CN115240991B - Manufacturing method of ionic supercapacitor based on electroactive ionic liquid - Google Patents
Manufacturing method of ionic supercapacitor based on electroactive ionic liquid Download PDFInfo
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- 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
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- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a construction method of a novel ionic supercapacitor based on electroactive ionic liquid. Firstly, reacting a polymeric ionic liquid of alkyl imidazole chloride or bromide with a graphene oxide material, and reducing to obtain a polymeric ionic liquid-reduced graphene oxide composite PILs-rGO. By utilizing the ion exchange property of the ionic liquid, inorganic/organic anions with electrochemical redox activity are exchanged into a structural unit of the ionic liquid, so that the graphene material EAI-PILs-rGO with electric activity is constructed. Further, the novel asymmetric ionic supercapacitor is constructed by taking the electroactive graphene material with the positive oxidation-reduction potential as a positive electrode and taking the negative electroactive graphene material as a negative electrode, so that the energy density of the graphene-based capacitor can be effectively improved while rapid charge and discharge can be realized, and the novel asymmetric ionic supercapacitor has excellent structural stability. The method is simple, easy to operate, universal and has excellent application prospect.
Description
Technical Field
The invention relates to the technical field of electrode materials and energy storage, in particular to a manufacturing method and application of a novel ionic supercapacitor based on electroactive ionic liquid.
Background
With the rapid development of global economy, the worldwide consumption of fossil fuels has increased greatly, so that the depletion of existing fossil fuel reserves has been accelerated, and therefore, the development and expansion of sustainable clean energy and related technical needs are regarded as urgent worldwide. The super capacitor has the advantages of high safety performance, long cycle life, large storage capacity and the like, and has received a great deal of attention from a plurality of researchers in recent years.
Supercapacitors can be classified into electric double layer capacitors and faraday quasicapacitors according to the energy storage mechanism. Among them, the electric double layer capacitor stores energy mainly by adsorption of charges on the electrode surface. The Faraday super capacitor mainly generates Faraday capacitance through reversible oxidation-reduction reaction on the surface of an active electrode material and the vicinity thereof, thereby realizing energy storage and conversion. Thus, the electrode material in faraday supercapacitors is critical to achieving energy storage and conversion, and is typically composed of metal oxide and carbon-based materials. Compared with an electric double layer capacitor, the Faraday super capacitor has higher specific capacitance and energy density, but the metal oxide generally undergoes phase change in the process of dissolution or deposition, which is likely to cause structural stability problems such as electrode structural damage, dendrite formation and the like, and influences the cycle stability of the battery to a certain extent. Therefore, in order to meet the increasing energy demand of electronic devices, it is important to promote the development of novel energy storage technologies and find novel electrode materials with low cost, high power and energy density and good cycle stability.
Graphene is a commonly used electrode material component of a capacitor, however, due to the existence of Van der Waals force, graphene obtained by a chemical reduction method is extremely easy to agglomerate, so that the effective specific surface area of the graphene is reduced, the specific capacitance is reduced, the conductivity and the structural stability are also reduced, and therefore, the inhibition of the agglomeration of the graphene is a key for improving the application performance of the graphene. The imidazole-based polymeric ionic liquid has pi conjugated structure and is a cationic ionic liquid polymer, so that the imidazole-based polymeric ionic liquid can be compounded with graphene oxide through pi-pi interaction or electrostatic adsorption, and the aggregation and accumulation problems of graphene materials are effectively inhibited. In addition, the ionic liquid has stronger structural designability and ion interchangeability, and can further endow the graphene material with special functionality.
A series of electroactive ionic liquids and polymers thereof having different redox potentials can be prepared by exchanging anions having electrochemical redox activity into structural units of the ionic liquid. The electroactive ionic liquid polymer is combined with the graphene material with high active surface area, so that the structural stability of the graphene material can be effectively improved, and a specific electrochemical reaction active center of the graphene material is endowed. Furthermore, the electroactive graphene electrode material with positive oxidation-reduction potential is selected as a positive electrode and the electroactive graphene electrode material with negative oxidation-reduction potential is selected as a negative electrode, so that a series of novel ionic super capacitors with different voltage windows, stable electrode structure and high power density and high energy density can be assembled.
Disclosure of Invention
Based on the problems of low energy density of the traditional capacitor, poor structural stability of the metal oxide-based pseudocapacitor electrode material and low power density of the traditional secondary battery, electrochemical active anions are introduced into the surface of the graphene material with high specific surface area, a series of electroactive graphene electrode materials are prepared, and the electrochemical active graphene electrode materials are applied to novel ionic supercapacitors. Only the ion valence state changes in the electrode during the charge and discharge process, and the phase change or dissolution deposition process of the active component is not involved, so that the electrode has excellent structural stability, and simultaneously has the high power density of the traditional capacitor and the high energy density of the secondary battery.
In order to achieve the above purpose, the invention adopts the following technical scheme: the manufacturing method of the novel ionic supercapacitor based on the electroactive ionic liquid comprises the following steps:
1) Dispersing Graphene Oxide (GO) in deionized water, and obtaining low-lamellar two-dimensional Graphene Oxide (GO) nano-sheets by adopting a grading centrifugation method;
2) Dissolving alkyl imidazole bromine salt or alkyl imidazole chloride salt ionic liquid monomer and initiator in chloroform, and adding the ionic liquid monomer and initiator in N 2 Heating and refluxing for 5-7 h at 70 ℃ under protection, cooling, washing and vacuum drying to obtain Polymeric Ionic Liquid (PILs);
3) Dispersing a proper amount of the two-dimensional Graphene Oxide (GO) nanosheets obtained in the step 1) in deionized water, sequentially adding the PILs and the hydrazine hydrate obtained in the step 2), reacting for 1-2 hours at 90-100 ℃, filtering the obtained product, and centrifugally washing to obtain a polymeric ionic liquid-reduced graphene oxide compound (PILs-rGO);
4) Mixing the PILs-rGO obtained in the step 3) with inorganic salt or organic salt aqueous solution of Electroactive Anions (EAI) with different electrochemical redox activities, stirring for 1h at room temperature, and carrying out exchange reaction between the electroactive anions with different electrochemical redox activities and bromine or chloride ions in the ionic liquid to obtain electroactive anions-polymeric ionic liquid-reduced graphene oxide compounds (EAI-PILs-rGO) with different redox properties;
5) Dispersing the EAI-PILs-rGO with different redox properties obtained in the step 4) in deionized water, immersing or dripping the current collector into the obtained EAI-PILs-rGO dispersion liquid, drying for 12-24 hours at 60-80 ℃, repeatedly immersing or dripping and drying for 2-3 times to obtain active electrode materials with different redox potentials, selecting electrode materials with positive redox potentials as positive electrodes, selecting electrode materials with negative redox potentials as negative electrodes, and assembling the novel asymmetric ionic supercapacitor based on the electroactive ionic liquid.
Further, in the above manufacturing method, in step 1), the method of using fractional centrifugation obtains the low-lamellar two-dimensional graphene oxide GO nanoplatelets, specifically: step centrifugation is carried out on GO aqueous dispersion liquid from low rotation speed to high rotation speed at the rotation speed of 1000 r/min-12000r/min, supernatant obtained by low rotation speed centrifugation is taken to continue high rotation speed centrifugation until no sediment exists after centrifugation, and sediment obtained by centrifugation at the highest rotation speed is taken as a low-lamellar two-dimensional graphene oxide GO nano-sheet.
In the above manufacturing method, in step 2), the alkyl imidazole bromide or alkyl imidazole chloride ionic liquid monomer is an alkyl imidazole bromide or alkyl imidazole chloride ionic liquid monomer containing an unsaturated bond.
Further, in the above production method, in step 2), the initiator is Azobisisobutyronitrile (AIBN).
Further, in the above manufacturing method, the mass ratio of the ionic liquid monomer to the initiator=50:1.
Further, in the above manufacturing method, in step 3), the mass ratio of the two-dimensional Graphene Oxide (GO) nanoplatelets to the Polymeric Ionic Liquid (PILs) =1:10.
Further, in the above-described production method, in step 4), the inorganic salt or the organic salt of an Electroactive Anion (EAI) having different electrochemical redox activities includes: potassium ferricyanide, phosphotungstic acid, ammonium cerium nitrate, amino acid, anthraquinone-2-sodium sulfonate, disodium 4, 5-dihydroxy-1, 3-benzenedisulfonate and sodium ferrocene benzenesulfonate.
Further, in the above manufacturing method, in step 5), the current collector includes foamed nickel, carbon paper, graphite felt, graphite plate, and conductive glass.
Further, in the above production method, in the step 5), the concentration of the EAI-PILs-rGO dispersion liquid is 1 to 10mg/mL.
The beneficial effects of the invention are as follows:
1. the ionic liquid ion exchange property, the high conductivity and the high specific surface area of the graphene material are utilized to prepare a series of electroactive graphene-based composite electrode materials, and the materials have excellent reversibility of electrochemical oxidation-reduction reaction, larger specific surface area and adjustable oxidation-reduction potential, so that a series of novel ionic super capacitor systems with different electrochemical windows can be manufactured, and the method is simple and has universality.
2. The novel ionic super capacitor based on the electroactive ionic liquid, which is manufactured by the method, has the advantages that the energy storage element is mainly a graphene nano sheet and electroactive anions, and the novel ionic super capacitor has high power density and high energy density, does not generate phase change of electrode materials, and has better structural stability.
3. The novel ionic supercapacitor based on the electroactive ionic liquid provided by the invention introduces electrochemical active anions into the surface of a graphene material with high specific surface area to prepare a series of electroactive graphene electrode materials, and applies the materials to the novel ionic supercapacitor. Only the ion valence state changes in the electrode during the charge and discharge process, and the phase change or dissolution deposition process of the active component is not involved, so that the electrode has excellent structural stability, and simultaneously has the high power density of the traditional capacitor and the high energy density of the secondary battery.
Drawings
FIG. 1 is a TEM image of GO (a) and PILs-rGO composite (b) prepared in example 1.
FIG. 2 shows the composition of example 1 [ Fe (CN) 6 ] 3- -cyclic voltammogram of PILs-rGO (a) and PWA-PILs-rGO (b) versus PILs-rGO in sulfuric acid electrolyte.
FIG. 3 is a charge and discharge curve for two EAI-PILs-rGO assembled asymmetric supercapacitors and a PILs-rGO assembled symmetric supercapacitor prepared in example 1.
FIG. 4 is a graph comparing the cyclic voltammograms of BQDS-PILs-rGO (a) and AQS-PILs-rGO (b) prepared in example 2 with that of PILs-rGO in potassium chloride electrolyte.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and examples for better understanding of the technical scheme of the present invention to those skilled in the art.
Example 1
The manufacturing method of the novel ionic supercapacitor based on the inorganic electroactive ionic liquid comprises the following steps:
1. synthesis of low-lamellar two-dimensional Graphene Oxide (GO) nanoplatelets
Preparation of Graphene Oxide (GO): graphene Oxide (GO) was prepared by Hummers method. A three-necked round bottom flask containing 135mL of concentrated sulfuric acid (98 wt%) was placed in an ice-water bath and 4g of high purity graphite powder and 3.2g of NaNO were added 3 After stirring to a uniform dispersion, 18g KMnO was slowly added 4 The powder is kept at a temperature of 5 ℃ or lower in the bottle. Then the temperature was adjusted to 5℃and reacted for 30min until the black suspension had all turned to a dark brown viscous mass. After five days at room temperature, it was diluted with a large amount of hot water and 30wt% hydrogen peroxide was added dropwise to reduce the remaining high valent manganese ions until the solution turned bright yellow. And (5) centrifugally washing the mixture to be neutral when the mixture is hot, and obtaining Graphene Oxide (GO).
Dispersing the obtained GO with deionized water, centrifuging at 1000r/min for 10min, taking upper brown dispersion liquid, centrifuging at 3000r/min for 10min, taking supernatant, centrifuging at high rotation speed, sequentially performing gradient grading centrifugation from low rotation speed to high rotation speed within the range of 3000r/min-12000r/min, namely taking supernatant obtained by centrifuging at low rotation speed, centrifuging at high rotation speed until no precipitate exists after centrifugation, taking precipitate at the highest rotation speed as a final product, namely the low-lamellar two-dimensional Graphene Oxide (GO) nano-sheets, and vacuum drying for later use.
2. Synthesis of Polymeric Ionic Liquids (PILs)
Synthesizing a 1-vinyl-3-ethylimidazole bromide ionic liquid monomer: 1-vinyl imidazole and bromoethane with the molar ratio of 1:1.7 are sequentially added into a round-bottom flask, oil bath reflux is carried out at 70 ℃, the reaction is carried out for 10 hours, and heating is stopped when the reflux is not obvious. Recrystallizing the obtained reactant with acetonitrile-ethyl acetate for three times, and drying in vacuum to obtain the 1-vinyl-3-ethylimidazole bromide ionic liquid.
Synthesis of polymeric ionic liquid 1-vinyl-3-ethylimidazole bromide: 5g of 1-vinyl-3-ethylimidazole bromide ionic liquid monomer is added into 100mL of chloroform, 0.1g of Azodiisobutyronitrile (AIBN) is added into the chloroform, the mixture is heated and refluxed for 6h in an oil bath at 70 ℃ under the protection of nitrogen, the obtained product is washed three times by chloroform, and the obtained product is dried in vacuum, thus obtaining the Polymerized Ionic Liquid (PILs) of 1-vinyl-3-ethylimidazole bromide.
3. Synthesis of polymeric ionic liquid-reduced graphene oxide complexes (PILs-rGO)
50mg of low-lamellar two-dimensional Graphene Oxide (GO) nanosheets are dispersed in 50mL of deionized water, 500mg of polymerized ionic liquid of 1-vinyl-3-ethylimidazole bromide is added into the mixture, 35 mu L of hydrazine hydrate reducing agent is added into the mixture by a liquid transfer device under magnetic stirring, and the mixture is reacted for 1h in an oil bath at 90 ℃. The resulting product was filtered and centrifugally washed with deionized water to remove excess reducing agent. Vacuum drying to obtain PILs-rGO compound.
4. Synthesis of inorganic electrochemical redox active anion-polymeric ionic liquid-reduced graphene oxide complexes (EAI-PILs-rGO)
4.1 Ferricyanide-polymeric ionic liquid-reduced graphene oxide complex ([ Fe (CN)) 6 ] 3- -PILs-rGO)
10mL of aqueous dispersion liquid prepared from PILs-rGO compound prepared in the step 3 is mixed with 5mL of potassium ferricyanide solution with the concentration of 5mmol/L, stirred for 1h at room temperature, and the product is centrifugally washed with distilled water for 5 times and dried in vacuum to obtain [ Fe (CN) 6 ] 3- -PILs-rGO complex for use.
4.2 Synthesis of phosphotungstic acid radical-polymeric ionic liquid-reduced graphene oxide complexes (PWA-PILs-rGO)
10mL of aqueous dispersion liquid which is prepared from the PILs-rGO compound prepared in the step 3 and is 2mg/mL is mixed with 5mL of phosphotungstic acid solution with the concentration of 5mmol/L, the mixture is stirred for 1h at room temperature, the product is centrifugally washed for 5 times by distilled water, and the PWA-PILs-rGO compound is obtained after vacuum drying for standby.
5. Novel ionic supercapacitor based on electroactive ionic liquid
Respectively [ Fe (CN) 6 ] 3- Dispersing the PILs-rGO compound and the PWA-PILs-rGO compound by using 0.05wt% of nafion aqueous solution, respectively dripping the dispersed materials on the surface of carbon paper with the concentration of 1cm multiplied by 1cm, drying the carbon paper at the temperature of 60 ℃ in vacuum to constant weight, and repeating the steps for three times to obtain the electrode material. By loading [ Fe (CN) 6 ] 3- The carbon paper electrode of PILs-rGO is used as a positive electrode, the carbon paper electrode of PWA-PILs-rGO is used as a negative electrode, and the electrolyte is 2.5M H 2 SO 4 And (3) an aqueous solution, namely assembling the sandwich type asymmetric ionic super capacitor by taking the GF40 glass fiber membrane as a diaphragm.
(II) detection
1. FIG. 1 is a TEM image of the prepared GO (a) and PILs-rGO composite (b).
Fig. 1 (a) shows a transmission electron microscope image of the resulting GO. As shown in fig. 1, the graphene oxide obtained is a two-dimensional lamellar structure, and the surface has abundant wrinkles.
FIG. 1 (b) is a transmission electron micrograph of the obtained PILs-rGO. As shown in fig. 1, the PILs-rGO composite material has a structure and morphology similar to that of graphene oxide, which indicates that the introduction of PILs suppresses aggregation and stacking of GO in the reduction process, and the composite material still maintains a two-dimensional lamellar structure.
2. Electrochemical property testing of an electroactive anion-polymeric ionic liquid-graphene composite
The method comprises the following steps: PILs-rGO, [ Fe (CN) respectively 6 ] 3- -PILs-rGO and PWA-PILs-rGO are dispersed in 0.05wt% aqueous nafion solution. mu.L of PILs-rGO (2 mg. ML) was taken separately -1 )、[Fe(CN) 6 ] 3- -PILs-rGO(5mg·mL -1 ) And PWA-PILs-rGO (5 mg. ML) -1 ) The aqueous dispersion is dripped on the surface of a polished glassy carbon electrode with the diameter of 4mm, and a layer of film can be formed on the surface of the electrode after the electrode is dried at room temperature, so that PILs-rGO, [ Fe (CN) can be obtained 6 ] 3- -PILs-rGO and PWA-PILs-rGO modified electrodes.
Cyclic voltammetry test conditions: the prepared modified electrodes are respectively used as working electrodes, silver/silver chloride electrode (Ag/AgCl) is used as reference electrode, and platinum sheet is used as counter electrode to form a three-electrode system, 2.5M H 2 SO 4 The aqueous solution is a supporting electrolyte solution, and the voltage windows are respectively set as follows: 0.2V-0.8V, -0.6V-0.1V, the sweep speed is 50mV/s, and the cycle scan is 100 circles.
FIG. 2 shows the PILs-rGO, [ Fe (CN) of the preparation 6 ] 3- -cyclic voltammogram comparison of PILs-rGO (a) and PWA-PILs-rGO (b) in sulfuric acid electrolyte. As shown in FIG. 2, the blank PILs-rGO modified electrode showed no significant redox peaks at both the positive and negative potential windows, corresponding to [ Fe (CN) 6 ] 3- CV curves of the electrodes of the PILs-rGO (a) and PWA-PILs-rGO (b) are shown by the respective [ Fe (CN) 6 ] 3- And the characteristic oxidation-reduction peak of the phosphate-tungsten acid radical, and has good reversibility; [ Fe (CN) 6 ] 3- Peak position value of about 0.55V (vs. ag/AgCl) for the PILs-rGO, and most negative peak position value of about-0.55V (vs. ag/AgCl) for PWA-PILs-rGO, indicating positive electrode material selection [ Fe (CN) for subsequent assembly of asymmetric ionic super capacitor 6 ] 3- -PILs-rGO, and the negative electrode material is PWA-PILs-rGO, and the asymmetric capacitor assembled by the two materials can obtain a voltage window of about 1.1V. In addition, after 100 consecutive scans, the peak current attenuation of the two is smaller, which indicates that the electrode has good stability.
3. Capacitor electrochemical property testing
And (3) carrying out charge and discharge test on the sandwich type asymmetric ionic super capacitor assembled in the step (5) in a voltage window of-0.1V to 1.2V, wherein the current is 2mA.
FIG. 3 is a charge and discharge curve for two EAI-PILs-rGO assembled asymmetric supercapacitors and a PILs-rGO assembled symmetric supercapacitor prepared in example 1. As shown in fig. 3, the asymmetric supercapacitor loaded with the electroactive anions can realize stable charge and discharge, and the charge and discharge efficiency is about 93.44%; in addition, the discharge capacity of the graphene material is improved by about 21% compared with that of a symmetrical capacitor, which shows that the electroactive graphene material can provide additional Faraday capacitance, so that the storage capacity of the capacitor is effectively increased.
Example 2
The manufacturing method of the novel ionic supercapacitor based on the organic electroactive ionic liquid comprises the following steps:
1. synthesis of low-lamellar two-dimensional Graphene Oxide (GO) nanoplatelets
As in example 1.
2. Synthesis of Polymeric Ionic Liquids (PILs)
As in example 1.
3. Synthesis of polymeric ionic liquid-reduced graphene oxide complexes (PILs-rGO)
As in example 1.
4. Synthesis of organic electrochemical redox active anion-polymeric ionic liquid-reduced graphene oxide complexes (EAI-PILs-rGO)
4.1 Synthesis of anthraquinone-2-sulfonate-polymeric ionic liquid-reduced graphene oxide complexes (AQS-PILs-rGO)
Taking 10mL of PILs-rGO complex prepared in the step 3 to prepare 2 mg.mL -1 Mixing with 2mL of anthraquinone-2 sodium sulfonate solution with the concentration of 1mmol/L, stirring for 1h at room temperature, centrifugally washing the product with distilled water for 5 times, and vacuum drying to obtain the AQS-PILs-rGO compound for later use.
4.2 Synthesis of 4, 5-dihydroxy-1, 3-benzenedisulfonate-polymeric ionic liquid-reduced graphene oxide complexes (BQDS-PILs-rGO)
10mL of the aqueous dispersion liquid which is prepared from the PILs-rGO compound prepared in the step 3 and is 2mg/mL is mixed with 2mL of 4, 5-dihydroxyl-1, 3-benzene disulfonic acid disodium salt solution with the concentration of 1mmol/L, the mixture is stirred for 1h at room temperature, the product is centrifugally washed for 5 times by distilled water, and the BQDS-PILs-rGO compound is obtained for standby.
5. Novel ionic supercapacitor based on electroactive ionic liquid
Dispersing the AQS-PILs-rGO compound and the BQDS-PILs-rGO compound by using 0.05wt% of nafion aqueous solution, respectively dripping the dispersed compositions on the surface of carbon paper with the concentration of 1cm multiplied by 1cm, drying the compositions to constant weight at the temperature of 60 ℃ in vacuum, and repeating the steps for three times to obtain the electrode material. The BQDS-PILs-rGO loaded carbon paper electrode is used as an anode, the AQS-PILs-rGO loaded carbon paper electrode is used as a cathode, and the electrolyte is 2.5M H 2 SO 4 And (3) an aqueous solution, namely assembling the sandwich type asymmetric ionic super capacitor by taking the GF40 glass fiber membrane as a diaphragm.
(II) detection
1. Electrochemical property testing of electroactive anion-polymeric ionic liquid-graphene composite materials
The method comprises the following steps: PILs-rGO, AQS-PILs-rGO and BQDS-PILs-rGO were dispersed in 0.05wt% of a nafion aqueous solution, respectively. mu.L of PILs-rGO (2 mg. ML) was taken separately -1 )，AQS-PILs-rGO(5mg·mL -1 ) And BQDS-PILs-rGO (5 mg.mL) -1 ) The aqueous dispersion is dripped on the surface of a polished glassy carbon electrode with the diameter of 4mm, and a layer of film can be formed on the surface of the electrode after the electrode is dried at room temperature, so that PILs-rGO, AQS-PILs-rGO and BQDS-PILs-rGO modified electrodes are obtained.
Cyclic voltammetry test conditions: the prepared modified electrodes are respectively used as working electrodes, silver/silver chloride electrodes (Ag/AgCl) are used as reference electrodes, platinum sheets are used as counter electrodes to form a three-electrode system, 0.5M KCl aqueous solution is used as supporting electrolyte solution, and voltage windows are respectively set as follows: 0.45V-0.85V, -0.9V-0.2V, the scanning speed is 50mV/s, and the scanning is 100 circles.
FIG. 4 is a graph comparing the cyclic voltammograms of BQDS-PILs-rGO (a) and AQS-PILs-rGO (b) prepared in example 2 with that of PILs-rGO in potassium chloride electrolyte. As shown in fig. 4, no obvious oxidation-reduction peak appears in the blank PILs-rGO modified electrode under the positive and negative potential window, while characteristic oxidation-reduction peaks of BQDS and AQS appear in CV curves corresponding to BQDS-PILs-rGO (a) and AQS-PILs-rGO (b) electrodes respectively, and the reversibility is good; the peak value of BQDS-PILs-rGO is about 0.6V (vs. Ag/AgCl), and the most negative peak value of AQS-PILs-rGO is about-0.6V (vs. Ag/AgCl), which indicates that when the asymmetric ionic super capacitor is assembled later, the BQDS-PILs-rGO is selected as the positive electrode material, the AQS-PILs-rGO is selected as the negative electrode material, and the asymmetric capacitor assembled by the two materials can obtain a voltage window of about 1.2V. In addition, after 100 consecutive scans, the peak current attenuation of the two is smaller, which indicates that the electrode has good stability.
Claims (9)
1. The manufacturing method of the ionic supercapacitor based on the electroactive ionic liquid is characterized by comprising the following steps of:
1) Dispersing graphene oxide GO in deionized water, and obtaining low-lamellar two-dimensional graphene oxide GO nano-sheets by adopting a grading centrifugation method;
2) Dissolving alkyl imidazole bromine salt or alkyl imidazole chloride salt ionic liquid monomer and initiator in chloroform, and adding the ionic liquid monomer and initiator in N 2 Heating and refluxing for 5-7 hours at the temperature of 70 ℃ under protection, cooling, washing and vacuum drying to obtain the polymeric ionic liquid PILs;
3) Dispersing a proper amount of the two-dimensional graphene oxide GO nano-sheets obtained in the step 1) into deionized water, sequentially adding the PILs and the hydrazine hydrate obtained in the step 2), reacting for 1-2 hours at 90-100 ℃, filtering the obtained product, and centrifugally washing to obtain a polymeric ionic liquid-reduced graphene oxide composite PILs-rGO;
4) Mixing the PILs-rGO obtained in the step 3) with inorganic salt or organic salt aqueous solution of electroactive anions EAI with different electrochemical redox activities, and stirring at room temperature for 1h to obtain electroactive anions-polymeric ionic liquid-reduced graphene oxide compounds EAI-PILs-rGO with different redox properties;
5) Dispersing the EAI-PILs-rGO with different redox properties obtained in the step 4) in deionized water, immersing or dripping the current collector into the obtained EAI-PILs-rGO dispersion liquid, drying for 12-24 hours at 60-80 ℃, repeatedly immersing or dripping and drying for 2-3 times to obtain active electrode materials with different redox potentials, selecting electrode materials with positive redox potentials as positive electrodes, selecting electrode materials with negative redox potentials as negative electrodes, and assembling the asymmetric ionic supercapacitor based on the electroactive ionic liquid.
2. The manufacturing method according to claim 1, wherein in step 1), the method of fractional centrifugation is adopted to obtain low-lamellar two-dimensional graphene oxide GO nanoplatelets, specifically: step-type centrifugation is carried out on GO aqueous dispersion liquid from low rotation speed to high rotation speed at the rotation speed of 1000 r/min-12000r/min, supernatant obtained by low rotation speed centrifugation is taken to continue high rotation speed centrifugation until no sediment exists after centrifugation, and sediment obtained by centrifugation at the highest rotation speed is taken as a low-lamellar two-dimensional graphene oxide GO nano sheet.
3. The method according to claim 1, wherein in step 2), the alkyl imidazole bromide or alkyl imidazole chloride ionic liquid monomer is an alkyl imidazole bromide or alkyl imidazole chloride ionic liquid monomer containing an unsaturated bond.
4. The method of claim 1, wherein in step 2), the initiator is azobisisobutyronitrile.
5. The method according to claim 4, wherein the ionic liquid monomer is initiator=50:1 in mass ratio.
6. The method according to claim 1, wherein in the step 3), the two-dimensional graphene oxide GO nanoplatelets are polymerized ionic liquid pils=1:10 in terms of mass ratio.
7. The method of claim 1, wherein in step 4), the inorganic or organic salt of electroactive anionic EAI having different electrochemical redox activities comprises: potassium ferricyanide, ammonium ceric nitrate, sodium anthraquinone-2-sulfonate, disodium 4, 5-dihydroxy-1, 3-benzene disulfonate and sodium ferrocene benzenesulfonate.
8. The method of manufacturing according to claim 1, wherein in step 5), the current collector comprises nickel foam, carbon paper, graphite felt, graphite plate, and conductive glass.
9. The method according to claim 1, wherein in step 5), the concentration of the EAI-PILs-rGO dispersion is 1 to 10mg/mL.
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| US9779882B2 (en) * | 2015-11-23 | 2017-10-03 | Nanotek Instruments, Inc. | Method of producing supercapacitor electrodes and cells having high active mass loading |
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