CN112687476A - Preparation and application of graphene oxide carbon aerogel - Google Patents
Preparation and application of graphene oxide carbon aerogel Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene oxide carbon aerogel capacitance electrode, which comprises the following steps: acid oxidation: acidifying and oxidizing graphite powder, and adding polyethylene glycol to react to form a carbon aerogel solution; drying and forming: washing the carbon aerogel solution with alkali liquor, uniformly shaking, drying to remove water, and performing fire combustion at room temperature to obtain graphene oxide carbon aerogel; electrode pretreatment: cleaning the conductive glass for more than three times, standing and drying, and then sticking the graphene oxide carbon aerogel on the conductive glass; and preparing a capacitance electrode: coating a conductive polymer on the surface of the combination of the graphene oxide carbon aerogel and the conductive glass; or the combination of the graphene oxide carbon aerogel and the conductive glass is placed in an electroplating solution for electroplating. The carbon aerogel obtained by the method can achieve excellent conductive property close to that of common carbon aerogel without the energy consumption step of high-temperature carbonization.
Description
Technical Field
The invention relates to preparation and application of carbon aerogel, in particular to preparation and application of graphene oxide carbon aerogel.
Background
Graphene (graphene) is a single-layer two-dimensional material of graphite (graphite) and is sp in a hexagonal honeycomb lattice arrangement2A planar layer of carbon atoms with a thickness of one atom, the spacing between the layers being 0.3354nm and havingThe metal is electrically conductive. Due to the strong Van der Waals force (Van der Waals force) between graphene layers in the graphite structure, it is very difficult to delaminate and disperse graphene. The Hummers method obtains graphene oxide, which is a hydrophilic carbon material with poor conductivity, and the principle is that a stacked layered graphite structure is oxidized by an oxidant, so that electron-delocalized carbon atoms generate functional groups through oxidation reaction to form the graphene oxide, and part of the carbon atoms in the structure are bonded by carbon-carbon double bonds (sp) in a planar structure2Hybrid domains) into a three-dimensional or non-planar structure of carbon-carbon single bond bonds (sp)3Hybrid domains) and the interpoly layers are functionalized to effectively open the interply spacing and delaminate the graphite material into graphene oxide.
The graphene manufacturing techniques include mechanical lift-off, epitaxial growth, chemical vapor deposition, and chemical lift-off. Although the mechanical exfoliation method and the epitaxial growth method can obtain graphene with good quality, neither method can synthesize graphene in a large area. The chemical vapor deposition process requires the use of expensive metal substrates at temperatures approaching thousands of degrees Celsius, and is mainly used for capacitor and energy storage materials. The chemical stripping method can effectively strip the nano-layered graphene which is similar to a monoatomic layer. For example: firstly weighing graphite powder, cooling for a period of time after pre-reaction, then adding a mixed solution of sodium nitrate, potassium permanganate, concentrated sulfuric acid and the like, and adding deionized water under ice bath for holding the temperature for several hours to carry out reaction; then, a large amount of deionized water and peroxide are used for stopping reaction, the mixed solution is washed until the mixed solution is statically precipitated, and then a large amount of deionized water is used for washing to obtain the nano flaky/layered graphene. Due to the stereo effect of the edge modified structure, a plurality of layers of modified graphene can be dispersed in partial solvent or polymerization monomer, so as to obtain a large-area modified graphene film. An electric double layer capacitor consisting of cellulose and carbon nanotubes, the component thickness being only a few tens of microns and being able to bend like paper. The electric double-layer capacitor is composed of a multi-wall carbon nano-tube which is formed on a cellulose membrane taking cellulose as a main component and is in a brush shape and two cellulose membranes, and has the electrostatic capacity of 22F/g, the maximum working voltage of 2.3V and the energy density of about 13 Wh/kg.
Nitrogen-doped activated carbon (NAC) can be prepared by one-step method to 2900m2High surface area per gram, nitrogen content up to 4 wt%, NAC has high specific capacitance of 129mA.h/g (185F/g) in organic electrolyte with current density of 0.4A/g, excellent rate capability and cycle stability, and capacity retention rate still reaches 76.3% after 8,000 cycles of test at 1.6A/g.
Graphene sheet-like porous activated carbon (GPAC) with high specific surface area is synthesized by using jicamaige as a precursor in a chemical activation method. In addition, the synthesized GPAC is used for a super capacitor and is subjected to electrochemical research with an electrode material for sensing catechin, the specific capacitance of the GPAC is 233F/g (the current density is 1.6A/g), the energy density of a symmetrical battery is 7.2W.h/kg, the GPAC has good sensitivity for sensing the catechin in a convection sensing process, and the GPAC has a wide linear range and a low detection line, and the values of the GPAC and the detection line are 7.2 muA/muM.cm22-368 μ M and 0.67 μ M.
Mixed metal or transition metal oxides have excellent stability, reliable conductivity and convenience of use and have been the most promising energy storage materials. CuMnO2The nano particles are successfully prepared by a simple hydrothermal method by virtue of a Cetyl Trimethyl Ammonium Bromide (CTAB) dispersing agent, have uniform quadrilateral appearance (25x25-35x35nm), excellent dispersibility and large specific surface area (56.9 m)2/g) and has an interparticle mesoporous structure. Both of these characteristics may provide benefits in supercapacitor applications. With CuMnO2The nano particles are used as a positive electrode and a negative electrode to assemble a quasi-solid-state symmetrical super capacitor, the device has good super capacitance performance, high specific capacitance (272F/g), maximum power density of 7.56kW/kg and excellent cycle stability of 18,000 continuous cycles.
In a high-performance electrochemical super capacitor consisting of a polyaniline (polyaniline, PANI)/reduced graphene oxide electrode and a cuprous ion active electrolyte, polyaniline/reduced graphene oxide hydrogel is used as an anode, and cuprous ions are used as a cathode active electrolyte, and because the specific capacitance of the polyaniline and the cuprous ions is very high, the average specific capacitance of a single electrode is up to 1,120F/g under 2.6A/g, and the cuprous ions are excellent cathode active electrolyte materials.
Carbon microporous structures are the main materials for energy storage applications of supercapacitors, while graphene is commonly used in ac line filter capacitors, and researchers have proposed that graphene has a filtering rate capability several orders of magnitude higher than microporous structure carbon materials. This ultra-fast rate performance is more achievable when the graphene sheets are vertically aligned, since the rate capability of the graphene electrodes is similar to that of microporous supercapacitors.
The all-carbon aerogel has extremely low density and large specific surface area, and has a plurality of application prospects in the aspects of environmental treatment, catalysts, electrode materials and the like. The all-carbon aerogel is an artificial foaming substance, is microscopically composed of conjugated carbon structures, has a three-dimensional interconnected porous network structure material, and has the density of about 0.16mg/cm3About one sixth of air, is currently the lightest structural material in the world. The all-carbon aerogel is a product obtained by drying and removing a solvent from a semisolid gel, is solid in appearance, contains a plurality of pores inside, and is filled with air, so that the density is extremely low.
Super capacitors are receiving attention because they have high power density, high specific capacitance, long shelf life, long cycle life, high discharge efficiency, excellent cycle stability, and the like, and can complete charging within a short time and maintain stable charging and discharging within a wide temperature range. By utilizing electron energy loss spectroscopy (electron energy loss spectroscopy) and electrical conductivity, it can be known that the carbon bond in the all-carbon aerogel has sp2The nature of the hybrid rail domain. When the all-carbon aerogel is squeezed by external force, the conductivity of the all-carbon aerogel obviously increases from 0.2S/m to 37S/m.
The commercial super capacitor mainly takes porous carbon as an active electrode material, but has relatively low energy density, which leads to the wide application of transition metal oxide and conductive polymer as the active electrode material, and the purpose of storing energy is achieved by oxidation reduction on the basis of electric energy storage; however, transition metal oxides and conductive polymers suffer from low charge-discharge cyclicity and rate.
Disclosure of Invention
The invention provides a preparation method of a graphene oxide carbon aerogel capacitance electrode, which comprises the following steps:
acid oxidation step: after graphite powder is acidified by strong acid and oxidized by strong oxidizer, polyethylene glycol is added to react to form a carbon aerogel solution, so that the distance between graphene layers is effectively expanded;
drying and forming: washing the carbon aerogel solution with alkali liquor, uniformly shaking, drying to remove water, and performing fire combustion at room temperature to obtain graphene oxide carbon aerogel;
an electrode pretreatment step: sequentially cleaning conductive glass with acetone, alcohol and deionized water for more than three times, standing, drying, and adhering graphene oxide carbon aerogel on the conductive glass;
and a capacitor electrode preparation step: coating a conductive polymer on the surface of the combination of the graphene oxide carbon aerogel and the conductive glass; or the combination of the graphene oxide carbon aerogel and the conductive glass is placed in an electroplating solution for electroplating.
The invention has the following effects:
1. the electrical conductivity of the carbon aerogel obtained by the invention is close to that of carbon aerogel obtained after phenolic resin carbonization, namely, the excellent electrical conductivity of common carbon aerogel can be achieved without the energy consumption step of high-temperature carbonization, and the electrical conductivity of the carbon aerogel can reach that of commercial graphene, so that the preparation cost is greatly reduced, and the industrial application value is improved.
2. The carbon aerogel obtained by the invention is mixed with conductive polymers, different nano graphene oxide electroplating solutions and other process parameters to prepare the graphene oxide carbon aerogel electric double layer and the pseudo capacitor electrode, so as to achieve the same capacitance value of the commercial graphene.
3. The invention shows that the microcrystalline crystalline phase structure of the carbon aerogel prepared by different process parameters, and the analysis of the grain size and the interlayer spacing (d-spacing) can be adjusted by different process parameters to change the conductive property.
4. The carbon aerogel prepared by the invention has the advantages that the capacitance of the electrode is reduced by less than 10 percent after hundreds of cyclic voltammetry scans in 3M KOH solution.
5. The capacitance of the electrode of the carbon aerogel prepared by the method in a 3M KOH solution is improved by more than ten times compared with that of the commercial graphene.
Drawings
Fig. 1 is a schematic flow chart illustrating a method for manufacturing a capacitor electrode according to an embodiment of the present invention.
Fig. 2 is a photograph showing the appearance of the graphene oxide carbon aerogel according to the present invention.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph showing the side surface of the graphene oxide carbon aerogel according to the present invention.
Fig. 4 is an X-ray diffraction (XRD) analysis diagram illustrating a crystal lattice of the graphene oxide carbon aerogel according to the present invention.
Fig. 5 is a graph of cyclic voltammetry results comparing electrochemical characteristics of the capacitive electrode of the present invention with those of the capacitive electrode made of commercial graphene.
Detailed Description
In order to make the aforementioned and/or other objects, features, and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below:
referring to fig. 1, the preparation of the capacitor electrode using carbon aerogel obtained by modifying nano graphite powder according to one embodiment of the present invention comprises the following steps: an acid oxidation step (S1), a dry forming and electrode pretreatment step (S2), a capacitor electrode preparation step (S3), wherein:
acid oxidation step (S1): after graphite powder with stacked layered graphene is acidified by strong acid and oxidized by strong oxidant, a small amount of polyethylene glycol is added and reacts at high temperature to form a carbon aerogel solution, and the concentration of the carbon aerogel solution is about 0.01-10.0 g/mL. In addition, the carbon aerogel solution contains solvents such as: water, deionized water, or alcohols to adjust the concentration of the graphite layer. The electron delocalized carbon atom in the carbon aerogel generates a keto group-C ═ O, a hydroxyl group-OH, an acid group-COOH, an amino group-NH2Or imino group (NH) and the like, so that part of carbon atoms are changed from a planar structure to a three-dimensional or non-planar structure, and the distance between layers can be effectively expanded, and thus the graphite material can be delaminated into flake or layered graphene.
Dry forming and electrode pretreatment step (S2): washing carbon aerogel solution with concentration of 0.01-10.0g/mL with 0.01-10.0g/mL alkali solution, shaking, freeze drying for several days to remove water, drying, and burning at room temperature under room pressure to obtain graphene oxide carbon aerogel (S21).
In addition, the alkali solution may be a strong base, a weak base, a quasi-alkali solution, a Bronsted base, or a Lewis base in an amount of 0.001 to 1,000 g/mL. In addition, freeze-drying may be replaced by other drying means, such as: supercritical drying or solvent extraction drying.
In this step, the conductive glass is sequentially washed with acetone, alcohol, and deionized water for more than three times, then left to stand and dry, the relevant carbon material is weighed and recorded, and then coated on a carbon tape to be adhered (S22). Thereafter, the combination of graphene oxide carbon aerogel and conductive glass was kept at room temperature for a while the dry weight of the carbon material actually coated was between 0.00001 and 10 g.
Capacitance electrode preparation step (S3): applying a conductive polymer having a concentration of 0.001-10.0g/mL to the surface of the assembly, drying the applied conductive polymer at a temperature of less than 100 ℃ for one night or more, and then performing electrochemical analysis (S31); or placing the combination in graphene oxide solution with the concentration of 0.001-100.0g/mL, electroplating for 1-120 minutes, drying at the temperature of less than 100 ℃ for more than one night, and then performing electrochemical analysis (S32). In addition, the conductive polymer may be a polymer blend of poly (3, 4-vinyldioxythiophene) -poly (4-styrenesulfonic acid) (PEDOT-PSS), Polythiophene (PT), polypyrrole (PPY), Polyaniline (PANI), poly (4-styrenesulfonic acid), Polyacetylene (PAC), or polyphenylacetylene (PPV). In addition, the graphene oxide solution may be replaced with other electroplating solutions, such as: a carbon-like solution, an inorganic carbon solution, or an organic carbon solution.
Referring to FIG. 2, the carbon aerogel is golden or black in appearance, can stand without a support, and can be moldedThe graphite has variable volume and shape, density lower than 0.02g/mL, corrugation, elastic deformation and restorability, and low Poisson's ratio. In addition, after burning, the carbon aerogel can reduce keto-C ═ O, hydroxyl-OH, acid group-COOH and amino-NH2Or imino group (NH) to increase the carbon atom structure.
Referring to fig. 3, the surface morphology of the carbon aerogel was confirmed by the wide corrugated board, which had no significant cracks and interstitial structures, and consisted of about 8-10 graphene layers.
Referring to fig. 4, the characteristic peak of the powdered graphite mainly appears at 26.5 degrees, which is the diffraction peak signal of the 002 crystal lattice arrangement of six ring carbon atoms of graphite, and the layer spacing is calculated to be about 0.340nm by Bragg's equation. The characteristic peak of graphene oxide and carbon aerogel mainly appears at about 9.4 degrees, which is the diffraction peak signal of the 001 crystal lattice arrangement of graphite six-ring carbon atoms. Compared with the powdered graphite, the spacing between the carbon aerogel layers is increased from 0.340nm to 0.940nm, the grain size is reduced from 39.4nm to 28nm, and the number of graphite layers is also reduced from 116 layers to 38 layers, so that the graphite interlayer structure in the carbon aerogel is obviously stripped and spread or delaminated.
Please refer to fig. 5, which is a graph of the cyclic voltammetry results of the capacitor electrode obtained by coating the conductive polymer. When a cyclic voltammetry test is carried out, cyclic voltammetry specific capacitance of-1.0-1.0V is applied to a 1-10M KOH electrolytic solution, and the capacitance electrode of the invention is seen to have more than twice of the cyclic voltammetry specific capacitance compared with the commercial graphene.
In addition, a capacitance electrode cyclic voltammetry test obtained by electroplating graphene oxide is carried out. In the process, the cyclic voltammetry specific capacitance of-1.2-1.2V is applied to the 1-10M KOH electrolytic solution, and the cyclic voltammetry specific capacitance is more than ten times higher than that of the commercial graphene.
However, those skilled in the art should realize that the above embodiments are illustrative only and not limiting to the present invention, and that changes and modifications to the above described embodiments are intended to fall within the scope of the appended claims, as long as they fall within the true spirit and scope of the present invention.
Claims (7)
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