CN109704305B

CN109704305B - Preparation method and application of melamine resin-based carbon material synthesized by taking ZIF-67 as template

Info

Publication number: CN109704305B
Application number: CN201910057174.4A
Authority: CN
Inventors: 李梅; 岳嘉继; 刘鹏
Original assignee: Qilu University of Technology
Current assignee: Qilu University of Technology
Priority date: 2019-01-22
Filing date: 2019-01-22
Publication date: 2022-03-18
Anticipated expiration: 2039-01-22
Also published as: CN109704305A

Abstract

The invention relates to a preparation method and application of a melamine resin-based carbon material synthesized by taking ZIF-67 as a template. The preparation method comprises the following steps: 2.80g of melamine and 0.050g of ZIF-67 are dissolved in 90.0ml of deionized water, the mixture is placed in a three-neck flask and stirred for 0.5h, 6.0ml of formaldehyde solution is added into the three-neck flask after the solution is stirred uniformly, and the mixture is stirred for 0.5 h. Dropping a certain amount of glacial acetic acid into a three-neck flask at 60%^oAnd C, obtaining milky suspension by reaction. And (3) alternately centrifuging and washing the obtained product by using ethanol and deionized water, and drying the product in an oven after the supernatant is neutral. The obtained copolymer is put under the protection of argon at 700 DEG^oAnd C, carbonizing to obtain the melamine resin-based carbon material synthesized by taking ZIF-67 as a template. The preparation method disclosed by the invention is simple in preparation process and high in yield, and the prepared melamine resin-based carbon material synthesized by taking ZIF-67 as a template has the advantages of stable structure, good rate capability, excellent electrochemical performance and the like, and is very suitable for being applied to the field of supercapacitors as an electrode material.

Description

Preparation method and application of melamine resin-based carbon material synthesized by taking ZIF-67 as template

Technical Field

The invention belongs to the technical field of new energy electronic materials, and relates to a preparation method and application of a melamine resin-based carbon material synthesized by taking ZIF-67 as a template.

Background

In recent years, extensive research is carried out on melamine resin-based carbon materials and zeolite-like imidazolate framework compounds ZIFs, wherein the single melamine resin-based carbon material has higher nitrogen content and can provide considerable pseudocapacitance when being used as an electrode material of a super capacitor. Ma et al firstly prepare melamine formaldehyde solution resin (MF) balls by a hydrothermal method, and then carbonize the balls to obtain NHCS, the specific capacitance value of which at 0.1A/g current density is 306F/g, which has excellent specific capacitance, but poor cycle stability, and further improvement in performance is required (Ma FW, ZHao H, Sun LP, et al. A factor route for nitro-large hole mapping carbon spheres with super performance for in supercapacis [ J ] Journal of Materials Chemistry, 2012, 22(27):13464 13468.).

The ZIFs are novel porous coordination polymers PCPs, N atoms on imidazole rings of the ZIFs are complexed on divalent transition metal ions to form a porous crystal material with a zeolite-like topological structure, the material has high crystallinity, narrow pore size distribution, large specific surface area, good thermal stability and chemical stability due to the special structure, and the specific capacitance value of 93F/g in 2.0 mol/L KOH electrolyte at the current density of 0.5A/g is smaller than the specific capacitance, and the cycling stability is poor, so that the ZIFs can be applied by further improvement. (Research on inorganic associated mapping of zeolitic inorganic azoate frame-67 (ZIF-67) and its superparameter performance [ J ]. Journal of Light Industry, 2017, 32(5): 24-31.).

Chinese patent document CN105671692A discloses a preparation method of a melamine resin modified nitrogen-rich porous carbon fiber electrode material, which comprises the following steps: (1) mixing melamine and formaldehyde solution, reacting under the condition that the pH value of a mixed system is 8.5-9.5, and adding methanol after the reaction is finished to separate out melamine resin; (2) dissolving polyacrylonitrile in N, N-Dimethylformamide (DMF), adding melamine resin, stirring and dissolving to obtain spinning solution; (3) carrying out high-voltage electrostatic spinning on the spinning solution to obtain MF/PAN composite fiber; (4) and carrying out preoxidation treatment and carbonization treatment on the MF/PAN composite fiber to prepare the nitrogen-rich porous carbon fiber electrode material. However, when the carbon material obtained by the method is used as an electrode material, the specific capacitance is low, and when 6.0 mol/L KOH is used as an electrolyte, the specific capacitance is only 125F/g when the constant current discharge current density is 1A/g.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a melamine resin-based carbon material which has high specific capacitance and good rate performance and is synthesized by taking ZIF-67 as a template.

The technical scheme of the invention is as follows:

according to the invention, the synthesis of the melamine resin-based carbon material by taking the ZIF-67 as the template comprises the following steps:

(1) dissolving 1.80-3.80 g of melamine and 0.050-0.150 g of ZIF-67 in 90.0mL of deionized water, and stirring for 0.5 h;

(2) slowly adding 4.0-20.0 mL of formaldehyde solution (37% wt, the same below) into the solution obtained in the step (1), and stirring for 0.5 h;

(3) adding 0.50-1.20 ml of glacial acetic acid into the mixed solution in the step (2) at 60%^oCReacting for 1-8 h in a water bath;

(4) centrifuging the product obtained in the step (3), alternately centrifuging and washing by using ethanol and deionized water, and drying in an oven for 8 hours after the supernatant is neutral;

(5) under the protection of argon, 600-800 parts of the copolymer obtained in the step (4)^oAnd carbonizing for 3 hours under C to obtain the melamine resin-based carbon material synthesized by taking ZIF-67 as a template.

According to the present invention, it is preferable that the melamine used in the step (1) is used in an amount of 2.80g and the ZIF-67 is used in an amount of 0.050 g.

According to the present invention, it is preferred that the amount of the formaldehyde solution used in the step (2) is 6.0 ml.

According to the present invention, it is preferable that the amount of glacial acetic acid used in step (3) is 1.0 ml.

According to the present invention, it is preferred that the reaction time in step (3) is 6 hours.

According to the present invention, it is preferable that the reaction temperature in the step (5) is 700 deg.C^oC。

A melamine resin-based carbon material synthesized by using ZIF-67 as a template is used as an electrode material of a super capacitor.

The technical advantages of the invention are as follows:

(1) the preparation method is simple in preparation process, high in yield and controllable, and the electrode material with good electrochemical performance can be prepared by controlling the amount and reaction time of the ZIF-67.

(2) The melamine resin-based carbon material synthesized by taking ZIF-67 as a template has high nitrogen content, so that the material has the advantages of excellent electrochemical performance, good rate capability, high specific capacitance and the like, and is very suitable for being applied to the field of super capacitors as an electrode material.

Drawings

FIG. 1 is a constant current charge-discharge diagram of a melamine resin-based carbon material synthesized using ZIF-67 as a template according to example 2 of the present invention.

FIG. 2 is a cyclic voltammogram obtained by synthesizing a melamine resin-based carbon material using ZIF-67 as a template in example 2 of the present invention.

Detailed Description

The present invention will be further described with reference to the following embodiments and drawings, but is not limited thereto.

Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.

Example 1:

2.80g of melamine and 0.050g of ZIF-67 are dissolved in 90.0ml of deionized water, the mixture is placed in a three-neck flask and stirred for 0.5h, 4.50 ml of formaldehyde solution is added into the three-neck flask after the solution is stirred uniformly, and the mixture is stirred for 0.5 h. Slowly dropping 1.00 ml glacial acetic acid into three-neck flask, and adding 60 portions of glacial acetic acid^oCThe reaction is carried out for 6 hours to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging by using ethanol and deionized water, and drying in an oven for 8 hours after the supernatant is neutral. The obtained copolymer is put under the protection of argon at 700 DEG^oAnd C, carbonizing to obtain the melamine resin-based carbon material synthesized by using ZIF-67 as a template.

The constant current charge-discharge diagram of the melamine resin-based carbon material synthesized by using ZIF-67 as a template in the example is shown in FIG. 1.

In the embodiment, the melamine resin-based carbon material is synthesized by taking ZIF-67 as a template, a three-electrode system is adopted, a 2.0 mol/L sulfuric acid solution is taken as an electrolyte, the specific capacitance value measured at 0.5A/g is 298F/g, the specific capacitance value measured at 1A/g is 282F/g, the specific capacitance value measured at 10A/g is 217F/g, and the multiplying power performance is better.

Example 2:

2.80g of melamine and 0.10 g of ZIF-67 are dissolved in 90.0ml of deionized water, placed in a three-neck flask and stirred for 0.5h, 4.50 ml of formaldehyde solution is added into the three-neck flask after the solution is stirred uniformly, and the mixture is stirred for 0.5 h. To three1.00 ml of glacial acetic acid is slowly dropped into the flask, and the mixture is placed in a 60-degree flask^oAnd reacting for 6 hours under C to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging and washing by using ethanol and deionized water, and drying in an oven for 8 hours after the supernatant is neutral. The obtained copolymer is put under the protection of argon gas at 600 DEG^oCAnd (3) carbonizing to obtain the melamine resin-based carbon material synthesized by taking ZIF-67 as a template.

A three-electrode system is adopted, 2.0 mol/L sulfuric acid solution is used as electrolyte, the specific capacitance value is 241F/g when the current density is 1A/g, the specific capacitance value is 170F/g when the current density is 10A/g, and the multiplying power performance is excellent.

Example 3:

2.80g of melamine and 0.150 g of ZIF-67 are dissolved in 90.0ml of deionized water, placed in a three-neck flask and stirred for 0.5h, 4.50 ml of formaldehyde solution is added into the three-neck flask after the solution is stirred uniformly, and the mixture is stirred for 0.5 h. 0.60 ml of glacial acetic acid is slowly dropped into the three-neck flask and then the mixture is placed in a container with 60 percent^oAnd C, reacting for 8 hours to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging by using ethanol and deionized water, and drying in an oven for 8 hours after the supernatant is neutral. The obtained copolymer is put under the protection of argon at 800 DEG^oAnd C, carbonizing to obtain the melamine resin-based carbon material synthesized by taking ZIF-67 as a template.

A three-electrode system is adopted, a 2.0 mol/L sulfuric acid solution is taken as an electrolyte, the specific capacitance is 261F/g when measured at 1A/g, and the specific capacitance is 187F/g when measured at 10A/g.

Example 4:

2.80g of melamine and 0.050g of ZIF-67 are dissolved in 90.0ml of deionized water, the mixture is placed in a three-neck flask and stirred for 0.5h, 4.50 ml of formaldehyde solution is added into the three-neck flask after the solution is stirred uniformly, and the mixture is stirred for 0.5 h. 0.80 ml of glacial acetic acid is slowly dropped into the three-neck flask and then the mixture is placed in a container with 60 percent^oAnd C, reacting for 8 hours to obtain milky suspension. And centrifuging the obtained product, alternately centrifuging by using ethanol and deionized water, and drying in an oven for 8 hours after the supernatant is neutral. The obtained copolymer is put under the protection of argon at 700 DEG^oCarbonizing at C to obtain melamine resin base synthesized by ZIF-67 as templateA carbon material.

A three-electrode system is adopted, 2.0 mol/L sulfuric acid solution is taken as electrolyte, the specific capacitance measured at 1A/g is 241F/g, and the specific capacitance measured at 10A/g is 168F/g.

Comparative example 1:

putting 2.80g of melamine and 4.50 ml of formaldehyde solution into a three-neck flask, adding 90.0ml of deionized water, and stirring for 0.5 h; adding 1.0ml of glacial acetic acid, reacting for 6h, alternately centrifuging the obtained product by using ethanol and deionized water until the supernatant is neutral, and drying in an oven for 8 h; the obtained melamine resin is put under the protection of argon gas at 700 DEG^oAnd C, carbonizing for 3 hours to obtain the melamine resin-based carbon material.

A three-electrode system is adopted, a 2.0 mol/L sulfuric acid solution is taken as an electrolyte, and the specific capacitance is 188F/g when the specific capacitance is measured at 1A/g.

Comparative example 2:

respectively dissolving 0.291 g of cobalt nitrate hexahydrate and 0.328 g of 2-methylimidazole in 25.0 ml of anhydrous methanol, after fully dissolving, quickly mixing the two solutions, standing for 24 h to obtain a purple reaction solution, centrifuging, centrifugally washing for 3 times by the anhydrous methanol,

60 ^oc, vacuum drying for 5 hours; to obtain the zeolite imidazole framework like compound ZIF-67 material.

A three-electrode system is adopted, 2.0 mol/L potassium hydroxide solution is taken as electrolyte, the specific volume is 93F/g when measured at 0.5A/g, and the specific capacitance is 88F/g when measured at 1A/g.

Claims

1. A melamine resin-based carbon material synthesized by taking ZIF-67 as a template comprises the following steps:

(1) 2.80g of melamine and 0.050g of ZIF-67 are dissolved in 90.0mL of deionized water and stirred for 0.5 h;

(2) slowly adding 6.0mL of formaldehyde solution into the solution obtained in the step (1), and stirring for 0.5 h;

(3) adding 1.0mL of glacial acetic acid into the solution obtained in the step (2), and reacting for 6h in a water bath at 60 ℃;

(4) centrifuging the product obtained in the step (3), alternately centrifuging by using ethanol and deionized water, and drying in an oven for 8 hours after the supernatant is neutral;

(5) and (3) carbonizing the copolymer obtained in the step (4) at 700 ℃ for 3h under the protection of argon to obtain the melamine resin-based carbon material synthesized by taking ZIF-67 as a template.