the method.
The invention provides a super capacitor which is made of the electrode material.
Advantageous effects
According to the method, excessive accumulation of sheets is avoided in the process of synthesizing the sulfonic acid graphene, the defects of small specific surface area and the like of the graphene are overcome, the synthesized sulfonic acid graphene is good in quality, the specific surface area of the sulfonic acid graphene is more than 600 square meters per gram, and the yield is high and is more than 90%. Due to the introduction of the sulfonic acid group, the graphene has the advantages of widening the variety of graphene, having excellent electrical properties as an electrode material, being also used as carriers of other compounds (such as medicines) and the like, and having good application prospects. In the present application, the carbon of the graphene sheets forms a covalent bond directly with sulfur. The chlorinated graphene and sulfite react chemically. Clear principle, clear product, simple and convenient operation and suitability for mass preparation by practitioners.
Drawings
FIG. 1 is a scanning electron microscope image of products T1, T2, T3 and T4;
FIG. 2 is an XRD pattern of graphene T0 and each product (T1, T2, T3, T4);
FIG. 3 is a cyclic voltammogram of a symmetric supercapacitor electrode composed of graphene T0 and products (T1, T2, T3, and T4);
fig. 4 is a constant current charge-discharge graph of a symmetrical supercapacitor composed of graphene T0 and products (T1, T2, T3, and T4).
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples:
the homemade chlorinated graphene used in the following examples was prepared by the following method. (1) Adding graphene into a sodium hypochlorite solution, and regulating the graphene to be neutral or acidic by hydrochloric acid; (2) carrying out illumination reaction for 36-72h at the constant temperature of 20-60 ℃ in a sealing way; (3) And (3) filtering, washing and drying the film to obtain the chlorinated graphene.
Example 1
Self-made graphene chloride (30 g), sodium sulfite (30 g) and N, N-dimethylacetamide (100 mL) are added into a reaction kettle, and are mixed by ultrasonic and heated at 153 ℃ for 24 hours. After cooling, the mixture was poured into 300 mL water, acidified with hydrochloric acid, filtered, washed and dried at 80℃for 10 hours. Graphene sulfonate 32 g (T1) was obtained. The specific surface area of the sulfonic acid graphene is measured to be 674 square meters per gram, and the content of sulfur atoms in the sulfonic acid graphene is 6.7%.
Example 2
Self-made graphene chloride (10 g), sodium bisulphite (20 g), sodium sulfite (20 g) and acetonitrile (150 mL) are added into a reaction kettle, and are mixed by ultrasonic and heated at 80 ℃ for 6 hours. After cooling, the mixture was poured into 300 mL water. Acidifying with hydrochloric acid, filtering, washing, heating to 80 deg.C, and drying for 12 hr. Graphene sulfonate 12 g (T2) was obtained. The specific surface area 677 square meters per gram of the sulfonic acid graphene is measured, and the content of sulfur atoms in the sulfonic acid graphene is 6.8%.
Example 3
Self-made graphene chloride (30 g), potassium sulfite (80 g), 1,4 dioxane (100 mL) and acetonitrile (100 mL) are added into a reaction kettle, and are mixed by ultrasonic waves, and heated at 80 ℃ for 18 hours. After cooling, the mixture was poured into 300 mL water. Acidifying with hydrochloric acid, filtering, washing, heating to 80 deg.C, and drying for 12 hr. Graphene sulfonate 31 g (T3) was obtained. The specific surface area 676 square meters per gram of the sulfonic acid graphene was measured, and the content of sulfur atoms in the sulfonic acid graphene was 6.9%.
Example 4
In a reaction kettle, self-made graphene chloride (10 g), potassium hydrogen sulfite (25 g) and 1,4 dioxane (100 mL) were added, and the mixture was ultrasonically mixed and heated at 100℃for 15 hours. After cooling, the mixture was poured into 100 mL water. Acidifying with hydrochloric acid, filtering, washing, heating to 80 deg.C, and drying for 10 hr. Graphene sulfonate 12 g (T4) was obtained. The specific surface area 677 square meters per gram of the sulfonic acid graphene is measured, and the content of sulfur atoms in the sulfonic acid graphene is 6.8%.
From the scanning electron microscope image in fig. 1, the sheets of the products T1, T2, T3 and T4 are clear, and the folds and the twists are more, which is the morphological characteristics of single-layer and few-layer graphene. Single-layer and few-layer graphene are more likely to contact the electrolyte, increasing capacitor capacity.
The sulfur content of each product was analyzed by XPS, as shown in the following Table.
The sulfur atom content of the products T1, T2, T3 and T4 was about 6.8%, indicating that the chlorinated graphene reacted with sulfite. And introducing groups on the sheets prevents the excessive accumulation of the sheets, and the excessive accumulation is unfavorable for the contact of graphene and electrolyte, so that the capacity of the supercapacitor is affected.
As can be seen from fig. 2, the graphene T0 diffraction peak is at 27.6 degrees, the corresponding interlayer spacing is 0.37 nm, which is the interlayer spacing of normal graphene. The diffraction peaks of the products T1, T2, T3 and T4 of the sulfoacid graphene are near 27.1 degrees, the interlayer spacing is about 0.38 nanometer, and the crystal phase structures are very similar. The interlayer spacing is increased, so that electrolyte can enter between the sheets, the electrolyte can be fully contacted with graphene, and the capacity of the super capacitor is improved. The compositions and properties of the graphite sulfonates T1, T2, T3 and T4 are very similar.
Grinding a proper amount of common graphene (commercially available, number T0) and products (respectively numbered T1, T2, T3 and T4) of examples 1-4, adding a small amount of alcohol, performing ultrasonic dispersion, mixing with conductive graphite and polyvinylidene fluoride (PVDF) with a mole fraction of 5% according to a mass ratio of 8:1:1, dripping a proper amount of N-methylpyrrolidone (NMP), and stirring to be uniform paste. The paste is evenly coated on a foam nickel sheet (1 cm multiplied by 1 cm) in a scraping way, dried at 100 ℃ for 12 h, pressed into an electrode sheet in a tablet press under the pressure of 10 MPa, the quality of the sulfoacid graphene is controlled to be 0.002-0.003 g, and Na2SO4 with the concentration of 0.1 mol/L is taken as electrolyte solution, and a diaphragm is added to assemble the symmetrical super capacitor.
As can be seen from FIG. 3, at 100mv/s, the cyclic voltammograms of the symmetric supercapacitor electrodes of the products T1, T2, T3, T4 differ little, and the product compositions are very close to cause little difference in performance; the product volt-ampere curve is similar to the shape of the comparative graphene T0, and the sulfonic acid graphene has high response voltage, so that the sulfonic acid graphene is easier to conduct and has better electrode performance.
As can be seen from fig. 4, the products T1, T2, T3 and T4 and the comparative graphene T0 form a symmetrical supercapacitor, and constant current charge-discharge cycles indicate that the charge-discharge cycle curves of the symmetrical supercapacitor of the products T1, T2, T3 and T4 have little difference under the condition of 1A/g current density, the product charge-discharge cycle curve is similar to the charge-discharge cycle curve of the comparative graphene T0 in shape, and the sulfonic graphene has higher specific capacitance.
Claims (2)
1. The synthesis method of the graphene sulfonate electrode material is characterized by comprising the following steps of:
(1) Mixing chlorinated graphene, sulfite and a solvent, ultrasonically mixing, and reacting at a certain temperature and time; the reaction temperature is 80-153 ℃, and the reaction time is 6-24 hours;
(2) Acidifying, filtering, washing, and drying a filter cake to obtain the sulfonic acid graphene electrode material;
the solvent is one or more of N, N-dimethylformamide, 1, 4-epoxy hexacyclic ring or acetonitrile; the sulfite is one or two of sodium sulfite, potassium sulfite, sodium bisulfite or potassium bisulfite.
2. The method for synthesizing the graphene sulfonate electrode material according to claim 1, wherein the mass ratio of the sulfite to the chlorinated graphene is 1-4:1.
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| CN1072407A (en) * | 1991-11-19 | 1993-05-26 | 中国科学院上海有机化学研究所 | The preparation method of polyhalogen alkyl sulfonite |
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| CN104445167A (en) * | 2014-11-28 | 2015-03-25 | 湖南科技大学 | Preparation method of water-soluble graphene |
| CN105385148A (en) * | 2015-12-04 | 2016-03-09 | 浙江华峰合成树脂有限公司 | Sulfonated graphene-modified waterborne polyurethane resin and preparation method thereof |
| CN106433121A (en) * | 2016-09-09 | 2017-02-22 | 江南大学 | Preparation method of polyaniline-graphene hollow microspheres |
| CN108335917A (en) * | 2018-01-26 | 2018-07-27 | 渤海大学 | A kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material |
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