CN112713007A - Electrode based on aerogel and preparation method - Google Patents
Electrode based on aerogel and preparation method Download PDFInfo
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- CN112713007A CN112713007A CN202011600262.3A CN202011600262A CN112713007A CN 112713007 A CN112713007 A CN 112713007A CN 202011600262 A CN202011600262 A CN 202011600262A CN 112713007 A CN112713007 A CN 112713007A
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- pss
- aerogel
- pedot
- graphene oxide
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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
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
- H01G11/24—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
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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
- H01G11/84—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the 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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
Abstract
An aerogel-based electrode comprising reduced graphene oxide and PEDOT: PSS; reduced graphene oxide and PEDOT: PSS forms aerogel and then presses to form an electrode plate, and PEDOT: PSS. In the electrode, reduced graphene oxide (rGO) mainly serves as an active material, and PEDOT (PSS) is a separant and a cross-linking agent between reduced graphene oxide sheets, so that the reduced graphene oxide sheets are effectively prevented from being stacked, and the resistance of the connection part of the reduced graphene oxide sheets is reduced. Layered structure of graphene and PEDOT: the excellent conductivity of PSS contributes to the rapid transport of electrolyte ions.
Description
Technical Field
The invention relates to an electrode material, in particular to an aerogel-based electrode, a preparation method and a solid-state aluminum electrolytic capacitor.
Background
The graphene derivative has a great potential in the field of energy storage due to high specific surface area, good conductivity and stable electrochemical performance. For graphene-based electrodes with three-dimensional (3D) porous structures, the interlayer stacking of graphene sheets greatly limits their capacitive performance, thus preventing their widespread use.
Graphene and graphene derivatives are widely used as electrode materials for supercapacitors due to their good electrical conductivity and stable electrochemical properties. The unique layered structure, particularly the higher specific surface area and ion transmission rate imparted to graphene-based materials unfortunately, the simultaneous strong pi-pi interactions and van der waals forces generated by the thin layer structure can lead to irreversible aggregation and severe stacking between graphene layers. Due to the fact that graphene sheets are aggregated, the capacitance of macroscopic graphene-based electrodes is typically much lower than expected due to the sacrifice of a large amount of surface area. Several strategies have been proposed to overcome this obstacle. Coupling of graphene with other materials, such as carbon allotropes; new two-dimensional materials, such as conductive polymers, for example polypyrrole, have been found to be one of the effective solutions. However, the rate capability and cycling stability of these electrodes become worse, either by the addition of materials or by the synthesis method.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide an aerogel-based electrode and a preparation method thereof, wherein the electrode has high specific capacitance, excellent rate capability and high capacitance retention rate.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: an aerogel-based electrode comprising reduced graphene oxide and PEDOT: PSS; reduced graphene oxide and PEDOT: and pressing the PSS to form an electrode plate after forming aerogel, wherein PEDOT: PSS.
In the above aerogel-based electrode, preferably, the reduced graphene oxide is mixed with PEDOT: PSS weight ratio is 5: 1-2: 1.
a method of preparing an aerogel-based electrode, comprising the steps of;
1) dispersing reduced graphene oxide into deionized water to form a dispersion solution of the reduced graphene oxide, wherein each gram of the reduced graphene oxide is dispersed into 0.2-0.5L of the deionized water;
2) and (3) mixing PEDOT: PSS powder was dispersed in deionized water to form PEDOT: (ii) an aqueous solution of PSS;
3) mixing the PEDOT obtained in the step 2): adding the aqueous solution of the PSS into the dispersion liquid of the reduced graphene oxide obtained in the step 1), wherein the ratio of the reduced graphene oxide to PEDOT: PSS weight ratio is 5: 1-2: 1;
4) h is to be2SO4Gradually adding the solution into the mixed solution obtained in the step 3) to ensure that the pH value of the mixed solution is less than 2, wherein H is2SO4The concentration of the solution is 0.5-1.5 mol/L;
5) transferring the mixed solution in the step 4) into an autoclave, and heating the mixed solution at the temperature of 150-;
6) immersing the hydrogel formed in step 5) in HNO3Washing the solution for 2-4 hours with deionized water until the solution is neutral (removing redundant PSS); HNO3The temperature of the solution is 50-70 ℃;
7) freeze-drying the hydrogel of step 6) to form aerogel;
8) pressing the aerogel obtained in the step 7) into a preset size to form an electrode, wherein the pressure is not less than 6MPa when the aerogel is pressed.
In the above method for preparing an aerogel-based electrode, preferably, the aerogel obtained in step 8) is pressed on the electrode sheet.
In the above method for preparing an aerogel-based electrode, preferably, the electrode sheet includes an aluminum foil, a titanium foil, or a carbon sheet.
Compared with the prior art, the invention has the advantages that: in the electrode, reduced graphene oxide (rGO) mainly serves as an active material, and PEDOT (PSS) is a separant and a cross-linking agent between reduced graphene oxide sheets, so that the reduced graphene oxide sheets are effectively prevented from being stacked, and the resistance of the connection part of the reduced graphene oxide sheets is reduced. Layered structure of graphene and PEDOT:the excellent conductivity of PSS contributes to the rapid transport of electrolyte ions. The electrode prepared by the invention has the current density of 0.2Ag-1The specific capacitance by weight of 471Fg-1(in 1mol/L sulfuric acid (H2SO 4)). 0.2Ag-1At 20Ag-1The capacity retention rate is excellent and is 98.71% in 20,000 cycles.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
It should be particularly noted that when an element is referred to as being "fixed to, connected to or communicated with" another element, it can be directly fixed to, connected to or communicated with the other element or indirectly fixed to, connected to or communicated with the other element through other intermediate connecting components.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1
An aerogel-based electrode comprising reduced graphene oxide and PEDOT: PSS; reduced graphene oxide and PEDOT: and pressing the PSS to form an electrode plate after forming aerogel, wherein PEDOT: PSS.
In this example, the reduction of graphene oxide with PEDOT: PSS weight ratio of 4: 1.
3. the method for preparing an aerogel-based electrode according to claim 1 or 2, wherein: comprises the following steps; 1) dispersing reduced graphene oxide into deionized water to form a dispersion solution of the reduced graphene oxide, wherein each gram of the reduced graphene oxide is dispersed into 0.2-0.5L of the deionized water;
2) and (3) mixing PEDOT: PSS powder was dispersed in deionized water to form PEDOT: (ii) an aqueous solution of PSS;
3) mixing the PEDOT obtained in the step 2): adding the aqueous solution of the PSS into the dispersion liquid of the reduced graphene oxide obtained in the step 1), wherein the ratio of the reduced graphene oxide to PEDOT: PSS weight ratio of 4: 1;
4) h is to be2SO4Gradually adding the solution into the mixed solution obtained in the step 3) to ensure that the pH value of the mixed solution is less than 2, wherein H is2SO4The concentration of the solution is 1 mol/L;
5) transferring the mixed solution in the step 4) into an autoclave, and heating the mixed solution at the temperature of 150-;
6) immersing the hydrogel formed in step 5) in HNO3Washing the solution for 2-4 hours with deionized water until the solution is neutral (removing redundant PSS); HNO3The temperature of the solution is 50-70 ℃; HNO3The concentration of the solution is 1 mol/L;
7) freeze-drying the hydrogel of step 6) to form aerogel;
8) pressing the aerogel obtained in the step 7) into a preset size to form an electrode, wherein the pressure is not less than 6MPa when the aerogel is pressed.
In the present embodiment, the aerogel obtained in step 7) may be pressed onto the electrode sheet in step 8). The electrode sheet may be an aluminum foil, a titanium foil, or a carbon sheet. Of course, the aerogel can also be directly pressed into the product.
In this example the pH of the mixture was adjusted to <2 prior to hydrothermal reaction, since the strongly acidic environment promoted PEDOT: gelling of PSS. During hydrothermal treatment, GO sheet portions are reduced to rGO sheets, which may lead to self-assembly of graphene sheets into hydrogel structures due to strong pi-pi interactions. By the action of these two steps, a robust heterogeneous rGO/PEDOT was successfully obtained: PSS composite hydrogel. After treatment of the hydrogel with 1mol/L of HNO3, not only the PEDOT: the excess of PSS in PSS, moreover, increases the degree of graphitization of the graphene sheet, thus resulting in a significant increase in the electrical conductivity of the electrode.
In this example, if reducing graphene oxide and PEDOT: PSS weight ratio too much PEDOT when too low: PSS tightly wrapped around the rGO sheet, so that no aerogel-like porous structure could be formed on the electrode; however, if the weight ratio is too high, stacking of rGO aerogel occurs.
Two electrodes in the embodiment are used as an anode and a cathode, and the electrolyte adopts gel electrolyte; 1 part by weight of PVA powder mixed with a gel electrolyte based on PVA/H2SO4 was prepared by the following method, H2SO41 part by weight and 9 parts by weight of deionized water. The mixture was kept stirring at 90 ℃ until the solution became clear. Mixing PVA/H2SO4The gel is clamped between two circular electrode plates with the diameter of 12mm, and the two circular electrode plates are assembled into a symmetrical super capacitor together. PVA/H2SO4The gel acts as both the electrolyte and the separator.
In this example, the electrode made without any binder or conductive additive exhibited a considerable specific capacitance, very excellent speed capability and excellent cycling stability. These excellent electrochemical properties can be attributed to the combination of PEDOT: PSS incorporates a layered porous structure in the rGO layer, which brings a highly conductive charge transport path and additional pseudo-capacitance. Further, the maximum energy density of the symmetrical supercapacitor based on the electrode composition of the present embodiment was 47.18Wh/kg and a power density of 13600W/kg. Meanwhile, after the super capacitor manufactured by the embodiment is cycled 3000 times under the current density of 8A/g, the capacity of the super capacitor can be reserved by 85%.
The electrode used in this example was used as a working electrode, the (Hg/HgSO4) electrode and a platinum sheet were used as a reference electrode and a counter electrode, respectively, and the electrolyte was 1mol/L of H2SO4An aqueous solution; thereby constituting an electrochemical workstation. Under the conditions of this electrochemical workstation, the electrode of this example had a gravimetric capacitance of 471F/g (in 1mol/L sulfuric acid (H2SO 4)) at a current density of 0.2A/g. 0.2A/g, with an excellent capacity retention of 98.71% over 20,000 cycles of 20A/g.
It is noted that the electrode of the present embodiment can be used not only in batteries and supercapacitors, but also in solid-state aluminum electrolytic capacitors as a negative electrode. At the time of hydrothermal reaction and in HNO3Aqueous solution washing, which enables removal of PEDOT: redundant in PSSPSS can improve the conductivity of the negative electrode, so that the internal resistance of the solid-state aluminum electrolytic capacitor is reduced, and the ripple current resistance is improved. Meanwhile, when the aerogel of the embodiment is pressed on an aluminum foil or a titanium foil, the aerogel can directly bear the electrolyte of the solid-state aluminum electrolytic capacitor.
In the electrode in the embodiment, reduced graphene oxide (rGO) mainly serves as an active material, and PEDOT: PSS is a release agent and a cross-linking agent between the reduced graphene oxide sheets, so that stacking of layers of the reduced graphene oxide is effectively prevented, and the resistance of the connection part of the reduced graphene oxide is reduced. Layered structure of graphene and PEDOT: the excellent conductivity of PSS contributes to the rapid transport of electrolyte ions. The electrode prepared in the present invention had a gravimetric capacitance of 471F/g (in 1mol/L sulfuric acid (H2SO 4)) at a current density of 0.2A/g. 0.2A/g, with an excellent capacity retention of 98.71% over 20,000 cycles of 20A/g.
Claims (5)
1. An aerogel-based electrode, comprising: comprising reducing graphene oxide and PEDOT: PSS; reduced graphene oxide and PEDOT: and pressing the PSS to form an electrode plate after forming aerogel, wherein PEDOT: PSS.
2. The aerogel-based electrode of claim 1, wherein: the reduced graphene oxide is mixed with PEDOT: PSS weight ratio is 5: 1-2: 1.
3. the method for preparing an aerogel-based electrode according to claim 1 or 2, wherein: comprises the following steps;
1) dispersing reduced graphene oxide into deionized water to form a dispersion solution of the reduced graphene oxide, wherein each gram of the reduced graphene oxide is dispersed into 0.2-0.5L of the deionized water;
2) and (3) mixing PEDOT: PSS powder was dispersed in deionized water to form PEDOT: (ii) an aqueous solution of PSS;
3) mixing the PEDOT obtained in the step 2): adding the aqueous solution of the PSS into the dispersion liquid of the reduced graphene oxide obtained in the step 1), wherein the ratio of the reduced graphene oxide to PEDOT: PSS weight ratio is 5: 1-2: 1;
4) h is to be2SO4Gradually adding the solution into the mixed solution obtained in the step 3) to ensure that the pH value of the mixed solution is less than 2, wherein H is2SO4The concentration of the solution is 0.5-1.5 mol/L;
5) transferring the mixed solution in the step 4) into an autoclave, and heating the mixed solution at the temperature of 150-;
6) immersing the hydrogel formed in step 5) in HNO3Washing the solution for 2-4 hours with deionized water until the solution is neutral (removing redundant PSS); HNO3The temperature of the solution is 50-70 ℃;
7) freeze-drying the hydrogel of step 6) to form aerogel;
8) pressing the aerogel obtained in the step 7) into a preset size to form an electrode, wherein the pressure is not less than 6MPa when the aerogel is pressed.
4. The method of preparing an aerogel-based electrode of claim 3, wherein: in the step 8), the aerogel obtained in the step 7) is pressed on the electrode sheet.
5. The method of preparing an aerogel-based electrode of claim 4, wherein: the electrode plate comprises an aluminum foil, a titanium foil or a carbon plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011600262.3A CN112713007A (en) | 2020-12-29 | 2020-12-29 | Electrode based on aerogel and preparation method |
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| CN202011600262.3A CN112713007A (en) | 2020-12-29 | 2020-12-29 | Electrode based on aerogel and preparation method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
| CN110085436A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of graphene/Polyglycolic acid fibre composite fibre assembly |
| CN111446423A (en) * | 2020-04-24 | 2020-07-24 | 深圳市海盈科技有限公司 | Lithium ion battery electrode material, preparation method thereof and lithium ion battery |
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2020
- 2020-12-29 CN CN202011600262.3A patent/CN112713007A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
| CN110085436A (en) * | 2019-04-21 | 2019-08-02 | 北京工业大学 | A kind of preparation method of graphene/Polyglycolic acid fibre composite fibre assembly |
| CN111446423A (en) * | 2020-04-24 | 2020-07-24 | 深圳市海盈科技有限公司 | Lithium ion battery electrode material, preparation method thereof and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| HUI HUANG等: "Three-dimensional porous reduced graphene oxide/PEDOT:PSS aerogel: Facile preparation and high performance for supercapacitor electrodes", 《ELECTROCHIMICA ACTA》 * |
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Application publication date: 20210427 |