CN110668431A - Preparation method and energy storage application of sulfonated graphene - Google Patents
Preparation method and energy storage application of sulfonated graphene Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004146 energy storage Methods 0.000 title claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 104
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 42
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- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960002442 glucosamine Drugs 0.000 claims abstract description 19
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 18
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 37
- 238000004108 freeze drying Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- CQXXYOLFJXSRMT-UHFFFAOYSA-N 5-diazocyclohexa-1,3-diene Chemical compound [N-]=[N+]=C1CC=CC=C1 CQXXYOLFJXSRMT-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
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- 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
- C01B32/184—Preparation
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- 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
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Abstract
The invention belongs to the technical field of materials, and particularly relates to a preparation method of sulfonated graphene, which is used for preparing sulfonated graphene with high abundance of sulfonic acid groups. The method comprises the following steps: reducing the graphene oxide by using glucosamine to obtain saccharified graphene; ultrasonically dispersing the saccharified graphene into a dichloromethane solution, adding chlorosulfonic acid into the saccharified graphene dispersion solution, stirring, washing and drying to obtain the sulfonated graphene. The synthesis method of the sulfonated graphene prepared by the invention can effectively improve the abundance of the hydrophilic structure in the sulfonated graphene, so that the dispersion characteristic of the sulfonated graphene in various solvent systems is obviously improved, and the sulfonated graphene as a supercapacitor material has higher capacity and good stability.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of sulfonated graphene, which is used for preparing sulfonated graphene with high abundance of sulfonic acid groups.
Background
In 2004, professor geom of manchester university in england, etc. successfully peeled a novel two-dimensional carbon material, graphene, from highly oriented pyrolytic graphite by a mechanical peeling method, and rapidly became a hot spot in research directions in various fields such as materials due to its large specific surface area, excellent mechanical properties, high electrical conductivity and stable chemical properties. However, graphene sheets have strong van der waals force and are easy to agglomerate, so that the graphene sheets are difficult to disperse in water and common organic solvents, and further research and application of graphene are greatly limited. Based on the inherent defects of the graphene material, the dispersibility and the solubility of the graphene material can be improved by modifying the surface of the graphene. The sulfonic acid group has high hydrophilicity, and the sulfonation treatment of the graphene can improve the dispersing capacity of the graphene and retain the two-dimensional planar structure of the graphene, so that the sulfonation becomes one of hot spots for the graphene modification research. Liang et al uses phenyl functionalized single-walled carbon nanotubes in fuming sulfuric acid (H)2 SO 420% free SO3) The sulfonated carbon nano tube with high quality is obtained by sulfonation treatment[1]. Si and the like pre-reduce graphene oxide with sodium borohydride to remove most of the oxygen functional groups; then sulfonating by using aryl diazonium salt of sulfanilic acid in ice bath; finally, hydrazine is used for post reduction to remove the residual oxygen functional groups, so that sulfonated graphene with high water solubility and high conductivity is obtained[2]. Nicolas Oger et al, which oxidizes and peels graphite into graphene oxide and reduces the graphene oxide with hydrazine to prepare reduced graphene oxide, and the obtained reduced graphene oxide and 4-diazobenzene sulfonic acidSalt reaction to obtain sulfonated graphene[3]. Most of the existing preparation methods of sulfonated graphene require harsh reaction conditions or adopt toxic reduction reagents, so that the simple and environment-friendly preparation of high-quality sulfonated graphene is one of the key points of the current research.
Disclosure of Invention
The invention mainly designs a preparation method of sulfonated graphene with high sulfonic acid group abundance, solves the problems that graphene is easy to agglomerate and difficult to disperse, and the prepared sulfonated graphene has excellent energy storage performance.
In order to achieve the purpose, the invention adopts the following technical scheme that the preparation method of the sulfonated graphene comprises the following steps:
a preparation method of sulfonated graphene, comprising the following steps:
(1) mixing the graphene oxide aqueous solution and glucosamine, carrying out ultrasonic treatment, adjusting the pH to be more than or equal to 8, reacting at the temperature of 40-100 ℃ for 4-12 h, carrying out suction filtration, washing, and freeze drying to obtain saccharified graphene powder;
(2) ultrasonically dispersing the obtained saccharified graphene into a dichloromethane solution to obtain a saccharified graphene dispersion solution, adding chlorosulfonic acid into the saccharified graphene dispersion solution, stirring for reaction, washing, and freeze-drying to obtain sulfonated graphene powder.
In the technical scheme, the concentration of the graphene oxide aqueous solution is 0.5-1.5 mg/mL, and the concentration of the glucosamine solution is 10-60 mg/mL; the mass ratio of the graphene oxide to the glucosamine is 1: 10-40.
In the technical scheme, furthermore, in the step (1), the ultrasonic time is 30-60 min, and the ultrasonic power is 500-1200W.
In the technical scheme, the ratio of the saccharified graphene to the dichloromethane is 2-50 mg:1mL, and the mass ratio of the chlorosulfonic acid to the saccharified graphene is 17.7-70.8: 1;
in the technical scheme, furthermore, in the step (2), the ultrasonic time is 30-60 min, and the ultrasonic power is 500-1200W.
In the technical scheme, the stirring reaction temperature of the saccharified graphene and the chlorosulfonic acid is 0-40 ℃, and the stirring reaction time is 4-36 hours.
In the above technical scheme, further, in the step (2), after the stirring reaction of the saccharified graphene and chlorosulfonic acid is finished, sulfonated graphene containing impurities is obtained, the sulfonated graphene containing impurities is subjected to centrifugal separation and filtration, and then is washed with deionized water and absolute ethyl alcohol and dried, so that sulfonated graphene is obtained.
In the technical scheme, the temperature of the freeze drying in the step (2) is-53 to-30 ℃, and the time of the freeze drying is 12 to 24 hours.
Sulfonated graphene prepared by the preparation method.
The sulfonated graphene is applied to energy storage.
Compared with the prior art, the invention has the following advantages:
1. glucosamine is used as a reducing agent, so that the abundance of hydroxyl groups on the surface of graphene is improved while the graphene oxide is reduced, and the abundance of sulfonic acid groups is improved.
2. By adopting a freeze-drying auxiliary method, water in the saccharified graphene obtained after reduction of the glucosamine is directly frozen into a solid state and then directly changed into a gaseous state, which is beneficial to dispersion of the saccharified graphene in a dichloromethane solution.
3. The reaction condition is mild, safe, stable and reliable; the problem of poor dispersing ability of the existing graphene in water and common organic matters is solved; and the graphene oxide is reduced in the preparation process of the sulfonated graphene, so that the conductivity of the sulfonated graphene is improved, and the sulfonated graphene can be industrially produced. Has wide application prospect in the aspects of energy storage, solid acid catalysis and the like.
Drawings
FIG. 1 is a dispersion diagram of sulfonated graphene prepared in example 1 in different dispersants;
FIG. 2 is a TEM image of sulfonated graphene prepared in example 2;
FIG. 3 is an infrared spectrum of sulfonated graphene prepared in example 3;
FIG. 4 is an XPS energy spectrum of carbon of sulfonated graphene prepared in example 4;
FIG. 5 is an XPS energy spectrum of elemental sulfur of sulfonated graphene prepared in example 5;
FIG. 6 is a cyclic voltammogram at a sweep rate of 5mv/s for sulfonated graphene prepared in example 7;
FIG. 7 is a graph comparing the impedance of sulfonated graphene and glycated graphene prepared in example 7;
FIG. 8 is a charge and discharge diagram of sulfonated graphene prepared in example 8;
FIG. 9 is a graph of rate capability of sulfonated graphene prepared in example 8;
fig. 10 is a graph of the cycling stability performance of the sulfonated graphene prepared in example 8.
Detailed Description
The present invention will be further described with reference to the following embodiments. The technical solution of the present invention is not limited to the following examples.
Example 1
(1) Mixing 50mL of graphene oxide solution with 0.8mg/mL of glucosamine with 30mL of 0.0296g/mL, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH to be more than or equal to 8, reacting for 8 hours at 80 ℃, performing suction filtration, washing, and freeze-drying. Obtaining the saccharified graphene powder.
(2) Ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 7.08g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 24 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
Fig. 1 is a picture of sulfonated graphite prepared in this example after being dispersed in deionized water, 1mol/L sulfuric acid, pH 13 sodium hydroxide, formamide, DMF, absolute ethyl alcohol, and n-butanol, respectively, and standing for 64 hours, which shows that the prepared sulfonated graphene has good dispersibility in common dispersants.
Example 2
(1) Mixing 50mL of graphene oxide solution with the concentration of 0.8mg/mL and 30mL of glucosamine with the concentration of 0.0296g/mL, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH value to be more than or equal to 8, reacting for 8 hours at 70 ℃, performing suction filtration, washing, and freeze-drying to obtain the saccharified graphene powder.
(2) Ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 3.54g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 24 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
Fig. 2 is a transmission electron microscope image of the sulfonated graphene prepared in this embodiment, and it is clear that the surface of the sulfonated graphene having a wrinkle structure is nearly transparent.
Example 3
(1) Mixing 50mL of graphene oxide solution with the concentration of 0.8mg/mL and 30mL of glucosamine with the concentration of 0.0296g/mL, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH value to be more than or equal to 8, reacting for 8 hours at the temperature of 60 ℃, performing suction filtration, washing, and freeze drying to obtain saccharified graphene powder;
(2) ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 3.54g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 24 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
Fig. 3 is an infrared spectrum of sulfonated graphene obtained in this example; from FIG. 1, it can be seen that the sulfonated graphene is at 1550 cm and 1165cm-1Two absorption peaks are formed and can be attributed to the characteristic absorption peak of a carbon-nitrogen bond, which indicates that glucosamine is successfully anchored on the surface of graphene in the process of reducing graphene oxide and is positioned at 1126 and 1037cm-1Two absorption peaks exist at the position, which can be attributed to a sulfur-oxygen bond, and therefore, chlorosulfonic acid is used for further sulfonating the saccharified graphene obtained by reducing glucosamine.
Example 4
(1) Mixing 50mL of graphene oxide solution with the concentration of 0.8mg/mL and 30mL of glucosamine with the concentration of 0.0296g/mL, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH value to be more than or equal to 8, reacting for 8 hours at the temperature of 90 ℃, performing suction filtration, washing, and freeze drying to obtain saccharified graphene powder;
(2) ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 3.54g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 24 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
Fig. 4 is an XPS spectrum of the C element of the sulfonated graphene prepared in this example, and C1s shows XPS peaks respectively assigned to C-C (284.7eV), C-N (285.7eV), C-O (286.4eV), and C ═ O (287.9 eV); the proportion of the C-N structure reaches 33.1 percent, which provides rich active sites for subsequent sulfonation treatment.
Example 5
(1) Mixing 50mL of graphene oxide solution with the concentration of 0.8mg/mL and 30mL of glucosamine with the concentration of 0.0296g/mL, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH value to be more than or equal to 8, reacting for 8 hours at the temperature of 80 ℃, performing suction filtration, washing, and freeze drying to obtain saccharified graphene powder;
(2) ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 3.54g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 12 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
FIG. 5 is an XPS spectrum of S element of sulfonated graphene prepared in this example, S2p168.99 eV and 168.26eV are both attributed to sulfur-oxygen bonds, and the proportion of sulfur element is up to 1.92% according to XPS analysis.
Example 6
(1) Mixing 50mL of graphene oxide solution with 0.8mg/mL of 30mL of glucosamine with 0.0296g/mL of the graphene oxide solution, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH value to be more than or equal to 8, reacting for 8 hours at 70 ℃, performing suction filtration, washing, and freeze-drying. Obtaining saccharified graphene powder;
(2) ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 1.77g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 12 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
Example 7
(1) Mixing 50mL of graphene oxide solution with 0.8mg/mL and 30mL of glucosamine with 0.0296g/mL, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH value to be more than or equal to 8, reacting for 8 hours at 80 ℃, performing suction filtration, washing, and freeze-drying. Obtaining the saccharified graphene powder.
(2) Ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 3.54g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 24 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
FIG. 6 is a cyclic voltammogram of sulfonated graphene prepared in this example at a sweeping speed of 5mv/s, with an approximately rectangular structure.
Fig. 7 is a graph comparing the impedance of sulfonated graphene prepared in example 7 with that of saccharified graphene, the sulfonated graphene having a lower impedance.
Example 8
(1) Mixing 50mL of graphene oxide solution with the concentration of 1.2mg/mL and 30mL of glucosamine with the concentration of 0.0296g/mL, performing ultrasonic treatment to uniformly disperse the graphene oxide solution, adjusting the pH value to be more than or equal to 8, reacting for 8 hours at the temperature of 60 ℃, performing suction filtration, washing, and freeze-drying. Obtaining the saccharified graphene powder.
(2) Ultrasonically dispersing 0.1g of the obtained saccharified graphene into 40mL of dichloromethane solution to obtain saccharified graphene dispersion liquid, adding 3.54g of chlorosulfonic acid into the saccharified graphene dispersion liquid, stirring and reacting at 0-40 ℃ for 36 hours, washing, and freeze-drying to obtain sulfonated graphene powder.
Fig. 8 is a charge and discharge diagram of the sulfonated graphene prepared in this embodiment at different current densities, and fig. 9 is a graph of rate performance of the sulfonated graphene prepared in this embodiment. Under the current density of 1A/g, the discharge specific capacity can reach 135.3F/g. Fig. 10 is a graph of the cycle stability of the sulfonated graphene prepared in this embodiment, and after 1000 cycles of charging and discharging at a current density of 1.5A/g, the capacity retention rate is 99.38%, which has an excellent energy storage behavior.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Reference to the literature
1.Liang F,Beach J M,Rai P K,et al.Highly exfoliated water-solublesingle-walled carbon nanotubes[J].Chemistry of materials,2006,18(6):1520-1524.
2.Si Y,Samulski E T.Synthesis of water soluble graphene[J].Nanoletters,2008,8(6):1679-1682.3.Oger N,Lin Y F,Labrugère C,et al.Practical andscalable synthesis of sulfonated graphene[J].Carbon,2016,96:342-350.
Claims (10)
1. A preparation method of sulfonated graphene is characterized by comprising the following steps:
(1) mixing the graphene oxide aqueous solution and glucosamine, carrying out ultrasonic treatment, adjusting the pH to be more than or equal to 8, reacting at the temperature of 40-100 ℃ for 4-12 h, carrying out suction filtration, washing, and freeze drying to obtain saccharified graphene powder;
(2) ultrasonically dispersing the obtained saccharified graphene into a dichloromethane solution to obtain a saccharified graphene dispersion solution, adding chlorosulfonic acid into the saccharified graphene dispersion solution, stirring for reaction, washing, and freeze-drying to obtain sulfonated graphene powder.
2. The preparation method according to claim 1, wherein the concentration of the graphene oxide aqueous solution is 0.5-1.5 mg/mL, and the concentration of the glucosamine solution is 10-60 mg/mL; the mass ratio of the graphene oxide to the glucosamine is 1: 10-40.
3. The preparation method according to claim 1, wherein the ultrasonic time in the step (1) is 30-60 min, and the ultrasonic power is 500-1200W.
4. The preparation method according to claim 1, wherein the ratio of the saccharified graphene to the dichloromethane is 2-50 mg:1mL, and the mass ratio of the chlorosulfonic acid to the saccharified graphene is 17.7-70.8: 1.
5. The preparation method according to claim 1, wherein the ultrasonic time in the step (2) is 30-60 min, and the ultrasonic power is 500-1200W.
6. The preparation method according to claim 1, wherein the temperature of the stirring reaction of the saccharified graphene and the chlorosulfonic acid is 0-40 ℃, and the time of the stirring reaction is 4-36 h.
7. The preparation method according to claim 1, wherein in the step (2), after the stirring reaction of the saccharified graphene and the chlorosulfonic acid is finished, the sulfonated graphene containing the impurities is obtained, and is subjected to centrifugal separation and filtration, washed with deionized water and absolute ethyl alcohol, and dried to obtain the sulfonated graphene.
8. The preparation method according to claim 1, wherein the temperature of the freeze-drying in the step (2) is-53 to-30 ℃, and the time of the freeze-drying is 12 to 24 hours.
9. Sulfonated graphene, which is prepared by the preparation method of any one of claims 1 to 8.
10. The sulfonated graphene of claim 9, for use in energy storage.
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Citations (7)
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| CN103359728A (en) * | 2013-07-26 | 2013-10-23 | 武汉理工大学 | Preparation method of sulfonated graphene |
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