CN113675003B - Preparation and application of kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material - Google Patents
Preparation and application of kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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Abstract
The invention discloses preparation and application of a kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material, and belongs to the field of new energy materials. The kelp is placed in a mixed solution of cobalt chloride and sodium dihydrogen phosphate, the kelp is soaked at room temperature to obtain the kelp loaded with metal cobalt, the kelp is frozen and stored, then the kelp is frozen and dried, then the kelp is carbonized and dried, then the kelp is placed in a hydrochloric acid solution, the kelp is soaked at room temperature, and then the kelp is washed, filtered and dried. The invention takes the kelp as the raw material, the kelp is a renewable resource, the source is wide, the cost is lower, the preparation process of the composite material is simple, the operation process is stable, and the composite material is clean and has no secondary pollution; the kelp is used as a source carbon-based material, and the composite material prepared by loading the transition metal phosphide is used as an electrode material of the supercapacitor, so that the conductivity of the kelp is effectively increased, and the kelp is excellent in pseudocapacitance property.
Description
Technical Field
The invention belongs to the field of new energy materials, and relates to preparation and application of a supercapacitor electrode material taking kelp as a source carbon-based material to load cobalt phosphide and a cobalt phosphate metal composite material.
Background
With the increasing demand of people for fossil fuels, the environmental crisis is gradually increased, and in addition, because of the wide use of new energy automobiles, portable electronic devices and the like, clean energy and energy storage devices are widely favored by people. Among them, the super capacitor has the characteristics of high power density, ultra-fast charge and discharge, good stability, long cycle life, cleanness, no pollution and the like, so the super capacitor is concerned as a high-efficiency electric energy storage device.
Among all the components of a supercapacitor, the electrode material is the key to its energy conversion. The carbon material is the electrode material with the highest commercialization degree at present, however, non-renewable raw materials such as coal and petroleum coke adopted for producing the traditional activated carbon are increasingly deficient, and the preparation processes of novel carbon materials such as graphene and carbon nanotubes are complex and the cost is high. Therefore, biomass is selected as a carbon-containing precursor, and the biomass-containing precursor is the best choice for electrode materials due to the characteristics of easy acquisition of raw materials, environmental friendliness, low cost and the like.
Disclosure of Invention
The invention aims to provide a preparation method and application of a kelp-derived porous carbon-loaded cobalt phosphide and cobalt phosphate metal composite supercapacitor electrode material.
A preparation method of a kelp-derived porous carbon-loaded cobalt phosphide and cobalt phosphate electrode material comprises the following process steps:
(1) Putting the kelp into a mixed solution of cobalt chloride and sodium dihydrogen phosphate, soaking for 8-12 h at room temperature, filtering the redundant solution to obtain the kelp (the kelp soaked in the mixed solution) loaded with metal cobalt, freezing and storing, and then freezing and drying;
(2) Carbonizing the kelp obtained in the step (1), and drying to obtain the carbonized kelp.
(3) And (3) placing the kelp obtained in the step (2) in a hydrochloric acid solution, soaking for 8-10 h at room temperature, washing, filtering and drying to obtain the kelp-derived porous carbon-loaded cobalt phosphide and cobalt phosphate electrode material (the composite material of cobalt phosphide and cobalt phosphate loaded by a carbon-based material taking the kelp as a source).
Based on the technical scheme, preferably, in the step (1), the proportion of the kelp to the deionized water in the mixed solution of cobalt chloride and sodium dihydrogen phosphate is 3-5 g:100mL.
Based on the technical scheme, preferably, in the step (1), the kelp is cut into blocks (3 +/-1 cm multiplied by 3 +/-1 cm), and then is soaked in a mixed solution of sodium dihydrogen phosphate and cobalt chloride.
Based on the above technical solution, preferably, in step (1), the mass concentration of cobalt chloride in the mixed solution of cobalt chloride and sodium dihydrogen phosphate is 0.5wt.% to 1.5wt.%, and the mass concentration of sodium dihydrogen phosphate is 2wt.% to 4wt.%.
Based on the above technical scheme, preferably, in the step (1), the preparation method of the mixed solution of cobalt chloride and sodium dihydrogen phosphate comprises: dissolving sodium dihydrogen phosphate and cobalt chloride in deionized water, and stirring for 5-10 min until the cobalt chloride and the sodium dihydrogen phosphate are completely dissolved to obtain a mixed solution of the cobalt chloride and the sodium dihydrogen phosphate.
Based on the above technical solution, preferably, in the step (1), the cryopreservation conditions are as follows: the temperature is minus 60 to minus 50 ℃, and the time is 8 to 12 hours; the conditions of freeze drying are as follows: the temperature is minus 70 to minus 50 ℃, the pressure is 0 to 50Pa, and the time is 10 to 12 hours.
Based on the above technical solution, preferably, in the step (2), the carbonization conditions are: the temperature is 700-800 ℃, and the heat preservation time is 1-2 h; the carbonization is carried out under the protection of nitrogen, the carbonization process adopts a tubular furnace for temperature programming, and the temperature is raised to the carbonization temperature within the speed range of 0.5-10 ℃ for min -1 。
Based on the above technical solution, preferably, in the step (3), the mass concentration of the hydrochloric acid solution is 0.5wt.% to 1wt.%.
Based on the technical scheme, preferably, in the step (3), the ratio of the kelp to the hydrochloric acid solution is 3-5 g:60mL to 80mL.
Based on the above technical solution, preferably, in the step (3), the liquid used in the washing is deionized water.
Based on the above technical scheme, the drying temperature in the steps (2) and (3) is preferably 50-80 ℃.
The kelp as a widely existing food resource has abundant alginic acid, amino acid and various trace elements, has a special layered porous structure and a large specific surface area, and can promote the interaction between an electrolyte and an electrode and optimize the storage and conversion efficiency of electric energy when being used as a carbon-based material and being prepared into the electrode by chelating with a transition metal phosphide.
The invention also relates to application of the porous carbon loaded cobalt phosphide and cobalt phosphate electrode material prepared by the method in the super capacitor.
Compared with the prior art, the invention has the advantages that:
(1) The invention takes the kelp as raw material, and the kelp is renewable resource, which has wide source and lower cost. The composite material has simple preparation process, stable operation process, cleanness and no secondary pollution, and meets the commercialization requirement when being used as the electrode material of the super capacitor.
(2) The porous carbon electrode material derived from kelp has a unique microstructure which is favorable for the charge transfer and mass transfer processes in the electrochemical process.
(3) According to the invention, kelp is taken as a source carbon-based material, and the composite material prepared by loading the transition metal phosphide is taken as the electrode material of the supercapacitor, so that the conductivity of the composite material is effectively increased, and the composite material shows excellent pseudocapacitance property.
Drawings
FIG. 1 is an X-ray diffraction pattern of the kelp-derived porous carbon-supported cobalt phosphide and cobalt phosphate metal composite material prepared in example 1 as an electrode material;
FIG. 2 is a scanning electron microscope chromatogram of the porous carbon-supported cobalt phosphide and cobalt phosphate metal composite material prepared in example 1 as an electrode material;
FIG. 3 shows that the porous carbon supported cobalt phosphide and cobalt phosphate metal composite material prepared in example 1 is used as an electrode material at 6 mol. L -1 Cyclic voltammograms at different scanning speeds in the KOH electrolyte;
FIG. 4 shows that the porous carbon supported cobalt phosphide and cobalt phosphate metal composite material prepared in example 1 is used as an electrode material at 6 mol. L -1 The constant current charge-discharge curve diagram under different current densities in the KOH electrolyte.
FIG. 5 shows that the porous carbon-supported cobalt phosphide and cobalt phosphate metal composite material derived from kelp prepared in example 1 is used as an electrode material at 6 mol. L -1 Ac impedance plot in KOH electrolyte.
FIG. 6 shows that the porous carbon-supported cobalt phosphide and cobalt phosphate metal composite material derived from kelp prepared in example 1 is used as an electrode material at 6 mol. L -1 Current density in KOH electrolyteThe degree of the silver paste is 10Ag -1 The cycle stability test chart of (1).
Detailed Description
The preparation of the carbon-based material loaded cobalt phosphide and cobalt phosphate metal composite material using kelp as a source, the preparation of the electrode material thereof and the electrochemical properties thereof are further described in detail by specific examples.
Example 1
1. Preparation of kelp-derived porous carbon-loaded cobalt phosphide and cobalt phosphate metal composite material
(1) 2g of sodium dihydrogen phosphate and 0.9g of cobalt chloride were added to 100mL of deionized water, and the mixture was stirred at room temperature for 10min until completely dissolved, thereby obtaining a mixed solution of sodium dihydrogen phosphate and cobalt chloride.
(2) Cutting 3.5g of kelp into small pieces (3 cm multiplied by 3 cm), soaking in a mixed solution of sodium dihydrogen phosphate and cobalt chloride for 10h, filtering to obtain kelp loaded with metal cobalt, freezing in a refrigerator at-50 ℃ for 10h, and then vacuum freeze-drying in a vacuum freeze-dryer at-60 ℃ and 10Pa for 12h.
(3) Subjecting the herba Zosterae Marinae obtained in step (2) to tubular furnace at 10 deg.C for 10min -1 And (4) heating to 700 ℃ by program, carbonizing, preserving heat for 2 hours, and then cooling to room temperature to obtain the carbonized kelp.
(4) Adding the kelp obtained in the step (3) into 80mL of 1wt.% hydrochloric acid solution, soaking for 10h, washing, filtering and carrying out vacuum drying at 80 ℃ for 10h to obtain the kelp-derived porous carbon-supported cobalt phosphide and cobalt phosphate metal composite material (Co) 2 P-Co 3 (PO 4 ) 2 @ KPC) as an electrode material for a supercapacitor.
FIG. 1 shows the electrode material (Co) of the supercapacitor prepared as described above 2 P-Co 3 (PO 4 ) 2 @ KPC), and different lattice planes corresponding to cobalt phosphide and cobalt phosphate seed crystals appear in the graph, so that the kelp is successfully loaded with cobalt phosphide and cobalt phosphate, and the electrode material of kelp-derived porous carbon loaded with cobalt phosphide and cobalt phosphate is obtained.
Fig. 2 is a scanning electron microscope atlas of the prepared supercapacitor electrode material, and the images (a) - (d) are scanning pictures with multiplying power of x 200, x 500, x 1000 and x 10000 respectively, so that the prepared electrode material can be observed to perfectly inherit the honeycomb porous structure special for kelp, the transmission path of electrolyte ions can be shortened, and the ions can be conveniently stored. And cobalt phosphide and cobalt phosphate nanoparticles (60-100 nm) were grown uniformly in each chamber. Therefore, the successful preparation of the electrode material of porous carbon loaded cobalt phosphide and cobalt phosphate derived from kelp can be proved.
2. Preparation of the electrodes
Grinding the prepared carbon-based material loaded cobalt phosphide and cobalt phosphate metal composite material taking kelp as a source into powder in an agate mortar, uniformly mixing 4mg of the powder, 0.5mg of acetylene black and 0.5mg of polytetrafluoroethylene, coating the mixture on foamed nickel (1 cm multiplied by 1 cm), drying the mixture in vacuum at the temperature of 60 ℃ for 10 hours, and tabletting the dried mixture for 2 minutes under the condition of 8MPa of a tabletting machine to obtain the test electrode.
3. Testing of electrochemical Performance
The prepared electrode is taken as a working electrode, a platinum wire is taken as a counter electrode, a saturated calomel electrode is taken as a reference electrode to form a three-electrode system, and the electrolyte is 6 mol.L -1 The KOH solution is used for carrying out electrochemical performance test under the voltage window range of-0.3-0.6V.
FIG. 3 shows that the electrode material of the super capacitor prepared in the way is at 6 mol.L -1 In the KOH electrolyte, the voltage window ranges from-0.3 to 0.6V, and the cyclic voltammetry Curves (CV) at different scanning speeds. The result proves that the CV curve shows a pair of oxidation-reduction peaks at all scanning speeds, the graph distortion degree of the CV curve is smaller along with the continuous increase of the scanning speed, and the prepared composite material has good double-capacity rate and is suitable for being used as a supercapacitor electrode material.
FIG. 4 shows that the electrode material of the super capacitor prepared in the way is at 6 mol.L -1 In the KOH electrolyte, the voltage window is-0.3 to 0.3V, and a constant current charge-discharge curve chart is obtained under different current densities. As can be seen from the graph, when the current density was 0.5A · g -1 The prepared electrode material achieves 2080.3 F.g -1 The specific capacitance of (d); when the current density is increased to 10A g -1 Electrode materialThe material can still maintain a higher specific capacitance of 1238.9 F.g -1 This demonstrates that the prepared composite material has excellent electrochemical properties, consistent with the CV curve test results of fig. 3.
FIG. 5 shows that the electrode material of the supercapacitor prepared in the step (A) is at 6 mol.L -1 In the KOH electrolyte of (1), an AC impedance diagram in a frequency range of 0.1 to 100 kHz. As can be seen from the figure, the charge transfer resistance of the composite material is small, and the slope of the linear part of the low-frequency region is small, so that the ionic diffusion resistance and the electron transfer speed of the composite material in the electrolyte are small, and the composite material has the potential of being used as an electrode material of a supercapacitor.
FIG. 6 shows that the electrode material of the supercapacitor prepared in the step (A) is at 6 mol.L -1 In the KOH electrolyte, the voltage window is-0.3 to 0.3V, and the current density is 10Ag -1 Lower cycle stability test chart. As can be seen from the figure, the capacity retention rate of the composite material can still reach 80.73 percent after 5000 cycles, which proves that the prepared composite material has high cycle life and potential of being used as an electrode material of a super capacitor.
The carbon-based material loaded cobalt phosphide and cobalt phosphate metal composite material taking kelp as a source shows high electrochemical capacitance behavior and excellent electrochemical performances such as good cycling stability, and therefore can be applied as a supercapacitor electrode material.
Claims (10)
1. A preparation method of a kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material is characterized by comprising the following process steps:
(1) Putting the kelp into a mixed solution of cobalt chloride and sodium dihydrogen phosphate, soaking for 8-12 h at room temperature to obtain the kelp loaded with metal cobalt, freezing for storage, and then freezing and drying;
(2) Carbonizing the kelp obtained in the step (1), and drying;
(3) And (3) placing the kelp obtained in the step (2) in a hydrochloric acid solution, soaking for 8-10 h at room temperature, washing, filtering and drying to obtain the kelp-derived porous carbon-loaded cobalt phosphide and cobalt phosphate electrode material.
2. The preparation method according to claim 1, wherein in the step (1), the mass concentration of the cobalt chloride in the mixed solution of the cobalt chloride and the sodium dihydrogen phosphate is 0.5wt.% to 1.5wt.%, and the mass concentration of the sodium dihydrogen phosphate is 2wt.% to 4wt.%.
3. The preparation method according to claim 1, wherein in the step (1), the ratio of the kelp to the deionized water in the mixed solution of cobalt chloride and sodium dihydrogen phosphate is 3-5 g:100mL.
4. The method according to claim 1, wherein in the step (1), the conditions for cryopreservation are: the temperature is minus 60 to minus 50 ℃, and the time is 8 to 12 hours; the conditions of freeze drying are as follows: the temperature is-70 to-50 ℃, the pressure is 0 to 50Pa, and the time is 10 to 12 hours.
5. The production method according to claim 1, wherein in the step (2), the carbonization conditions are: the temperature is 700-800 ℃, and the heat preservation time is 1-2 h.
6. The method according to claim 1, wherein in the step (2), the carbonization is performed under the protection of nitrogen gas, and the temperature is raised to the carbonization temperature at a rate of 0.5 to 10 ℃ for min -1 。
7. The preparation method according to claim 1, wherein in the step (3), the hydrochloric acid solution has a mass concentration of 0.5wt.% to 1wt.%.
8. The production method according to claim 1, wherein in the step (3), the ratio of the kelp to the hydrochloric acid solution is 3 to 5g:60mL to 80mL.
9. The method according to claim 1, wherein the drying temperature in steps (2) and (3) is 50 to 80 ℃.
10. Use of the porous carbon-loaded cobalt phosphide and cobalt phosphate electrode material derived from kelp prepared by the method according to any one of claims 1 to 9 in supercapacitors.
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| CN101774563A (en) * | 2010-01-08 | 2010-07-14 | 上海交通大学 | High-voltage positive electrode material used by lithium ion battery and preparation method thereof |
| CN109289894A (en) * | 2018-10-19 | 2019-02-01 | 浙江大学 | A kind of phosphatization cobalt/nitrogen mixes porous carbon composite catalytic material and its preparation method and application |
| CN109433240A (en) * | 2018-10-26 | 2019-03-08 | 济南大学 | A kind of nitrogen-doped carbon nano-array load iron phosphide/phosphatization cobalt preparation method |
| CN112657521A (en) * | 2020-11-20 | 2021-04-16 | 北京化工大学 | Preparation method of chromium-doped cobalt phosphide nanorod array grown on carbon cloth in situ |
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2021
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| CN101774563A (en) * | 2010-01-08 | 2010-07-14 | 上海交通大学 | High-voltage positive electrode material used by lithium ion battery and preparation method thereof |
| CN109289894A (en) * | 2018-10-19 | 2019-02-01 | 浙江大学 | A kind of phosphatization cobalt/nitrogen mixes porous carbon composite catalytic material and its preparation method and application |
| CN109433240A (en) * | 2018-10-26 | 2019-03-08 | 济南大学 | A kind of nitrogen-doped carbon nano-array load iron phosphide/phosphatization cobalt preparation method |
| CN112657521A (en) * | 2020-11-20 | 2021-04-16 | 北京化工大学 | Preparation method of chromium-doped cobalt phosphide nanorod array grown on carbon cloth in situ |
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