CN112509823A - 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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- 239000004005 microsphere Substances 0.000 title claims abstract description 143
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000007772 electrode material Substances 0.000 title claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 201
- 239000004793 Polystyrene Substances 0.000 claims abstract description 69
- 229920002223 polystyrene Polymers 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims description 123
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 120
- 235000019441 ethanol Nutrition 0.000 claims description 96
- 230000035484 reaction time Effects 0.000 claims description 88
- 238000001354 calcination Methods 0.000 claims description 76
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 43
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 41
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 36
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 15
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006561 solvent free reaction Methods 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000004945 emulsification Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 description 29
- 239000003990 capacitor Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000002178 crystalline material Substances 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
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- H01G11/32—Carbon-based
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
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 forming the metal organic framework material have the characteristics of diversity, rich valence state and diverse coordination, and different organic ligands can form different framework structures, so that the metal organic framework material has various structures and rich physical and chemical properties, and 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: 0.1-2.5: 0.1, the reaction temperature is 105-115 ℃, and the reaction time is 60-80 h.
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: 0.1-2.5: 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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