阅读说明：本技术 一种针状C-Na2CO3的制备方法 (Needle-shaped C-Na2CO3Preparation method of (1) ) 是由 李健宁 张春勇 张颖 舒莉 文颖频 程洁红 朱炳龙 郑纯智 梁国斌 秦恒飞 于 2020-08-28 设计创作，主要内容包括：本发明公开了一种针状C-Na<Sub>2</Sub>CO<Sub>3</Sub>的制备方法,具体包括前处理过程和后处理过程；前处理时先将钠型强酸性苯乙烯树脂用无水乙醇浸泡,用去离子水进行洗涤后,依次用5％盐酸、超纯水、5％氢氧化钠进行酸碱处理,去离子水洗涤至中性,干燥处理后得到前驱体；后处理时将前躯体装入瓷舟,放入管式炉进行煅烧炭化得到针状C-Na<Sub>2</Sub>CO<Sub>3</Sub>。本发明以一步法再经炭化制备C-Na<Sub>2</Sub>CO<Sub>3</Sub>纳米材料,制备工艺简单,反应条件温和,生产周期短,制备效率有明显提升；产品的形貌呈针状且排列有序。(The invention discloses needle-shaped C-Na 2 CO 3 The preparation method specifically comprises a pretreatment process and a post-treatment process; the pretreatment comprises the steps of soaking a sodium type strong-acid styrene resin in absolute ethyl alcohol, washing with deionized water, sequentially carrying out acid-base treatment with 5% hydrochloric acid, ultrapure water and 5% sodium hydroxide, washing with deionized water to neutrality, and drying to obtain a precursor; during post-treatment, the precursor is put into a porcelain boat and put into a tube furnace for calcination and carbonization to obtain needle-shaped C-Na 2 CO 3 . The invention prepares C-Na by a one-step method and carbonization 2 CO 3 The nano material has simple preparation process, mild reaction conditions, short production period and obviously improved preparation efficiency; the appearance of the product is needle-shaped and is arranged orderly.)

1. Needle-shaped C-Na₂CO₃The preparation method is characterized by comprising a pretreatment process and a post-treatment process;

pretreatment: soaking a sodium type strong-acidity styrene resin in absolute ethyl alcohol, washing with deionized water, sequentially carrying out acid-base treatment with 5% hydrochloric acid, ultrapure water and 5% sodium hydroxide, washing with deionized water to neutrality, and drying to obtain a precursor;

and (3) post-treatment: loading the precursor into a porcelain boat, and calcining and carbonizing in a tube furnace to obtain acicular C-Na₂CO_3。

2. The needle-like C-Na of claim 1₂CO₃A process for the preparation ofCharacterized in that in the pretreatment process, the volume ratio of the sodium type strongly acidic styrene resin to 5% hydrochloric acid, ultrapure water and 5% sodium hydroxide is 1: (1-5): (1-5): (1-5).

3. The needle-like C-Na of claim 1₂CO₃The preparation method is characterized in that in the pretreatment process, the soaking time of the sodium type strong acid styrene resin in absolute ethyl alcohol is 8-12 h.

4. The needle-like C-Na of claim 1₂CO₃The preparation method is characterized in that in the post-treatment process, the calcination is carried out in the argon atmosphere, the calcination temperature is 550-900 ℃, and the calcination time is 1-4 h.

5. The needle-like C-Na of claim 2₂CO₃The preparation method is characterized in that in the pretreatment process, the volume ratio of the sodium type strongly acidic styrene resin to 5% hydrochloric acid, ultrapure water and 5% sodium hydroxide is 1: 3: 3: 3.

6. the needle-like C-Na of claim 3₂CO₃The preparation method is characterized in that in the pretreatment process, the time for soaking the sodium type strongly acidic styrene resin in absolute ethyl alcohol is 10 hours.

7. The needle-like C-Na of claim 4₂CO₃The preparation method is characterized in that in the post-treatment process, the calcination temperature is 850 ℃ and the calcination time is 2 hours.

Technical Field

The invention belongs to the technical field of carbon materials, and particularly relates to needle-shaped C-Na₂CO₃The preparation method of (1).

Background

The ion exchange resin is a high molecular compound with functional groups. Ion exchange resins can be classified into cation exchange resins and anion exchange resins, depending on the nature of the exchangeable ions carried by the resin. The cation exchange resin is a kind of resin with sulfonic acid group (-SO) connected to the skeleton₃H) Or a polymer having an acidic functional group such as a carboxylic acid group (-COOH). When the ion exchange resin is immersed in water, the exchange groups are ionized. Anion exchange resins are those in which the resin backbone R-is grafted with, for example, a quaternary ammonium acid (-N (CH)₃)₃OH), primary amino (-NH (CH)₃)₂OH), para-amino acid (-NH)₂(CH₃) OH), tertiary amine acid (-NH)₃OH) is used.

Du et al adsorbed K using strongly basic anion exchange resin of polystyrene ion₃[Fe(CN)₆]And carbonizing for 4 hours in a nitrogen atmosphere to obtain the activated carbon with higher graphitization degree and large specific surface area.

Bratek et al carbonized with waste ion exchange resin at different heating rates to obtain spherical porous carbon of different types, and the collapse of the mesopore and macropore structure of the resin during carbonization generates a large number of micropores again after CO₂After activation, it is further converted into micropores and mesopores.

Meng et al use ion exchange resin as a carbon source, utilize solid state pyrolysis to prepare highly graphitized nanocarbons, and regulate the morphology of the carbon by changing the type of resin, the type of adsorbed metal, and the crosslinking manner of the resin and the metal.

However, the existing preparation process is generally complex, the production period is long, the preparation efficiency is low, and the research on the preparation of the graphene carbon nano material by the one-step method is less.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides the needle-shaped C-Na which does not need a template, has simple and convenient process and short production period₂CO₃The preparation method of (1).

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

needle-shaped C-Na₂CO₃The preparation method specifically comprises a pretreatment process and a post-treatment process;

pretreatment: soaking a sodium type strong-acid styrene resin in absolute ethyl alcohol, washing with deionized water, sequentially carrying out acid-base treatment with 5% hydrochloric acid, ultrapure water and 5% sodium hydroxide to obtain a precursor, washing with deionized water to neutrality, and drying to obtain the precursor;

and (3) post-treatment: loading the precursor into a porcelain boat, and calcining and carbonizing in a tube furnace to obtain acicular C-Na₂CO_3。

Further, in the pretreatment process, the volume ratio of the sodium type strongly acidic styrene resin to 5% hydrochloric acid, ultrapure water and 5% sodium hydroxide is 1: (1-5): (1-5): (1-5).

Further, in the pretreatment process, the soaking time of the sodium type strongly acidic styrene resin in absolute ethyl alcohol is 8-12 h.

Furthermore, in the post-treatment process, the calcination is carried out in an argon atmosphere, the calcination temperature is 550-900 ℃, and the calcination time is 1-4 h.

Preferably, in the pretreatment, the volume ratio of the sodium strongly acidic styrene resin to 5% hydrochloric acid, ultrapure water and 5% sodium hydroxide is 1: 3: 3: 3.

preferably, the calcination temperature in the post-treatment process is 850 ℃ and the calcination time is 2 h.

Preferably, in the pretreatment, the sodium strongly acidic styrene resin is soaked in absolute ethanol for 10 hours.

Through a large number of experiments, the following results are found: if the soaking time of the sodium type strong acid styrene resin in absolute ethyl alcohol is less than 8 hours, when the volume ratio of the sodium type strong acid styrene resin to hydrochloric acid, ultrapure water and sodium hydroxide is 1: x₁：X₂：X₃（X₁=X₂=X₃) And when x is less than 1.0, the prepared sample can generate other impurities; when x is more than 5, the synthesized nano material is easy to agglomerate together; if the calcination temperature is lower than 550 ℃ or the calcination time is less than 2 hours, the sample is not carbonized completely and is accompanied by impurity generation; if the calcination temperature is higher than 900 ℃ or the calcination time is longer than 4 hours, agglomeration may occur.

The beneficial effects are that:

the invention prepares C-Na by a one-step method and carbonization₂CO₃The nano material has simple preparation process, mild reaction conditions, short production period and obviously improved preparation efficiency;

prepared C-Na₂CO₃The shape of the nano material has certain regularity and is needle-shaped, so that the specific surface area of the material can be increased, more active sites are exposed, and the electrochemical performance of the material is effectively improved.

Drawings

FIG. 1 shows C-Na obtained in example 1₂CO₃XRD pattern of (a);

FIG. 2 shows C-Na obtained in example 1₂CO₃SEM topography of (a).

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the following describes the technical solution of the present invention with reference to fig. 1 and the embodiment.

It should be noted that the embodiment provided by the present invention is only for effectively explaining the technical features of the present invention, and the terms of positioning such as left side, right side, upper end, lower end, etc. are only for better describing the embodiment of the present invention and should not be construed as limiting the technical solution of the present invention.