Super capacitor slurry preparation method

Abstract

The invention discloses a supercapacitor slurry preparation method which comprises the following steps: carrying out high-temperature heat preservation on a modified filler as a raw material in a hydrogen and argon mixed atmosphere to prepare a pretreated filler, carrying out high-temperature heat preservation on the pretreated filler in an air atmosphere to prepare a precursor, mixing the precursor with potassium permanganate, and preparing a modified additive under the action of a sulfuric acid solution. High-temperature heat preservation is conducted in the mixed atmosphere of hydrogen and argon, tungstic acid in the modified filler can be converted into tungsten trioxide, tungsten trioxide can be reduced by hydrogen, stable nitrogen and boron doped carbon is formed on the surface of the modified filler, then high-temperature heat preservation is conducted on the pretreated filler in air, cobalt and nickel are converted into cobalt oxide and nickel oxide, and the modified filler is prepared. The modified additive has high specific capacitance through cooperation with surface manganese dioxide, electrons can be rapidly transmitted through carbon grid channel linkage, stability can still be kept after multiple charging and discharging cycles, and the service life of the supercapacitor is further prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of capacitor preparation, and in particular to a method for preparing supercapacitor slurry. Background Art

[0002] Supercapacitors, also known as electrochemical capacitors, have broad application prospects in the fields of new energy generation, electric vehicles, information technology, aerospace, and national defense because of their moderate energy density and power density, long cycle life, and green environmental protection. For supercapacitors, electrodes are generally composed of three parts: electrode materials, conductive agents, and binders. The electrode material is the carrier of charge storage, so the electrode material determines the main performance parameters of the supercapacitor. Currently, the commonly used electrode materials are carbon-based material electrodes, conductive polymer electrodes, and metal oxides. As the electrode material of the supercapacitor, it is required not only to have a high specific surface area, but also to have a low internal resistance, so as to meet the requirements of large current rapid charging and discharging. However, the specific capacity and rate performance of the current supercapacitor electrode materials are not high, which limits the use of advanced capacitors. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing a supercapacitor slurry, which solves the problems of poor rate performance and short service life of supercapacitors at the current stage.

[0004] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing supercapacitor slurry is prepared by the following steps: Step A1: keeping the modified filler at a temperature of 550-600° C. in a mixed atmosphere of hydrogen and argon for 3-5 hours to obtain a pretreated filler, and keeping the pretreated filler at a temperature of 300-350° C. for 2-3 hours to obtain a precursor; Step A2: Dispersing the precursor in deionized water, stirring and adding potassium permanganate at a speed of 200-300 r / min and a temperature of 25-30° C., stirring for 2-3 hours, adding sulfuric acid solution, stirring for 1-1.5 hours, heating to 80-85° C., stirring for 2-3 hours, and obtaining a modified additive; Step A3: Weigh the following raw materials in parts by weight: 80-90 parts of modified additives, 10-15 parts of carbon black, 2-5 parts of sodium carboxymethyl cellulose and 4-8 parts of styrene-butadiene rubber, mix the raw materials evenly, and prepare supercapacitor slurry.

[0005] Furthermore, the volume ratio of hydrogen to argon in the hydrogen and nitrogen mixed atmosphere described in step A1 is 8:92.

[0006] Furthermore, the amount ratio of the precursor, deionized water, potassium permanganate and sulfuric acid solution described in step A2 is 20 mg: 100 mL: 1 g: 50 mL, and the mass fraction of the sulfuric acid solution is 0.5%.

[0007] Further, the modified filler is prepared by the following steps: Step B1: Mix carboxylated carbon nanotubes, ethylenediamine and DMF uniformly, stir for 30-40 min at a speed of 120-150 r / min and a temperature of 60-65° C., add thionyl chloride, stir for 30-40 min, cool to 50-55° C., add dicyclohexylcarbodiimide, and react for 18-20 h to obtain amino carbon nanotubes, and introduce nitrogen protection into 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieves, and react for 10-15 h at a speed of 120-150 r / min and a temperature of 60-65° C. to obtain an intermediate; Step B2: The intermediate, the amino carbon nanotubes, triethylamine and DMF are mixed, and the reaction is carried out for 3-5 hours at a speed of 200-300 r / min and a temperature of 20-25° C. to obtain pretreated carbon nanotubes. The pretreated carbon nanotubes, 2-mercaptoimidazole, benzophenone and DMF are mixed uniformly, and the reaction is carried out for 2-3 hours at a speed of 150-200 r / min, a temperature of 25-30° C. and irradiation with 365 nm ultraviolet light to obtain modified carbon nanotubes; Step B3: uniformly mix the modified carbon nanotubes, 2-methylimidazole and methanol, perform ultrasonic treatment and add cobalt nitrate hexahydrate and nickel nitrate hexahydrate at a speed of 200-300 r / min and a temperature of 35-40°C, react for 3-5 hours, filter and remove the filtrate, disperse the substrate in deionized water, perform ultrasonic treatment and add sodium tungstate and hydrochloric acid solution at a frequency of 20-30 kHz and a temperature of 20-25°C, raise the temperature to 180-185°C, react for 8-10 hours, and obtain a modified filler.

[0008] Furthermore, the amount ratio of the carboxylated carbon nanotubes, ethylenediamine, thionyl chloride and dicyclohexylcarbodiimide described in step B1 is 1g:6:30mL:15g, and the amount ratio of 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieve is 3mmol:3mmol:30mL:1g.

[0009] Furthermore, the molar ratio of the amino group on the amination carbon nanotubes and the intermediate in step B2 is 1:1, the amount of triethylamine used is 3% of the mass of the intermediate, the molar ratio of the double bond on the pretreated carbon nanotubes and 2-mercaptoimidazole is 1:1, and the amount of benzophenone used is 1% of the mass of 2-mercaptoimidazole.

[0010] Furthermore, the amount ratio of the modified carbon nanotubes, 2-methylimidazole, methanol, cobalt nitrate hexahydrate and nickel nitrate hexahydrate described in step B3 is 1g:2g:50mL:1.5g:1.5g, the amount ratio of the substrate, deionized water, sodium tungstate and hydrochloric acid solution is 2g:30mL:7mmol:5mL, and the mass fraction of the hydrochloric acid solution is 1.5%.

[0011] Beneficial effects of the present invention: A supercapacitor slurry prepared by the present invention includes the following raw materials: a modified additive, carbon black, sodium carboxymethyl cellulose and styrene-butadiene rubber. The modified additive uses a modified filler as a raw material and is heat-insulated at high temperature in a mixed atmosphere of hydrogen and argon to obtain a pretreated filler. The pretreated filler is heat-insulated at high temperature in an air atmosphere to obtain a precursor. The precursor is mixed with potassium permanganate, and under the action of a sulfuric acid solution, manganese dioxide crystals are formed on the surface of the precursor to obtain the modified additive.

[0012] The modified filler uses carboxylated carbon nanotubes and ethylenediamine as raw materials, undergoes a dehydration reaction under the action of dicyclohexylcarbodiimide, so that the carboxyl groups on the carboxylated carbon nanotubes react with the amino groups on the ethylenediamine, and then the amino groups are grafted on the surface to obtain amino carbon nanotubes, and 4-formylphenylboronic acid and 3,4-dihydroxystyrene are reacted, so that the boric acid group on the 4-formylphenylboronic acid reacts with the catechol on the 3,4-dihydroxystyrene to obtain an intermediate, and the intermediate and the amino carbon nanotubes are reacted under the action of triethylamine, so that the aldehyde group on the intermediate reacts with the amino group. The amino groups on the carbon nanotubes react to obtain pretreated carbon nanotubes, the pretreated carbon nanotubes and 2-mercaptoimidazole react under ultraviolet light, so that the double bonds on the pretreated carbon nanotubes react with the thiol groups on the 2-mercaptoimidazole to obtain modified carbon nanotubes, the modified carbon nanotubes and 2-methylimidazole are uniformly mixed, and then cobalt nitrate hexahydrate and nickel nitrate hexahydrate are added to form a cobalt-nickel composite organic framework on the surface of the modified carbon nanotubes, and then sodium tungstate is added and treated with a hydrochloric acid solution to load tungstic acid in the surface pores of the cobalt-nickel composite organic framework to obtain a modified filler.

[0013] By keeping the pretreated filler at high temperature in a mixed atmosphere of hydrogen and argon, the tungstic acid in the modified filler can be converted into tungsten trioxide. The tungsten trioxide will be reduced by hydrogen, and the absence of oxygen allows the nitrogen and boron elements in the cobalt-nickel composite organic framework on the surface of the modified filler to form a stable doping. The pretreated filler is then kept at high temperature in the air to convert cobalt and nickel into cobalt oxide and nickel oxide, which are combined with surface manganese dioxide to give the modified additive a higher specific capacitance. The carbon grid channel is connected to quickly transmit electrons and maintain stability after multiple charge and discharge cycles, thereby extending the service life of the supercapacitor. The capacitance of the modified additive comes from the pseudocapacitive reaction, which can store and release charges through a fast Faraday reaction on the electrode surface, thereby improving the rate performance of the supercapacitor. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0015] Figure 1 The slurry prepared in Example 1 was processed into a supercapacitor for constant current charge and discharge rate performance test.

[0016] Figure 2 The slurry prepared in Example 1 was processed into a constant current charge-discharge long cycle curve of a supercapacitor.

[0017] Figure 3 The slurry prepared in Example 2 was processed into a supercapacitor for constant current charge and discharge rate performance test.

[0018] Figure 4 The slurry prepared in Example 2 was processed into a constant current charge-discharge long cycle curve of a supercapacitor.

[0019] Figure 5 The slurry prepared in Example 3 was processed into a supercapacitor for constant current charge and discharge rate performance test.

[0020] Figure 6 The slurry prepared in Example 3 was processed into a constant current charge-discharge long cycle curve of a supercapacitor.

[0021] Figure 7 The slurry prepared in Comparative Example 1 was processed into a supercapacitor for constant current charge and discharge rate performance test.

[0022] Figure 8 The slurry prepared in Comparative Example 1 was processed into a constant current charge-discharge long cycle curve of a supercapacitor.

[0023] Fig. 9 The slurry prepared in Comparative Example 2 was processed into a supercapacitor for constant current charge and discharge rate performance test.

[0024] Fig.10 The slurry prepared in Comparative Example 2 was processed into a constant current charge-discharge long cycle curve of a supercapacitor.

[0025] Fig.11 The slurry prepared in comparative example 3 was processed into a supercapacitor for constant current charge and discharge rate performance test.

[0026] Fig.12 The slurry prepared in Comparative Example 3 was processed into a constant current charge-discharge long cycle curve of a supercapacitor. DETAILED DESCRIPTION

[0027] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] Example 1: A method for preparing a supercapacitor slurry, comprising the following steps: Step A1: The modified filler is kept at a temperature of 550° C. in a mixed atmosphere of hydrogen and argon for 3 hours to obtain a pretreated filler, and the pretreated filler is kept at a high temperature of 300° C. for 2 hours to obtain a precursor; Step A2: Dispersing the precursor in deionized water, stirring and adding potassium permanganate at a speed of 200 r / min and a temperature of 25-30° C., stirring for 2 hours, adding sulfuric acid solution, stirring for 1 hour, heating to 80° C., stirring for 2 hours, and preparing a modified additive; Step A3: Weigh the following raw materials in parts by weight: 80 parts of modified additives, 10 parts of carbon black, 2 parts of sodium carboxymethyl cellulose and 4 parts of styrene-butadiene rubber, mix the raw materials evenly, and prepare supercapacitor slurry.

[0029] The volume ratio of hydrogen to argon in the hydrogen and nitrogen mixed atmosphere described in step A1 is 8:92.

[0030] The amount ratio of the precursor, deionized water, potassium permanganate and sulfuric acid solution described in step A2 is 20 mg: 100 mL: 1 g: 50 mL, and the mass fraction of the sulfuric acid solution is 0.5%.

[0031] The model of the styrene-butadiene rubber described in step A3 is ACN40.

[0032] The modified filler is prepared by the following steps: Step B1: Carboxylated carbon nanotubes, ethylenediamine and DMF are mixed uniformly, stirred for 30 minutes at a speed of 120 r / min and a temperature of 60°C, thionyl chloride is added, stirred for 30 minutes, the temperature is lowered to 50°C, dicyclohexylcarbodiimide is added, and the reaction is carried out for 18 hours to obtain amino carbon nanotubes, 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieves are passed through nitrogen protection, and the reaction is carried out for 10 hours at a speed of 120 r / min and a temperature of 60°C to obtain an intermediate; Step B2: The intermediate, the amino carbon nanotubes, triethylamine and DMF were mixed, and the reaction was carried out for 3 hours at a speed of 200 r / min and a temperature of 20° C. to obtain pretreated carbon nanotubes. The pretreated carbon nanotubes, 2-mercaptoimidazole, benzophenone and DMF were mixed evenly, and the reaction was carried out for 2 hours at a speed of 150 r / min, a temperature of 25° C. and irradiation with 365 nm ultraviolet light to obtain modified carbon nanotubes; Step B3: The modified carbon nanotubes, 2-methylimidazole and methanol are mixed evenly, and cobalt nitrate hexahydrate and nickel nitrate hexahydrate are added under ultrasonic treatment at a speed of 200 r / min and a temperature of 35°C. After reacting for 3 hours, the filtrate is removed by filtration, and the substrate is dispersed in deionized water. Under the conditions of a frequency of 20 kHz and a temperature of 20°C, sodium tungstate and hydrochloric acid solution are added under ultrasonic treatment, and the temperature is raised to 180°C. The mixture is reacted for 8 hours to obtain a modified filler.

[0033] The amount ratio of the carboxylated carbon nanotubes, ethylenediamine, thionyl chloride and dicyclohexylcarbodiimide described in step B1 is 1g:6:30mL:15g, and the amount ratio of 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieve is 3mmol:3mmol:30mL:1g.

[0034] The molar ratio of the amino group on the amination carbon nanotubes and the intermediate in step B2 is 1:1, the amount of triethylamine used is 3% of the mass of the intermediate, the molar ratio of the double bond on the pretreated carbon nanotubes and 2-mercaptoimidazole is 1:1, and the amount of benzophenone used is 1% of the mass of 2-mercaptoimidazole.

[0035] The amount ratio of the modified carbon nanotubes, 2-methylimidazole, methanol, cobalt nitrate hexahydrate and nickel nitrate hexahydrate described in step B3 is 1g:2g:50mL:1.5g:1.5g, the amount ratio of the substrate, deionized water, sodium tungstate and hydrochloric acid solution is 2g:30mL:7mmol:5mL, and the mass fraction of the hydrochloric acid solution is 1.5%.

[0036] Example 2: A method for preparing a supercapacitor slurry, comprising the following steps: Step A1: keeping the modified filler at 550° C. in a mixed atmosphere of hydrogen and argon for 4 hours to obtain a pretreated filler, and keeping the pretreated filler at 350° C. for 2 hours to obtain a precursor; Step A2: Disperse the precursor in deionized water, stir and add potassium permanganate at a speed of 300 r / min and a temperature of 25° C., stir for 3 hours, add sulfuric acid solution, stir for 1 hour, heat to 85° C., stir for 2 hours, and prepare a modified additive; Step A3: Weigh the following raw materials in parts by weight: 85 parts of modified additives, 13 parts of carbon black, 3 parts of sodium carboxymethyl cellulose and 6 parts of styrene-butadiene rubber, mix the raw materials evenly, and prepare supercapacitor slurry.

[0037] The volume ratio of hydrogen to argon in the hydrogen and nitrogen mixed atmosphere described in step A1 is 8:92.

[0038] The amount ratio of the precursor, deionized water, potassium permanganate and sulfuric acid solution described in step A2 is 20 mg: 100 mL: 1 g: 50 mL, and the mass fraction of the sulfuric acid solution is 0.5%.

[0039] The model of the styrene-butadiene rubber described in step A3 is XNBR.

[0040] The modified filler is prepared by the following steps: Step B1: Carboxylated carbon nanotubes, ethylenediamine and DMF are mixed uniformly, stirred for 35 minutes at a speed of 120 r / min and a temperature of 65°C, thionyl chloride is added, stirred for 35 minutes, the temperature is lowered to 50°C, dicyclohexylcarbodiimide is added, and the reaction is carried out for 20 hours to obtain amino carbon nanotubes, 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieves are passed through nitrogen protection, and the reaction is carried out for 10 hours at a speed of 120 r / min and a temperature of 65°C to obtain an intermediate; Step B2: The intermediate, the amino carbon nanotubes, triethylamine and DMF were mixed, and the reaction was carried out for 4 hours at a speed of 200 r / min and a temperature of 25° C. to obtain pretreated carbon nanotubes. The pretreated carbon nanotubes, 2-mercaptoimidazole, benzophenone and DMF were mixed evenly, and the reaction was carried out for 2 hours at a speed of 150 r / min, a temperature of 30° C. and irradiation with 365 nm ultraviolet light to obtain modified carbon nanotubes; Step B3: The modified carbon nanotubes, 2-methylimidazole and methanol are mixed evenly, and cobalt nitrate hexahydrate and nickel nitrate hexahydrate are added under ultrasonic treatment at a speed of 200 r / min and a temperature of 40°C. After reacting for 4 hours, the filtrate is removed by filtration, and the substrate is dispersed in deionized water. Under the conditions of a frequency of 25 kHz and a temperature of 20°C, sodium tungstate and hydrochloric acid solution are added under ultrasonic treatment, and the temperature is raised to 185°C. The mixture is reacted for 9 hours to obtain a modified filler.

[0041] The amount ratio of the carboxylated carbon nanotubes, ethylenediamine, thionyl chloride and dicyclohexylcarbodiimide described in step B1 is 1g:6:30mL:15g, and the amount ratio of 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieve is 3mmol:3mmol:30mL:1g.

[0042] The molar ratio of the amino group on the amination carbon nanotubes and the intermediate in step B2 is 1:1, the amount of triethylamine used is 3% of the mass of the intermediate, the molar ratio of the double bond on the pretreated carbon nanotubes and 2-mercaptoimidazole is 1:1, and the amount of benzophenone used is 1% of the mass of 2-mercaptoimidazole.

[0043] The amount ratio of the modified carbon nanotubes, 2-methylimidazole, methanol, cobalt nitrate hexahydrate and nickel nitrate hexahydrate described in step B3 is 1g:2g:50mL:1.5g:1.5g, the amount ratio of the substrate, deionized water, sodium tungstate and hydrochloric acid solution is 2g:30mL:7mmol:5mL, and the mass fraction of the hydrochloric acid solution is 1.5%.

[0044] Embodiment 3: A method for preparing a supercapacitor slurry, comprising the following steps: Step A1: The modified filler is kept at a temperature of 600° C. in a mixed atmosphere of hydrogen and argon for 5 hours to obtain a pretreated filler, and the pretreated filler is kept at a high temperature of 350° C. for 3 hours to obtain a precursor; Step A2: Disperse the precursor in deionized water, stir and add potassium permanganate at a speed of 300 r / min and a temperature of 30° C., stir for 3 hours, add sulfuric acid solution, stir for 1-1.5 hours, heat to 85° C., stir for 3 hours, and prepare a modified additive; Step A3: Weigh the following raw materials in parts by weight: 90 parts of modified additives, 15 parts of carbon black, 5 parts of sodium carboxymethyl cellulose and 8 parts of styrene-butadiene rubber, mix the raw materials evenly, and prepare supercapacitor slurry.

[0045] The volume ratio of hydrogen to argon in the hydrogen and nitrogen mixed atmosphere described in step A1 is 8:92.

[0046] The amount ratio of the precursor, deionized water, potassium permanganate and sulfuric acid solution described in step A2 is 20 mg: 100 mL: 1 g: 50 mL, and the mass fraction of the sulfuric acid solution is 0.5%.

[0047] The model of the styrene-butadiene rubber described in step A3 is XNBR.

[0048] The modified filler is prepared by the following steps: Step B1: Carboxylated carbon nanotubes, ethylenediamine and DMF are mixed uniformly, stirred for 40 minutes at a speed of 150 r / min and a temperature of 65°C, thionyl chloride is added, stirred for 40 minutes, the temperature is lowered to 55°C, dicyclohexylcarbodiimide is added, and the reaction is carried out for 20 hours to obtain amino carbon nanotubes, 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieves are passed through nitrogen protection, and the reaction is carried out for 15 hours at a speed of 150 r / min and a temperature of 65°C to obtain an intermediate; Step B2: The intermediate, the amino carbon nanotubes, triethylamine and DMF were mixed, and the reaction was carried out for 5 hours at a speed of 300 r / min and a temperature of 25° C. to obtain pretreated carbon nanotubes. The pretreated carbon nanotubes, 2-mercaptoimidazole, benzophenone and DMF were mixed evenly, and the reaction was carried out for 3 hours at a speed of 200 r / min, a temperature of 30° C. and irradiation with 365 nm ultraviolet light to obtain modified carbon nanotubes; Step B3: The modified carbon nanotubes, 2-methylimidazole and methanol are mixed evenly, and cobalt nitrate hexahydrate and nickel nitrate hexahydrate are added under ultrasonic treatment at a speed of 300 r / min and a temperature of 40°C. After reacting for 5 hours, the filtrate is removed by filtration, and the substrate is dispersed in deionized water. Under the conditions of a frequency of 30 kHz and a temperature of 25°C, sodium tungstate and hydrochloric acid solution are added under ultrasonic treatment, and the temperature is raised to 185°C. The mixture is reacted for 10 hours to obtain a modified filler.

[0049] The amount ratio of the carboxylated carbon nanotubes, ethylenediamine, thionyl chloride and dicyclohexylcarbodiimide described in step B1 is 1g:6:30mL:15g, and the amount ratio of 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieve is 3mmol:3mmol:30mL:1g.

[0050] The molar ratio of the amino group on the amination carbon nanotubes and the intermediate in step B2 is 1:1, the amount of triethylamine used is 3% of the mass of the intermediate, the molar ratio of the double bond on the pretreated carbon nanotubes and 2-mercaptoimidazole is 1:1, and the amount of benzophenone used is 1% of the mass of 2-mercaptoimidazole.

[0051] The amount ratio of the modified carbon nanotubes, 2-methylimidazole, methanol, cobalt nitrate hexahydrate and nickel nitrate hexahydrate described in step B3 is 1g:2g:50mL:1.5g:1.5g, the amount ratio of the substrate, deionized water, sodium tungstate and hydrochloric acid solution is 2g:30mL:7mmol:5mL, and the mass fraction of the hydrochloric acid solution is 1.5%.

[0052] Comparative Example 1. Compared with Example 1, the following raw materials were weighed in parts by weight: 40 parts of modified additives, 40 parts of activated carbon YP-50F, 10 parts of carbon black, 2 parts of sodium carboxymethyl cellulose and 4 parts of styrene-butadiene rubber, and the raw materials were mixed to replace the supercapacitor slurry.

[0053] Comparative Example 2: Compared with Example 1, modified carbon nanotubes, 2-methylimidazole and methanol are uniformly mixed, ultrasonically treated and cobalt nitrate hexahydrate and nickel nitrate hexahydrate are added at a speed of 200 r / min and a temperature of 35°C, and the reaction is carried out for 3 hours. The product replaces the modified filler, and the other steps are the same.

[0054] Comparative Example 3: Compared with Example 1, this comparative example uses a precursor instead of the modified additive, and the remaining steps are the same.

[0055] The slurries prepared in Examples 1-3 and Comparative Examples 1-3 were evenly coated on aluminum foil with an automatic coating machine to a coating thickness of 100 μm, and dried for 12 h in an air atmosphere at a temperature of 80° C. to obtain supercapacitor electrode materials. The electrochemical performance tests were performed. Figure 1 , 3 , 5 It can be seen that when the current density is 0.1A / g, the specific capacity is 1726-1935F / g, and when the current density is 20A / g, the specific capacity is 875-1010F / g. Figure 2 , 4 From Figure 6, it can be seen that after 10000 cycles of charge and discharge at 10A / g, the capacitance retention rate is 93.63-96.11%, indicating that the present application has good rate performance and long service life.

[0056] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing supercapacitor slurry, characterized in that: Made by the following steps: Step A1: keeping the modified filler at a temperature of 550-600° C. in a mixed atmosphere of hydrogen and argon for 3-5 hours to obtain a pretreated filler, and keeping the pretreated filler at a temperature of 300-350° C. for 2-3 hours to obtain a precursor; Step A2: Dispersing the precursor in deionized water, stirring and adding potassium permanganate at a speed of 200-300 r / min and a temperature of 25-30° C., stirring for 2-3 hours, adding sulfuric acid solution, stirring for 1-1.5 hours, heating to 80-85° C., stirring for 2-3 hours, and obtaining a modified additive; Step A3: Weigh the following raw materials in parts by weight: 80-90 parts of modified additives, 10-15 parts of carbon black, 2-5 parts of sodium carboxymethyl cellulose and 4-8 parts of styrene-butadiene rubber, mix the raw materials evenly, and prepare supercapacitor slurry.

2. The method for preparing supercapacitor slurry according to claim 1, characterized in that: The volume ratio of hydrogen to argon in the hydrogen and nitrogen mixed atmosphere described in step A1 is 8:

92.

3. The method for preparing supercapacitor slurry according to claim 1, characterized in that: The amount ratio of the precursor, deionized water, potassium permanganate and sulfuric acid solution described in step A2 is 20 mg: 100 mL: 1 g: 50 mL, and the mass fraction of the sulfuric acid solution is 0.5%.

4. The method for preparing supercapacitor slurry according to claim 1, characterized in that: The modified filler is prepared by the following steps: Step B1: Mix carboxylated carbon nanotubes, ethylenediamine and DMF uniformly, stir for 30-40 min at a speed of 120-150 r / min and a temperature of 60-65° C., add thionyl chloride, stir for 30-40 min, cool to 50-55° C., add dicyclohexylcarbodiimide, and react for 18-20 h to obtain amino carbon nanotubes, and introduce nitrogen protection into 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieves, and react for 10-15 h at a speed of 120-150 r / min and a temperature of 60-65° C. to obtain an intermediate; Step B2: The intermediate, the amino carbon nanotubes, triethylamine and DMF are mixed, and the reaction is carried out for 3-5 hours at a speed of 200-300 r / min and a temperature of 20-25° C. to obtain pretreated carbon nanotubes. The pretreated carbon nanotubes, 2-mercaptoimidazole, benzophenone and DMF are mixed uniformly, and the reaction is carried out for 2-3 hours at a speed of 150-200 r / min, a temperature of 25-30° C. and irradiation with 365 nm ultraviolet light to obtain modified carbon nanotubes; Step B3: uniformly mix the modified carbon nanotubes, 2-methylimidazole and methanol, perform ultrasonic treatment and add cobalt nitrate hexahydrate and nickel nitrate hexahydrate at a speed of 200-300 r / min and a temperature of 35-40°C, react for 3-5 hours, filter and remove the filtrate, disperse the substrate in deionized water, perform ultrasonic treatment and add sodium tungstate and hydrochloric acid solution at a frequency of 20-30 kHz and a temperature of 20-25°C, raise the temperature to 180-185°C, react for 8-10 hours, and obtain a modified filler.

5. The method for preparing supercapacitor slurry according to claim 4, characterized in that: The amount ratio of the carboxylated carbon nanotubes, ethylenediamine, thionyl chloride and dicyclohexylcarbodiimide described in step B1 is 1g:6:30mL:15g, and the amount ratio of 4-formylphenylboronic acid, 3,4-dihydroxystyrene, chloroform and 5A molecular sieve is 3mmol:3mmol:30mL:1g.

6. The method for preparing supercapacitor slurry according to claim 4, characterized in that: The molar ratio of the amino group on the amination carbon nanotubes and the intermediate in step B2 is 1:1, the amount of triethylamine used is 3% of the mass of the intermediate, the molar ratio of the double bond on the pretreated carbon nanotubes and 2-mercaptoimidazole is 1:1, and the amount of benzophenone used is 1% of the mass of 2-mercaptoimidazole.

7. The method for preparing supercapacitor slurry according to claim 4, characterized in that: The amount ratio of the modified carbon nanotubes, 2-methylimidazole, methanol, cobalt nitrate hexahydrate and nickel nitrate hexahydrate described in step B3 is 1g:2g:50mL:1.5g:1.5g, the amount ratio of the substrate, deionized water, sodium tungstate and hydrochloric acid solution is 2g:30mL:7mmol:5mL, and the mass fraction of the hydrochloric acid solution is 1.5%.

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