CN104934583B - Preparation method of elemental silicon-graphene nanoribbon composite material - Google Patents
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Images
Classifications
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A preparation method of an elemental silicon-graphene nanoribbon composite material is to uniformly mix elemental silicon and a binder to form an elemental silicon suspension. Then adding the graphene nanoribbon prepared by chemically cutting and ultrasonically stripping the carbon nanotube, ultrasonically mixing to prepare a simple substance silicon-graphene nanoribbon colloid, and drying and thermally treating to prepare the composite cathode material product. The method has the characteristics of simple process, convenient operation, contribution to large-scale production, convenient popularization and application, low energy consumption, low production cost, good production safety and the like, and the elemental silicon-graphene nanoribbon composite material prepared by the method has the characteristics of strong binding force, excellent conductivity, high ion diffusion speed, long cycle service life and the like.
Description
Technical Field
The invention belongs to the technical field of nano composite material preparation, and particularly relates to a method for preparing a simple substance silicon-graphene nanoribbon composite material in the field of nano composite materials.
Background
In recent years, lithium ion batteries have been the focus of research due to their advantages of high energy density, fast charge and discharge speed, no memory effect, long service life, etc. At present, graphite is generally adopted as a negative electrode material of the lithium ion battery, but the performance of the lithium ion battery is severely limited by the lower specific capacity (theoretical capacity 372mAh/g) of the graphite. Silicon is considered to be the most promising material to replace graphite to become the negative electrode of the next generation of novel lithium ion batteries because of the large specific capacity (the theoretical capacity reaches 4200 mAh/g). However, silicon has a severe volume effect in the charging and discharging processes, the silicon electrode material is seriously pulverized along with the proceeding of lithium ion intercalation-intercalation, and meanwhile, the conductivity of silicon is low, so that the application of silicon as a negative electrode material in the field of lithium ion batteries is greatly limited by the two factors. Therefore, it is of great practical significance to design a method that can solve both of these problems. The graphene nanoribbon is one-dimensional strip-shaped graphene, and is bound with the wound elemental silicon-graphene nanoribbon composite structure through designing the graphene nanoribbon, so that the pulverization phenomenon of elemental silicon can be well relieved, and meanwhile, the graphene nanoribbon has good conductivity, and is more favorable for transmission and storage of electrons or ions.
The existing preparation method of the silicon and graphene composite material generally comprises the steps of preparing graphene oxide from graphite through chemical oxidation, then preparing graphene through high-temperature stripping, then obtaining modified graphene through plasma treatment, and then performing silicon deposition through a vapor deposition method to obtain the silicon and graphene composite material. The main disadvantages of this method are: the method adopts a vapor deposition method, has low yield and high production cost, and is inconvenient to popularize and apply. Secondly, the method adopts a silicon silane source, is expensive, toxic and not beneficial to mass production. The method has the advantages of high temperature, high energy consumption, energy conservation and consumption reduction, and limited practical application. And fourthly, the product graphene prepared by the method is not tightly combined with the simple substance silicon, so that the simple substance silicon is still easy to be pulverized and fall off in the electrochemical reaction process, and the cycle stability and the service life are influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a simple substance silicon-graphene nanoribbon composite material aiming at the defects of the existing preparation method of a silicon and graphene composite material, and the preparation method has the advantages of convenience in operation, low production cost, greenness, no toxicity and the like; the elemental silicon-graphene nanoribbon composite material prepared by the method has a stable structure, and has a static adhesion effect between the elemental silicon and the graphene nanoribbon composite material, and the static adhesion of the graphene nanoribbon on the surface of the elemental silicon can obviously improve the transmission rate of electrons and lithium ions, so that the lithium intercalation activity of the lithium ions is enhanced, the service life of the lithium ions is prolonged, and the material can be used as a high-power lithium ion battery cathode material.
The technical scheme for realizing the purpose of the invention is as follows: a preparation method of a simple substance silicon-graphene nanoribbon composite material takes simple substance silicon and a carbon nanotube as raw materials, and firstly, the simple substance silicon is mixed with a binder to prepare a silicon suspension; secondly, preparing the graphene nanoribbon by chemical cutting and ultrasonic stripping; then, preparing simple substance silicon-graphene nanoribbon jelly through ultrasonic mixing; and finally, preparing the elemental silicon-graphene nanoribbon composite material through heat treatment. The method comprises the following specific steps:
1) preparation of elemental silicon suspensions
Adding the simple substance silicon material into deionized water, and stirring for 0.5-12 h to obtain a suspension of the simple substance silicon, wherein the concentration of the simple substance silicon in the deionized water is 0.001-0.01 g/mL; and then adding a binder into the suspension, and carrying out ultrasonic treatment for 10-300 min to obtain a uniform simple substance silicon suspension. The mass ratio of the binder to the simple substance silicon is 1: 0.1-50.
2) Preparation of graphene nanoribbons
2.1) adding the graphitized carbon nano tube into oxidizing acid and stirring for 1-24 h to prepare a mixture I.
2.2) adding a transition metal oxidation auxiliary agent into the mixture I, stirring at room temperature for 0.1-5 h, transferring into a water bath kettle, and stirring at a constant temperature of 50-90 ℃ for 1-10 h to obtain a mixture II; the concentration of the carbon nano tube in the step 2.1) in the strong oxidizing acid in the step 2.1) is 0.0005-0.02g/mL, and the concentration of the transition metal oxidation auxiliary agent in the step 2.2) in the strong oxidizing acid in the step 2.1) is 0.0005-0.2 g/mL;
2.3) adding 30 percent by mass of hydrogen peroxide and deionized water into the mixture II, and mixing and reacting for 0.5-3h to obtain a mixture III; the volume ratio of the hydrogen peroxide to the deionized water to the oxidizing acid is 1: 5-20: 0.5-5.
2.4) carrying out ultrasonic cleaning on the mixture III by using hydrochloric acid with the mass fraction of 2-5%; and (2) performing ultrasonic treatment at the frequency of 20-1000Hz for 10-300 min for 2-5 times, repeatedly performing centrifugal cleaning with deionized water until the mixture is neutral, and drying at the temperature of 60-150 ℃ for 6-24 hours to obtain the graphene nanoribbon.
3) Preparation of elemental silicon-graphene nanoribbon composite
Adding the graphene nanoribbon obtained in the step 2.4) into the elemental silicon suspension obtained in the step 1), wherein the mass ratio of the graphene nanoribbon to the elemental silicon in the step 1) is 1: 0.1-20, performing ultrasonic oscillation at the frequency of 50-1000 Hz for 30-240 min to obtain an elemental silicon-graphene nanoribbon colloid, drying the colloid at 60-150 ℃ for 6-24 h, heating to the sintering temperature of 200-600 ℃ at the heating rate of 2-5 ℃/min, and sintering for 1-10 h under the protection of inert atmosphere to obtain the elemental silicon-graphene nanoribbon composite material.
After the technical scheme is adopted, the invention mainly has the following effects:
1. the method has the advantages of less working procedures in the production process, low temperature and no use of toxic raw materials, so the method has low energy consumption, good production safety, low production cost and environmental protection.
2. The method adopts the procedures of chemical oxidation, mechanical stirring, ultrasonic dispersion mixing and the like, has simple process and convenient operation, is beneficial to realizing large-scale production and is convenient to popularize and apply;
3. the method can directly adopt commercial simple substance silicon material, and is beneficial to direct large-scale production;
4. the simple substance silicon-graphene nanoribbon composite material prepared by the method not only can be tightly combined with simple substance silicon due to the unique ribbon-shaped structure of the graphene nanoribbon, but also can form tiny gaps and the defects of the nanoribbon, so that the prepared composite has excellent performances of high conductivity and good ion transmission performance, and has the characteristics of excellent multiplying power performance and the like;
5. according to the elemental silicon-graphene nanoribbon composite material prepared by the invention, as the graphene nanoribbon can be flexibly adhered to the elemental silicon in a winding manner, and an electrostatic adhesion effect exists between the graphene nanoribbon and the elemental silicon, the pulverization phenomenon of the silicon can be effectively prevented, and the electrochemical performance of the electrode material is improved.
The method is widely used for preparing the graphene nanoribbon composite material, and the elemental silicon-graphene nanoribbon composite material prepared by the method can be widely used for high-power lithium ion batteries.
Drawings
Fig. 1 is an SEM image of the elemental silicon-graphene nanoribbon composite prepared in example 1.
Fig. 2 is an enlarged view of fig. 1.
In the figure, 1 is simple substance silicon, and 2 is a graphene nanoribbon.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
The preparation method of the elemental silicon-graphene nanoribbon composite material comprises the following specific steps:
1) preparation of elemental silicon suspensions
Adding the simple substance silicon material into deionized water, stirring for 3h to obtain a suspension of the simple substance silicon, wherein the concentration of the simple substance silicon in the deionized water is 0.002g/mL, and then adding glucose into the suspension for ultrasonic treatment for 90min to obtain a uniform simple substance silicon suspension. The mass ratio of the glucose to the simple substance silicon is 1: 10.
2) Preparation of graphene nanoribbons
2.1) adding the graphitized carbon nano tube into concentrated sulfuric acid and stirring for 12 hours to prepare a mixture I,
2.2) then adding potassium permanganate into the mixture I, stirring for 1h at room temperature, then transferring into a water bath kettle, and stirring for 4h at the constant temperature of 80 ℃ to obtain a mixture II; the concentration of the carbon nano tube in the step 2.1) in the strong oxidizing acid in the step 2.1) is 0.0025g/mL, and the concentration of the transition metal oxidation auxiliary agent in the step 2.2) in the strong oxidizing acid in the step 2.1) is 0.0125 g/mL;
2.3) adding 30 percent by mass of hydrogen peroxide and deionized water into the mixture II, and mixing and reacting for 3 hours to obtain a mixture III; the volume ratio of the hydrogen peroxide to the deionized water to the oxidizing acid is 1: 10: 2.
And 2.4) ultrasonically cleaning the mixture III by using hydrochloric acid with the mass fraction of 3%, wherein the ultrasonic frequency is 100Hz, the time is 30-300 min, the cleaning frequency is 3 times, then repeatedly centrifugally cleaning the mixture III by using deionized water to be neutral, and drying the mixture III for 12 hours at 80 ℃ to obtain the graphene nanoribbon.
3) Preparation of elemental silicon-graphene nanoribbon composite
Adding the graphene nanoribbon obtained in the step 2.4) into the elemental silicon suspension obtained in the step 1), wherein the mass ratio of the graphene nanoribbon to the elemental silicon in the step 1) is 1: 2, then carrying out ultrasonic oscillation for 120min at the frequency of 100Hz to obtain an elemental silicon-graphene nanoribbon colloidal material, drying the colloidal material at 120 ℃ for 12h, heating to the sintering temperature of 400 ℃ at the heating rate of 3 ℃/min, and sintering for 3h under the protection of an inert atmosphere to obtain the elemental silicon-graphene nanoribbon composite material.
Example 2
The preparation method of the elemental silicon-graphene nanoribbon composite material is the same as that in example 1, wherein:
in the step 1), stirring for 0.5h, adding a binder into deionized water at a concentration of 0.01g/mL, and performing ultrasonic treatment for 10min, wherein the mass ratio of the binder to the simple substance silicon is 1: 0.1.
In the step 2), the transition metal oxidation auxiliary agent is osmium tetroxide, the concentrated sulfuric acid is oxidizing acid, the graphitized carbon nano tube is added into strong oxidizing acid to be stirred for 1h, the stirring time is 0.1h at room temperature, the water bath temperature is 50 ℃, and the water bath stirring time is 1 h; the mass concentration of the carbon nano tube in the strong oxidizing acid is 0.02g/mL, and the concentration of the transition metal oxidation auxiliary agent in the strong oxidizing acid is 0.02 g/mL; . Adding hydrogen peroxide and deionized water into the mixture II, and mixing and reacting for 0.5 h; the volume ratio of the hydrogen peroxide to the deionized water to the oxidizing acid is 1: 5: 0.5. The mass fraction of the hydrochloric acid is 2%, and the mixture III is subjected to ultrasonic treatment at the frequency of 20Hz for 10min, the cleaning times are 2 times, the drying temperature is 60 ℃, and the drying time is 6 h.
In the step 3), the ultrasonic frequency is 50Hz, the ultrasonic time is 30min, the drying temperature is 60 ℃, the drying time is 6h, the heating rate is 2 ℃/min, the sintering temperature is 200 ℃, the sintering time is 1h, and the mass ratio of the mass of the graphene nanoribbon to the mass of the simple substance silicon in the step 1) is 1: 0.1.
Example 3
The preparation method of the elemental silicon-graphene nanoribbon composite material is the same as that in example 1, wherein:
in the step 1), stirring time is 12 hours, the concentration of the simple substance silicon in deionized water is 0.001g/mL, a binder is added, and ultrasound treatment is carried out for 300min, wherein the mass ratio of the binder to the simple substance silicon is 1: 50.
2) adding the graphitized carbon nano tube into strong oxidizing acid for stirring for 24 hours at room temperature for 5 hours, at the water bath temperature of 90 ℃, and for 1-10 hours; the mass concentration of the carbon nano tube in the strong oxidizing acid is 0.1g/mL, and the concentration of the transition metal oxidation auxiliary agent in the strong oxidizing acid is 0.005 g/mL; . Adding hydrogen peroxide and deionized water into the mixture II, and mixing and reacting for 0.5 h; the volume ratio of the hydrogen peroxide to the deionized water to the oxidizing acid is 1: 20: 5. The mass fraction of the hydrochloric acid is 5%, and the mixture III is subjected to ultrasonic treatment, wherein the ultrasonic treatment frequency is 1000Hz, the ultrasonic treatment time is 300min, the cleaning times are 5 times, the drying temperature is 150 ℃, and the drying time is 24 h.
In the step 3), the ultrasonic frequency is 1000Hz, the ultrasonic time is 240min, the drying temperature is 150 ℃, the drying time is 24h, the heating rate is 5 ℃/min, the sintering temperature is 600 ℃, the sintering time is 10h, and the mass ratio of the graphene nanoribbon to the simple substance silicon in the step 1) is 1: 20.
Test results
The scanning electron microscope observation of the positive electrode composite material prepared in example 1 is carried out, and the electron microscope images are shown in fig. 1 and fig. 2, wherein fig. 2 is an enlarged view of fig. 1. From the analysis of the test results, it can be known that the elemental silicon particles of the elemental silicon-graphene nanoribbon composite material product obtained in the embodiment 1 are uniformly bound and wound by the nanoribbons to form a three-dimensional network structure, and meanwhile, the graphene nanoribbons are tightly combined with the elemental silicon particles, so that the structure is beneficial to preventing the pulverization phenomenon of the elemental silicon in the charging and discharging processes, and meanwhile, the conductivity of the elemental silicon can be improved, the lithium ion transmission is facilitated, and the electrochemical performance of the elemental silicon is improved.
Claims (2)
1. The preparation method of the elemental silicon-graphene nanoribbon composite material is characterized by comprising the following steps of:
1) preparation of elemental silicon suspensions
Adding the simple substance silicon material with the particle size of less than 300nm into deionized water, and stirring for 0.5-12 h to obtain a suspension of the simple substance silicon, wherein the concentration of the simple substance silicon in the deionized water is 0.001-0.01 g/mL; then adding a binder into the suspension, and carrying out ultrasonic treatment for 10-300 min at the frequency of 20-1000Hz to prepare a uniform simple substance silicon suspension; the mass ratio of the binder to the simple substance silicon is 1: 0.1-50;
2) preparation of graphene nanoribbons
2.1) adding the graphitized carbon nano tube into strong oxidizing acid and stirring for 1-24 hours to prepare a mixture I;
2.2) adding a transition metal oxidation auxiliary agent into the mixture I, stirring at room temperature for 0.1-5 h, transferring into a water bath kettle, and stirring at a constant temperature of 50-90 ℃ for 1-10 h to obtain a mixture II; the concentration of the carbon nano tube in the step 2.1) in the strong oxidizing acid in the step 2.1) is 0.0005-0.02g/mL, and the concentration of the transition metal oxidation auxiliary agent in the step 2.2) in the strong oxidizing acid in the step 2.1) is 0.0005-0.2 g/mL;
2.3) adding 30 percent by mass of hydrogen peroxide and deionized water into the mixture II, and mixing and reacting for 0.5-3h to obtain a mixture III; the volume ratio of the hydrogen peroxide to the deionized water to the strong oxidizing acid is 1: 5-20: 0.5-5;
2.4) carrying out ultrasonic cleaning on the mixture III by using hydrochloric acid with the mass fraction of 2-5%; the ultrasonic frequency is 20-1000Hz, the time is 10-300 min, the cleaning frequency is 2-5 times, then deionized water is used for repeatedly centrifugally cleaning the mixture to be neutral under the condition that the rotating speed is 1000-15000 r/s, and then the mixture is dried for 6-24 hours at the temperature of 60-150 ℃ to prepare the graphene nanoribbon;
3) preparation of elemental silicon-graphene nanoribbon composite
Adding the graphene nanoribbons obtained in the step 2.4) into the elemental silicon suspension obtained in the step 1), wherein the mass ratio of the graphene nanoribbons to the elemental silicon in the step 1) is 1: 0.1-20; performing ultrasonic oscillation at the frequency of 50-1000 Hz for 30-240 min to obtain simple substance silicon-graphene nanoribbon jelly; drying the jelly at 60-150 ℃ for 6-24 h, heating to a sintering temperature of 200-600 ℃ at a heating rate of 2-5 ℃/min, and sintering in an inert atmosphere for 1-10 h to obtain the elemental silicon-graphene nanoribbon composite material.
2. The method for preparing the elemental silicon-graphene nanoribbon composite material according to claim 1, wherein the method comprises the following steps:
the transition metal oxidation auxiliary agent in the step 2.2) is selected from one or more of potassium permanganate, sodium permanganate, potassium ferrate, sodium ferrate and osmium tetroxide;
the strong oxidizing acid in the step 2.1) is selected from one of concentrated sulfuric acid, concentrated nitric acid, oxyacid of chlorine, oxyacid of bromine or oxyacid of iodine;
the binder in the step 1) is selected from one or more of polyethylene, polypropylene, polyvinyl acetate, polyvinyl chloride, polyacrylonitrile, polybutadiene, polyvinyl formal, polytetrafluoroethylene, polymethyl methacrylate, glucose, sucrose, polymethyl cellulose or polyethyl cellulose.
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