CN109103035B - Preparation method of modified super capacitor electrode - Google Patents
Preparation method of modified super capacitor electrode Download PDFInfo
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- CN109103035B CN109103035B CN201810947230.7A CN201810947230A CN109103035B CN 109103035 B CN109103035 B CN 109103035B CN 201810947230 A CN201810947230 A CN 201810947230A CN 109103035 B CN109103035 B CN 109103035B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method of a modified super capacitor electrode, which comprises the steps of taking a graphite rod as a cathode and an anode of an additive prepared by an arc method, relatively placing the cathode and the anode of 2 graphite rods in a liquid nitrogen, liquid argon or water reaction medium, introducing high-voltage current to carry out direct current arc discharge to prepare the additive carbon nanohorn or carbon onion, then applying a voltage of 300V-500V to react for one end time in the atmosphere of any one or a mixed gas of nitrogen and ammonia gas to obtain the modified additive, adding the modified additive into electrode slurry consisting of resorcinol solution or hydroquinone solution, formaldehyde solution or furfural solution, a catalyst and distilled water, and stirring at high speed in a vacuum ring shape to obtain the modified super capacitor electrode; the invention has the advantages of effectively enhancing the electrical conductivity and the thermal conductivity of the electrode, effectively improving the lithium ion adsorption performance of the negative electrode, effectively improving the specific energy density and the specific power density of the electrode and prolonging the cycle service life of the electrode.
Description
Technical Field
The invention belongs to the technical field of battery electrode preparation, and particularly relates to a preparation method of a modified super capacitor electrode.
Background
The super capacitor is a power supply which is between a traditional capacitor and a battery and has special performance, and electric energy is stored mainly by electric double layers and redox pseudocapacitance charges. With the wide popularization and use of super capacitors, the defects of the super capacitors are increasingly highlighted, and the super capacitors have the following defects at present: 1. the motor of the conventional super capacitor has weak charge adsorption capacity and poor conductivity and heat dissipation performance; 2. the low charge activity inside the capacitor causes low working efficiency and brings serious inconvenience to the use; 3. the specific energy density and the specific power density of the capacitor electrode are low, the cycle service life is short, and the capacitor on electricity needs to be replaced frequently, so that the resource waste is caused, and the economic burden is generated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a modified super capacitor electrode, which effectively enhances the electrical conductivity and the thermal conductivity of the electrode, effectively improves the performance of the capacitor electrode for adsorbing charges, effectively improves the specific energy density and the specific power density of the capacitor electrode, and prolongs the cycle service life of the electrode.
The technical scheme of the invention is as follows:
a preparation method of a modified super-capacitor electrode takes any one of or a mixture of modified carbon onions and carbon nanohorns as an additive to be added into super-capacitor electrode slurry, and comprises the following specific steps:
step 1, mixing resorcinol solution or hydroquinone solution, formaldehyde solution or furfural solution, catalyst and distilled water, and uniformly stirring to obtain capacitor electrode slurry;
step 2, adding a certain mass percentage of the additive into the capacitance electrode slurry prepared in the step 1, and stirring at a high speed for 1-3 hours in a vacuum environment to obtain an initial liquid;
and 3, treating the initial liquid crystal gel prepared in the step 2, drying, carbonizing, performing heat treatment and tabletting to obtain the super capacitor electrode.
Further, the additive added in the step 2 accounts for 0.5-100% of the mass of the capacitor electrode slurry.
Further, the particle size of the additive is 20nm-120 nm.
Further, the stirring speed in the step 2 is 1500r/min-2500 r/min.
Further, the specific preparation process of the additive comprises the following steps:
s51, preparing the cathode and anode of the additive by taking a graphite rod as an electric arc method, placing the cathode and anode of 2 graphite rods in a reaction medium oppositely, and introducing high-voltage current of 1.5 kiloamperes to perform direct current arc discharge to prepare an anode product of the graphite rod, namely the additive;
s52, placing the additive prepared in the step S51 in a constant temperature area of a quartz tube, introducing atmosphere, heating to 400-1500 ℃, and applying a voltage of 300-500V to react for 1-48 h to obtain the modified additive.
Further, the reflecting medium in the step S51 is any one of liquid nitrogen, liquid argon or water;
preferably, when the reaction medium in step S51 is liquid nitrogen or liquid argon, the anode product of the graphite rod is a carbon nanohorn;
preferably, when the reaction medium in step S51 is water, the anode product of the graphite rod is carbon onion.
Further, the atmosphere in step S52 is either nitrogen or ammonia or a mixture of both.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the additive is added into the slurry for preparing the capacitor electrode according to a certain proportion, so that the additive is fully filled into gaps of the capacitor electrode, the specific energy density and the specific power density of the electrode are effectively improved, and the performance of the capacitor electrode for adsorbing charges is enhanced, thereby enhancing the electrical conductivity and the thermal conductivity of the capacitor electrode;
2. the carbon nanohorn and/or the carbon onion introduced into the capacitor electrode have good adsorption performance on charges, effectively promote the circulation of the charges in the capacitor and effectively prolong the cycle service life of the super capacitor;
3. the additive is prepared by taking a graphite rod as an electrode and adopting an arc method as the additive for manufacturing the lithium ion battery electrode, and carbon-nitrogen bonds are introduced into the additive through nitriding treatment, so that the activity of the additive is improved, and the modified additive is further improved in the conductivity and the durability of the electrode and the like;
in a word, the invention has the advantages of effectively enhancing the electrical conductivity and the thermal conductivity of the electrode, effectively improving the performance of the capacitor electrode for adsorbing charges, effectively improving the specific energy density and the specific power density of the capacitor electrode and prolonging the cycle service life of the electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a modified super-capacitor electrode takes any one of or a mixture of modified carbon onions and carbon nanohorns as an additive to be added into super-capacitor electrode slurry, and comprises the following specific steps:
step 1, mixing resorcinol solution, formaldehyde solution, catalyst and distilled water, and uniformly stirring to prepare capacitor electrode slurry;
step 2, adding a certain mass percentage of the additive into the capacitor electrode slurry prepared in the step 1, and stirring the mixture at a high speed in a vacuum environment for 1 to obtain an initial solution;
and 3, treating the initial liquid crystal gel prepared in the step 2, drying, carbonizing, performing heat treatment and tabletting to obtain the super capacitor electrode.
Further, the additive added in the step 2 is 0.5% of the mass of the capacitor electrode slurry.
Further, the particle size of the additive is 20 nm.
Further, the stirring speed in the step 2 is 1500 r/min.
Further, the specific preparation process of the additive comprises the following steps:
s51, preparing the cathode and anode of the additive by taking a graphite rod as an electric arc method, placing the cathode and anode of 2 graphite rods in a reaction medium oppositely, and introducing high-voltage current of 1.5 kiloamperes to perform direct current arc discharge to prepare an anode product of the graphite rod, namely the additive;
s52, placing the additive prepared in the step S51 in a constant temperature area of a quartz tube, introducing atmosphere, heating to 400 ℃, and then applying 300V voltage to react for 20 hours to obtain the modified additive.
Further, the reflecting medium in the step S51 is any one of liquid nitrogen, liquid argon or water;
preferably, when the reaction medium in step S51 is liquid nitrogen or liquid argon, the anode product of the graphite rod is a carbon nanohorn;
preferably, when the reaction medium in step S51 is water, the anode product of the graphite rod is carbon onion.
Further, the atmosphere in step S52 is nitrogen.
Example 2
A preparation method of a modified super-capacitor electrode takes any one of or a mixture of modified carbon onions and carbon nanohorns as an additive to be added into super-capacitor electrode slurry, and comprises the following specific steps:
step 1, mixing a hydroquinone solution, a furfural solution, a catalyst and distilled water, and uniformly stirring to prepare capacitor electrode slurry;
step 2, adding a certain mass percentage of the additive into the capacitance electrode slurry prepared in the step 1, and stirring at a high speed in a vacuum environment for h to obtain an initial solution;
and 3, treating the initial liquid crystal gel prepared in the step 2, drying, carbonizing, performing heat treatment and tabletting to obtain the super capacitor electrode.
Further, the additive added in the step 2 is 100% of the mass of the capacitor electrode slurry.
Further, the particle size of the additive is 120 nm.
Further, the stirring speed in the step 2 is 2500 r/min.
Further, the specific preparation process of the additive comprises the following steps:
s51, preparing the cathode and anode of the additive by taking a graphite rod as an electric arc method, placing the cathode and anode of 2 graphite rods in a reaction medium oppositely, and introducing high-voltage current of 1.5 kiloamperes to perform direct current arc discharge to prepare an anode product of the graphite rod, namely the additive;
s52, placing the additive prepared in the step S51 in a constant temperature area of a quartz tube, introducing atmosphere, heating to 1500 ℃, and then applying a voltage of 500V to react for 48 hours to obtain the modified additive.
Further, the reflecting medium in the step S51 is any one of liquid nitrogen, liquid argon or water;
preferably, when the reaction medium in step S51 is liquid nitrogen or liquid argon, the anode product of the graphite rod is a carbon nanohorn;
preferably, when the reaction medium in step S51 is water, the anode product of the graphite rod is carbon onion.
Further, the atmosphere in step S52 is ammonia gas.
Example 3
A preparation method of a modified super-capacitor electrode takes any one of or a mixture of modified carbon onions and carbon nanohorns as an additive to be added into super-capacitor electrode slurry, and comprises the following specific steps:
step 1, mixing resorcinol solution or hydroquinone solution, formaldehyde solution or furfural solution, catalyst and distilled water, and uniformly stirring to obtain capacitor electrode slurry;
step 2, adding a certain mass percentage of the additive into the capacitance electrode slurry prepared in the step 1, and stirring at a high speed for 2 hours in a vacuum environment to obtain an initial solution;
and 3, treating the initial liquid crystal gel prepared in the step 2, drying, carbonizing, performing heat treatment and tabletting to obtain the super capacitor electrode.
Further, the additive added in the step 2 is 50% of the mass of the capacitor electrode slurry.
Further, the particle size of the additive is 100 nm.
Further, the stirring speed in the step 2 is 2000 r/min.
Further, the specific preparation process of the additive comprises the following steps:
s51, preparing the cathode and anode of the additive by taking a graphite rod as an electric arc method, placing the cathode and anode of 2 graphite rods in a reaction medium oppositely, and introducing high-voltage current of 1.5 kiloamperes to perform direct current arc discharge to prepare an anode product of the graphite rod, namely the additive;
s52, placing the additive prepared in the step S51 in a constant temperature area of a quartz tube, introducing atmosphere, heating to 500 ℃, and then applying 350V voltage for reaction for 24 hours to obtain the modified additive.
Further, the reflecting medium in the step S51 is any one of liquid nitrogen, liquid argon or water;
preferably, when the reaction medium in step S51 is liquid nitrogen or liquid argon, the anode product of the graphite rod is a carbon nanohorn;
preferably, when the reaction medium in step S51 is water, the anode product of the graphite rod is carbon onion.
Further, the atmosphere in step S52 is a mixed gas of nitrogen and ammonia.
Example 4
A preparation method of a modified super-capacitor electrode takes any one of or a mixture of modified carbon onions and carbon nanohorns as an additive to be added into super-capacitor electrode slurry, and comprises the following specific steps:
step 1, mixing resorcinol solution or hydroquinone solution, formaldehyde solution or furfural solution, catalyst and distilled water, and uniformly stirring to obtain capacitor electrode slurry;
step 2, adding a certain mass percentage of the additive into the capacitance electrode slurry prepared in the step 1, and stirring at a high speed for 1-3 hours in a vacuum environment to obtain an initial liquid;
and 3, treating the initial liquid crystal gel prepared in the step 2, drying, carbonizing, performing heat treatment and tabletting to obtain the super capacitor electrode.
Further, the additive added in the step 2 accounts for 20% of the mass of the capacitor electrode slurry.
Further, the particle size of the additive is 70 nm.
Further, the stirring speed in the step 2 is 1800 r/min.
Further, the specific preparation process of the additive comprises the following steps:
s51, preparing the cathode and anode of the additive by taking a graphite rod as an electric arc method, placing the cathode and anode of 2 graphite rods in a reaction medium oppositely, and introducing high-voltage current of 1.5 kiloamperes to perform direct current arc discharge to prepare an anode product of the graphite rod, namely the additive;
s52, placing the additive prepared in the step S51 in a constant temperature area of a quartz tube, introducing atmosphere, heating to 800 ℃, and applying a voltage of 450V to react for 1-48 h to obtain the modified additive.
Further, the reflecting medium in the step S51 is any one of liquid nitrogen, liquid argon or water;
preferably, when the reaction medium in step S51 is liquid nitrogen or liquid argon, the anode product of the graphite rod is a carbon nanohorn;
preferably, when the reaction medium in step S51 is water, the anode product of the graphite rod is carbon onion.
Further, the atmosphere in step S52 is either nitrogen or ammonia or a mixture of both.
Example 5
A preparation method of a modified super-capacitor electrode takes any one of or a mixture of modified carbon onions and carbon nanohorns as an additive to be added into super-capacitor electrode slurry, and comprises the following specific steps:
step 1, mixing resorcinol solution or hydroquinone solution, formaldehyde solution or furfural solution, catalyst and distilled water, and uniformly stirring to obtain capacitor electrode slurry;
step 2, adding a certain mass percentage of the additive into the capacitance electrode slurry prepared in the step 1, and stirring at a high speed for 1-3 hours in a vacuum environment to obtain an initial liquid;
and 3, treating the initial liquid crystal gel prepared in the step 2, drying, carbonizing, performing heat treatment and tabletting to obtain the super capacitor electrode.
Further, the additive added in the step 2 is 50% of the mass of the capacitor electrode slurry.
Further, the particle size of the additive is 80 nm.
Further, the stirring speed in the step 2 is 2000 r/min.
Further, the specific preparation process of the additive comprises the following steps:
s51, preparing the cathode and anode of the additive by taking a graphite rod as an electric arc method, placing the cathode and anode of 2 graphite rods in a reaction medium oppositely, and introducing high-voltage current of 1.5 kiloamperes to perform direct current arc discharge to prepare an anode product of the graphite rod, namely the additive;
s52, placing the additive prepared in the step S51 in a constant temperature area of a quartz tube, introducing the atmosphere, heating to 1200 ℃, and then applying 400V voltage to react for 30h to obtain the modified additive.
Further, the reflecting medium in the step S51 is any one of liquid nitrogen, liquid argon or water;
preferably, when the reaction medium in step S51 is liquid nitrogen or liquid argon, the anode product of the graphite rod is a carbon nanohorn;
preferably, when the reaction medium in step S51 is water, the anode product of the graphite rod is carbon onion.
Further, the atmosphere in step S52 is either nitrogen or ammonia or a mixture of both.
According to the invention, carbon nanohorns or carbon onions with the particle size of 20nm-120nm are added as additives according to the mass percentage of the capacitor electrode slurry, so that the additives are fully filled in gaps of the electrode, the specific energy density and the specific power density of the electrode are improved, and the electric conductivity and the heat conductivity of the electrode are effectively enhanced.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (2)
1. A preparation method of a modified supercapacitor electrode is characterized in that any one of or a mixture of modified carbon onions and modified carbon nanohorns is used as a modification additive to be added into supercapacitor electrode slurry, and the specific method is as follows:
step 1, mixing resorcinol solution or hydroquinone solution, formaldehyde solution or furfural solution, catalyst and distilled water, and uniformly stirring to obtain capacitor electrode slurry;
step 2, adding the modified additive which accounts for 0.5-100% of the mass of the capacitor electrode slurry into the capacitor electrode slurry prepared in the step 1, and stirring for 1-3 hours at a stirring speed of 1500-2500 r/min under a vacuum environment to obtain an initial liquid;
step 3, performing gel treatment, drying treatment, carbonization heat treatment and tabletting on the initial solution prepared in the step 2 to prepare the super capacitor electrode;
the specific preparation process of the modified additive comprises the following steps:
s51, preparing the cathode and anode of the additive by taking a graphite rod as an electric arc method, placing the cathode and anode of 2 graphite rods in a reaction medium oppositely, and introducing high-voltage current of 1.5 kiloamperes to perform direct current arc discharge to prepare an anode product of the graphite rod, namely the additive;
s52, putting the additive prepared in the step S51 into a constant temperature area of a quartz tube, introducing any one or a mixed gas of nitrogen and ammonia gas, heating to 400-1500 ℃, and applying a voltage of 300-500V to react for 1-48 h to obtain a modified additive;
the reflecting medium in the step S51 is any one of liquid nitrogen, liquid argon or water;
when the reaction medium in the step S51 is liquid nitrogen or liquid argon, the anode product of the graphite rod is a carbon nanohorn;
when the reaction medium is water in step S51, the anode product of the graphite rod is carbon onion.
2. The method for preparing the modified supercapacitor electrode according to claim 1, wherein the method comprises the following steps: the particle size of the modified additive is 20nm-120 nm.
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