CN112509823B - Hollow carbon microsphere supercapacitor electrode material and solvent-free preparation method thereof - Google Patents
Hollow carbon microsphere supercapacitor electrode material and solvent-free preparation method thereof Download PDFInfo
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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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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
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Abstract
The invention discloses a hollow carbon microsphere supercapacitor electrode material and a solvent-free preparation method thereof. Firstly, preparing monodisperse Polystyrene (PS) microspheres by a soap-free emulsion method, then sulfonating the Polystyrene (PS) microspheres to prepare sulfonated PS microspheres, and secondly, dissolving the sulfonated PS microspheres, metal salt and strong base in alcohol to carry out chemical synthesis to obtain a hollow oxide material; then obtaining a hollow Metal Organic Framework (MOF) material by a solvent-free method; and finally sintering the MOF material to obtain the hollow carbon microsphere. The hollow carbon microsphere supercapacitor electrode material prepared by the method has high specific capacitance, rate capability and cycling stability.
Description
Technical Field
The invention belongs to the technical field of electric energy storage material chemistry, and particularly relates to a hollow carbon microsphere supercapacitor electrode material and a solvent-free preparation method thereof.
Background
Along with the development of production, more and more energy is needed in society, and efficient electrochemical energy storage and conversion technologies, such as lithium batteries, solar batteries, super capacitors and the like, have entered the field of people. The super capacitor is used as an environment-friendly and efficient novel energy storage element, and becomes a new research hotspot in the field of energy storage in recent years.
The super capacitor has many advantages of the traditional capacitor and battery, such as short charging and discharging time, large energy density, long cycle life and the like, thereby having wide application space and development prospect. The super capacitor can be divided into two categories, namely an electric double layer capacitor and a pseudo capacitor according to different energy storage mechanisms. The super capacitor generally comprises three parts, namely an electrode (active substance, a current collector and a conductive agent), a diaphragm and electrolyte, wherein the active substance, also called as an electrode material, is one of key factors influencing the electrochemical performance of the super capacitor and restricts the performance of the super capacitor, so that the development of a novel high-performance electrode material with high capacity is of great significance.
Metal-organic frameworks (MOFs) are a class of crystalline materials with periodic network structure due to their ultra-high porosity (up to 90%) and large specific surface area (over 6000 m)2The unique properties of/g) make such materials rapidly one of the hot topics of international research. More importantly, the metal ions composing the metal organic framework material have diversity,The characteristics of rich valence state and various coordination, and different organic ligands can form different framework structures, so that the structure is various, the physical and chemical properties are rich, and the method has great potential application value in the fields of clean energy, gas separation, adsorption, storage and the like. Therefore, the application of the MOF material to the electrode material of the super capacitor greatly improves the electrochemical performance of the super capacitor. The invention provides a hollow carbon microsphere supercapacitor electrode material and a solvent-free preparation method thereof, and the hollow carbon microsphere supercapacitor electrode material has excellent electrochemical performance of a supercapacitor.
Disclosure of Invention
The invention aims to provide a hollow carbon microsphere supercapacitor electrode material and a solvent-free preparation method thereof; the preparation method is simple, and the prepared super capacitor electrode material can effectively improve the performance of the conventional super capacitor.
Firstly, preparing monodisperse Polystyrene (PS) microspheres by a soap-free emulsion method, then sulfonating the Polystyrene (PS) microspheres to prepare sulfonated PS microspheres, and secondly, dissolving the sulfonated PS microspheres, metal salt and strong base in alcohol to carry out chemical synthesis to obtain a hollow oxide material; then obtaining a hollow Metal Organic Framework (MOF) material by a solvent-free method; and finally sintering the MOF material to obtain the hollow carbon microsphere. The specific embodiments of the present invention are described below.
A preparation method of a hollow carbon microsphere supercapacitor electrode material comprises the following steps:
step 1, dissolving Sodium Dodecyl Sulfate (SDS) in deionized water, stirring uniformly, adding styrene, heating to a certain temperature, adding potassium persulfate (KPS), reacting for a certain time to obtain a mixed solution A, centrifugally cleaning for several times by absolute ethyl alcohol and methanol, and drying to obtain Polystyrene (PS) microspheres;
step 2, dissolving the polystyrene PS microspheres in concentrated sulfuric acid, heating for several hours at a certain temperature, centrifugally cleaning for several times by using ethanol after the reaction is finished, and drying in an oven to obtain sulfonated polystyrene PS microspheres;
step 3, dissolving the sulfonated polystyrene PS microspheres in alcohol, adding an alcohol solution of a metal salt, reacting for several hours at a certain temperature, adding an alcohol solution of a strong base, continuing to react for several hours, centrifugally cleaning for several times by using ethanol after the reaction is finished, and drying in an oven to obtain hollow oxide powder; wherein: the metal salt is cobalt salt or zinc salt;
step 4, simultaneously placing the dimethylimidazole and the hollow oxide powder in a polytetrafluoroethylene tank for separation, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, placing the reaction kettle in an oven for heating at a certain temperature for solvent-free reaction, and obtaining the hollow metal organic framework MOF material after the reaction is finished;
and 5, putting the hollow MOF material into a tube furnace, and calcining for several hours at a certain temperature in an inert atmosphere to obtain the hollow carbon microspheres.
In the step 1, the dosage ratio of the SDS, the KPS, the styrene and the deionized water is (0.025-0.1) g: (0.05-0.5) g: (4-20) ml: 250ml, the reaction time is 2-12 h, and the reaction temperature is 50-80 ℃; preferably, the dosage ratio of SDS, KPS, styrene and deionized water is (0.07-0.08) g: (0.15-0.25) g: (15-18) ml: 250ml, the reaction time is 2-4 h, and the reaction temperature is 65-75 ℃;
in the step 2, the dosage ratio of the styrene PS microspheres to the concentrated sulfuric acid is 0.5: 70-2: 40g/mL, the reaction temperature is 40-70 ℃, and the reaction time is 6-24 hours; the drying temperature in the drying oven is 60-90 ℃, and the drying time is 6-24 h. Preferably, the dosage ratio of the styrene PS microspheres to the concentrated sulfuric acid is 0.8: 50-1.2: 30g/mL, the reaction temperature is 55-65 ℃, and the reaction time is 10-14 h.
In the step 3, the metal salt is any one of zinc acetate dihydrate, zinc nitrate hexahydrate, cobalt acetate tetrahydrate or cobalt nitrate hexahydrate, the strong base is potassium hydroxide or sodium hydroxide, the alcohol is any one of ethanol, ethylene glycol or propylene glycol, and the dosage ratio of the sulfonated PS microsphere, the metal salt, the strong base and the alcohol is (0.05-0.2) g: (0.099-0.396) g: (0.1-0.4) g: (20-40) ml, the reaction temperature is 50-80 ℃, and the reaction time is 2-5 h. Preferably, the dosage ratio of the sulfonated PS microspheres, the metal salt, the strong base and the alcohol is 0.1 g: (0.15-0.3) g: (0.18-0.22) g: 20ml, the reaction temperature is 55-65 ℃, and the reaction time is 2.5-3.5 h.
In the step 4, the mass ratio of the dimethyl imidazole to the hollow oxide powder is 0.2: 0.1-2: 0.01, the reaction temperature is 100-130 ℃, and the reaction time is 12-96 hours. Preferably, the mass ratio of the dimethyl imidazole to the hollow oxide powder is 1.5: 0.1-2: 0.1, the reaction temperature is 105-115 ℃, and the reaction time is 60-80 hours.
In the step 5, the calcining temperature is 600-900 ℃, and the calcining time is 2-6 h. Preferably, the calcining temperature is 750-850 ℃, and the calcining time is 3-5 h.
The invention further provides the hollow carbon microsphere supercapacitor electrode material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the experimental operation steps are simple, the process is efficient, and the experimental steps only need polymerization reaction, synthesis reaction, atmosphere sintering and the like; the polystyrene prepared by the soap-free emulsion method is microspherical, the spherical structure of the polystyrene is regular and ordered, the monodispersity is good, and the size is about 250 nm; the PS microspheres sulfonated by concentrated sulfuric acid have regular and ordered morphology and structure, and a large number of sulfonic groups exist; the hollow oxide microspheres obtained through the synthesis reaction have regular and ordered spherical structures, nanoscale sizes and higher specific surface areas; the hollow MOF material is prepared by a solvent-free method, and the specific surface area of the material is greatly increased due to the hollow structure; the existence of carbon element in the hollow carbon microsphere obtained after atmosphere sintering greatly increases the electrochemical performance of the material; the hollow carbon microspheres are applied to the super capacitor, and show higher specific capacitance and more stable cycle performance.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the following examples.
Implementation mode one
A hollow carbon microsphere super capacitor electrode material and a solvent-free preparation method thereof comprise the following steps:
step 1, dissolving Sodium Dodecyl Sulfate (SDS) with a certain mass in deionized water, uniformly stirring, adding styrene with a certain volume, heating to a certain temperature, adding potassium persulfate (KPS) aqueous solution with a certain volume, reacting for a certain time to obtain a mixed solution A, centrifugally cleaning for several times by absolute ethyl alcohol and methanol, and drying to obtain Polystyrene (PS) microspheres;
step 2, dissolving PS microspheres with a certain mass in concentrated sulfuric acid with a certain volume, heating for several hours at a certain temperature, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain sulfonated polystyrene microspheres;
step 3, dissolving sulfonated polystyrene microspheres with a certain mass in an alcohol solution with a certain volume, adding an alcohol solution of metal salt with a certain volume, reacting for several hours at a certain temperature, adding an alcohol solution of strong base with a certain volume, continuing to react for several hours, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain hollow oxide powder;
and 4, simultaneously placing the dimethylimidazole and the hollow oxide powder with certain mass in a polytetrafluoroethylene tank, separating, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, placing the reaction kettle in an oven, heating at a certain temperature for reaction, and obtaining the hollow Metal Organic Framework (MOF) material after the reaction is finished.
And 5, putting the hollow MOF material with a certain mass into a tube furnace, and calcining for several hours at a certain temperature in an inert atmosphere to obtain the hollow carbon microspheres.
In the electrode material of the hollow carbon microsphere supercapacitor and the solvent-free preparation method thereof according to the embodiment, in step 1, the usage ratio of SDS, KPS, styrene and deionized water is (0.025-0.1 g): (0.05-0.5 g): (4-20 ml): 250ml, the reaction time is 2-12 h, and the reaction temperature is 50-80 ℃.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of PS microspheres added is 0.5-2 g, the amount of concentrated sulfuric acid added is 40-70 ml, the reaction temperature is 40-70 ℃, and the reaction time is 6-24 hours; the drying temperature in the drying oven is 60-90 ℃, and the drying time is 6-24 h.
In step 3, soluble metal salts are zinc acetate dihydrate, zinc nitrate hexahydrate, cobalt acetate tetrahydrate and cobalt nitrate hexahydrate, strong bases are potassium hydroxide and sodium hydroxide, alcohols are ethanol, ethylene glycol and propylene glycol, and the dosage ratio of the sulfonated PS microspheres, the metal salts, the strong bases and the alcohols is (0.05-0.2 g): (0.099-0.396 g): (0.1-0.4 g): (20-40 ml), the reaction temperature is 50-80 ℃, and the reaction time is 2-5 h.
In the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof according to the embodiment, in the step 4, the amount of the dimethylimidazole is 0.1-2 g, the amount of the hollow oxide powder is 0.01-0.1 g, the reaction temperature of the solvent-free method is 100-130 ℃, and the reaction time is 12-96 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600-900 ℃, and the calcination time is 2-6 hours.
The hollow carbon microsphere supercapacitor electrode material and the supercapacitor based on the hollow carbon microsphere prepared by the solvent-free preparation method are provided by the embodiment. The specific surface area of the hollow MOF material is greatly increased due to the existence of the hollow structure, and the conductivity of the hollow carbon microsphere is greatly increased due to the existence of carbon elements, so that the electrochemical performance of the material is favorably improved.
The hollow carbon microsphere supercapacitor electrode material and the supercapacitor based on the hollow carbon microsphere prepared by the solvent-free preparation method are provided by the embodiment. In the electrochemical performance test process, a three-electrode system is adopted to carry out constant current charge and discharge test on the specific capacitance, the counter electrode is a platinum electrode, the reference electrode is a saturated calomel electrode, the electrolyte is 6M KOH solution, and the charge and discharge current density is 1A/g; the constant current charge and discharge test is carried out on the cycle stability, the current density is 1A/g, and the cycle is carried out for 500 times.
Example 1
According to the first embodiment of the present invention, in the step 1, the ratio of the Sodium Dodecyl Sulfate (SDS), the potassium persulfate (KPS), the styrene, and the deionized water is 0.025 g: 0.05 g: 4 ml: 250ml, reaction time 2h, reaction temperature 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of the added PS microspheres is 0.5g, the amount of the added concentrated sulfuric acid is 40ml, the reaction temperature is 40 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃; the reaction time was 3 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 700 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 231F/g, the capacity is still 177F/g after 500 cycles, and the capacity retention rate reaches 76.62%.
Example 2
According to the first embodiment of the present invention, in the step 1, the ratio of the Sodium Dodecyl Sulfate (SDS), the potassium persulfate (KPS), the styrene, and the deionized water is 0.05 g: 0.1 g: 10 ml: 250ml, reaction time 2h, reaction temperature 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of the added PS microspheres is 0.5g, the amount of the added concentrated sulfuric acid is 40ml, the reaction temperature is 40 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600 ℃, and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 233F/g, and after 500 cycles, the capacity still maintains 171F/g, and the capacity retention rate reaches 73.39%.
Example 3
According to the first embodiment of the present invention, in the step 1, the usage ratio of Sodium Dodecyl Sulfate (SDS), potassium persulfate (KPS), styrene, and deionized water is 0.075 g: 0.2 g: 16 ml: 250ml, reaction time 2h, reaction temperature 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of the added PS microspheres is 0.5g, the amount of the added concentrated sulfuric acid is 40ml, the reaction temperature is 40 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600 ℃, and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 257F/g, the capacity is still maintained at 201F/g after 500 cycles, and the capacity retention rate reaches 78.21%.
Example 4
According to the first embodiment of the present invention, in the step 1, the usage ratio of Sodium Dodecyl Sulfate (SDS), potassium persulfate (KPS), styrene, and deionized water is 0.075 g: 0.2 g: 16 ml: 250ml, reaction time of 3h and reaction temperature of 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of the added PS microspheres is 0.5g, the amount of the added concentrated sulfuric acid is 40ml, the reaction temperature is 40 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600 ℃, and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 263F/g, the capacity is still kept to be 211F/g after 500 cycles, and the capacity retention rate reaches 80.23%.
Example 5
According to the first embodiment of the present invention, in the step 1, the usage ratio of Sodium Dodecyl Sulfate (SDS), potassium persulfate (KPS), styrene, and deionized water is 0.075 g: 0.2 g: 16 ml: 250ml, reaction time 4h, reaction temperature 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of the added PS microspheres is 0.5g, the amount of the added concentrated sulfuric acid is 40ml, the reaction temperature is 40 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600 ℃, and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 259F/g, the capacity is still kept to 199F/g after 500 cycles, and the capacity retention rate reaches 76.83 percent.
Example 6
According to the first embodiment of the present invention, in the step 1, the usage ratio of Sodium Dodecyl Sulfate (SDS), potassium persulfate (KPS), styrene, and deionized water is 0.075 g: 0.2 g: 16 ml: 250ml, reaction time of 3h and reaction temperature of 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of the added PS microspheres is 0.5g, the amount of the added concentrated sulfuric acid is 40ml, the reaction temperature is 50 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600 ℃, and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 266F/g, the capacity is still maintained to be 202F/g after 500 cycles, and the capacity retention rate reaches 75.94%.
Example 7
According to the first embodiment of the present invention, in the step 1, the usage ratio of Sodium Dodecyl Sulfate (SDS), potassium persulfate (KPS), styrene, and deionized water is 0.075 g: 0.2 g: 16 ml: 250ml, reaction time of 3h and reaction temperature of 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, the amount of the added PS microspheres is 0.5g, the amount of the added concentrated sulfuric acid is 40ml, the reaction temperature is 60 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free thermal method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600 ℃, and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 272F/g, the capacity is still 219F/g after 500 cycles, and the capacity retention rate reaches 80.51 percent.
Example 8
According to the first embodiment of the present invention, in the step 1, the usage ratio of Sodium Dodecyl Sulfate (SDS), potassium persulfate (KPS), styrene, and deionized water is 0.075 g: 0.2 g: 16 ml: 250ml, reaction time of 3h and reaction temperature of 70 ℃.
According to the first embodiment of the preparation method of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 2, 1g of PS microspheres are added, 40ml of concentrated sulfuric acid is added, the reaction temperature is 60 ℃, and the reaction time is 12 hours; the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.05 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the first embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 0.2g, the amount of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free thermal method is 100 ℃, and the reaction time is 12 hours.
According to the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 5, the calcination temperature is 600 ℃, and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 277F/g, the capacity is still 219F/g after 500 cycles, and the capacity retention rate reaches 79.06%.
According to the electrochemical performance test results of examples 1 to 8, the preferable conditions for preparing the sulfonated PS microspheres are that the ratio of the Sodium Dodecyl Sulfate (SDS), the potassium persulfate (KPS), the styrene and the deionized water is 0.075 g: 0.2 g: 16 ml: 250ml, reaction time of 3h and reaction temperature of 70 ℃. The preferable conditions of the sulfonation reaction are 1g of PS microspheres and 40ml of concentrated sulfuric acid, the reaction temperature is 60 ℃, and the reaction time is 12 h.
The following examples 9 to 13 were prepared according to the preferred conditions obtained in the above examples 1 to 8.
Second embodiment
A hollow carbon microsphere super capacitor electrode material and a solvent-free preparation method thereof comprise the following steps:
step 1, dissolving Sodium Dodecyl Sulfate (SDS) with a certain mass in deionized water, stirring uniformly, adding styrene with a certain volume, heating to a certain temperature, adding potassium persulfate (KPS) aqueous solution with a certain mass, reacting for a certain time to obtain a mixed solution A, centrifugally cleaning for several times by absolute ethyl alcohol and methanol, and drying to obtain Polystyrene (PS) microspheres;
step 2, dissolving PS microspheres with a certain mass in concentrated sulfuric acid with a certain volume, heating for several hours at a certain temperature, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain sulfonated polystyrene microspheres;
dissolving sulfonated polystyrene microspheres with a certain mass in an alcohol solution with a certain volume, adding an alcohol solution of metal salts with a certain volume, reacting for several hours at a certain temperature, adding an alcohol solution of strong base with a certain volume, continuing to react for several hours, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain hollow oxide powder;
and 4, simultaneously placing the dimethylimidazole and the hollow oxide powder with certain mass in a polytetrafluoroethylene tank, separating, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, placing the reaction kettle in an oven, heating at a certain temperature for reaction, and obtaining the hollow Metal Organic Framework (MOF) material after the reaction is finished.
And 5, putting the hollow MOF material with a certain mass into a tube furnace, and calcining for several hours at a certain temperature in an inert atmosphere to obtain the hollow carbon microspheres.
Example 9
According to the second embodiment, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.1 g: 0.099 g: 0.1 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the second embodiment, in the step 4, the dosage of the dimethylimidazole is 0.2g, the dosage of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the second embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 279F/g, the capacity is still kept to be 223F/g after 500 cycles, and the capacity retention rate reaches 79.93%.
Example 10
According to the second embodiment, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.1 g: 0.099 g: 0.2 g: 20ml, the reaction temperature is 50 ℃, and the reaction time is 3 hours.
According to the second embodiment, in the step 4, the dosage of the dimethylimidazole is 0.2g, the dosage of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the second embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 295F/g, the capacity is still kept to be 231F/g after 500 cycles, and the capacity retention rate reaches 78.31 percent.
Example 11
According to the second embodiment, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.1 g: 0.198 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the second embodiment, in the step 4, the dosage of the dimethylimidazole is 0.2g, the dosage of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free thermal method is 100 ℃, and the reaction time is 12 hours.
According to the second embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 303F/g, the capacity is kept to 247F/g after 500 cycles, and the capacity retention rate reaches 81.52%.
Example 12
According to the second embodiment, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.1 g: 0.297 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the second embodiment, in the step 4, the dosage of the dimethylimidazole is 0.2g, the dosage of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the second embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 287F/g, the capacity is still maintained to be 214F/g after 500 cycles, and the capacity retention rate reaches 74.56 percent.
Example 13
According to the second embodiment, in the step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.1 g: 0.198 g: 0.2 g: 20ml, 60 ℃ of reaction temperature and 4 hours of reaction time.
According to the second embodiment, in the step 4, the dosage of the dimethylimidazole is 0.2g, the dosage of the hollow oxide powder is 0.01g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the second embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 326F/g, after 500 cycles, the capacity is still kept to be 256F/g, and the capacity retention rate reaches 78.53%.
According to the electrochemical performance test results of examples 9 to 13, the preferable conditions for preparing the hollow oxide powder are that the dosage ratio of the sulfonated PS microspheres, the zinc acetate dihydrate, the sodium hydroxide and the ethanol is 0.1 g: 0.198 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
The following examples 14 to 23 were prepared according to the preferred conditions obtained in the above examples 1 to 13.
Third embodiment
A hollow carbon microsphere super capacitor electrode material and a solvent-free preparation method thereof comprise the following steps:
step 1, dissolving Sodium Dodecyl Sulfate (SDS) with a certain mass in deionized water, stirring uniformly, adding styrene with a certain volume, heating to a certain temperature, adding potassium persulfate (KPS) aqueous solution with a certain mass, reacting for a certain time to obtain a mixed solution A, centrifugally cleaning for several times by absolute ethyl alcohol and methanol, and drying to obtain Polystyrene (PS) microspheres;
step 2, dissolving PS microspheres with a certain mass in concentrated sulfuric acid with a certain volume, heating for several hours at a certain temperature, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain sulfonated polystyrene microspheres;
step 3, dissolving sulfonated polystyrene microspheres with a certain mass in an alcohol solution with a certain volume, adding an alcohol solution of metal salt with a certain volume, reacting for several hours at a certain temperature, adding an alcohol solution of strong base with a certain volume, continuing to react for several hours, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain hollow oxide powder;
and 4, simultaneously placing the dimethylimidazole and the hollow oxide powder with certain mass in a polytetrafluoroethylene tank, separating, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, placing the reaction kettle in an oven, heating at a certain temperature for reaction, and obtaining the hollow Metal Organic Framework (MOF) material after the reaction is finished.
And 5, putting the hollow MOF material with a certain mass into a tube furnace, and calcining for several hours at a certain temperature in an inert atmosphere to obtain the hollow carbon microspheres.
Example 14
According to the third embodiment of the invention, in the step 4, the amount of the dimethylimidazole is 0.5g, the amount of the hollow oxide powder is 0.025g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 12 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 329F/g, after 500 cycles, the capacity is still kept at 255F/g, and the capacity retention rate reaches 77.51%.
Example 15
According to the third embodiment of the invention, in the step 4, the dosage of the dimethylimidazole is 0.5g, the dosage of the hollow oxide powder is 0.025g, the reaction temperature of the solvent-free thermal method is 100 ℃, and the reaction time is 24 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 328F/g, the capacity is still 243F/g after 500 cycles, and the capacity retention rate reaches 74.09%.
Example 16
According to the third embodiment of the invention, in the step 4, the dosage of the dimethylimidazole is 0.5g, the dosage of the hollow oxide powder is 0.025g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 48 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 343F/g, after 500 cycles, the capacity is still kept at 264F/g, and the capacity retention rate reaches 76.97%.
Example 17
According to the third embodiment of the invention, in the step 4, the amount of the dimethylimidazole is 0.5g, the amount of the hollow oxide powder is 0.025g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 377F/g, the capacity is still maintained to be 301F/g after 500 cycles, and the capacity retention rate reaches 79.84%.
Example 18
According to the third embodiment of the invention, in the step 4, the amount of the dimethylimidazole is 0.7g, the amount of the hollow oxide powder is 0.025g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 371F/g, the capacity is still maintained to be 299F/g after 500 cycles, and the capacity retention rate reaches 80.59 percent.
Example 19
According to the third embodiment of the hollow carbon microsphere supercapacitor electrode material and the solvent-free preparation method thereof, in the step 4, the amount of the dimethylimidazole is 1g, the amount of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 100 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 373F/g, after 500 cycles, the capacity is still 293F/g, and the capacity retention rate reaches 78.55%.
Example 20
According to the third embodiment of the invention, in the step 4, the dosage of the dimethylimidazole is 1g, the dosage of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 385F/g, the capacity is still maintained to be 301F/g after 500 cycles, and the capacity retention rate reaches 78.18 percent.
Example 21
According to the third embodiment of the invention, in the step 4, the dosage of the dimethylimidazole is 1g, the dosage of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free thermal method is 120 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 600 ℃ and the calcination time is 2 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 363F/g, the capacity is still 287F/g after 500 cycles, and the capacity retention rate reaches 79.06%.
Example 22
According to the third embodiment of the invention, in the step 4, the dosage of the dimethylimidazole is 1g, the dosage of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free thermal method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 700 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 381F/g, after 500 cycles, the capacity is still maintained at 307F/g, and the capacity retention rate reaches 80.58%.
Example 23
According to the third embodiment of the invention, in the step 4, the dosage of the dimethylimidazole is 1g, the dosage of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 800 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 393F/g, after 500 cycles, the capacity is still maintained to be 316F/g, and the capacity retention rate reaches 80.41%.
According to the electrochemical performance test results of the embodiments 14 to 23, the optimal conditions for preparing the hollow carbon microsphere are dimethyl imidazole: the hollow oxide powder is 1: 0.05g, the reaction temperature of the solvent-free thermal method is 110 ℃, and the reaction time is 72 h. The calcining temperature is 800 ℃, and the calcining time is 4 h.
The following examples 24 to 29 were prepared according to the preferred conditions obtained in the above examples 1 to 23.
Embodiment IV
A hollow carbon microsphere super capacitor electrode material and a solvent-free preparation method thereof comprise the following steps:
step 1, dissolving Sodium Dodecyl Sulfate (SDS) with a certain mass in deionized water, stirring uniformly, adding styrene with a certain volume, heating to a certain temperature, adding potassium persulfate (KPS) aqueous solution with a certain mass, reacting for a certain time to obtain a mixed solution A, centrifugally cleaning for several times by absolute ethyl alcohol and methanol, and drying to obtain Polystyrene (PS) microspheres;
step 2, dissolving PS microspheres with a certain mass in concentrated sulfuric acid with a certain volume, heating for several hours at a certain temperature, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain sulfonated polystyrene microspheres;
step 3, dissolving sulfonated polystyrene microspheres with a certain mass in an alcohol solution with a certain volume, adding an alcohol solution of metal salt with a certain volume, reacting for several hours at a certain temperature, adding an alcohol solution of strong base with a certain volume, continuing to react for several hours, centrifugally cleaning for several times by using a large amount of ethanol after the reaction is finished, and drying in an oven to obtain hollow oxide powder;
and 4, simultaneously placing the dimethylimidazole and the hollow oxide powder with certain mass in a polytetrafluoroethylene tank, separating, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, placing the reaction kettle in an oven, heating at a certain temperature for reaction, and obtaining the hollow Metal Organic Framework (MOF) material after the reaction is finished.
And 5, putting the hollow MOF material with a certain mass into a tube furnace, and calcining for several hours at a certain temperature in an inert atmosphere to obtain the hollow carbon microspheres.
Example 24
According to the first to third embodiments, in step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethanol, the strong base is potassium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the potassium hydroxide, and the ethanol is 0.1 g: 0.198 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the first to third embodiments, in the step 4, the amount of the dimethylimidazole is 1g, the amount of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 800 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 386F/g, the capacity is still maintained to be 308F/g after 500 cycles, and the capacity retention rate reaches 79.79 percent.
Example 25
According to the first to third embodiments, in step 3, the soluble metal salt is zinc nitrate hexahydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc nitrate hexahydrate, the sodium hydroxide, and the ethanol is 0.1 g: 0.268 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the first to third embodiments, in the step 4, the amount of the dimethylimidazole is 1g, the amount of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 800 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 412F/g, the capacity is still maintained to be 335F/g after 500 cycles, and the capacity retention rate reaches 81.31 percent.
Example 26
According to the first to third embodiments, in step 3, the soluble metal salt is cobalt acetate tetrahydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, cobalt acetate tetrahydrate, sodium hydroxide, and ethanol is 0.1 g: 0.225 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the first to third embodiments, in the step 4, the amount of the dimethylimidazole is 1g, the amount of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 800 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 401F/g, the capacity is still 329F/g after 500 cycles, and the capacity retention rate reaches 82.04%.
Example 27
According to the first to third embodiments, in step 3, the soluble metal salt is cobalt acetate tetrahydrate, the alcohol is ethanol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, cobalt acetate tetrahydrate, sodium hydroxide, and ethanol is 0.1 g: 0.224 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the first to third embodiments, in the step 4, the amount of the dimethylimidazole is 1g, the amount of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 800 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 396F/g, the capacity is still maintained at 302F/g after 500 cycles, and the capacity retention rate reaches 76.26 percent.
Example 28
According to the first to third embodiments, in step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is ethylene glycol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide, and the ethylene glycol is 0.1 g: 0.198 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the first to third embodiments, in the step 4, the amount of the dimethylimidazole is 1g, the amount of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 800 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 413F/g, the capacity is still maintained to be 322F/g after 500 cycles, and the capacity retention rate reaches 77.97%.
Example 29
According to the first to third embodiments, in step 3, the soluble metal salt is zinc acetate dihydrate, the alcohol is propylene glycol, the strong base is sodium hydroxide, and the dosage ratio of the sulfonated PS microsphere, the zinc acetate dihydrate, the sodium hydroxide, and the propylene glycol is 0.1 g: 0.198 g: 0.2 g: 20ml, the reaction temperature is 60 ℃, and the reaction time is 3 hours.
According to the first to third embodiments, in the step 4, the amount of the dimethylimidazole is 1g, the amount of the hollow oxide powder is 0.05g, the reaction temperature of the solvent-free method is 110 ℃, and the reaction time is 72 hours.
According to the third embodiment, in the step 5, the calcination temperature is 800 ℃ and the calcination time is 4 hours.
When the charge-discharge current density is 1A/g, the first discharge capacity is 405F/g, the capacity is still maintained to be 319F/g after 500 cycles, and the capacity retention rate reaches 78.77%.
Claims (10)
1. A preparation method of a hollow carbon microsphere supercapacitor electrode material is characterized by comprising the following steps:
step 1, dissolving Sodium Dodecyl Sulfate (SDS) in deionized water, stirring uniformly, adding styrene, heating to a certain temperature, adding potassium persulfate (KPS), reacting for a certain time to obtain a mixed solution A, centrifugally cleaning for several times by absolute ethyl alcohol and methanol, and drying to obtain Polystyrene (PS) microspheres;
step 2, dissolving the polystyrene PS microspheres in concentrated sulfuric acid, heating for several hours at a certain temperature, centrifugally cleaning for several times by using ethanol after the reaction is finished, and drying in an oven to obtain sulfonated polystyrene PS microspheres;
step 3, dissolving the sulfonated polystyrene PS microspheres in alcohol, adding an alcohol solution of a metal salt, reacting for several hours at a certain temperature, adding an alcohol solution of a strong base, continuing to react for several hours, centrifugally cleaning for several times by using ethanol after the reaction is finished, and drying in an oven to obtain hollow oxide powder; wherein: the metal salt is cobalt salt or zinc salt;
step 4, simultaneously placing the dimethylimidazole and the hollow oxide powder in a polytetrafluoroethylene tank for separation, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, placing the reaction kettle in an oven for heating at a certain temperature for solvent-free reaction, and obtaining the hollow metal organic framework MOF material after the reaction is finished;
and 5, putting the hollow MOF material into a tube furnace, and calcining for several hours at a certain temperature in an inert atmosphere to obtain the hollow carbon microspheres.
2. The method according to claim 1, wherein in step 1, the ratio of the amounts of SDS, KPS, styrene and deionized water is (0.025-0.1) g: (0.05-0.5) g: (4-20) ml: 250ml, the reaction time is 2-12 h, and the reaction temperature is 50-80 ℃; in the step 2, the dosage ratio of the styrene PS microspheres to the concentrated sulfuric acid is 0.5: 70-2: 40g/mL, the reaction temperature is 40-70 ℃, and the reaction time is 6-24 hours; the drying temperature in the drying oven is 60-90 ℃, and the drying time is 6-24 h.
3. The preparation method according to claim 1, wherein in the step 1, the ratio of the amounts of SDS, KPS, styrene and deionized water is (0.07-0.08) g: (0.15-0.25) g: (15-18) ml: 250ml, the reaction time is 2-4 h, and the reaction temperature is 65-75 ℃; in the step 2, the dosage ratio of the styrene PS microspheres to the concentrated sulfuric acid is 0.8: 50-1.2: 30g/mL, the reaction temperature is 55-65 ℃, and the reaction time is 10-14 h.
4. The method according to claim 1, wherein in step 3, the metal salt is any one of zinc acetate dihydrate, zinc nitrate hexahydrate, cobalt acetate tetrahydrate and cobalt nitrate hexahydrate, the strong base is potassium hydroxide or sodium hydroxide, the alcohol is any one of ethanol, ethylene glycol and propylene glycol, and the ratio of the amount of the sulfonated polystyrene PS microspheres, the metal salt, the strong base and the alcohol is (0.05-0.2) g: (0.099-0.396) g: (0.1-0.4) g: (20-40) ml, the reaction temperature is 50-80 ℃, and the reaction time is 2-5 h.
5. The method according to claim 1, wherein in step 3, the sulfonated polystyrene PS microspheres, the metal salt, the strong base and the alcohol are used in a ratio of 0.1 g: (0.15-0.3) g: (0.18-0.22) g: 20ml, the reaction temperature is 55-65 ℃, and the reaction time is 2.5-3.5 h.
6. The method according to claim 1, wherein in step 4, the mass ratio of the dimethylimidazole to the hollow oxide powder is 0.2: 0.1-2: 0.01, the reaction temperature is 100-130 ℃, and the reaction time is 12-96 hours.
7. The preparation method according to claim 1, wherein in the step 4, the mass ratio of the dimethylimidazole to the hollow oxide powder is 1.5: 0.1-2: 0.1, the reaction temperature is 105-115 ℃, and the reaction time is 60-80 hours.
8. The preparation method according to claim 1, wherein in the step 5, the calcination temperature is 600 to 900 ℃ and the calcination time is 2 to 6 hours.
9. The preparation method according to claim 1, wherein in the step 5, the calcination temperature is 750 to 850 ℃ and the calcination time is 3 to 5 hours.
10. The MOF-based hollow carbon microsphere supercapacitor electrode material prepared by the preparation method according to any one of claims 1 to 9.
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