CN113675003A - 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
- Publication number
- CN113675003A CN113675003A CN202110955638.0A CN202110955638A CN113675003A CN 113675003 A CN113675003 A CN 113675003A CN 202110955638 A CN202110955638 A CN 202110955638A CN 113675003 A CN113675003 A CN 113675003A
- Authority
- CN
- China
- Prior art keywords
- kelp
- cobalt
- preparation
- electrode material
- phosphide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 241000512259 Ascophyllum nodosum Species 0.000 title claims abstract description 63
- 239000007772 electrode material Substances 0.000 title claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 32
- 239000010941 cobalt Substances 0.000 title claims abstract description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910000152 cobalt phosphate Inorganic materials 0.000 title claims abstract description 30
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 16
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 16
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000005138 cryopreservation Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 17
- 239000003575 carbonaceous material Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002905 metal composite material Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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 a supercapacitor electrode material, so that the conductivity of the composite material is effectively increased, and the composite material shows excellent pseudocapacitance properties.
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 a cobalt phosphide and cobalt phosphate metal composite material.
Background
With the increasing demand of people for fossil fuels, the environmental crisis is also 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, the biomass is selected as the carbon-containing precursor, and the biomass-containing precursor is the best choice for the electrode material due to the characteristics of easy raw material acquisition, environmental friendliness, low cost price 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 hours at room temperature, washing, filtering and drying to obtain the kelp-derived porous carbon-loaded cobalt phosphide and cobalt phosphate electrode material (a composite material with kelp as a source carbon-based material loaded with cobalt phosphide and cobalt phosphate).
Based on the technical scheme, preferably, in the step (1), the proportion of the kelp to deionized water in the mixed solution of cobalt chloride and sodium dihydrogen phosphate is 3-5 g: 100 mL.
Based on the technical scheme, preferably, in the step (1), the kelp is cut into pieces (3 +/-1 cm multiplied by 3 +/-1 cm), and then the pieces are soaked in the 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 0.5 wt.% to 1.5 wt.%, and the mass concentration of sodium dihydrogen phosphate is 2 wt.% to 4 wt.%.
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: and dissolving sodium dihydrogen phosphate and cobalt chloride in deionized water, and stirring for 5-10 min until the cobalt chloride and the cobalt chloride 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-60 to-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.
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 temperature is raised by adopting a tube furnace program in the carbonization process, and the speed range of raising the temperature to the carbonization temperature is 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 0.5 wt.% to 1 wt.%.
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 80 mL.
Based on the above technical scheme, preferably, in the step (3), the liquid used in the washing is deionized water.
Based on the technical scheme, preferably, in the steps (2) and (3), the drying temperature is 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 kelp derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material prepared by the method in a super capacitor.
Compared with the prior art, the invention has the advantages that:
(1) the invention takes the kelp as the raw material, and the kelp is a renewable resource, so the source is wide and the cost is lower. 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 unique microstructure of the porous carbon electrode material derived from kelp is beneficial to the charge transfer and mass transfer processes of the electrochemical process.
(3) According to the invention, kelp is taken as a source carbon-based material, and a composite material prepared by loading transition metal phosphide is taken as a supercapacitor electrode material, so that the conductivity of the composite material is effectively increased, and the composite material shows excellent pseudocapacitance properties.
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 atlas of the kelp-derived porous carbon-supported cobalt phosphide and cobalt phosphate metal composite material prepared in example 1 as an electrode material;
FIG. 3 is a drawing showing a structure of example 1The prepared kelp derived porous carbon loaded cobalt phosphide and cobalt phosphate metal composite material is used as an electrode material at 6 mol.L-1Cyclic voltammograms of the KOH electrolyte at different scanning speeds;
FIG. 4 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-1The 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-1Ac impedance diagram 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-1The current density of the KOH electrolyte is 10Ag-1The 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 (3cm multiplied by 3cm), 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 vacuum freeze-drying in a vacuum freeze-dryer at-60 ℃ and 10Pa for 12 h.
(3) Subjecting the herba Zosterae Marinae obtained in step (2) to tubular furnace at 10 deg.C for 10min-1And (4) raising the temperature to 700 ℃ by program, carbonizing, preserving the heat for 2h, and then cooling to room temperature to obtain the carbonized kelp.
(4) Adding the kelp obtained in the step (3) into 80mL of 1 wt.% hydrochloric acid solution, soaking for 10h, washing, filtering, and vacuum-drying at 80 ℃ for 10h to obtain the kelp-derived porous carbon-supported cobalt phosphide and cobalt phosphate metal composite (Co)2P-Co3(PO4)2@ KPC) as an electrode material for a supercapacitor.
FIG. 1 shows the electrode material (Co) of the supercapacitor prepared as described above2P-Co3(PO4)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 respectively scanning pictures under x 200, x 500, x 1000 and x 10000, so that the prepared electrode material can be observed to perfectly inherit the honeycomb porous structure specific to kelp, the transmission path of electrolyte ions can be shortened, and the storage of the ions is facilitated. And cobalt phosphide and cobalt phosphate nanoparticles (60-100nm) were grown uniformly in each chamber. Therefore, the successful preparation of the electrode material of porous carbon loaded with 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 (1cm multiplied by 1cm), drying the mixture in vacuum for 10 hours at the temperature of 60 ℃, 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-1The KOH solution is subjected to electrochemical performance test under the voltage window range of-0.3-0.6V.
FIG. 3 shows the above-mentioned systemThe prepared electrode material of the super capacitor is 6 mol.L-1In the KOH electrolyte, the voltage window range is a cyclic voltammetry Curve (CV) under different scanning speeds of-0.3 to 0.6V. 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 supercapacitor prepared in the step (A) is at 6 mol.L-1In the KOH electrolyte, the voltage window is-0.3 to 0.3V, and constant current charging and discharging curves under different current densities are shown. As can be seen from the graph, when the current density was 0.5A · g-1The electrode material thus prepared achieved 2080.3F g-1The specific capacitance of (d); when the current density is increased to 10A g-1When the electrode material is used, a high specific capacitance of 1238.9F g can be still maintained-1This 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-1In 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 super capacitor.
FIG. 6 shows that the electrode material of the supercapacitor prepared in the step (A) is at 6 mol.L-1In the KOH electrolyte, the voltage window is-0.3 to 0.3V, and the current density is 10Ag-1Lower cycle stability test chart. As can be seen, the capacity retention rate of the composite material can still reach 80.73% 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 supercapacitor.
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 hours 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 0.5 wt.% to 1.5 wt.%, and the mass concentration of the sodium dihydrogen phosphate is 2 wt.% to 4 wt.%.
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: 100 mL.
4. The method according to claim 1, wherein the conditions for cryopreservation in step (1) are as follows: the temperature is-60 to-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 preparation method according to claim 1, wherein in the step (2), the carbonization is performed under the protection of nitrogen, and the temperature is raised to the carbonization temperature at a speed of 0.5-10 ℃ 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 0.5 wt.% to 1 wt.%.
8. The preparation method according to claim 1, wherein in the step (3), the ratio of the kelp to the hydrochloric acid solution is 3-5 g: 60mL to 80 mL.
9. The method according to claim 1, wherein the drying temperature in steps (2) and (3) is 50 to 80 ℃.
10. Use of the kelp-derived porous carbon-loaded cobalt phosphide and cobalt phosphate electrode material prepared by the method of any one of claims 1 to 9 in a supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110955638.0A CN113675003B (en) | 2021-08-19 | 2021-08-19 | Preparation and application of kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110955638.0A CN113675003B (en) | 2021-08-19 | 2021-08-19 | Preparation and application of kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113675003A true CN113675003A (en) | 2021-11-19 |
| CN113675003B CN113675003B (en) | 2022-10-14 |
Family
ID=78544125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110955638.0A Active CN113675003B (en) | 2021-08-19 | 2021-08-19 | Preparation and application of kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113675003B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2021
- 2021-08-19 CN CN202110955638.0A patent/CN113675003B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| ZUGUANG YANG等: ""Self-supported cobalt phosphate nanoarray with pseudocapacitive"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113675003B (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Natural sisal fibers derived hierarchical porous activated carbon as capacitive material in lithium ion capacitor | |
| Du et al. | Three-dimensional carbonaceous for potassium ion batteries anode to boost rate and cycle life performance | |
| CN111453726A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN110379646B (en) | Preparation method of asymmetric supercapacitor based on molybdenum diselenide/charcoal | |
| CN105152170A (en) | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor | |
| CN111422865B (en) | Nitrogen-containing carbon material for supercapacitor and preparation method and application thereof | |
| CN107777685A (en) | The method that Carbon-based supercapacitor electrode material is prepared using wood powder as raw material | |
| Chen et al. | Lignin-derived nitrogen-doped porous ultrathin layered carbon as a high-rate anode material for sodium-ion batteries | |
| CN113307254A (en) | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application | |
| CN110620226A (en) | Preparation method of nitrogen and boron co-doped carbon fiber loaded molybdenum selenide electrode material | |
| CN109637843A (en) | A method of supercapacitor is prepared by electrode material of celery | |
| CN112133572A (en) | Three-dimensional porous biomass carbon material used as supercapacitor and preparation method thereof | |
| CN109003828B (en) | Porous biomass charcoal electrode material derived from wheat straw and preparation method thereof | |
| Liu et al. | Modulating pore nanostructure coupled with N/O doping towards competitive coal tar pitch-based carbon cathode for aqueous Zn-ion storage | |
| He et al. | Hierarchical tubular porous carbon derived from mulberry branches for long-life lead-carbon battery | |
| CN108010734A (en) | A kind of micro super capacitor production method based on graphene/carbon nano-tube aeroge | |
| CN111969201A (en) | Preparation method of fluorine-doped phenolic resin-based hard carbon negative electrode material | |
| CN111547719A (en) | 3D porous carbon material and preparation method and application thereof | |
| CN110610812B (en) | B, N double-doped carbon aerogel based on methyl cellulose and preparation method and application thereof | |
| CN113675003B (en) | Preparation and application of kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material | |
| CN115285991B (en) | Method for generating hierarchical porous carbon based on biomass derivative self-assembly and application thereof | |
| CN111924843B (en) | Preparation method of cyano-modified biomass derived carbon and application of cyano-modified biomass derived carbon in potassium storage field | |
| CN111892051B (en) | Biomass graded porous carbon for capacitor electrode material and preparation method thereof | |
| Zhang et al. | Hard Carbon Derived from Straw as Anode materials for sodium-ion batteries | |
| Zhai et al. | Mesopore-dominant defective nitrogen-doped tubular porous carbon for electrochemical energy storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |