CN112951614A - Cobaltosic oxide @ reticular biomass carbon composite material and preparation method and application thereof - Google Patents
Cobaltosic oxide @ reticular biomass carbon composite material and preparation method and application thereof Download PDFInfo
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- 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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- 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
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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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- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- 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
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- H—ELECTRICITY
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- 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
Abstract
The invention belongs to the technical field of electrode materials, and particularly relates to a cobaltosic oxide @ reticular biomass carbon composite material and a preparation method and application thereof. The cobaltosic oxide @ reticulated biomass carbon composite material provided by the invention comprises reticulated biomass carbon and cobaltosic oxide nanoparticles loaded on the reticulated biomass carbon, wherein the reticulated biomass carbon has a three-dimensional network structure; the cobaltosic oxide nanoparticles are supported in the three-dimensional network structure of the reticulated biomass carbon. The results of the embodiment show that the specific capacitance of the cobaltosic oxide @ reticulated biomass carbon composite material modified foamed nickel electrode is 1212.4F/g at the highest under the current density of 0.5A/g, the capacity retention rate of the electrode after 4000 cycles under the current density of 2A/g is 95.99-98.96%, and the alternating current impedance test result shows that the charge transfer resistance of the electrode is 2.1-2.4 omega.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a cobaltosic oxide @ reticular biomass carbon composite material and a preparation method and application thereof.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristics of quick charge and discharge and the energy storage characteristic of the battery.
The biomass carbon is cheap, renewable, has an ordered microstructure, and is widely applied to multiple fields of water treatment, catalysis, energy storage and the like. Chinese patent CN108010749A discloses a preparation method of a kelp biomass charcoal-based supercapacitor electrode material, but the specific capacitance range of the obtained biomass charcoal supercapacitor electrode is only 180-250F/g.
The theoretical specific capacitance of the cobaltosic oxide is up to 3560F/g, and the cobaltosic oxide is a potential supercapacitor electrode material. Like other pseudo-capacitance electrode materials, the pseudo-capacitance electrode material is influenced by the conductivity, the size and the surface property of the pseudo-capacitance electrode material, and the specific capacitance of the cobaltosic oxide in practical application is far from a theoretical value, and Chinese patent CN104810162A discloses a preparation method of a titanium mesh in-situ grown layered cobaltosic oxide super capacitor electrode material, but no record is provided for improving the specific capacitance of the capacitor electrode material.
Disclosure of Invention
In view of the above, the invention provides a cobaltosic oxide @ reticulated biomass carbon composite material, and a preparation method and application thereof.
The invention provides a cobaltosic oxide @ reticulated biomass carbon composite material, which comprises reticulated biomass carbon and cobaltosic oxide loaded on the reticulated biomass carbon, wherein the reticulated biomass carbon has a three-dimensional network structure; the cobaltosic oxide nanoparticles are supported in the three-dimensional network structure of the reticulated biomass carbon.
Preferably, the specific surface area of the reticular biomass carbon is 1200-1700 m2The particle size of the cobaltosic oxide is 30-50 nm.
Preferably, the mass of the cobaltosic oxide and the reticular biomass carbon is (0.3-1.4): 1.
The invention provides a preparation method of cobaltosic oxide @ reticulated biomass carbon composite material in the technical scheme, which comprises the following steps:
mixing the reticular biomass carbon, cobalt salt and an organic solvent, and carrying out solvothermal reaction on the obtained mixed dispersion liquid to obtain a cobalt salt @ reticular biomass carbon precursor;
and calcining the cobalt salt @ reticulated biomass carbon precursor to obtain the cobaltosic oxide @ reticulated biomass carbon composite material.
Preferably, the mass ratio of the cobalt salt to the reticular biomass carbon is (0.25-1): 0.5; the cobalt salt is organic cobalt salt.
Preferably, the mass concentration of the reticular biomass carbon in the mixed dispersion liquid is 0.00625-0.025 g/mL;
the organic solvent is one or more of tert-heptane, ethanol, acetone, benzene and diethyl ether.
Preferably, the temperature of the solvothermal reaction is 100-150 ℃ and the time is 5-10 h.
Preferably, the calcining temperature is 350-500 ℃, the heat preservation time is 2-4 h, and the heating rate of heating to the calcining temperature is preferably 5-10 ℃/min.
Preferably, the preparation method of the reticular biomass carbon comprises the following steps:
mixing a biomass raw material and a strong alkali solution for alkaline etching to obtain an alkaline-etched biomass;
and carbonizing the alkaline-etched biomass in protective gas to obtain the reticular biomass carbon.
The invention provides an application of the cobaltosic oxide @ reticulated biomass carbon composite material in the technical scheme or the cobaltosic oxide @ reticulated biomass carbon composite material prepared by the preparation method in the technical scheme in a supercapacitor electrode material.
The invention provides a cobaltosic oxide @ reticulated biomass carbon composite material, wherein the reticulated biomass carbon has a three-dimensional network structure; the cobaltosic oxide nanoparticles are supported in the three-dimensional network structure of the reticulated biomass carbon. The microstructure of the reticular biomass carbon in the composite material provided by the invention is a three-dimensional network structure, is formed by curling and folding a porous two-dimensional carbon film, has a large specific surface area, is beneficial to loading cobaltosic oxide nanoparticles, and has the characteristics of a three-dimensional reticular structure, thereby effectively avoiding the agglomeration of the loaded cobaltosic oxide and being beneficial to improving the specific capacitance of the cobaltosic oxide in actual use. The results of the embodiment show that the specific capacitance of the cobaltosic oxide @ reticulated biomass carbon composite material modified foamed nickel electrode is 1212.4F/g at the highest under the current density of 0.5A/g, the capacity retention rate of the electrode after 4000 cycles under the current density of 2A/g is 95.99-98.96%, and the alternating current impedance test result shows that the charge transfer resistance of the electrode is 2.1-2.4 omega.
Drawings
FIG. 1 is a scanning electron micrograph of reticulated biomass carbon prepared in example 1;
FIG. 2 is a scanning electron microscope image of the cobaltosic oxide @ reticulated biomass carbon composite prepared in example 1;
FIG. 3 is an X-ray diffraction pattern of the tricobalt tetraoxide @ reticulated biomass carbon composite prepared in example 1;
FIG. 4 is an X-ray photoelectron spectrum of the cobaltosic oxide @ reticulated biochar composite prepared in example 1;
FIG. 5 is a core energy level region XPS spectrum of Co2p in the tricobalt tetraoxide @ reticulated biomass carbon composite prepared in example 1;
FIG. 6 is a core energy level region XPS spectrum of O1s in the tricobalt tetraoxide @ reticulated biomass carbon composite prepared in example 1;
FIG. 7 is a core energy level region XPS spectrum of C1s in a tricobalt tetraoxide @ reticulated biomass carbon composite prepared in example 1;
FIG. 8 is a plot of cyclic voltammetry for a scan using the cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode of example 1 as the working electrode;
FIG. 9 is a constant current charge and discharge graph of the Cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode of application example 1 scanned as a working electrode;
FIG. 10 is a graph of application example 1 cobaltosic oxide @ reticulated biomass carbon composite/nickel foam supercapacitor electrode cycling stability testing;
FIG. 11 is a Nyquist plot of the Cobaltosic oxide @ reticulated Biomass carbon composite/foamed nickel supercapacitor electrode of application example 1 as the working electrode;
FIG. 12 is a plot of cyclic voltammetry for a scan using the cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode of example 2 as the working electrode;
FIG. 13 is a constant current charge and discharge graph of an application example 2 CoO @ reticulated Biomass carbon composite/foam nickel supercapacitor electrode as a working electrode for scanning;
FIG. 14 is a graph of application example 2 cobaltosic oxide @ reticulated biomass carbon composite/nickel foam supercapacitor electrode cycling stability testing;
FIG. 15 is a Nyquist plot for the application of the cobaltosic oxide @ reticulated biomass carbon composite/nickel foam supercapacitor electrode of example 2 as the working electrode;
FIG. 16 is a plot of cyclic voltammetry for the scan using the Cobaltosic oxide @ reticulated biomass carbon composite/nickel foam supercapacitor electrode of application example 3 as the working electrode;
fig. 17 is a constant current charge-discharge curve graph of an application example 3 cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode as a working electrode for scanning;
FIG. 18 is a graph of application example 3 Cobaltosic oxide @ reticulated Biomass carbon composite/nickel foam supercapacitor electrode cycling stability testing;
fig. 19 is a Nyquist plot for the application example 3 cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode as the working electrode.
Detailed Description
The invention provides a cobaltosic oxide @ reticulated biomass carbon composite material, which comprises reticulated biomass carbon and cobaltosic oxide nanoparticles loaded on the reticulated biomass carbon, wherein the reticulated biomass carbon has a three-dimensional network structure; the cobaltosic oxide nanoparticles are supported in the three-dimensional network structure of the reticulated biomass carbon.
The composite material provided by the invention comprises reticular biomass carbon, wherein the biomass carbon has a three-dimensional network structure, and the three-dimensional network structure is formed by curling and folding a porous two-dimensional carbon film; the specific surface area of the reticular biomass carbon is preferably 1200-1700 m2(ii)/g, more preferably 1350 to 1650m2/g。
In the present invention, the method for producing reticulated biomass carbon preferably includes the steps of:
mixing a biomass raw material and a strong alkali solution for alkaline etching to obtain an alkaline-etched biomass;
and carbonizing the alkaline-etched biomass in protective gas to obtain the reticular biomass carbon.
In the present invention, the biomass raw material is preferably kelp; in the present invention, the biomass raw material is preferably subjected to a pretreatment, and in the present invention, the pretreatment preferably includes: the biomass raw material is washed, dried and crushed in sequence, wherein the washing is preferably water washing, the drying is not particularly required in the specific implementation process, and the crushing is preferably shearing; in the invention, the particle size of the biomass raw material is preferably 1-5 cm.
In the invention, the strong alkali solution is preferably a potassium hydroxide solution and/or a sodium hydroxide solution, and the mass concentration of the strong alkali solution is preferably 10-30%, and more preferably 15-25%.
In the invention, the dry weight mass of the biomass raw material and the volume ratio of the strong base solution are preferably (4-5) g: (7-10) mL.
The specific implementation process of mixing the biomass raw material and the strong alkali solution is not specially required, in the invention, the time of the alkaline etching is preferably 7-10 days, and the temperature of the alkaline etching is preferably room temperature.
In the present invention, it is preferable to perform post-treatment on the system obtained by alkaline etching to obtain an alkaline-etched biomass, and in the present invention, the post-treatment preferably includes: the method comprises the following steps of sequentially carrying out solid-liquid separation and drying, wherein the solid-liquid separation is preferably filtration, the solid product after the solid-liquid separation is preferably dried, the drying is preferably vacuum drying, the drying temperature is preferably 40-60 ℃, and the drying time is not particularly required so as to completely remove the moisture in the solid product.
After the alkaline-etched biomass is obtained, the alkaline-etched biomass is carbonized in protective gas to obtain the reticular biomass carbon.
In the invention, the carbonization temperature is preferably 700-1200 ℃, the carbonization time is 1-2 h, and the temperature rise speed for raising the temperature to the carbonization temperature is preferably 3-6 ℃/min, and more preferably 4-5 ℃/min; in the present invention, the shielding gas is preferably any one of nitrogen, argon and helium, and more preferably nitrogen. The flow rate of the protective gas is preferably 50-100 mL/min, and more preferably 60-80 mL/min.
According to the invention, most organic matters in the biomass raw material are removed through alkaline etching, a micro-framework structure in the original biomass raw material is reserved, and then a three-dimensional network structure formed by curling and folding a porous two-dimensional carbon film is obtained through carbonization, so that the biomass carbon film has the characteristic of large specific surface area.
The invention preferably carries out post-treatment on the solid product obtained after carbonization to obtain the reticular biomass carbon, and in the invention, the post-treatment preferably comprises washing, the washing is preferably water washing, and the invention has no special requirement on the washing times so as to wash the solid product to be neutral.
The composite material provided by the invention comprises cobaltosic oxide nanoparticles loaded in a three-dimensional network structure of the reticular biomass carbon, wherein the particle size of the cobaltosic oxide nanoparticles is preferably 30-50 nm, and more preferably 35-45 nm.
In the invention, the mass ratio of the cobaltosic oxide nanoparticles to the reticulated biomass carbon is preferably (0.3-1.4): 1, more preferably (0.66-1.5): 1.
the microstructure of the reticular biomass carbon in the composite material provided by the invention is a three-dimensional network structure, the specific surface area is large, the loading of cobaltosic oxide nano particles is facilitated, and the characteristics of the three-dimensional network structure effectively avoid the agglomeration of the loaded cobaltosic oxide and are beneficial to improving the specific capacitance of the cobaltosic oxide in actual use.
The invention provides a preparation method of cobaltosic oxide @ reticulated biomass carbon composite material in the technical scheme, which comprises the following steps:
mixing the reticular biomass carbon, cobalt salt and an organic solvent, and carrying out solvothermal reaction on the obtained mixed dispersion liquid to obtain a cobalt salt @ reticular biomass carbon precursor;
and calcining the cobalt salt @ reticulated biomass carbon precursor to obtain the cobaltosic oxide @ reticulated biomass carbon composite material.
The method comprises the steps of mixing the reticulated biomass carbon, the cobalt salt and the organic solvent, and carrying out solvothermal reaction on the obtained mixed dispersion liquid to obtain the cobalt salt @ reticulated biomass carbon precursor.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
In the present invention, the cobalt salt is preferably an organic cobalt salt, more preferably one or more of cobalt decanoate, cobalt neodecanoate, cobalt stearate, and cobalt naphthenate, and more preferably cobalt decanoate or cobalt neodecanoate.
The invention adopts the organic cobalt salt to realize large loading capacity on the reticular biomass carbon and the organic cobalt salt is pyrolyzed to generate the cobaltosic oxide.
In the invention, the mass ratio of the cobalt salt to the reticular biomass carbon is preferably (0.25-1): 0.5.
in the present invention, the organic solvent is preferably one or more of tert-heptane, ethanol, acetone, benzene and diethyl ether, more preferably tert-heptane, and in the present invention, the mass concentration of the reticulated biomass carbon in the mixed dispersion liquid is preferably 0.00625 to 0.025g/mL, more preferably 0.00825 to 0.020g/mL, and most preferably 0.010 to 0.015 g/mL.
In the invention, the mixing of the reticular biomass carbon, the organic cobalt salt and the organic solvent is preferably carried out under the condition of stirring, and the invention has no special requirement on the specific implementation process of the stirring.
In the invention, the temperature of the solvothermal reaction is preferably 100-150 ℃, more preferably 120-130 ℃, and the time of the solvothermal reaction is preferably 5-10 h, more preferably 5.5-8 h; in a specific embodiment of the invention, the solvothermal reaction is carried out in a reaction kettle.
After the cobalt salt @ reticulated biomass carbon precursor is obtained, the cobalt salt @ reticulated biomass carbon precursor is preferably calcined to obtain the cobaltosic oxide @ reticulated biomass carbon composite material.
In the invention, the calcination temperature is preferably 350-500 ℃, more preferably 400-450 ℃, the heat preservation time is preferably 2-4 h, more preferably 2.5-3 h, and the heating rate of heating to the calcination temperature is preferably 5-10 ℃/min, more preferably 6-8.5 ℃/min; in a particular embodiment of the invention, the calcination is carried out in a muffle furnace.
The invention provides an application of the cobaltosic oxide @ reticulated biomass carbon composite material in the technical scheme or the cobaltosic oxide @ reticulated biomass carbon composite material prepared by the preparation method in the technical scheme in a supercapacitor electrode material.
In the invention, the supercapacitor electrode material preferably comprises the following components in parts by mass:
60-90 parts of cobaltosic oxide @ mesh biomass carbon composite material; 5-20 parts of a conductive agent; 5-20 parts of a binder;
the supercapacitor electrode material comprises, by mass, 60-90 parts of cobaltosic oxide @ reticulated biomass carbon composite material, preferably 80 parts of cobaltosic oxide @ reticulated biomass carbon composite material.
By taking cobaltosic oxide @ reticular biomass carbon composite material as a reference, the supercapacitor electrode material provided by the invention comprises 5-20 parts of a conductive agent, preferably 10 parts. In the present invention, the conductive agent preferably includes acetylene black and/or carbon black Super-p.
By taking cobaltosic oxide @ reticular biomass carbon composite material as a reference, the supercapacitor electrode material provided by the invention comprises 5-20 parts of adhesive, preferably 10 parts. In the present invention, the binder is preferably polyvinylidene fluoride and/or polytetrafluoroethylene.
The invention provides a preparation method for preparing a supercapacitor electrode by using the supercapacitor electrode material in the technical scheme, which comprises the following steps:
mixing cobaltosic oxide @ mesh biomass carbon composite material, conductive agent, adhesive and polar organic solvent to obtain electrode slurry;
and coating the electrode slurry on the surface of a conductive plate, and drying and tabletting to obtain the supercapacitor electrode.
In the invention, the polar organic solvent is preferably N-methyl-2-pyrrolidone, and the dosage of the polar organic solvent is not particularly required; the invention has no special requirements on the specific implementation process of mixing so as to realize uniform mixing of the materials.
After obtaining the electrode slurry, the invention preferably coats the electrode slurry on the surface of the conductive plate, and then carries out drying and tabletting to obtain the supercapacitor electrode. In the present invention, the conductive plate is preferably nickel foam, and the size of the conductive plate is preferably 1cm × 1 cm; the invention has no special requirements on the thickness of the coating and the specific implementation process of the coating, and the conventional coating thickness and operation which are well known to the technical personnel in the field can be adopted; in the invention, the drying temperature is preferably 70-120 ℃, and more preferably 80-100 ℃; the drying time is preferably 8-12 h, and more preferably 10 h; in the present invention, the pressure of the tablet is preferably 8 MPa; the invention has no special requirements on the specific implementation process of the stamping.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Cleaning and airing kelp, cutting the kelp into pieces, weighing 50g of the cut kelp, soaking the kelp in 70mL of 20 wt% KOH solution, carrying out alkaline etching for 7 days, taking out the kelp, carrying out vacuum drying on the obtained alkaline-etched kelp at 60 ℃, then carbonizing the kelp in a 800 ℃ nitrogen-filled quartz tube furnace for 2 hours, and washing a carbonized product to be neutral to obtain a net-shaped biomass carbon material;
adding 0.5g of cobalt neodecanoate and 0.5g of reticular biomass carbon material into 40mL of tert-heptane, and stirring for 1 hour to form a uniformly mixed dispersion liquid; transferring the mixed dispersion liquid into a reaction kettle to perform solvothermal reaction at 140 ℃, cooling and collecting reaction filter residue after 5 hours of reaction, washing the filter residue with water, performing vacuum drying at 60 ℃, placing the filter residue into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, and performing heat preservation and calcination for 3 hours to obtain cobaltosic oxide @ reticular biomass carbon composite material;
FIG. 1 is a scanning electron microscope characterization of the prepared reticular biomass carbon composite material, wherein (A) in FIG. 1 is an electron microscope photograph at an enlargement of 1 μm, and (B) in FIG. 1 is an electron microscope photograph at an enlargement of 100 nm; as can be seen from FIG. 1, the reticular biomass carbon prepared by the present example is a three-dimensional network structure formed by rolling and folding a porous two-dimensional carbon film, and the specific surface area of the reticular biomass carbon is 1516.76m2/g；
FIG. 2 is a scanning electron microscope image of the prepared cobaltosic oxide @ reticulated biomass carbon composite; as can be seen from (a) in fig. 2, the cobaltosic oxide @ reticulated biomass carbon composite material prepared in the present example has the cobaltosic oxide uniformly supported in the three-dimensional network structure of the reticulated biomass carbon material, and as can be seen from (B) in fig. 2, the particle size of the cobaltosic oxide @ reticulated biomass carbon composite material prepared in the present example is 50 nm;
fig. 3 is an X-ray diffraction spectrum diagram of the prepared cobaltosic oxide @ reticulated biomass carbon composite material, and from fig. 3, it can be obtained that cobalt element is loaded on the biomass carbon material in a cobaltosic oxide cubic crystal form.
Fig. 4 is an X-ray photoelectron spectrum of the prepared cobaltosic oxide @ reticulated biomass carbon composite material, and from fig. 4, it can be determined that the main constituent elements of the composite material are carbon, cobalt and oxygen;
FIG. 5 is a core energy level region XPS spectrum of Co2p in the prepared cobaltosic oxide @ reticulated biomass carbon composite, showing from FIG. 5 that the two main peaks at 780.6eV and 796.6eV correspond to Co2p3/2And Co2p1/2The spin orbit peaks of (a), the spin energies are 16.0eV apart, while the satellite peaks at 786.4eV and 803.5eV are characteristic peaks of the cobaltosic oxide phase, confirming the presence of cobaltosic oxide in the composite material;
FIG. 6 is a core level region XPS spectrum of O1s in the prepared cobaltosic oxide @ reticulated biomass carbon composite, splitting from FIG. 6 into three peaks at 529.2eV, 531.2eV, and 533.6eV, respectively, indicating the presence of Co-O, C ═ O and C-OH/C-O-C;
fig. 7 is a core level region XPS spectrum of C1s in the prepared cobaltosic oxide @ reticulated biomass carbon composite, showing from fig. 7 the binding energies corresponding to sp 2C, sp 3C, C-O bond and C ═ O bond at 284.7eV,285.6eV,288.7eV and 289.6eV, respectively, for the four splitting peaks.
Application example 1
The cobaltosic oxide @ reticulated biomass carbon composite material prepared in example 1 was mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, mixed, slurried with N-methyl-2-pyrrolidone, and coated on a substrate having an area size of 1X 1cm2The foamed nickel substrate coated with the slurry is dried at the constant temperature of 80 ℃ for 10 hours and then placed in a tabletting machineAnd pressing the carbon composite material into a cobaltosic oxide @ reticular biomass carbon composite material/foamed nickel supercapacitor electrode on the machine under the pressure of 8 MPa.
Test example 1
The cobaltosic oxide @ mesh biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 1 is used as a working electrode, a mercury/mercury oxide electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the three electrodes are inserted into 6mol/L KOH solution to perform cyclic voltammetry, constant current charging and discharging, cyclic stability of the electrode, alternating current impedance and other electrochemical performance tests.
Fig. 8 shows cyclic voltammetry curves of cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode in application example 1 as a working electrode at scan rates of 0.01V/s, 0.04V/s, 0.07V/s and 0.10V/s in an electrochemical window of-0.2-0.6V, and it can be obtained from fig. 8 that the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 1 has two pairs of redox peaks on the cyclic voltammetry curves at different scan rates, and the peak current increases with the increase of the scan rate.
Fig. 9 is a constant current charging and discharging curve of the cobaltosic oxide @ mesh biomass carbon composite material/foamed nickel supercapacitor electrode in application example 1 as a working electrode in an electrochemical window of 0-0.5V, where the current density is 0.5A/g, 1.0A/g, 1.5A/g, 2.0A/g and 2.5A/g, and it can be obtained from fig. 9 that the cobaltosic oxide @ mesh biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 1 is subjected to constant current charging and discharging under different current densities, the smaller the current density is, the longer the discharging time is, and the nonlinear constant current discharging curve shows the pseudo-capacitance performance of cobaltosic oxide in the composite material.
Fig. 10 is a graph showing the result of detecting the electrode stability of the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode as the working electrode in application example 1, and it can be seen from fig. 10 that the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 1 has a capacitance retention rate of 98.96% after 4000 cycles at a current density of 2A/g, and has high stability.
FIG. 11 is a graph showing the results of AC impedance measurements of electrodes using the Cobaltosic oxide @ reticulated Biomass carbon composite/foamed nickel supercapacitor electrode of application example 1 as the working electrode, and it can be seen from FIG. 11 that the Cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode prepared in application example 1 was used at 10-2～105The linear slope of the Nyquist curve in the frequency range of HZ in the low frequency region is very large, because the reticular biomass carbon in the composite material shows stronger characteristics of the double electric layer capacitor, and the intersection value of the curve and the real part Z' is 2.1 omega, which proves that the ohmic internal resistance of the prepared electrode material is relatively small.
Example 2
Cleaning and airing kelp, cutting the kelp into pieces, weighing 50g of the cut kelp, soaking the kelp in 70mL of 30 wt% KOH solution, carrying out alkaline etching for 10 days, taking out the kelp, drying the obtained alkaline-etched kelp at 60 ℃ in vacuum, then carbonizing the kelp in a 800 ℃ nitrogen-filled quartz tube furnace for 2 hours, and washing a carbonized product to be neutral to obtain a net-shaped biomass carbon material;
adding 1.0g of cobalt neodecanoate and 0.5g of reticular biomass carbon material into 40mL of tert-heptane, and stirring for 1 hour to form a uniformly mixed dispersion liquid; and transferring the mixed dispersion liquid into a reaction kettle to perform solvothermal reaction at 120 ℃, cooling and collecting reaction filter residue after 8 hours of reaction, washing the filter residue with water, performing vacuum drying at 60 ℃, placing the filter residue into a muffle furnace, heating to 450 ℃ at a heating rate of 10 ℃/min, and performing heat preservation and calcination for 3 hours to obtain the cobaltosic oxide @ mesh biomass carbon composite material.
Application example 2
The cobaltosic oxide @ reticulated biomass carbon composite material prepared in example 2 was mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, and after mixing, the mixture was slurried with N-methyl-2-pyrrolidone and coated on a substrate having an area size of 1X 1cm2After the foamed nickel substrate coated with the slurry is dried at the constant temperature of 80 ℃ for 10 hours, the foamed nickel substrate is placed on a tablet press and is pressed under the pressure of 8MPa to form the cobaltosic oxide @ reticular biomass carbon composite material/foamed nickel supercapacitor electrode.
Test example 2
The cobaltosic oxide @ mesh biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 2 is used as a working electrode, a mercury/mercury oxide electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the three electrodes are inserted into 6mol/L KOH solution to perform cyclic voltammetry, constant current charging and discharging, cyclic stability of the electrode, alternating current impedance and other electrochemical performance tests.
Fig. 12 shows the cyclic voltammetry curves of the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode in application example 2 as a working electrode at the scan rates of 0.01V/s, 0.04V/s, 0.07V/s and 0.10V/s in an electrochemical window of-0.2-0.6V, and it can be seen from fig. 12 that the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 2 has two pairs of redox peaks on the cyclic voltammetry curves at different scan rates, and the peak current increases with the increase of the scan rate.
Fig. 13 is a constant current charging and discharging curve when the cobaltosic oxide @ mesh biomass carbon composite material/foamed nickel supercapacitor electrode in application example 2 is used as a working electrode and the current density is 0.5A/g, 1.0A/g, 1.5A/g, 2.0A/g and 2.5A/g in an electrochemical window of 0-0.5V, which can be obtained from fig. 13.
Fig. 14 is a graph showing the result of electrode stability performance test of the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode as the working electrode in application example 2, and it can be seen from fig. 14 that the capacity retention ratio of the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 2 after 4000 cycles at a current density of 2A/g is 95.99%, and the stability is high.
FIG. 15 is a graph showing the results of the AC impedance detection of the working electrode made of Cobaltosic oxide @ reticulated Biomass carbon composite/foamed nickel supercapacitor electrode in application example 2, and it can be seen from FIG. 15 that Cobaltosic oxide prepared in application example 2The @ mesh biomass carbon composite/foam nickel supercapacitor electrode is 10-2～105The linear slope of the Nyquist curve in the frequency range of HZ in the low frequency region is very large, because the reticular biomass carbon in the composite material shows stronger characteristics of the double electric layer capacitor, and the intersection value of the curve and the real part Z' is 2.4 omega, which proves that the ohmic internal resistance of the prepared electrode material is relatively small.
Example 3
Cleaning and airing kelp, cutting the kelp into pieces, weighing 50g of the cut kelp, soaking the kelp in 70mL of 30 wt% KOH solution, carrying out alkaline etching for 10 days, taking out the kelp, carrying out vacuum drying on the obtained alkaline-etched kelp at 60 ℃, then carbonizing the kelp in a 800 ℃ nitrogen-filled quartz tube furnace for 2 hours, and washing a carbonized product to be neutral to obtain a net-shaped biomass carbon material;
adding 0.25g of cobalt neodecanoate and 0.5g of reticular biomass carbon material into 40mL of tert-heptane, and stirring for 1 hour to form a uniformly mixed dispersion liquid; and transferring the mixed dispersion liquid into a reaction kettle to perform solvothermal reaction at 140 ℃, cooling and collecting reaction filter residue after 5 hours of reaction, washing the filter residue with water, performing vacuum drying at 60 ℃, placing the filter residue into a muffle furnace, heating to 400 ℃ at the heating rate of 8 ℃/min, and performing heat preservation and calcination for 3 hours to obtain the cobaltosic oxide @ reticular biomass carbon composite material.
Application example 3
The cobaltosic oxide @ reticulated biomass carbon composite material prepared in example 3 was mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, and after mixing, the mixture was slurried with N-methyl-2-pyrrolidone and coated on a substrate having an area size of 1X 1cm2After the foamed nickel substrate coated with the slurry is dried at the constant temperature of 80 ℃ for 10 hours, the foamed nickel substrate is placed on a tablet press and is pressed under the pressure of 8MPa to form the cobaltosic oxide @ reticular biomass carbon composite material/foamed nickel supercapacitor electrode.
Test example 3
The cobaltosic oxide @ mesh biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 3 is used as a working electrode, a mercury/mercury oxide electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the three electrodes are inserted into 6mol/L KOH solution to perform cyclic voltammetry, constant current charging and discharging, cyclic stability of the electrode, alternating current impedance and other electrochemical performance tests.
Fig. 16 is a cyclic voltammetry curve of the cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode in application example 3 as a working electrode at scan rates of 0.01V/s, 0.04V/s, 0.07V/s and 0.10V/s in an electrochemical window of-0.2-0.6V, which can be obtained from fig. 16, and the cobaltosic oxide @ reticulated biomass carbon composite/foamed nickel supercapacitor electrode prepared in application example 3 has two pairs of redox peaks on the cyclic voltammetry curve at different scan rates, and the peak current increases with the increase of the scan rate.
Fig. 17 is a constant current charging and discharging curve of the cobaltosic oxide @ mesh biomass carbon composite material/foamed nickel supercapacitor electrode in application example 3 as a working electrode in an electrochemical window of 0-0.5V, where the current density is 0.5A/g, 1.0A/g, 1.5A/g, 2.0A/g, and 2.5A/g, which can be obtained from fig. 13.
Fig. 18 is a graph showing the result of electrode stability performance test of the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode as the working electrode in application example 3, and it can be obtained from fig. 14 that the capacity retention ratio of the cobaltosic oxide @ reticulated biomass carbon composite material/foamed nickel supercapacitor electrode prepared in application example 3 after 4000 cycles at a current density of 2A/g is 97.47%, and the stability is high.
FIG. 19 is a graph showing the results of AC impedance measurements of electrodes using the Cobaltosic oxide @ reticulated biomass carbon composite/nickel foam supercapacitor electrode of application example 3 as the working electrode, and it can be seen from FIG. 19 that the Cobaltosic oxide @ reticulated biomass carbon composite/nickel foam supercapacitor electrode prepared in application example 3 was at 10-2～105The slope of the line in the low frequency region of the Nyquist curve in the frequency range of HZ is very large, because the reticulated biomass carbon in the composite material exhibits a strong double effectThe electric layer capacitor is characterized in that the intersection value of the curve and the real part Z' is 2.3 omega, which proves that the ohmic internal resistance of the prepared electrode material is smaller.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A cobaltosic oxide @ reticulated biomass carbon composite comprising reticulated biomass carbon and cobaltosic oxide nanoparticles supported on the reticulated biomass carbon, the reticulated biomass carbon having a three-dimensional network structure; the cobaltosic oxide nanoparticles are supported in the three-dimensional network structure of the reticulated biomass carbon.
2. The cobaltosic oxide @ reticulated biomass carbon composite material as claimed in claim 1, wherein the reticulated biomass carbon has a specific surface area of 1200-1700 m2The particle size of the cobaltosic oxide nanoparticles is 30-50 nm.
3. The cobaltosic oxide @ reticulated biochar composite material as claimed in claim 1 or 2, wherein the mass of the cobaltosic oxide nanoparticles and reticulated biochar is (0.3-1.4): 1.
4. The preparation method of the cobaltosic oxide @ reticulated biomass carbon composite material as claimed in any one of claims 1 to 3, comprising the following steps:
mixing the reticular biomass carbon, cobalt salt and an organic solvent, and carrying out solvothermal reaction on the obtained mixed dispersion liquid to obtain a cobalt salt @ reticular biomass carbon precursor;
and calcining the cobalt salt @ reticulated biomass carbon precursor to obtain the cobaltosic oxide @ reticulated biomass carbon composite material.
5. The preparation method according to claim 4, wherein the mass ratio of the cobalt salt to the reticulated biomass carbon is (0.25-1): 0.5; the cobalt salt is organic cobalt salt.
6. The production method according to claim 4 or 5, wherein the mass concentration of the reticulated biomass carbon in the mixed dispersion liquid is 0.00625 to 0.025 g/mL;
the organic solvent is one or more of tert-heptane, ethanol, acetone, benzene and diethyl ether.
7. The preparation method according to claim 4, wherein the temperature of the solvothermal reaction is 100-150 ℃ and the time is 5-10 h.
8. The preparation method according to claim 4, wherein the calcination temperature is 350-500 ℃, the holding time is 2-4 h, and the heating rate of heating to the calcination temperature is preferably 5-10 ℃/min.
9. The method for preparing reticulated biomass carbon according to claim 4, comprising the steps of:
mixing a biomass raw material and a strong alkali solution for alkaline etching to obtain an alkaline-etched biomass;
and carbonizing the alkaline-etched biomass in protective gas to obtain the reticular biomass carbon.
10. The cobaltosic oxide @ reticulated biomass carbon composite material as defined in any one of claims 1 to 3 or obtained by the preparation method as defined in any one of claims 4 to 9 is applied to an electrode material.
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