阅读说明：本技术 一种基于蜜胺泡绵和金属有机骨架材料的多孔炭柔性自支撑电极的制备方法 (Preparation method of porous carbon flexible self-supporting electrode based on melamine foam and metal organic framework material ) 是由 姚建峰 曹梦觉 冯艺 田融融 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种基于蜜胺泡绵和金属有机骨架材料的多孔炭柔性自支撑电极的制备方法,其中,一种蜜胺泡绵柔性自支撑电极的制备方法,其包括,将蜜胺泡绵浸入钴盐溶液中；加入二甲基咪唑,静置后干燥；碱液洗涤,干燥,活化后洗涤干燥,得多孔炭柔性自支撑电极材料；一种蜜胺泡绵柔性自支撑电极,其BET比表面积可达1136m<Sup>2</Sup>/g。该多级孔结构的炭材料,保持柔性的同时,提高材料的比表面积,微孔比重和导电性,从而展现出优良的电化学性能。(The invention discloses a preparation method of a porous carbon flexible self-supporting electrode based on melamine foam and a metal organic framework material, wherein the preparation method of the melamine foam flexible self-supporting electrode comprises the steps of immersing the melamine foam in a cobalt salt solution; adding dimethyl imidazole, standing and drying; washing with alkali liquor, drying, and washing and drying after activation to obtain the porous carbon flexible self-supporting electrode material; the BET specific surface area of the flexible self-supporting electrode of the melamine foam can reach 1136m 2 (ii) in terms of/g. The carbon material with the hierarchical pore structure maintains flexibility, and simultaneously improves the specific surface area, micropore specific gravity and conductivity of the material, thereby showing excellent electrochemical performance.)

1. A preparation method of a melamine foam flexible self-supporting electrode is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,

immersing melamine foam into a cobalt salt solution;

adding dimethyl imidazole, standing and drying;

washing with alkali liquor, drying, and washing and drying after activation to obtain the porous carbon flexible self-supporting electrode material.

2. The method for preparing a melamine foam flexible self-supporting electrode as set forth in claim 1, wherein: the melamine foam is treated at constant temperature for 1-2h under the carbonization condition of hydrogen and argon atmosphere, the temperature rise rate is 5 ℃/min, the carbonization temperature is 700-900 ℃.

3. The method for preparing a melamine foam flexible self-supporting electrode as set forth in claim 1, wherein: and immersing the melamine foam into a cobalt salt solution, wherein the cobalt salt solution is a cobalt nitrate hexahydrate solution, the concentration of the cobalt nitrate hexahydrate solution is 10-30mg/mL, the solvent is water, and the standing time is 6-12 h.

4. A method for preparing a melamine foam flexible self-supporting electrode as set forth in claim 3, wherein: and washing with alkali liquor, wherein the alkali liquor comprises one or more of potassium hydroxide and sodium hydroxide, the solute concentration is 2-4mol/L, and the ratio of the sample to the solute is 1:3 (mass ratio) and the standing time is 3-5 h.

5. A method for preparing a melamine foam flexible self-supporting electrode as set forth in claim 3, wherein: the secondary carbonization is carried out under the carbonization conditions of argon, the temperature rising rate is 5 ℃/min, the carbonization temperature is 900 ℃ and the constant temperature is 3 hours.

6. A method for preparing a melamine foam flexible self-supporting electrode as claimed in any one of claims 1 to 5, wherein: and (3) drying after standing, wherein the standing time is 6-12h, the drying temperature is 60-80 ℃, and the drying temperature is 60-80 ℃ and the drying time is 12-24 h.

7. The method for preparing a melamine foam flexible self-supporting electrode as set forth in claim 1, wherein: and (3) after activation, washing and drying, namely standing in hydrochloric acid for 10h, washing with distilled water to be neutral, and drying at the drying temperature of 60-80 ℃ for 12-24 h.

8. The melamine foam flexible self-supporting electrode prepared by the method of any one of claims 1 to 7, which is characterized in that: the BET specific surface area can reach 1136m²/g。

9. The melamine foam flexible self-supporting electrode of claim 8, wherein: the specific volume reaches 238F/g, and after 10000 cycles, the specific volume retention rate is 94 percent.

10. The melamine foam flexible self-supporting electrode of claim 8, wherein: bending 180 degrees, and the specific volume retention rate is 90 percent.

Technical Field

The invention belongs to the technical field of super capacitors, and particularly relates to a preparation method of a porous carbon flexible self-supporting electrode based on melamine foam and a metal organic framework material.

Background

The energy storage element is one of the hot spots of research and research, especially a super capacitor, and has been widely applied in the fields of electric vehicle power supplies, portable electronic devices and the like due to its high-efficiency and practical energy storage characteristics and the advantages of large energy density, high power density and the like. With the emergence of the requirements of human beings on flexible and bendable electronic equipment and the like, the preparation of the flexible all-solid-state electrode is concerned by the majority of researchers.

The melamine foam is a cheap and environment-friendly porous material, and can maintain the original three-dimensional porous structure and excellent mechanical properties after carbonization. However, the directly carbonized melamine foam has poor electrochemical performance due to the low specific surface area and the lack of micropores.

Disclosure of Invention

This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.

The present invention has been made in view of the above-mentioned technical drawbacks.

Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art and provides a preparation method of a porous carbon flexible self-supporting electrode based on melamine foam and metal organic framework materials.

In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a melamine foam flexible self-supporting electrode comprises the steps of immersing melamine foam in a cobalt salt solution; adding dimethyl imidazole, standing and drying; washing with alkali liquor, drying, and washing and drying after activation to obtain the porous carbon flexible self-supporting electrode material.

The preferable scheme of the preparation method of the melamine foam flexible self-supporting electrode is as follows: the melamine foam is treated at constant temperature for 1-2h under the carbonization condition of hydrogen and argon atmosphere, the temperature rise rate is 5 ℃/min, the carbonization temperature is 700-900 ℃.

The preferable scheme of the preparation method of the melamine foam flexible self-supporting electrode is as follows: and immersing the melamine foam into a cobalt salt solution, wherein the cobalt salt solution is a cobalt nitrate hexahydrate solution, the concentration of the cobalt nitrate hexahydrate solution is 10-30mg/mL, the solvent is water, and the standing time is 6-12 h.

The preferable scheme of the preparation method of the melamine foam flexible self-supporting electrode is as follows: and washing with alkali liquor, wherein the alkali liquor comprises one or more of potassium hydroxide and sodium hydroxide, the solute concentration is 2-4mol/L, and the ratio of the sample to the solute is 1:3 (mass ratio) and the standing time is 3-5 h.

The preferable scheme of the preparation method of the melamine foam flexible self-supporting electrode is as follows: the secondary carbonization is carried out under the carbonization conditions of argon, the temperature rising rate is 5 ℃/min, the carbonization temperature is 900 ℃ and the constant temperature is 3 hours.

The preferable scheme of the preparation method of the melamine foam flexible self-supporting electrode is as follows: and (3) drying after standing, wherein the standing time is 6-12h, the drying temperature is 60-80 ℃, and the drying temperature is 60-80 ℃ and the drying time is 12-24 h.

The preferable scheme of the preparation method of the melamine foam flexible self-supporting electrode is as follows: and (3) after activation, washing and drying, namely standing in hydrochloric acid for 10h, washing with distilled water to be neutral, and drying at the drying temperature of 60-80 ℃ for 12-24 h.

In one aspect, the present invention overcomes the disadvantages of the prior art by providing a flexible self-supporting electrode made by the method of any one of claims 1 to 7, wherein: the BET specific surface area can reach 1136m²/g。

As a preferable scheme of the melamine foam flexible self-supporting electrode, the invention comprises the following components: the specific volume reaches 238F/g, and after 10000 cycles, the specific volume retention rate is 94 percent.

As a preferable scheme of the melamine foam flexible self-supporting electrode, the invention comprises the following components: bending 180 degrees, and the specific volume retention rate is 90 percent.

The invention has the beneficial effects that:

the invention provides a preparation method of porous carbon based on melamine foam and a metal organic framework material, which is used as an all-solid-state electrode for a super capacitor, the carbonized melamine foam is loaded, activated/carbonized through a metal organic framework material (Co-ZIF-L) with a sheet structure to obtain the carbon material with a hierarchical pore structure, and the specific surface area, micropore specific gravity and conductivity of the material are improved while the flexibility is maintained, so that excellent electrochemical performance is shown.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:

FIG. 1(a) is the apparent morphology of a porous carbon material based on carbonized melamine foam and Co-ZIF-L, (b) is the apparent morphology after bending 180 degrees, and (c-e) is the apparent morphology of the material before and after compression.

FIG. 2 is SEM images of carbonized melamine foam and porous carbon materials based on carbonized melamine foam and Co-ZIF-L in example 1 of the present invention, wherein (a) is an SEM image of carbonized melamine foam, and (b) and (c) are SEM images of porous carbon materials based on carbonized melamine foam and Co-ZIF-L, respectively.

FIG. 3 is a cyclic voltammetry curve and (b) a constant current charge and discharge curve of a porous carbon material based on melamine foam and Co-ZIF-L directly used as a flexible electrode.

FIG. 4 is a cyclic voltammogram of porous carbon materials based on melamine foam and Co-ZIF-L at different degrees of bending.

Fig. 5 shows a carbonized melamine foam having poor mechanical properties prepared in comparative example 2.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.

Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.

The melamine foam used in example 1 of the present invention was purchased from Sichuan new ultra-polymerized material Co., Ltd, and the performance indexes thereof are shown in Table 1 below: