阅读说明：本技术 棒状硫化铜颗粒的制备方法及其应用 (Preparation method and application of rod-shaped copper sulfide particles ) 是由 刘晓伟 杨宝朔 艾远 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种棒状硫化铜颗粒的制备方法及其应用,包括：将铜盐溶解到水中制成溶液A,将硫脲溶解到水中制成溶液B；将溶液A和溶液B混合,制成具有大量白色糊状沉淀的沉淀液；对沉淀液进行磁力搅拌处理,然后进行离心处理；离心后分离上层液体,得到白色糊状沉淀,将白色糊状沉淀真空加热至160～180℃反应,得到黑色粉末；对黑色粉末进行震荡、洗涤、离心,以去除副产物；烘干沉淀,得到产物。本发明通过控制铜盐溶液与硫脲溶液的体积比制备了一系列的长短可调的多种棒状形态,同时具备流程简单、无添加剂、成本低、易于规模化生产等优点。(The invention discloses a preparation method and application of rod-shaped copper sulfide particles, which comprises the following steps: dissolving copper salt into water to prepare a solution A, and dissolving thiourea into water to prepare a solution B; mixing the solution A and the solution B to prepare a precipitation solution with a large amount of white pasty precipitates; performing magnetic stirring treatment on the precipitation solution, and then performing centrifugal treatment; centrifuging and separating upper-layer liquid to obtain white pasty sediment, and heating the white pasty sediment to 160-180 ℃ in vacuum to react to obtain black powder; shaking, washing and centrifuging the black powder to remove byproducts; drying the precipitate to obtain the product. The method prepares a series of rod-shaped forms with adjustable length by controlling the volume ratio of the copper salt solution to the thiourea solution, and has the advantages of simple process, no additive, low cost, easy large-scale production and the like.)

1. A method for preparing rod-shaped copper sulfide particles is characterized by comprising the following steps: the method comprises the following steps:

s1: dissolving a copper salt into water to prepare a solution A with the concentration of 0.1-0.2 mol/L, and dissolving thiourea into water to prepare a solution B with the concentration of 0.5-1 mol/L;

s2: mixing the solution A and the solution B in the step S1 in a ratio of 1: mixing the raw materials in a volume ratio of 0.5-4 to prepare a precipitation solution with a large amount of white pasty precipitates;

s3: performing magnetic stirring treatment on the precipitation solution in the step S2 for 5-10 min, and then performing centrifugal treatment;

s4: centrifuging and separating the upper layer liquid to obtain white pasty sediment, and heating the white pasty sediment to 160-180 ℃ in vacuum to react for 1-2 h to obtain black powder;

s5: sequentially adopting deionized water, ethanol and acetone to respectively shake, wash and centrifuge the black powder obtained in the step S4 to remove byproducts;

s6: keeping the temperature at 50-70 ℃ for 0.5-1 h, drying and precipitating to obtain a rod-shaped copper sulfide particle product; the rod-shaped copper sulfide particles have a series of rod-shaped forms including a length of 1 to 2 μm, a length of 2 to 4 μm, and a length of 4 to 6 μm.

2. The method for producing rod-like copper sulfide particles according to claim 1, wherein:

in step S1, the copper salt is one of copper chloride or copper carbonate.

3. The method for producing rod-like copper sulfide particles according to claim 1 or 2, characterized in that:

in step S2, the volume ratio of solution a to solution B is further 1: 0.5-1, 1: 1-2, 1: 2 to 4.

4. The method for producing rod-like copper sulfide particles according to claim 1 or 2, characterized in that:

in the step S3, the magnetic stirring speed is 60-120 r/min; in step S3, the centrifugal separation condition is 4000-5000 r/min, 1-2 min.

5. The method for producing rod-like copper sulfide particles according to claim 3, wherein:

in the step S3, the magnetic stirring speed is 60-120 r/min; in step S3, the centrifugal separation condition is 4000-5000 r/min, 1-2 min.

6. The method for producing rod-like copper sulfide particles according to claim 1, 2 or 5, characterized in that:

in step S4, the vacuum heating environment is a normal vacuum drying oven.

7. Use of the method for producing rod-shaped copper sulfide particles according to claim 6 in the fields of lubrication and heat transfer materials.

8. The use of a series of rod-shaped copper sulfide particles in the form of rods, obtained by the method for preparing rod-shaped copper sulfide particles according to claim 7, in the field of lubricating and heat transfer materials.

Technical Field

The invention relates to the field of copper sulfide material preparation methods, and particularly relates to a preparation method and application of a rod-shaped copper sulfide particle.

Background

Copper sulfide is an important transition metal sulfide, is black brown, has excellent properties of light, electricity, catalysis and the like, and has wide application prospect in the fields of optical devices, photocatalysts, solar cells, superconductors, nonlinear optics, supercapacitors, photothermal therapy, nano-scale sensors and the like.

Copper sulfide structures with controllable sizes, shapes and components are widely developed and applied in the past decades, and copper sulfide particles with various shapes, such as lines, tubes, rods, lines, sheets, discs, flowers, leaves, spheres and the like, are successfully synthesized at present. Among them, the rod-like structure is applied to additives such as lubricating oil and heat transfer material due to its structural characteristics such as a large aspect ratio. Although a few reports have been made on rod-shaped preparation methods, many reports have been made on hydrothermal and solvothermal methods, which require harsh conditions such as high temperature and high pressure environments and equipment and are dangerous, and also require additives or templates, which are time-consuming. In addition, the quality of the prepared product is also to be improved.

For example: the preparation method (CN111777093A) of the short rod-shaped nano copper sulfide material disclosed by forest Bo et al adopts a hydrothermal method, requires glutathione besides a copper source and a sulfur source, has the reaction time of 10-24h, and can not be seen from the figure 3 of the specification that the prepared material has obvious short rod-shaped characteristics and has too many impurities in various shapes.

The preparation method (CN112279293A) of the copper sulfide nano material disclosed by Shu Tu et al adopts a hydrothermal method to prepare the copper sulfide nano rod with uniform particle size, but the steps and the period are too complicated, and the steps comprise three stages of reaction at 130-140 ℃ for 12h, reaction at 100-110 ℃ for 5h and reaction at 60-70 ℃ for 5h, and heating reflux treatment for 3h is additionally needed.

The method (CN102502774A) for preparing the rodlike copper sulfide nanocrystalline by microwave solvothermal method disclosed by the Huangjianfeng et al adopts a solvothermal method, the time consumption is short (only 5-60min), and the prepared product has good short rod characteristics, but needs a plurality of devices such as a reaction kettle, a microwave hydrothermal reactor and the like, and is complicated.

In a method (CN101367541A) for synthesizing nano copper sulfide, rod-shaped copper sulfide particles are obtained by a low-temperature solvothermal method, and a surfactant or a template is not required to be added in the synthesis process, but the reaction time is up to 24 hours.

Therefore, the development of a preparation method which is simple and efficient, has low requirements on environment and equipment, mild conditions and strong controllability, can prepare a series of rod-shaped copper sulfide particles with different morphologies and is easy to realize large-scale industrial production has important significance.

Disclosure of Invention

Aiming at the problems in the background technology, the invention provides a preparation method and application of rod-shaped copper sulfide particles. Meanwhile, the method has the advantages of simple process, no additive, short period, low cost, easiness in large-scale production and the like.

In order to achieve the above object, the present invention provides a method for producing a rod-shaped copper sulfide particle, comprising: the method comprises the following steps:

s1: dissolving a copper salt into water to prepare a solution A with the concentration of 0.1-0.2 mol/L, and dissolving thiourea into water to prepare a solution B with the concentration of 0.5-1 mol/L;

s2: mixing the solution A and the solution B in the step S1 in a ratio of 1: mixing the raw materials in a volume ratio of 0.5-4 to prepare a precipitation solution with a large amount of white pasty precipitates;

s3: performing magnetic stirring treatment on the precipitation solution in the step S2 for 5-10 min, and then performing centrifugal treatment;

s4: centrifuging and separating the upper layer liquid to obtain white pasty sediment, and heating the white pasty sediment to 160-180 ℃ in vacuum to react for 1-2 h to obtain black powder;

s5: sequentially adopting deionized water, ethanol and acetone to respectively shake, wash and centrifuge the black powder obtained in the step S4 to remove byproducts;

s6: keeping the temperature at 50-70 ℃ for 0.5-1 h, drying and precipitating to obtain a rod-shaped copper sulfide particle product; the rod-shaped copper sulfide particles have a series of rod-shaped forms including a length of 1 to 2 μm, a length of 2 to 4 μm, and a length of 4 to 6 μm.

Preferably, in step S1, the copper salt is one of copper chloride and copper carbonate.

Further, in step S2, the volume ratio of solution a to solution B is further 1: 0.5-1, 1: 1-2, 1: 2 to 4.

Furthermore, in the step S3, the magnetic stirring speed is 60 to 120 r/min; in step S3, the centrifugal separation condition is 4000-5000 r/min, 1-2 min.

Furthermore, in the step S3, the magnetic stirring speed is 60 to 120 r/min; in step S3, the centrifugal separation condition is 4000-5000 r/min, 1-2 min.

Further, in step S4, the vacuum heating environment is a normal vacuum drying oven.

In a second aspect, the invention provides a method for preparing the rod-shaped copper sulfide particles, and the method is applied to the field of lubricating and heat transfer materials.

In a third aspect, the invention provides a series of rod-shaped copper sulfide particles prepared by the preparation method of the rod-shaped copper sulfide particles, and the rod-shaped copper sulfide particles are applied to the field of lubricating and heat transfer materials.

The technical scheme of the invention has the following advantages and beneficial effects:

(1) the invention designs a method for obtaining black rod-shaped copper sulfide particles by adding thiourea into a medium copper source to obtain white pasty sediment and further heating the sediment in vacuum.

(2) The invention provides a controllable preparation method of a series of rod-shaped copper sulfide particles with different ranges and lengths by taking the volume ratio of a copper salt solution to a thiourea solution as a control variable, and meets different requirements of different applications on rod-shaped copper sulfide particles with different lengths.

(3) The preparation method provided by the invention has the advantages of simple flow, low required conditions, no need of adding any other components such as an active agent and the like, short reaction period, low energy consumption, one-time completion of the reaction, and suitability for industrial popularization and application.

(4) The invention also provides a preparation method of the rod-shaped copper sulfide particles, and the prepared rod-shaped copper sulfide particles have a series of rod-shaped forms with various lengths of 1-2 microns, 2-4 microns, 4-6 microns and the like.

Drawings

FIG. 1 is a transmission electron micrograph of 2 to 4 μm long rod-shaped copper sulfide particles prepared in example 1;

FIG. 2 is a scanning electron micrograph of 2 to 4 μm long rod-shaped copper sulfide particles prepared in example 1;

FIG. 3 is a transmission electron micrograph of a 1-2 μm long rod-shaped copper sulfide particle prepared in example 2;

FIG. 4 is a scanning electron micrograph of a 1-2 μm long rod-shaped copper sulfide particle prepared in example 2;

FIG. 5 is a transmission electron micrograph of 4 to 6 μm long rod-shaped copper sulfide particles prepared in example 3;

FIG. 6 is a scanning electron micrograph of 4 to 6 μm long rod-shaped copper sulfide particles prepared in example 3;

FIG. 7 is a transmission electron micrograph of copper sulfide particles having a rod-like structure prepared in comparative example 1;

FIG. 8 is a transmission electron micrograph of copper sulfide particles having no rod-like structure prepared in comparative example 2;

FIG. 9 is a transmission electron micrograph of copper sulfide particles having a rod-like structure prepared in comparative example 3;

FIG. 10 is a transmission electron micrograph of copper sulfide particles having no rod-like structure prepared in comparative example 4.

Detailed Description

The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.

The preparation steps of the following examples 1-3 are the same and mainly comprise the following 6 steps:

step S1: dissolving copper salt into water to prepare a solution A with the concentration of 0.15mol/L, and dissolving thiourea into water to prepare a solution B with the concentration of 0.75 mol/L;

step S2: mixing solution A and solution B in a ratio of 1: 0.5-4 or 1: 0.2 to 0.4 or 1: 5-6 volume ratio to prepare a precipitation solution with a large amount of white pasty precipitates;

step S3: performing magnetic stirring treatment on the precipitation solution for 7.5min, and then performing centrifugal treatment;

step S4: centrifuging, separating the upper layer liquid to obtain white pasty precipitate, and vacuum heating the white pasty precipitate to 170 deg.C for 1.5 hr to obtain black powder;

step S5: sequentially adopting deionized water, ethanol and acetone to respectively shake, wash and centrifuge the black powder so as to remove byproducts;

step S6: keeping the temperature at 60 ℃ for 0.75h, drying and precipitating to obtain the product.

Example 1

According to the steps, wherein the copper salt is copper chloride; the volume ratio of the solution A to the solution B is further 1: 1.5; the magnetic stirring speed is 100 r/min; the centrifugal separation condition is 4500r/min, 1.5 min; the vacuum heating environment is a common vacuum drying oven.

Fig. 1 and 2 show the volume ratio of the copper salt solution to the thiourea solution in example 1 controlled to 1: 1.5 Transmission electron microscope and scanning electron microscope images of the prepared rod-like copper sulfide particles with the length of 2-4 μm.

Example 2

According to the steps, wherein the copper salt is copper chloride; the volume ratio of the solution A to the solution B is further 1: 0.75 magnetic stirring speed is 100 r/min; the centrifugal separation condition is 4500r/min, 1.5 min; the vacuum heating environment is a common vacuum drying oven.

Fig. 3 and 4 show the volume ratio of the copper salt solution to the thiourea solution in example 2 controlled to 1: transmission electron microscope images and scanning electron microscope images of the rod-like copper sulfide particles having a length of 1 to 2 μm prepared by 0.75 method.

Example 3

According to the steps, wherein the copper salt is copper chloride; the volume ratio of the solution A to the solution B is further 1: 3; the magnetic stirring speed is 100 r/min; the centrifugal separation condition is 4500r/min, 1.5 min; the vacuum heating environment is a common vacuum drying oven.

Fig. 5 and 6 show the volume ratio of the copper salt solution to the thiourea solution in example 3 controlled to 1: 3 transmission electron microscope images and scanning electron microscope images of the prepared rod-shaped copper sulfide particles with the length of 4-6 mu m.

Comparative example 1

According to the steps, wherein the copper salt is copper chloride; the volume ratio of the solution A to the solution B is further 1: 0.4; the magnetic stirring speed is 100 r/min; the centrifugal separation condition is 4500r/min, 1.5 min; the vacuum heating environment is a common vacuum drying oven.

Fig. 7 is a transmission electron micrograph of copper sulfide particles having a rod-like structure prepared in comparative example 1, which formed a straight rod-like structure but had poor dimensional uniformity.

Comparative example 2

According to the steps, wherein the copper salt is copper chloride; the volume ratio of the solution A to the solution B is further 1: 0.2; the magnetic stirring speed is 100 r/min; the centrifugal separation condition is 4500r/min, 1.5 min; the vacuum heating environment is a common vacuum drying oven.

Fig. 8 is a transmission electron micrograph of copper sulfide particles prepared in comparative example 2 without a rod-like structure, a straight rod-like structure was not formed, and the dimensional uniformity was poor.

Comparative example 3

According to the steps, wherein the copper salt is copper chloride; the volume ratio of the solution A to the solution B is further 1: 5; the magnetic stirring speed is 100 r/min; the centrifugal separation condition is 4500r/min, 1.5 min; the vacuum heating environment is a common vacuum drying oven.

Fig. 9 is a transmission electron micrograph of copper sulfide particles having a rod-like structure prepared in comparative example 3, which are heavily aggregated with a tendency to form a straight rod-like structure, but are not finally formed.

Comparative example 4

According to the steps, wherein the copper salt is copper chloride; the volume ratio of the solution A to the solution B is further 1: 6; the magnetic stirring speed is 100 r/min; the centrifugal separation condition is 4500r/min, 1.5 min; the vacuum heating environment is a common vacuum drying oven.

Fig. 10 is a transmission electron microscope image of copper sulfide particles prepared in comparative example 4 without a rod-like structure, the particles were seriously aggregated and did not have a tendency to form a straight rod-like structure.

The difference between the different examples and the comparative example is only the volume ratio of the copper salt solution to the thiourea solution. The volume ratios of examples 1 to 3 were 1: 1.5,1: 0.75 and 1: 3, the copper salt solution and the thiourea solution are in the specified range of the invention, and rod-shaped copper sulfide particles with different lengths (1-2 μm, 2-4 μm and 4-6 μm) are obtained, so that the volume ratio of the copper salt solution to the thiourea solution is a key factor influencing the length of the rod-shaped product, and the rod-shaped structure can be obtained only in the proper volume ratio range provided by the invention.

It should be noted that, according to the implementation requirement, each step described in the present application can be divided into more steps, and two or more steps or partial operations of the steps can be combined into a new step to achieve the purpose of the present invention.

It should be understood that parts of the specification not set forth in detail are well within the prior art.