CN106981650B

CN106981650B - Preparation method of nanoscale elemental bismuth

Info

Publication number: CN106981650B
Application number: CN201710074141.1A
Authority: CN
Inventors: 卢锡洪; 郑海兵; 冯浩槟; 曾银香; 张敏; 程发良; 童叶翔
Original assignee: Dongguan University of Technology; National Sun Yat Sen University
Current assignee: Dongguan University of Technology; National Sun Yat Sen University
Priority date: 2017-02-10
Filing date: 2017-02-10
Publication date: 2020-03-13
Anticipated expiration: 2037-02-10
Also published as: CN106981650A

Abstract

The invention provides a preparation method of nanoscale simple substance bismuth, which is characterized in that nanoscale simple substance bismuth is generated on conductive carbon cloth through an electrochemical deposition method; the electrolyte is a mixed aqueous solution of bismuth salt, hexadecyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid sodium salt, wherein the concentration of the bismuth salt is (5-30) mmol/L; the concentration of the hexadecyl trimethyl ammonium bromide is (30-80) mmol/L; the concentration of the ethylene diamine tetraacetic acid sodium salt is (0.1-0.3) mol/L; the electroplating voltage is-1-0V; the electroplating time is 10-90 min. The preparation method provided by the invention has the advantages of low energy consumption, simple and convenient and easily-obtained raw materials, simple operation and easy realization, and the prepared elemental bismuth nano material has the advantages of high specific surface area, excellent conductivity and good energy storage performance, provides a good cathode material for the existing energy storage problem, and has great application prospect.

Description

Preparation method of nanoscale elemental bismuth

Technical Field

The invention belongs to the technical field of energy storage material preparation, and particularly relates to a preparation method of nanoscale elemental bismuth.

Background

With the explosive growth of population and the rapid development of society, various demands for energy resources are increasing as one of the cornerstones for society and urgent development. The existing traditional fossil energy can not meet various requirements of future society on energy for a long time, and in addition, along with the development of the fossil energy, the greenhouse effect is increasingly serious, the ecological environment is increasingly worsened, the problems of uneven distribution of regional energy and the like are solved, and renewable green energy has become the focus of attention of people. With the development of socioeconomic and scientific technologies, various new energy sources are developed and utilized to realize the efficient conversion and utilization of new energy sources by researching and developing different types of energy storage devices. The deep development and the high-efficiency utilization of new energy are realized, and the development of a novel high-efficiency and stable electric energy storage device is the key.

Conventional ion batteries using organic electrolytes have a wide electrochemical window, but organic electrolytes are flammable and toxic, and if not properly used, can cause serious safety and environmental problems. The aqueous electrolyte is environment-friendly and safe, the ionic conductivity of the aqueous electrolyte is two orders of magnitude higher than that of the organic electrolyte, the high power of the battery is expected to be realized, the strict manufacturing conditions required by the organic electrolyte are avoided, and the production cost is greatly reduced. Therefore, the water-based ion battery has an important application prospect in the field of large-scale energy storage at the power grid level, and with the intensive research, researchers have deeply realized that the key point is to find a high-performance energy storage negative electrode material for improving the performance of the water-based battery.

At present, common battery cathode materials comprise carbon cathode materials, such as carbon materials actually applied to lithium ion batteries, the cost of the materials is low, industrialization is easy to realize, but the material capacity is low, and the theoretical capacities of alloy materials and metal oxide materials are high, but the service life is short. The elementary bismuth as a novel cathode material has a high cathode working potential window and a proper potential working interval, and the theoretical specific capacitance value is high and is as high as 78.9 mAh/g. However, the cycle life of the elementary bismuth is poor, the large-scale preparation method is immature and imperfect, and various conditions restrict the application of the elementary bismuth in the battery cathode material.

The simple substance bismuth material found at present is mostly used in the aspects of chemical industry, catalysts, semiconductors, electronic ceramics and the like. Compared with other materials, the simple substance bismuth is rich in resources, low in price, environment-friendly, good in conductivity and suitable for negative potential working interval, and therefore is a high-performance cathode material with great development potential. However, the research on the elemental bismuth nano material is less, especially in the field of energy storage, and many reported methods are not suitable for mass production. Therefore, the development of a simple, convenient and efficient method for preparing the elemental bismuth nano material is of great significance.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and the like and provides a preparation method of nano-scale elementary bismuth.

The above purpose of the invention is realized by the following technical scheme:

a preparation method of nano-scale simple substance bismuth comprises the steps of generating nano-scale simple substance bismuth on conductive carbon cloth by an electrochemical deposition method; the electrolyte is a mixed aqueous solution of bismuth salt, hexadecyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid sodium salt, wherein the concentration of the bismuth salt is (5-30) mmol/L; the concentration of the hexadecyl trimethyl ammonium bromide is (30-80) mmol/L; the concentration of the ethylene diamine tetraacetic acid sodium salt is (0.1-0.3) mol/L; the electroplating voltage is-1-0V; the electroplating time is 10-90 min.

Preferably, the concentration of the bismuth salt in the electrolyte is 20mmol/L, the concentration of the hexadecyl trimethyl ammonium bromide is 50mmol/L, and the concentration of the ethylene diamine tetraacetic acid sodium salt is 0.1 mol/L.

Preferably, the electroplating voltage is-1V, and the electroplating time is 60 min.

Preferably, the bismuth salt is bismuth nitrate pentahydrate.

Preferably, the working electrode is conductive carbon cloth, the counter electrode is a graphite carbon rod, and the reference electrode is a saturated calomel electrode.

Compared with the prior art, the invention has the following advantages and beneficial effects:

the preparation method provided by the invention has the advantages of low energy consumption, simple and convenient and easily-obtained raw materials, simple operation and easy realization, and the prepared elemental bismuth nano material has high specific surface area and excellent conductivity, and the energy storage performance is greatly improved compared with the anode materials such as mature commercial graphite. The simple substance bismuth material with high specific surface area is directly synthesized from the conductive carbon cloth on the flexible substrate, and meanwhile, the electrochemical deposition method is adopted, so that the method can be widely applied to industrial production, provides a good cathode material for the current energy storage problem, and has great application prospect.

Drawings

In fig. 1, (a) is a high-magnification Scanning Electron Microscope (SEM) picture of the elemental bismuth in example 1, and (b) is a low-magnification Scanning Electron Microscope (SEM) picture of the elemental bismuth in example 1.

FIG. 2 is a cyclic voltammogram of elemental bismuth at 100 mV/s for example 1.

FIG. 3 shows the discharge time of elemental bismuth of example 1 at different current densities.

Figure 4 is an XRD of elemental bismuth of example 1.

Detailed Description

The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

The synthesis of the simple substance bismuth on the carbon cloth is realized by electrodeposition. Before current loading, the carbon cloth (1cm multiplied by 3cm) is sequentially subjected to ultrasonic cleaning for 10 minutes in the presence of deionized water, ethanol, acetone and deionized water, and then dried at 60 ℃ for later use. The cleaned carbon cloth was immersed in a three-electrode system containing 30ml of a mixed aqueous solution of bismuth nitrate (bismuth nitrate pentahydrate), cetyltrimethylammonium bromide and ethylenediaminetetraacetic acid sodium salt (ethylenediaminetetraacetic acid sodium salt dihydrate), wherein the amount of the mixed aqueous solution corresponded to 300mg of the nitric acid pentahydrate, 550mg of the cetyltrimethylammonium bromide and 1.12g of the ethylenediaminetetraacetic acid sodium salt. And (3) applying a negative 1V loading voltage to the system by taking carbon cloth as a working electrode, a graphite carbon electrode as a counter electrode and saturated calomel as a reference electrode, and keeping the reaction for 60 min. And (3) taking out the carbon cloth after the reaction is finished, repeatedly washing the obtained sample for three times by using the deionized water, and drying at 60 ℃.

Examples 2 to 5

Based on the scheme of example 1, the growth of elemental bismuth is influenced by regulating and controlling different reaction conditions, and the relationship is shown in table 1.

TABLE 1

Comparative example 1: the other conditions are the same as example 1, except that the electroplating time is 120min, powder agglomeration of elemental bismuth can be obviously observed, and the elemental bismuth does not uniformly grow on the working electrode carbon cloth.

Comparative example 2: the other conditions are the same as example 1, except that the amount of bismuth nitrate is 800mg, it can be obviously observed that the simple substance bismuth forms agglomeration on the working electrode carbon cloth, and cannot grow well.

Comparative example 3: the other conditions are the same as example 1, except that the plating voltage is 2V, it can be obviously observed that the voltage is higher, large-particle powder is obtained, and the simple substance bismuth cannot be well deposited.

Comparative example 4: the other conditions are the same as example 1, except that the amount of the cetyl trimethyl ammonium bromide is 700mg, it can be obviously observed that the simple substance bismuth can not be deposited on the carbon cloth more uniformly, and the conductivity of the simple substance bismuth is influenced.

From the results in fig. 1 and fig. 4, it can be seen that the elemental bismuth nanomaterial grows uniformly on the carbon cloth substrate, and fig. 3 shows the discharge time of the elemental bismuth of example 1 under different current densities. The cyclic voltammetry curve in fig. 2 shows that the elemental bismuth nanomaterial has good reversibility and energy storage characteristics. The area ratio capacitance value of the simple substance bismuth nano material is calculated to be 356.55mF/cm²Thus showing good energy storage performance.

Claims

1. A preparation method of nano-scale simple substance bismuth is characterized in that the nano-scale simple substance bismuth is generated on a conductive carbon cloth by an electrochemical deposition method; the electrolyte is a mixed aqueous solution of bismuth salt, hexadecyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid sodium salt, wherein the concentration of bismuth salt in the electrolyte is 20mmol/L, the concentration of hexadecyl trimethyl ammonium bromide is 50mmo1/L, the concentration of ethylene diamine tetraacetic acid sodium salt is 0.1mol/L, bismuth salt is bismuth nitrate pentahydrate, a working electrode of the electrochemical deposition method is carbon cloth, a counter electrode is a graphite carbon rod, a reference electrode is a saturated calomel electrode, a negative 1V loading voltage is applied to a system, and the reaction is kept for 60 min.