CN112185711A - Preparation method of poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material - Google Patents
Preparation method of poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 43
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- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims abstract description 23
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- 238000000034 method Methods 0.000 claims abstract description 10
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- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 9
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- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
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- 239000011593 sulfur Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
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- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 23
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
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- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of a poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material, and belongs to the technical field of preparation of electrode materials for supercapacitors. The composite material is prepared by taking ammonium molybdate tetrahydrate as a molybdenum source, thiourea as a sulfur source and graphene oxide as a carrier, preparing graphene-loaded molybdenum disulfide by using a hydrothermal reaction, taking 3, 4-ethylenedioxythiophene as a monomer, taking orange II as a dopant and a surfactant, taking the graphene-loaded molybdenum disulfide as a support material and ammonium persulfate as an oxidant through a chemical oxidation method. The composite material prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, is mainly used for manufacturing the electrode of the super capacitor, and has obvious economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of supercapacitors, and particularly relates to a preparation method of a poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material.
Background
The poly 3, 4-ethylenedioxythiophene has the characteristics of high conductivity, excellent redox activity, good environmental stability, high transparency, safety and no toxicity, and becomes an electrode material for a super capacitor with wide application prospect. However, the commercial application of poly 3, 4-ethylenedioxythiophene is limited due to the low theoretical specific capacitance of poly 3, 4-ethylenedioxythiophene itself, poor solubility of the monomer in water, and easy agglomeration during polymerization. Molybdenum disulfide has the unique properties of large surface area and variable oxidation state, can realize double-layer charge and rapid/reversible redox charge storage, and provides a large energy storage capacity for a super capacitor, but the electrochemical performance of molybdenum disulfide is limited by the defects of poor cycle life, low inherent conductivity, large volume change and easy agglomeration in the cycle process, and the effective utilization rate of molybdenum disulfide is greatly reduced. And due to the high surface energy and strong pi-pi interlayer action of the molybdenum disulfide, the interlayer is easy to accumulate into blocks, and the effective utilization rate of the electrode material is reduced.
Disclosure of Invention
The invention provides a preparation method of a poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material, aiming at the problems of easy agglomeration, low specific capacitance and the like of the existing poly (3, 4-ethylenedioxythiophene) when used as a supercapacitor electrode material. The composite material prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, is mainly used for manufacturing the electrode of the super capacitor, and has obvious economic value and social benefit.
In order to achieve the purpose, the invention adopts the following technical scheme:
a poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material is prepared by taking ammonium molybdate tetrahydrate as a molybdenum source, thiourea as a sulfur source and graphene oxide as a carrier and preparing graphene-loaded molybdenum disulfide by a hydrothermal reaction; and then 3, 4-ethylenedioxythiophene is used as a monomer, orange II is used as a dopant and a surfactant, graphene-loaded molybdenum disulfide is used as a support material, ammonium persulfate is used as an oxidant, and the graphene-loaded molybdenum disulfide is prepared by a chemical oxidation method.
Specifically, the preparation method comprises the following steps:
(1) adding 60-180 mg of graphene oxide into 30-90 mL of deionized water, mechanically stirring for 1-2 hours at room temperature, and then carrying out ultrasonic treatment for 2-4 hours to prepare a graphene oxide dispersion solution I; adding 0.4-0.6 g of ammonium molybdate tetrahydrate and 0.1-0.2 g of thiourea into 20-40 mL of deionized water, and mechanically stirring for 10-20 min at room temperature to prepare a mixed solution II of ammonium molybdate and thiourea; adding the mixed solution II into the dispersion solution I, mechanically stirring for 10-30 min, performing ultrasonic treatment for 30-60 min, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 180-220 ℃ for 12-36 h, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying at 60 ℃ for 24 h to prepare graphene-loaded molybdenum disulfide;
(2) adding 40-60 mg of graphene-loaded molybdenum disulfide and 20-120 mg of orange II into 10-20 mL of deionized water, mechanically stirring for 1-2 h, and performing ultrasonic treatment for 2-4 h to prepare a mixed dispersion liquid of the graphene-loaded molybdenum disulfide and the orange II; adding 60-240 mg of 3, 4-ethylenedioxythiophene into the mixed dispersion, mechanically stirring for 1-2 hours, performing ultrasound for 1-2 hours, dropwise adding 10-20 mL of ammonium persulfate hydrochloric acid solution at the speed of 30-50 drops/min, mechanically stirring for 12-36 hours at room temperature after dropwise adding is finished, performing methanol sedimentation, alternately performing suction filtration and washing on methanol and deionized water until filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 hours to prepare the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material.
In the hydrochloric acid solution of the ammonium persulfate in the step (2), the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
Compared with the prior art, the invention has the following advantages:
(1) the molybdenum disulfide has the unique property of variable oxidation states, can realize double-layer charge storage and rapid/reversible redox charge storage, and provides a larger energy storage capacity for the super capacitor. In the graphene-loaded molybdenum disulfide prepared by a hydrothermal method, the nano flower-shaped molybdenum disulfide is uniformly distributed on the surface of graphene, and the molybdenum disulfide and the graphene are connected through a Mo-O-C bond, so that the molybdenum disulfide is favorably stably distributed on the surface of the graphene, and the rapid charge transfer between the molybdenum disulfide and the graphene in the charging and discharging process is favorably realized.
(2) The graphene has an ultra-large specific surface area, and poly-3, 4-ethylenedioxythiophene and graphene are compounded, so that on one hand, the degree of agglomeration of the poly-3, 4-ethylenedioxythiophene can be reduced by utilizing the ultra-large specific surface area of the graphene, the contact area of the poly-3, 4-ethylenedioxythiophene and electrolyte is increased, and the specific capacitance of the composite material is favorably improved, and on the other hand, the graphene loaded molybdenum disulfide can be used as a supporting material of the poly-3, 4-ethylenedioxythiophene, so that the phenomenon that the structure of the poly-3, 4-ethylenedioxythiophene collapses to cause the deterioration of the electrochemical cycle stability in the charging and discharging process is effectively prevented. In addition, the large pi conjugated structure of the graphene can also enlarge the pi electron delocalization range of the poly-3, 4-ethylenedioxythiophene, so that the conjugation degree of the poly-3, 4-ethylenedioxythiophene is higher, and the conductivity is better.
(3) Both molybdenum disulfide and graphene are prone to agglomeration. In the process of preparing the graphene loaded molybdenum disulfide by a hydrothermal method, the surface of the graphene oxide has rich oxygen-containing functional groups, so that a molybdenum disulfide precursor can be uniformly adsorbed on the surface of the graphene oxide, and then nucleation and growth are performed. In the graphene-loaded molybdenum disulfide, the nano flower-shaped molybdenum disulfide and the graphene are stably connected through a Mo-O-C bond, so that the molybdenum disulfide and the graphene can be effectively prevented from self-aggregation.
(4) Orange II is used as a large pi conjugated molecular dopant to dope poly 3, 4-ethylenedioxythiophene, so that the conjugation degree and specific capacitance of the poly 3, 4-ethylenedioxythiophene can be improved. Meanwhile, the orange II can also play a role of a surfactant, can improve the solubility of the 3, 4-ethylenedioxythiophene in water, and can endow the poly-3, 4-ethylenedioxythiophene with a more loose microstructure.
(5) The poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material prepared by the invention has high specific capacitance and excellent electrochemical cycle stability, the specific capacitance is 237F/g, 209F/g, 194F/g and 180F/g when the charge-discharge current density is 1A/g, 2A/g, 4A/g and 8A/g respectively, the capacitance retention rate reaches 82.8% after 2000 cycles, the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material is mainly used for manufacturing electrodes of supercapacitors, and the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material has obvious economic value and social benefit.
Drawings
Fig. 1 is a scanning electron micrograph of the graphene-supported molybdenum disulfide prepared in example 1;
FIG. 2 is an IR spectrum of poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene prepared in example 1;
FIG. 3 is a scanning electron micrograph of poly-3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene prepared in example 1.
Detailed Description
The advantages and effects of the preparation method of the poly-3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material in the present embodiment are further illustrated by three groups of examples and three groups of comparative examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Adding 120 mg of graphene oxide into 60 mL of deionized water, mechanically stirring for 1.5 h at room temperature, and ultrasonically treating for 3 h to prepare a graphene oxide dispersion solution I; adding 0.5 g of ammonium molybdate tetrahydrate and 0.15 g of thiourea into 30 mL of deionized water, and mechanically stirring for 15 min at room temperature to prepare a mixed solution II of ammonium molybdate and thiourea; and adding the mixed solution II into the dispersion solution I, mechanically stirring for 15 min, performing ultrasonic treatment for 45 min, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 24 h at 200 ℃, after the reaction is finished, performing centrifugal separation, washing and vacuum drying at 60 ℃ for 24 h to prepare the graphene-loaded molybdenum disulfide.
(2) Adding 50 mg of graphene-loaded molybdenum disulfide and 70 mg of orange II into 15 mL of deionized water, mechanically stirring for 1.5 h, and performing ultrasonic treatment for 3 h to prepare a mixed dispersion liquid of the graphene-loaded molybdenum disulfide and the orange II; adding 150 mg of 3, 4-ethylenedioxythiophene into the mixed dispersion, mechanically stirring for 1.5 h, performing ultrasonic treatment for 1.5 h, dropwise adding 15 mL of ammonium persulfate hydrochloric acid solution at the speed of 40 drops/min, mechanically stirring for 24 h at room temperature after dropwise adding, performing methanol precipitation and methanol and deionized water alternative suction filtration washing until the filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 h to prepare the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material.
In the hydrochloric acid solution of the ammonium persulfate in the step (2), the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
Fig. 1 is a scanning electron microscope photograph of the graphene loaded molybdenum disulfide prepared in this embodiment. As can be seen from the figure, the nano flower-like molybdenum disulfide is distributed more uniformly on the surface of the graphene.
FIG. 2 is an IR spectrum of poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene prepared in this example. Shown therein at 1469 cm-1、1382 cm-1、1137 cm-1And 982 cm-1The stretching vibration absorption peak of C = C, C-C, C-O-C and C-S on the thiophene ring of poly 3, 4-ethylenedioxythiophene appears at 1141 cm-1And 646 cm-1On the surface of which orange II-SO appears3 -These indicate that the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material has been successfully prepared.
Fig. 3 is a scanning electron micrograph of the poly-3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material prepared in this example. From the figure, it can be found that the irregularly fallen orange II doped poly 3, 4-ethylenedioxythiophene is coated on the surface of the graphene loaded molybdenum disulfide. The structure is beneficial to increasing the contact area between the composite material and the electrolyte and improving the specific capacitance of the composite material.
Example 2
(1) Adding 60 mg of graphene oxide into 30 mL of deionized water, mechanically stirring for 1 h at room temperature, and performing ultrasonic treatment for 2 h to prepare a graphene oxide dispersion solution I; adding 0.4 g of ammonium molybdate tetrahydrate and 0.1 g of thiourea into 20 mL of deionized water, and mechanically stirring for 10 min at room temperature to prepare a mixed solution II of ammonium molybdate and thiourea; and adding the mixed solution II into the dispersion solution I, mechanically stirring for 10 min, performing ultrasonic treatment for 30 min, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 36 h at 180 ℃, after the reaction is finished, performing centrifugal separation, washing and vacuum drying at 60 ℃ for 24 h to prepare the graphene-loaded molybdenum disulfide.
(2) Adding 40 mg of graphene-loaded molybdenum disulfide and 20 mg of orange II into 10 mL of deionized water, mechanically stirring for 1 hour, and performing ultrasonic treatment for 2 hours to prepare a mixed dispersion liquid of the graphene-loaded molybdenum disulfide and the orange II; adding 60 mg of 3, 4-ethylenedioxythiophene into the mixed dispersion, mechanically stirring for 1 h, performing ultrasonic treatment for 1 h, dropwise adding 10 mL of ammonium persulfate hydrochloric acid solution at the speed of 30 drops/min, mechanically stirring for 12 h at room temperature after dropwise adding is finished, performing methanol precipitation and methanol and deionized water alternative suction filtration washing until filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 h to prepare the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material.
In the hydrochloric acid solution of the ammonium persulfate in the step (2), the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
Example 3
(1) Adding 180 mg of graphene oxide into 90 mL of deionized water, mechanically stirring for 2 hours at room temperature, and performing ultrasonic treatment for 4 hours to prepare a graphene oxide dispersion solution I; adding 0.6 g of ammonium molybdate tetrahydrate and 0.2 g of thiourea into 40 mL of deionized water, and mechanically stirring for 20 min at room temperature to prepare a mixed solution II of ammonium molybdate and thiourea; and adding the mixed solution II into the dispersion solution I, mechanically stirring for 30 min, performing ultrasonic treatment for 60 min, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 12 h at 220 ℃, after the reaction is finished, performing centrifugal separation, washing and vacuum drying at 60 ℃ for 24 h to prepare the graphene-loaded molybdenum disulfide.
(2) Adding 60 mg of graphene-loaded molybdenum disulfide and 120 mg of orange II into 20 mL of deionized water, mechanically stirring for 2 hours, and performing ultrasonic treatment for 4 hours to prepare a mixed dispersion liquid of the graphene-loaded molybdenum disulfide and the orange II; adding 240 mg of 3, 4-ethylenedioxythiophene into the mixed dispersion, mechanically stirring for 2 hours, performing ultrasound treatment for 2 hours, dropwise adding 20 mL of ammonium persulfate hydrochloric acid solution at the speed of 50 drops/min, mechanically stirring for 36 hours at room temperature after dropwise adding is finished, performing methanol precipitation and methanol and deionized water alternative suction filtration washing until filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 hours to prepare the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material.
In the hydrochloric acid solution of the ammonium persulfate in the step (2), the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
Comparative example 1
(1) Adding 0.5 g of ammonium molybdate tetrahydrate and 0.15 g of thiourea into 30 mL of deionized water, and mechanically stirring for 15 min at room temperature to prepare a mixed solution of ammonium molybdate and thiourea; and transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 24 hours, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying at 60 ℃ for 24 hours to prepare the nano molybdenum disulfide.
(2) Adding 50 mg of nano molybdenum disulfide and 70 mg of orange II into 15 mL of deionized water, mechanically stirring for 1.5 h, and performing ultrasonic treatment for 3 h to prepare a mixed dispersion liquid of the nano molybdenum disulfide and the orange II; adding 150 mg of 3, 4-ethylenedioxythiophene into the mixed dispersion, mechanically stirring for 1.5 h, performing ultrasonic treatment for 1.5 h, dropwise adding 15 mL of ammonium persulfate hydrochloric acid solution at the speed of 40 drops/min, mechanically stirring for 24 h at room temperature after dropwise adding, performing methanol precipitation and methanol and deionized water alternative suction filtration washing until the filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 h to prepare the poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide composite material.
In the hydrochloric acid solution of the ammonium persulfate in the step (2), the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
Comparative example 2
(1) Adding 120 mg of graphene oxide into 60 mL of deionized water, mechanically stirring for 1.5 h at room temperature, and ultrasonically treating for 3 h to prepare a graphene oxide dispersion liquid; and transferring the dispersion liquid into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 200 ℃ for 24 hours, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying at 60 ℃ for 24 hours to prepare the graphene.
(2) Adding 50 mg of graphene and 70 mg of orange II into 15 mL of deionized water, mechanically stirring for 1.5 h, and performing ultrasonic treatment for 3 h to prepare a mixed dispersion liquid of the graphene and the orange II; adding 150 mg of 3, 4-ethylenedioxythiophene into the mixed dispersion, mechanically stirring for 1.5 h, performing ultrasonic treatment for 1.5 h, dropwise adding 15 mL of ammonium persulfate hydrochloric acid solution at the speed of 40 drops/min, mechanically stirring for 24 h at room temperature after dropwise adding, performing methanol precipitation and methanol and deionized water alternative suction filtration washing until the filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 h to prepare the poly (3, 4-ethylenedioxythiophene)/graphene composite material.
In the hydrochloric acid solution of the ammonium persulfate in the step (2), the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
Comparative example 3
Adding 70 mg of orange II into 15 mL of deionized water, mechanically stirring for 1.5 h, and performing ultrasonic treatment for 3 h to prepare an orange II solution; adding 150 mg of 3, 4-ethylenedioxythiophene into the solution, mechanically stirring for 1.5 h, performing ultrasonic treatment for 1.5 h, dropwise adding 15 mL of ammonium persulfate hydrochloric acid solution at the speed of 40 drops/min, mechanically stirring for 24 h at room temperature after dropwise adding, performing methanol precipitation and methanol and deionized water alternative suction filtration washing until the filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 h to prepare the orange II-doped poly 3, 4-ethylenedioxythiophene.
In the hydrochloric acid solution of the ammonium persulfate, the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
The products prepared in the three groups of examples and the three groups of comparative examples are uniformly coated on a stainless steel net as a working electrode after being mixed with acetylene black and polyvinylidene fluoride according to the weight ratio of 80:15:5, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 1 mol/L sulfuric acid aqueous solution is used as electrolyte, the specific capacitance of the products is tested by a constant current charging and discharging method, the electrochemical cycling stability of the products is tested by a cyclic voltammetry method, wherein the voltage range is-0.2V-0.8V, and the scanning rate is 100 mV/s. The test results are shown in Table 1.
Table 1 results of performance testing
From the test results of the examples and the comparative examples, it can be seen that the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material prepared by the chemical oxidation method has high specific capacitance and excellent electrochemical cycling stability, wherein the 3, 4-ethylenedioxythiophene is used as a monomer, the orange II is used as a dopant and a surfactant, the graphene-supported molybdenum disulfide prepared by the hydrothermal method is used as a supporting material, and the ammonium persulfate is used as an oxidant.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. A preparation method of a poly (3, 4-ethylenedioxythiophene)/molybdenum disulfide/graphene composite material is characterized by comprising the following steps: the composite material is prepared by taking ammonium molybdate tetrahydrate as a molybdenum source, thiourea as a sulfur source and graphene oxide as a carrier and preparing graphene-loaded molybdenum disulfide by utilizing a hydrothermal reaction; the graphene supported molybdenum disulfide is prepared by a chemical oxidation method by taking 3, 4-ethylenedioxythiophene as a monomer, orange II as a dopant and a surfactant, graphene supported molybdenum disulfide as a support material and ammonium persulfate as an oxidant; the preparation method comprises the following steps:
(1) adding 60-180 mg of graphene oxide into 30-90 mL of deionized water, mechanically stirring for 1-2 hours at room temperature, and then carrying out ultrasonic treatment for 2-4 hours to prepare a graphene oxide dispersion solution I; adding 0.4-0.6 g of ammonium molybdate tetrahydrate and 0.1-0.2 g of thiourea into 20-40 mL of deionized water, and mechanically stirring for 10-20 min at room temperature to prepare a mixed solution II of ammonium molybdate and thiourea; adding the mixed solution II into the dispersion solution I, mechanically stirring for 10-30 min, performing ultrasonic treatment for 30-60 min, transferring to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 180-220 ℃ for 12-36 h, and after the reaction is finished, performing centrifugal separation, washing and vacuum drying at 60 ℃ for 24 h to prepare graphene-loaded molybdenum disulfide;
(2) adding 40-60 mg of graphene-loaded molybdenum disulfide and 20-120 mg of orange II into 10-20 mL of deionized water, mechanically stirring for 1-2 h, and performing ultrasonic treatment for 2-4 h to prepare a mixed dispersion liquid of the graphene-loaded molybdenum disulfide and the orange II; adding 60-240 mg of 3, 4-ethylenedioxythiophene into the mixed dispersion, mechanically stirring for 1-2 hours, performing ultrasound for 1-2 hours, dropwise adding 10-20 mL of ammonium persulfate hydrochloric acid solution at the speed of 30-50 drops/min, mechanically stirring for 12-36 hours at room temperature after dropwise adding is finished, performing methanol sedimentation, alternately performing suction filtration and washing on methanol and deionized water until filtrate is colorless, and performing vacuum drying at 60 ℃ for 24 hours to prepare the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material.
2. The preparation method of the poly 3, 4-ethylenedioxythiophene/molybdenum disulfide/graphene composite material according to claim 1, wherein: in the hydrochloric acid solution of the ammonium persulfate in the step (2), the concentration of the ammonium persulfate is 0.25 mol/L, and the concentration of the hydrochloric acid is 3 mol/L.
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