CN111933900B - Antimony sulfide/graphene composite nano material and preparation method and application thereof - Google Patents
Antimony sulfide/graphene composite nano material and preparation method and application thereof Download PDFInfo
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- CN111933900B CN111933900B CN202010578971.XA CN202010578971A CN111933900B CN 111933900 B CN111933900 B CN 111933900B CN 202010578971 A CN202010578971 A CN 202010578971A CN 111933900 B CN111933900 B CN 111933900B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an antimony sulfide/graphene composite nanomaterial and a preparation method and application thereof. The invention can rapidly and stably prepare the uniform antimony sulfide/graphene composite nano material at normal temperature by a simple and easy ultrasonic synthesis method, and the antimony sulfide/graphene composite nano material can be used as a sodium-ion battery cathode material to show excellent performance. The preparation method of the invention has simple process and easy popularization.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to an antimony sulfide/graphene composite nano material as well as a preparation method and application thereof.
Background
With the wide application of lithium ion batteries in the fields of electric vehicles, consumer electronics and energy storage, the problem of lithium resource shortage is gradually highlighted. Compared with lithium element, sodium element is more abundant in earth crust, and meanwhile, the sodium ion battery has the advantage of price. However, sodium ions have large ionic radius and slow kinetic rate, and suitable sodium storage materials are not easy to find, which becomes a main factor for restricting the development and application of sodium ion batteries. Based on the background, the development of the sodium storage material with high specific capacity has important theoretical research significance and application prospect.
Recent research shows that the antimony-based material has higher theoretical specific capacity as a sodium ion negative electrode material. Wherein, the antimony sulfide can store sodium because of sulfur element and antimony element, and the specific capacity can reach 757mAhg as the cathode material-1Has attractive prospect. But the material capacity decays rapidly during cycling due to the large volume change during its sodium intercalation/deintercalation.
Graphene has a unique two-dimensional single-layer extension structure, which determines its excellent conductivity and ductility. The composite nano material formed by compounding the graphene and the antimony sulfide and combining networks mutually not only improves the conductivity of the antimony sulfide, but also is expected to solve the problem caused by the volume effect during charging and discharging.
In terms of synthesis methods, many methods for synthesizing nanomaterials have been found, such as liquid-phase precipitation, phase-transition, high-temperature solid-phase, hydrothermal, vapor-phase deposition, micro-mechanical ball-milling, ultrasonic methods, and the like. The ultrasonic method has the obvious advantages of mild reaction conditions, high reaction rate, convenient operation and the like. In conclusion, the ultrasonic synthesis of the nano antimony sulfide/graphene composite material has a great promoting effect on the research of the high-performance sodium-ion battery cathode material and the application of the sodium-ion battery.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide an antimony sulfide/graphene composite nano material with good electrochemical performance, so that the antimony sulfide/graphene composite nano material can be used for electrode materials.
The technical problem to be solved by the invention is to provide a preparation method of the antimony sulfide/graphene composite nano material.
The invention finally aims to solve the technical problem of providing the application of the antimony sulfide/graphene composite nano material in the field of electrode materials.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of antimony sulfide/graphene composite nano material comprises the following steps:
(1) ultrasonically dispersing graphene in water, adding a mixed aqueous solution of antimony salt and inorganic acid, and uniformly mixing;
(2) and (2) adding a sulfur source water solution into the mixed solution obtained in the step (1), uniformly mixing, carrying out ultrasonic reaction, washing the obtained product with absolute ethyl alcohol and deionized water, and drying to obtain the sulfur-containing catalyst.
In the step (1), the concentration of the graphene is 0.01-10 mg/mL, preferably 0.1-2 mg/mL.
In the step (1), the antimony salt is one or a mixture of more of antimony trichloride, antimony nitrate and antimony sulfate, and preferably antimony trichloride.
In the step (1), the inorganic acid is one or a mixture of hydrochloric acid, nitric acid and sulfuric acid, preferably hydrochloric acid.
In the step (1), in the mixed aqueous solution of antimony salt and inorganic acid, the concentration of antimony salt is 0.0001-10 mol/L, preferably 0.001-1 mol/L; the concentration of the inorganic acid is 0.01-20 mol/L, preferably 1-10 mol/L.
In the step (2), the sulfur source is thioacetamide, and the concentration of the thioacetamide is 0.01-0.16 g/ml.
In the step (2), the ultrasonic frequency is more than 10 khz, preferably 20 khz; the ultrasonic time is 0.5-48 hours.
The antimony sulfide/graphene composite nanomaterial prepared by the preparation method of the antimony sulfide/graphene composite nanomaterial is within the protection scope of the invention.
The composite nano material is obtained by mixing antimony salt, a sulfur source and graphene in an acidified aqueous solution and then carrying out ultrasonic reaction, and the obtained composite nano material is formed by uniformly coating amorphous nano antimony sulfide on a graphene lamellar structure. The ultrasonic reaction is a process of chemical reaction under the action of sound wave with frequency of more than 10 kHz, and ultrasonic waves can be provided by ultrasonic equipment such as an ultrasonic cleaning machine, an ultrasonic cell crusher, an ultrasonic reactor and the like; the temperature of the ultrasonic reaction can be normal temperature.
The application of the antimony sulfide/graphene composite nano material in the battery cathode material is within the protection scope of the invention.
The reaction principle of the invention is as follows: when the aqueous solution is excited by ultrasonic waves, an oscillating cavitation effect is generated, and high temperature and high pressure are generated in the collapse process of cavitation bubbles. Sulfur ion S in solution2-And antimony ions Sb3+Under such special reaction conditions, the antimony sulfide/graphene composite material is attached to the graphene sheet layer and reacts in situ to form sulfide, and finally the antimony sulfide/graphene composite material is formed.
Has the advantages that:
(1) according to the invention, the uniform antimony sulfide/graphene composite nano material can be rapidly and stably prepared at normal temperature by a simple and easy ultrasonic synthesis method, and further heat treatment is not needed;
(2) the antimony sulfide/graphene composite nanomaterial prepared by the invention is used as an electrode material, and the graphene is used as a connecting network in the composite material, so that the conductivity of the nanomaterial is effectively enhanced, and the graphene is tightly combined with the nanometer antimony sulfide, so that the nanometer antimony sulfide/graphene composite material has good electrochemical performance and can be applied to a battery cathode material;
(3) the preparation method has the advantages of simple process, low cost and easy popularization.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of an antimony sulfide/graphene composite nanomaterial prepared in example 1;
FIG. 2 is an X-ray diffraction (XRD) spectrum of the antimony sulfide/graphene composite nanomaterial prepared in example 1;
fig. 3 is a sodium ion storage cycling performance graph of the antimony sulfide/graphene composite nanomaterial prepared in example 1.
FIG. 4 shows the current density of 100mAh g prepared in example 2-1First charge and discharge curve.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1:
the preparation method of the antimony sulfide/graphene composite nano material comprises the following steps:
step 1, ultrasonically dispersing graphene in water at normal temperature, adding a mixed aqueous solution of antimony trichloride and hydrochloric acid, and uniformly mixing. In the mixed solution, the concentration of graphene is 0.5mg/mL, the concentration of antimony trichloride is 8mmol/L, and the concentration of hydrochloric acid is 0.7 mol/L.
And 2, adding 0.6g of saturated aqueous solution of thioacetamide into the mixed solution obtained in the step 1, and further uniformly mixing.
And 3, carrying out ultrasonic reaction on the mixed solution obtained in the step 2 for 2 hours, further washing the obtained product with deionized water and absolute ethyl alcohol repeatedly for several times, and then carrying out vacuum drying at 80 ℃ to obtain the antimony sulfide/graphene composite nano material.
As shown in fig. 1 to 3, fig. 1, 2 and 3 are a transmission electron micrograph, an X-ray diffraction pattern and a sodium ion battery cycle performance curve of the antimony sulfide/graphene composite nanomaterial prepared in the present example, respectively. As can be seen from fig. 1, the synthesized composite material is formed by uniformly distributing nano antimony sulfide in a three-dimensional graphene network; as can be seen from fig. 2, the resulting material is amorphous; as can be seen from FIG. 3, the material shows excellent cycling performance, and after 30 cycles, the material can still maintain the reversible specific capacity of more than 600 mAh/g.
Example 2:
the preparation method of the antimony sulfide/graphene composite nano material comprises the following steps:
step 1, ultrasonically dispersing graphene in water, adding a mixed aqueous solution of antimony trichloride and hydrochloric acid, and uniformly mixing. In the mixed solution, the concentration of graphene is 1mg/mL, the concentration of antimony trichloride is 4mmol/L, and the concentration of hydrochloric acid is about 1 mol/L.
And 2, adding 0.3g of saturated aqueous solution of thioacetamide into the mixed solution obtained in the step 1, and further uniformly mixing.
And 3, carrying out ultrasonic reaction on the mixed solution obtained in the step 2 for 4 hours, further washing the obtained product with deionized water and absolute ethyl alcohol repeatedly for several times, and then carrying out vacuum drying at 80 ℃ to obtain the nano antimony sulfide/graphene composite material.
The antimony sulfide/graphene composite nanomaterial prepared in example 2 is similar in structure to the composite nanomaterial prepared in example 1.
Charging and discharging are carried out in the range of 0.01-2.5V. As shown in FIG. 3, the current density was 100mA g-1The first discharge capacity of the composite material reaches 1867.5mA g-1。
Example 3:
the preparation method of the antimony sulfide/graphene composite nanomaterial comprises the following steps:
step 1, ultrasonically dispersing graphene in water, adding a mixed aqueous solution of antimony trichloride and hydrochloric acid, and uniformly mixing. In the mixed solution, the concentration of graphene is 2mg/mL, the concentration of antimony trichloride is 2mmol/L, and the concentration of hydrochloric acid is about 1 mol/L.
And 2, adding 1g of saturated aqueous solution of thioacetamide into the mixed solution obtained in the step 1, and further uniformly mixing.
And 3, carrying out ultrasonic reaction on the mixed solution obtained in the step 2 for 10 hours, further washing the obtained product with deionized water and absolute ethyl alcohol repeatedly for several times, and then carrying out vacuum drying at 80 ℃ to obtain the nano antimony sulfide/graphene composite material.
The antimony sulfide/graphene composite nanomaterial prepared in example 3 is similar in structure to the composite nanomaterial prepared in example 1.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of antimony sulfide/graphene composite nano-material is characterized by comprising the following steps: the method comprises the following steps:
(1) ultrasonically dispersing graphene in water, adding a mixed aqueous solution of antimony salt and inorganic acid, and uniformly mixing;
(2) adding a sulfur source water solution into the mixed solution obtained in the step (1), uniformly mixing, carrying out ultrasonic reaction, and washing and drying the obtained product to obtain the sulfur source-containing composite material;
in the step (2), the ultrasonic frequency is more than 10 kHz, and the ultrasonic time is 0.5-48 hours.
2. The preparation method of the antimony sulfide/graphene composite nanomaterial according to claim 1, wherein in the step (1), the concentration of the graphene is 0.01-10 mg/mL.
3. The method for preparing antimony sulfide/graphene composite nanomaterial according to claim 1, wherein in step (1), the antimony salt is one or a mixture of antimony trichloride, antimony nitrate and antimony sulfate.
4. The method for preparing antimony sulfide/graphene composite nanomaterial according to claim 1, wherein in step (1), the inorganic acid is one or a mixture of hydrochloric acid, nitric acid and sulfuric acid.
5. The method for preparing antimony sulfide/graphene composite nanomaterial according to claim 1, wherein in the step (1), the concentration of antimony salt in the mixed aqueous solution of antimony salt and inorganic acid is 0.001-10 mol/L, and the concentration of inorganic acid is 0.01-20 mol/L.
6. The method for preparing the antimony sulfide/graphene composite nanomaterial according to claim 1, wherein in the step (2), the sulfur source is thioacetamide, and the concentration of the thioacetamide is 0.01-0.16 g/ml.
7. The antimony sulfide/graphene composite nanomaterial prepared by the preparation method of the antimony sulfide/graphene composite nanomaterial disclosed by any one of claims 1-6.
8. The use of the antimony sulfide/graphene composite nanomaterial of claim 7 in a battery negative electrode material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289657A (en) * | 2015-11-30 | 2016-02-03 | 湘潭大学 | Preparation method for graphene and antimony sulphide nano-rod composite visible light catalyst |
| CN105720251A (en) * | 2015-12-20 | 2016-06-29 | 华南理工大学 | Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material |
| CN106582718A (en) * | 2016-12-31 | 2017-04-26 | 湘潭大学 | Preparation method of graphene-antimony sulfide microrod composite photocatalyst |
| CN106622294A (en) * | 2016-12-31 | 2017-05-10 | 湘潭大学 | Preparation method of graphene-based composite Sb2S3 photocatalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289657A (en) * | 2015-11-30 | 2016-02-03 | 湘潭大学 | Preparation method for graphene and antimony sulphide nano-rod composite visible light catalyst |
| CN105720251A (en) * | 2015-12-20 | 2016-06-29 | 华南理工大学 | Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material |
| CN106582718A (en) * | 2016-12-31 | 2017-04-26 | 湘潭大学 | Preparation method of graphene-antimony sulfide microrod composite photocatalyst |
| CN106622294A (en) * | 2016-12-31 | 2017-05-10 | 湘潭大学 | Preparation method of graphene-based composite Sb2S3 photocatalyst |
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