CN113690059A - FeCo2O4// AC water system asymmetric photo-assisted supercapacitor and preparation method thereof - Google Patents
FeCo2O4// AC water system asymmetric photo-assisted supercapacitor and preparation method thereof Download PDFInfo
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- CN113690059A CN113690059A CN202110953562.8A CN202110953562A CN113690059A CN 113690059 A CN113690059 A CN 113690059A CN 202110953562 A CN202110953562 A CN 202110953562A CN 113690059 A CN113690059 A CN 113690059A
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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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
- H01G11/84—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to FeCo2O4// AC water system asymmetric photo-assisted supercapacitor and preparation method thereof. Belongs to the technical field of energy materials. The capacitor includes: in-situ growth of FeCo on foamed nickel by using foamed nickel as substrate2O4Taking the obtained material as a positive electrode material; coating active carbon AC on the foamed nickel by taking the foamed nickel as a substrate, and taking the obtained material as a negative electrode material; using 1M KOH solution as electrolyte, and assembling into FeCo under the irradiation of light2O4// AC water based asymmetric light assisted supercapacitors. The voltage window of the water system asymmetric photo-assisted supercapacitor prepared by the invention is 1.5V, and the specific capacitance after illuminationThe value is improved by 26.6%. Two of the devices are connected in series, and 4 red LED lamps can be lightened.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to FeCo2O4// AC water system asymmetric photo-assisted supercapacitor and preparation method thereof.
Background
With the continuous consumption of energy and the increasing deterioration of the environment, carbon neutralization has become a problem of general concern in countries around the world. Research into the development, utilization, and storage of renewable energy sources has been imminent. Super capacitors have irreplaceable characteristics such as high power density, fast charge-discharge capability, long cycle life and low maintenance cost, and are considered as potential energy storage devices in the fields of consumer electronics, electric vehicles and smart grids. Compared with the traditional capacitor, the super capacitor has higher capacitance and can release energy under higher power. However, the lower energy density makes it impossible to exert a larger energy storage effect.
Recently, the emergence of photo-assisted charging energy storage devices (photo-assisted supercapacitors) has provided an effective way for solar energy to participate in energy conversion and storage. A light-assisted supercapacitor, charged by electric energy and solar energy, and storing energy. In addition to electrical energy, photo-generated charge also contributes to the charging process, and thus, the capacitance and energy storage capacity of the light assisted supercapacitor increases under illumination. The charge and discharge process of the photo-assisted supercapacitor is similar to the principle of a common supercapacitor, and the only difference is that solar energy is utilized to induce the generation of photo-generated electrons. Semiconductor materials with photosensitivity and pseudocapacitance become the preferred electrodes for photo-assisted charging devices. Transition metal oxides (e.g., Co) due to low cost, environmental friendliness and higher activity3O4、Fe3O4) The method is widely used in the fields of super capacitors, lithium ion batteries, fuel cells, photocatalysis and the like. However, in order to improve the energy storage capacity, the photo-assisted supercapacitor electrode material should have high photogenerated hole-electron separation efficiency and long excited hole lifetime.
Disclosure of Invention
The invention aims to provide a method for making electrode material insensitive to light responseResulting in insufficient energy storage capacity, and provides FeCo2O4// AC water system asymmetric photo-assisted supercapacitor and preparation method thereof. The invention discloses a water system asymmetric photo-assisted supercapacitor prepared from a photosensitive material FeCo2O4As the positive electrode, activated carbon AC was used as the negative electrode. The voltage window is widened, and the energy storage capacity before and after illumination is obviously improved.
The technical scheme adopted by the invention is as follows: FeCo2O4The asymmetric photo-assisted supercapacitor of the AC water system takes foamed nickel as a substrate, and FeCo grows on the foamed nickel in situ2O4Taking the obtained material as a positive electrode material; coating active carbon AC on the foamed nickel by taking the foamed nickel as a substrate, and taking the obtained material as a negative electrode material; using 1M KOH solution as electrolyte, and assembling into FeCo under the irradiation of light2O4// AC water based asymmetric light assisted supercapacitors.
FeCo2O4The preparation method of the AC water system asymmetric photo-assisted supercapacitor comprises the following steps:
1) preparing a positive electrode material: FeSO (ferric oxide) is added4·7H2O、Co(NO3)2·6H2O、CO(NH2)2And NH4Dissolving F in distilled water, and stirring to fully dissolve to obtain a mixed solution; transferring the mixed solution into a high-pressure kettle, adding foamed nickel, carrying out hydrothermal reaction, and cooling to room temperature after the reaction is finished; taking out the foamed nickel, washing and drying to obtain FeCo grown in situ on the foamed nickel2O4Taking the obtained material as a positive electrode material;
2) preparing a negative electrode material: mixing active carbon AC, acetylene black and PVDF, adding a small amount of absolute ethyl alcohol, fully stirring, coating on foamed nickel, and tabletting to obtain a material serving as a negative electrode material;
3) using 1M KOH solution as electrolyte, wrapping the anode material and the cathode material, adding a layer of diaphragm in the middle, and assembling into FeCo under illumination2O4// AC water based asymmetric light assisted supercapacitors.
Further, the above-mentioned production method, step 1)In terms of mole ratio, FeSO4·7H2O:Co(NO3)2·6H2O:CO(NH2)2:NH4F＝1:2:5:2。
Further, in the above preparation method, step 1), the solid-to-liquid ratio is FeSO4·7H20.27g of distilled water: 30-50 mL.
Further, in the above preparation method, step 1), the hydrothermal reaction is carried out at 120 ℃ for 2-6 h.
Further, in the above preparation method, in step 1), the washing is washing with deionized water and absolute ethyl alcohol respectively; the drying is drying for 6-8h at 60-65 ℃.
Further, in the above preparation method, step 2), the activated carbon AC: acetylene black: PVDF is 8:1:1 by mass ratio.
Further, in the above preparation method, step 2), the amount of ethanol is 1mL per 10mg of the total mass of the activated carbon AC, the acetylene black and the PVDF.
Further, in the preparation method, step 2), the pressure is 10-15MPa during the tabletting treatment.
The FeCo provided by the invention2O4The application of the AC water system asymmetric light auxiliary super capacitor in energy storage.
Compared with the prior art, the invention has the following remarkable advantages:
1. according to the invention, FeCo is subjected to a hydrothermal method2O4Supported on a foamed nickel substrate to synthesize an integrated electrode. The synthesis method is simple, the price is low, and the use is safe.
2. In the present invention, FeCo having multiple oxidation states is selected2O4As a photosensitive electrode, the material is beneficial to carrier transmission and promotes quick and reversible Faraday reaction on the surface of the electrode. In addition, FeCo due to the presence of mixed oxidation states2O4Has better charge separation efficiency and can provide more active sites.
3. The invention utilizes FeCo2O4And AC assembled water system asymmetric lightThe voltage window of the auxiliary super capacitor can be widened to 1.5V. In practical application, two of the devices are connected in series to simulate sunlight irradiation, so that 4 red LED lamps can be lightened.
Drawings
FIG. 1 is FeCo prepared according to the present invention2O4The XRD pattern of the AC water system asymmetric light auxiliary supercapacitor positive electrode material.
FIG. 2 is FeCo prepared by the present invention2O4// schematic diagram of an AC water system asymmetric light assisted supercapacitor.
FIG. 3 is FeCo prepared by the present invention2O4v/AC Water System Voltage contribution of asymmetric light assisted supercapacitors.
FIG. 4 is FeCo prepared by the present invention2O4And// AC water system asymmetric light auxiliary supercapacitor before and after illumination, constant current charge and discharge curve under 1A/g.
FIG. 5 is FeCo prepared by the present invention2O4v/AC water system asymmetric photo-assisted supercapacitor specific capacitance value comparison graph under different current densities.
FIG. 6 is FeCo prepared by the present invention2O4V/photograph of the AC water system asymmetric light assisted supercapacitor lighting LED lamp under light.
Detailed Description
Example 1 FeCo2O4v/AC water system asymmetric light auxiliary super capacitor
The preparation method comprises
1. Preparation of cathode material
FeSO (ferric oxide) is added4·7H2O(0.27g，1mmol)、Co(NO3)2·6H2O(0.58g，2mmol)、CO(NH2)2(0.3, 5mmol) and NH4F (0.074g, 2mmol) was dissolved in 40mL of distilled water, and the solution was stirred until it was sufficiently dissolved to obtain a mixed solution.
The mixed solution was transferred to an autoclave and placed 1X 1.5cm2Taking foamed nickel with the size as a substrate, carrying out hydrothermal reaction for 6 hours at 120 ℃, and growing FeCo on the foamed nickel in situ2O4Cooling after the reaction is finishedCooling to room temperature, washing with deionized water and anhydrous ethanol for 3-5 times, and drying at 60 deg.C for 6 hr to obtain the final product as positive electrode material.
The XRD spectrum of the obtained cathode material is shown in figure 1, and the prepared sample has three strong peaks at 44.5 degrees, 51.9 degrees and 76.5 degrees, which correspond to the peaks of a foam nickel substrate (JCPDS No. 04-0850). The characteristic peaks at 23.7 °, 34.5 °, 39.0 °, 46.5 °, 56.0 °, 61.0 ° and 66.4 ° correspond to FeCo2O4The (111), (220), (311), (400), (511), (422) and (440) crystal planes of (a). Shows the successful synthesis of FeCo2O4And (3) a positive electrode material.
2. Preparation of negative electrode material
Mixing 8mg of activated carbon AC, 1mg of acetylene black and 1mg of PVDF, adding 1mL of anhydrous ethanol, stirring thoroughly, coating the mixture on a substrate of nickel foam at 1X 1.5cm2Drying the foam nickel with the size in an infrared drying box; subsequently, the resultant was treated with a tableting machine at 10MPa for 5 minutes, and the resultant material was used as a negative electrode material.
3. Assembly
As shown in fig. 2, 1M KOH was used as the electrolyte (1); in-situ growth of FeCo on foamed nickel by using foamed nickel (2) as a substrate2O4(3) The obtained material is used as a positive electrode material (4); taking foamed nickel (2) as a substrate, and coating a material obtained by activated carbon AC (5) as a negative electrode material (6); a layer of diaphragm (7) is added between the anode material (4) and the cathode material (6), and FeCo is assembled under illumination2O4// AC water based asymmetric light assisted supercapacitors.
Example 2 FeCo2O4Application of/AC water system asymmetric photo-assisted super capacitor in energy storage
Method (A)
FeCo prepared in example 12O4The AC water system asymmetric light auxiliary super capacitor uses a 500W xenon lamp equipped with an AM1.5 analog sunlight filter as a light source.
(II) detection
1、FeCo2O4V/voltage range of AC water system asymmetric photo-assisted supercapacitorDetermination of circumference
FIG. 3 shows 50mV s of a positive electrode material and a negative electrode material in a three-electrode system-1Cyclic voltammogram at sweep rate. The anode material FeCo of the water system asymmetric photo-assisted supercapacitor2O4The voltage window of the anode material AC is 0-0.5V, and the voltage window of the cathode material AC is-1-0V. In FeCo2O4The total voltage window obtained after the two electrodes are combined in the AC water system asymmetric photo-assisted supercapacitor can be expanded to 1.5V.
2、FeCo2O4Analysis of constant-current charge-discharge curve of asymmetric photo-assisted supercapacitor of AC water system
FIG. 4 is FeCo2O4The constant current charge-discharge curve chart of the AC water system asymmetric photo-assisted supercapacitor before and after illumination under the current density of 1A/g. It can be observed that after illumination, the charging and discharging time is obviously enhanced, and the specific capacitance value is improved.
3、FeCo2O4Specific capacitance performance analysis of AC water system asymmetric photo-assisted supercapacitor
The formula is calculated from the following specific capacitance C (F/g):
wherein, I: charge-discharge current (A)
Δ t: discharge time(s)
m: mass (g) of active material loaded on foam nickel
Δ V: charging and discharging voltage (V)
The specific capacitance values of the water system asymmetric photo-assisted supercapacitor before and after illumination are obtained through calculation, and are shown in fig. 5. Under the condition of 1A/g, the highest specific capacitance value can reach 157F/g after illumination, and is higher than 124F/g when the illumination is not performed. After illumination, the specific capacitance value is improved by 26.6 percent.
4、FeCo2O4Practical application of AC water system asymmetric photo-assisted supercapacitor
As shown in FIG. 6, two samples of example 1 were preparedFeCo prepared2O4The AC water system asymmetric light auxiliary super capacitor is connected in series, 4 red LED lamps can be lightened under the assistance of simulated sunlight, and further the fact that the LED lamp provided by the invention has a great practical application potential is proved.
Claims (10)
1. FeCo2O4The asymmetric photo-assisted supercapacitor is characterized in that foam nickel is used as a substrate, and FeCo grows on the foam nickel in situ2O4Taking the obtained material as a positive electrode material; coating active carbon AC on the foamed nickel by taking the foamed nickel as a substrate, and taking the obtained material as a negative electrode material; using 1M KOH solution as electrolyte, and assembling into FeCo under the irradiation of light2O4// AC water based asymmetric light assisted supercapacitors.
2. FeCo2O4The preparation method of the AC water system asymmetric photo-assisted supercapacitor is characterized by comprising the following steps:
1) preparing a positive electrode material: FeSO (ferric oxide) is added4·7H2O、Co(NO3)2·6H2O、CO(NH2)2And NH4Dissolving F in distilled water, and stirring to fully dissolve to obtain a mixed solution; transferring the mixed solution into a high-pressure kettle, adding foamed nickel, carrying out hydrothermal reaction, and cooling to room temperature after the reaction is finished; taking out the foamed nickel, washing and drying to obtain FeCo grown in situ on the foamed nickel2O4Taking the obtained material as a positive electrode material;
2) preparing a negative electrode material: mixing active carbon AC, acetylene black and PVDF, adding a small amount of absolute ethyl alcohol, fully stirring, coating on foamed nickel, and tabletting to obtain a material serving as a negative electrode material;
3) using 1M KOH solution as electrolyte, wrapping the anode material and the cathode material, adding a layer of diaphragm in the middle, and assembling into FeCo under illumination2O4// AC water based asymmetric light assisted supercapacitors.
3. Preparation according to claim 2The method is characterized in that in the step 1), FeSO is added according to the molar ratio4·7H2O:Co(NO3)2·6H2O:CO(NH2)2:NH4F＝1:2:5:2。
4. The method according to claim 2, wherein in the step 1), FeSO is added in a solid-to-liquid ratio4·7H20.27g of distilled water: 30-50 mL.
5. The method according to claim 2, wherein the hydrothermal reaction in step 1) is carried out at 120 ℃ for 2-6 h.
6. The method according to claim 2, wherein in step 1), the washing is washing with deionized water and absolute ethanol; the drying is drying for 6-8h at 60-65 ℃.
7. The preparation method according to claim 2, wherein in the step 2), the mass ratio of activated carbon AC to acetylene black to PVDF is 8:1: 1.
8. The method according to claim 2, wherein the ethanol is used in an amount of 1mL per 10mg of the sum of the mass of the activated carbon AC, the mass of the acetylene black and the mass of the PVDF in the step 2).
9. The production method according to claim 2, wherein in the step 2), the pressure in the tableting treatment is 10 to 15 MPa.
10. FeCo according to claim 12O4The application of the AC water system asymmetric light auxiliary super capacitor in energy storage.
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