阅读说明：本技术 一种针状控制剂及其制备方法和应用 (Needle-shaped control agent and preparation method and application thereof ) 是由 高延敏 张政 施方长 徐俊烽 杨红洲 孙存思 *** 于 2019-10-15 设计创作，主要内容包括：本发明公开了一种针状控制剂及其制备方法。该针状控制剂的制备方法包括以下步骤：按照等摩尔比例,将顺丁烯二酸酐加入丙烯腈,然后70～80℃的水浴反应2～4个小时；将所得物质按照等摩尔比例加入到苯乙烯中,75～90℃的水浴3～5个小时,即可。可将其应用于超级电容电极板：按照摩尔比称取钴源、硫源和针状控制剂,置于丙三醇中进行搅拌至钴源与硫源物质完全溶解,将获得的混合液转移到高压反应釜内,然后将清洗、干燥好的泡沫镍集流体插在混合液里,密封升温至180～220℃,保温10～14h后取出,清洗至干净,即可获得钴-镍基硫族化合物超级电容电极板。该电极板具有很高的电容容量和很低的电子转移电阻值。(The invention discloses a needle-shaped control agent and a preparation method thereof. The preparation method of the needle-shaped control agent comprises the following steps: adding maleic anhydride into acrylonitrile according to an equal molar ratio, and then reacting in a water bath at 70-80 ℃ for 2-4 hours; adding the obtained substances into styrene according to an equal molar ratio, and carrying out water bath at 75-90 ℃ for 3-5 hours. It can be applied to super capacitor electrode plates: weighing a cobalt source, a sulfur source and a needle-shaped control agent according to a molar ratio, placing the cobalt source, the sulfur source and the needle-shaped control agent in glycerol, stirring until the cobalt source and the sulfur source are completely dissolved, transferring the obtained mixed solution into a high-pressure reaction kettle, inserting a cleaned and dried foamed nickel current collector into the mixed solution, sealing, heating to 180-220 ℃, preserving heat for 10-14 hours, taking out, and cleaning to obtain the cobalt-nickel-based chalcogenide supercapacitor electrode plate. The electrode plate has high capacitance and low electron transfer resistance.)

1. A needle-like control agent characterized by having a molecular weight of 200 to 1000 and a structure as follows:

2. the method for producing a needle-like control agent according to claim 1, comprising the steps of:

(1) according to an equal molar ratio, adding maleic anhydride into acrylonitrile, then uniformly stirring the mixture under the heating of a water bath at the temperature of 70-80 ℃, and reacting for 2-4 hours;

(2) and (2) adding the substances obtained in the step (1) into styrene according to an equal molar ratio, and reacting for 3-5 hours under the heating of a water bath at the temperature of 75-90 ℃ to obtain the needle-shaped control agent.

3. The needle-like control agent according to claim 1, which is applied to an electrode plate of a supercapacitor.

4. A method according to claim 3, characterized in that it comprises the following steps:

(1) sequentially soaking a foamed nickel plate in acetone, 1M hydrochloric acid, 1M potassium hydroxide, absolute ethyl alcohol and deionized water, ultrasonically cleaning the foamed nickel plate to be clean, and then carrying out vacuum drying for 2-4 h at the temperature of 70-80 ℃ to obtain a foamed nickel current collector;

(2) weighing a cobalt source, a sulfur source substance and the needle-shaped control agent according to a molar ratio of 1: 2-4: 1, wherein the cobalt source is cobalt chloride, cobalt nitrate or cobalt acetate, and the sulfur source is thiourea or sodium sulfide;

(3) placing a cobalt source, a sulfur source substance and a needle-shaped control agent in glycerol, and stirring until the cobalt source and the sulfur source substance are completely dissolved, wherein the dosage of the glycerol is 10-15 times of the total mass of the cobalt source and the sulfur source substance;

(4) transferring the mixed solution obtained in the step (3) into a high-pressure reaction kettle, inserting the foamed nickel current collector processed in the step (1) into the mixed solution, sealing, heating to 180-220 ℃, and preserving heat for 10-14 hours;

(5) and (4) taking out the foamed nickel current collector obtained by the treatment in the step (4), and alternately cleaning the foamed nickel current collector with deionized water and alcohol until the foamed nickel current collector is clean, thereby obtaining the cobalt-nickel based chalcogenide electrode plate.

5. The method for applying the nickel alloy sheet according to claim 3, wherein the nickel foam sheet in the step (1) is a nickel foam sheet for a battery, which has a porosity of 60% to 98%.

6. The method of claim 3, wherein the cobalt source is cobalt acetate, the sulfur source is sodium sulfide, the needle control agent has a molecular weight of 200, the foamed nickel plate has a porosity of 75%, and the cobalt source, sulfur source, and needle control agent are present in a molar ratio of 1:4: 1.

Technical Field

The invention belongs to the field of preparation of super-capacitor electrode materials, and particularly relates to a needle-shaped control agent, and a preparation method and application thereof.

Background

With the continuous progress of scientific technology and the continuous development of economic society, the demand of human beings on energy is larger and larger, and the global warming and the environmental pollution are more and more serious. In order to better play the role of the new generation of clean energy, it is important to design a device capable of rapidly storing and releasing electric energy. The super capacitor is an energy storage device which can rapidly complete the charging and discharging process in a short time and achieve ultrahigh output power density. The super capacitor can be classified into a double electric layer super capacitor and a faraday pseudocapacitance according to the difference of the energy storage mechanism. The double-electric-layer super capacitor stores energy by utilizing the micropore adsorption characteristic of the surface of an active substance, and does not generate electrochemical reaction. The Faraday pseudo capacitor stores energy by means of highly reversible redox reaction of surface active substances, and although the service life of the Faraday pseudo capacitor is shorter than that of an electric double-layer super capacitor, the energy storage density of the Faraday pseudo capacitor can reach tens of times as high as that of the electric double-layer super capacitor.

For the study of the faradaic pseudocapacitance, the researchers mainly focused the study on the transition metal oxide. Currently, more common capacitive active materials include: ruthenium oxide, manganese oxide, vanadium oxide, cobalt oxide, nickel oxide, and other active materials containing polyvalent metal ions. Recent researchers found that not only the sulfide of the transition metal has better conductivity than the oxide of the corresponding metal, but also the electricity storage capacity of the transition metal is significantly improved after the sulfide. Researchers have begun looking at active materials such as nickel sulfide and cobalt sulfide. The traditional preparation process is to prepare the active substance and then bond the active substance to the current collector, and the process can effectively improve the conductivity of the electrode. However, the conventional adhesive is insulating, and if the adhesive is interposed between the active material and the current collector, the resistance thereof is increased and even the performance of a part of the active material is difficult to perform.

Disclosure of Invention

An object of the present invention is to provide a needle-like control agent. The specific technical scheme is as follows:

a needle-like control agent, the molecular weight of the needle-like control agent is 200-1000, and the structure of the needle-like control agent is as follows:

the other purpose of the invention is to provide a preparation method of the needle-shaped control agent. The specific technical scheme is as follows:

a preparation method of the needle-shaped control agent comprises the following steps:

(1) according to an equal molar ratio, adding maleic anhydride into acrylonitrile, then uniformly stirring the mixture under the heating of a water bath at the temperature of 70-80 ℃, and reacting for 2-4 hours;

(2) and (2) adding the substances obtained in the step (1) into styrene according to an equal molar ratio, and reacting for 3-5 hours under the heating of a water bath at the temperature of 75-90 ℃ to obtain the needle-shaped control agent.

Wherein, the molecular structural formula of the acrylonitrile is shown as follows:

the molecular structural formula of maleic anhydride is shown as follows:

the molecular structure of styrene is as follows:

it is a further object of the present invention to provide the use of said needle control agents. The specific technical scheme is as follows:

the needle-shaped control agent is applied to a super-capacitor electrode plate.

Preferably, the specific application method comprises the following steps:

(1) sequentially soaking a foamed nickel plate in acetone, 1M hydrochloric acid, 1M potassium hydroxide, absolute ethyl alcohol and deionized water, ultrasonically cleaning the foamed nickel plate to be clean, and then carrying out vacuum drying for 2-4 h at the temperature of 70-80 ℃ to obtain a foamed nickel current collector;

(2) weighing a cobalt source, a sulfur source substance and the needle-shaped control agent according to a molar ratio of 1: 2-4: 1, wherein the cobalt source is cobalt chloride, cobalt nitrate or cobalt acetate, and the sulfur source is thiourea or sodium sulfide;

(3) placing a cobalt source, a sulfur source substance and a needle-shaped control agent in glycerol, and stirring until the cobalt source and the sulfur source substance are completely dissolved, wherein the dosage of the glycerol is 10-15 times of the total mass of the cobalt source and the sulfur source substance;

(4) transferring the mixed solution obtained in the step (3) into a high-pressure reaction kettle, inserting the foamed nickel current collector processed in the step (1) into the mixed solution, sealing, heating to 180-220 ℃, and preserving heat for 10-14 hours;

(5) and (4) taking out the foamed nickel current collector obtained by the treatment in the step (4), and alternately cleaning the foamed nickel current collector with deionized water and alcohol until the foamed nickel current collector is clean, thereby obtaining the cobalt-nickel based chalcogenide electrode plate.

Preferably, the foamed nickel plate in the step (1) is a foamed nickel plate for a battery, which has a porosity of 60% to 98%.

Preferably, the cobalt source is cobalt acetate, the sulfur source is sodium sulfide, the molecular weight of the needle-shaped control agent is 200, the porosity of the foamed nickel plate is 75%, and the molar ratio of the cobalt source to the sulfur source to the needle-shaped control agent is 1:4: 1.

The technical principle is as follows:

the invention relates to a method for directly adding a nickel-based current collector into a reaction system together with a needle-shaped control agent as a growth template of an active substance, so that a nickel sulfide active substance can directly grow on a foamed nickel current collector. Because a large amount of sulfur exists in the system, the nickel substrate is etched to a certain degree, so that the surface of the nickel substrate has acicular nickel sulfide. The special morphology can be used as a template in the precipitation process of cobalt sulfide.

The invention has the beneficial effects that:

the super capacitor prepared by the traditional bonding method has the following effects: the capacitance value is about 550F/g, and the electron transfer resistance value is about 0.9 omega; the super capacitor prepared by the invention has the following effects: the capacitance value exceeds 750F/g, the electron transfer resistance value is reduced to be below 0.2 omega, and the best effect is that the capacitance value reaches 822F/g, and the electron transfer resistance value is reduced to 0.067 omega.

Drawings

FIG. 1 is an electron microscope photograph of an acicular cobalt-nickel based chalcogenide supercapacitor electrode plate prepared in example 1 of the present invention; in the figure, the needle-shaped substances are needle-shaped nickel sulfide formed on the foamed nickel current collector, and the particulate substances dotted on the nickel sulfide are cobalt sulfide nano-particles;

FIG. 2 is a graph of capacitance versus electron transfer resistance of the supercapacitor electrode plates obtained in examples 1-6.

Detailed Description

The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.