CN109867270B - Preparation method and application of nano carbon material spherical assembly - Google Patents
Preparation method and application of nano carbon material spherical assembly Download PDFInfo
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Abstract
A preparation method and application of a nano carbon material spherical assembly belong to the technical field of nano materials. Firstly preparing a carbon source aqueous solution, adding the carbon source aqueous solution into a low-temperature medium for freezing treatment, and then performing freeze-drying and carbonization to obtain a carbon material spherical assembly with the diameter of 10-50 mu m, wherein the carbon material spherical assembly is assembled by carbon nano sheets with the thickness of 3-10nm or carbon nano fibers with the diameter of 1-3 nm. The preparation method has the characteristics of simplicity, controllable appearance, easy removal of the solvent, no toxicity and the like. The nano carbon material spherical assembly is applied to energy storage and sewage treatment, lithium ion batteries, sodium ion batteries and super capacitors which take the prepared nano carbon material spherical assembly as an active substance all show good electrochemical performance, and the oil absorption sponge prepared from the obtained nano carbon material spherical assembly has the characteristics of low cost, simple and convenient operation and good repeatability.
Description
Technical Field
The invention relates to a preparation method of a nano carbon material, which can be used for preparing micron-sized spherical carbon assembled by carbon nano sheets and carbon nano wires and simultaneously applied to energy storage and oil stain adsorption and belongs to the technical fields of nano material preparation, electrode material preparation and oil stain adsorption materials.
Background
With the rapid development of science and technology, the discharge of a large amount of industrial wastewater and the leakage accidents of oil ships and oil tanks cause water body pollution, and oil pollutants are one of the main pollutants causing water body pollution and have seriously threatened the ecological environment. Oil pollutants in water are treated by an adsorption method. The oil absorption material is a functional material for recovering and treating waste oil, and is widely used for treating oil leakage of factory machines, oil content in factory waste water, waste food oil and crude oil leakage on the sea and land. Common organic oil absorption materials and inorganic oil absorption materials have the defects of low adsorption efficiency, high cost and the like, and are easy to cause secondary pollution. How to effectively treat the petroleum and the products thereof overflowing into the ocean or other water bodies is the key research point of many countries and organizations. The spherical carbon assembly has certain advantages due to the advantages of containing abundant pore structures, oxygen-containing functional groups and the like. Secondly, with the increasing severity of energy crisis and environmental pollution, all countries in the world are tightening to develop renewable energy power generation and large-scale energy storage technology, and strive to build efficient and safe future intelligent energy networks. Therefore, in recent years, the research and development of energy storage technology in various countries of the world are more and more important, and the research of searching for low-cost, safe and efficient electrochemical electrode materials is the key research point of many researchers.
Currently, various methods for preparing spherical carbon assemblies have been explored, wherein the main preparation method is to use Nano carbon materials such as graphene and carbon nanotubes as starting materials to form the spherical carbon assembly through modification and secondary assembly, and authors in the literature, "non-volatile self-assembly of carbon nanotubes for construction of" gels "(Nano Letters 2.5(2002): 531) 533) use charged silica gel to adsorb the acid-washed carbon nanotubes layer by layer, and after selective chemical etching, a spherical carbon cage composed of carbon nanotubes is formed. In the literature "fabrics of graphene-polymer nanocomposites with high-order-dimensional architecture" (Advanced Materials 21.21(2009): 2180-. In the document "Carbon nanotube capsules self-assembled by W/O emulsion technology" (Langmuir 23.6(2007):3199-3204), "the authors prepared multi-walled Carbon nanotube capsule spherical assemblies using a water-in-oil emulsion method, and similarly, in the document" Hollow graphene oxide spheres self-assembled by W/O emulsion "(Journal of Materials Chemistry 20.23(2010): 4867-4874)," the authors prepared graphene nanosheet Hollow graphene oxide spheres using a surfactant-free water-in-oil emulsion method. Generally, these methods require preparing a nano-carbon material such as graphene sheet, multi-walled carbon nanotube, carbon nanosheet, carbon nanocolloid, etc. in advance, and then performing secondary assembly by different means to obtain a spherical carbon assembly or spherical carbon capsule, and secondly, most methods require using an organic solvent to pre-disperse the nano-carbon material well, in addition, the prepared material also requires performing post-treatment such as washing or etching, and relatively speaking, a typical freeze-drying process has some incomparable advantages over other methods, for example, water is generally used for freeze-drying to prepare a porous material, is an environment-friendly solvent, and ice crystal is green and sustainable by using the ice crystal as a pore-forming agent, and secondly, when the solvent is removed, the freeze-drying process does not bring impurities into a sample, so that further post-treatment processes can be avoided.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a nano carbon material spherical assembly for electrochemical energy storage and oil stain adsorption by using a water-soluble polymer as a precursor and only performing one-step freeze-drying carbonization.
The spherical assembly of nano carbon material is characterized in that the diameter of the assembled spherical carbon is 10-50 mu m, and the spherical assembly is formed by assembling carbon nano sheets with the thickness of 3-10nm or/and carbon nano fibers with the diameter of 1-3 nm.
The technical scheme adopted by the invention is as follows: a method for preparing a nano carbon material spherical assembly comprises the following specific steps:
the method comprises the following steps: dispersing carbon source reactants in deionized water, wherein the preferable concentration is 1g/L-100 g/L;
step two: uniformly spraying the solution into liquid nitrogen, and then quickly freezing and drying a sample;
step three: and (3) putting the freeze-dried sample powder into a carbonization furnace for carbonization. Preferably in N2Raising the temperature to 3000 ℃ at the temperature raising rate of 1-5 ℃/min in the atmosphere and preserving the temperature for 1-2 h.
Preferably, the reactant raw material used in the first step is a water-soluble carbon material selected from water-soluble high molecular materials such as phenolic resin, chitosan, gelatin, carboxymethyl cellulose, gelatin agar, gum arabic, and hydroxyethyl starch.
Preferably, the mass volume concentration configured in the step one is 5g/L-15 g/L.
Preferably, the spraying into the liquid nitrogen in the second step is performed by spraying using a sprayer, injecting using a syringe, dropping using a dropper, slowly dipping using a test tube, or the like.
Preferably, the freeze-drying temperature in the second step is-20 ℃ to-100 ℃, preferably-90 ℃ to-100 ℃, and the freeze-drying time is 30-50 h.
Preferably, the preferred carbonization temperature in step three is 600-.
The invention also claims the spherical assembly of the nano carbon material obtained by any one of the technical schemes.
The spherical assembly of the nano carbon material can be used as a negative electrode material of a lithium ion battery and a sodium ion battery, and has excellent electrochemical performance.
The nano carbon material spherical assembly can be used as an electrode material of a super capacitor and has excellent electrochemical performance.
The nano carbon material spherical assembly is used for preparing a sewage treatment material.
The invention has the following advantages:
(1) the process flow is simple, the controllability is realized, and the nano carbon material spherical assembly can be obtained from the precursor by only one step; the ice template can be simply removed by freeze drying without environmental pollution, and the aim of controllably preparing the spherical assembly assembled by the carbon nano-sheets can be achieved by simply controlling reaction conditions such as reactant concentration, temperature and the like. The method has low requirement on reaction equipment, mild reaction conditions, no need of using extra reagents to remove templates and other steps, and high purity of the obtained product.
(2) The carbon nano material prepared by the invention is applied to lithium ion batteries, sodium ion batteries and super capacitors and has the advantages of stable structure, excellent electrochemical performance, good cycle performance and rate capability and the like.
(3) The carbon nano material prepared by the invention has the characteristics of low cost, simple and convenient operation and good repeatability when being applied to oil stain adsorption, and has potential application value in the fields of water body oil pollutant removal, oil exploitation, industrial oil pollutant separation and the like.
Drawings
FIG. 1 is a diagram of a carbon nanosheet assembly microsphere (SEM) prepared with a phenolic resin solution mass volume concentration of 5g/L and a carbonization temperature of 700 ℃.
FIG. 2 is a diagram of a carbon nanosheet assembly microsphere (SEM) prepared when the mass-volume concentration of the phenolic resin solution is 10g/L and the carbonization temperature is 700 ℃.
Detailed Description
The present invention is illustrated by way of example, but is not limited thereto.
Example 1
0.50g of phenolic resin powder was dissolved in 100ml of water to obtain a 5g/L phenolic resin solution. Adding the prepared phenolic resin solution into a sprayer, uniformly spraying the solution into a plastic container filled with liquid nitrogen, and then quickly transferring a sample into a freeze dryer for freeze drying for 45 hours at-90 ℃; freeze-drying the powder in a carbonization furnace in N2Heating to 700 ℃ at the heating rate of 2 ℃/min in the atmosphere and preserving the heat for 2h to obtain the carbon material spherical assembly. And (3) obtaining a carbon material spherical assembly body composed of the carbon nano-sheets as shown in a Scanning Electron Microscope (SEM) of figure 1, wherein the average diameter is 30 mu m, and the average thickness of the carbon nano-sheets is 3 nm.
The obtained carbon material spherical assembly is used as a lithium ion battery cathode material assembled battery, and the cycle performance and the rate performance of the lithium ion battery cathode material assembled battery are tested. And (3) testing conditions are as follows: at 25 deg.C, the current density is 0.05-2A/g, and the voltage range is 0.01-3V.
The obtained carbon material spherical assembly is used as a lithium battery cathode material, and the reversible specific capacity is 450mAh/g under the current density of 50 mA/g. Under the current density of 2A/g, the reversible specific capacity is 100 mAh/g. The cycle performance is excellent, and when the current density returns to 50mA/g, the reversible specific capacity reaches 400 mAh/g.
Example 2
1.00g of phenolic resin powder was dissolved in 100ml of water to obtain a 10g/L phenolic resin solution. Adding the prepared phenolic resin solution into a sprayer, uniformly spraying the solution into a plastic container filled with liquid nitrogen, and then quickly transferring a sample into a freeze dryer to be freeze-dried for 47 hours at the temperature of-98 ℃; freeze-drying the powder in a carbonization furnace in N2Heating to 700 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving the heat for 2h to obtain the carbon nano sheet assembly microspheres composed of the carbon nano sheets. And (3) obtaining a carbon material spherical assembly with the average diameter of 30 mu m and the average thickness of the carbon nano-sheet of 10nm as shown in a Scanning Electron Microscope (SEM) of figure 2. The obtained carbon nano material is used as the cathode of the sodium ion batteryThe material is used for assembling the battery, and the cycle performance and the rate performance of the battery are tested. The test conditions were: the current density is 0.05-10A/g at 25 ℃, the voltage range is 0.01-2.8V, the current density is under 50mAh/g, and the reversible specific capacity is 300 mAh/g. Under the current density of 10A/g, the reversible specific capacity is 110mAh/g, and the capacity retention rate after 200 times of circulation is 80%.
Example 3
0.1g of phenolic resin powder was dissolved in 100ml of water to obtain 1g/L of phenolic resin solution. Adding the prepared phenolic resin solution into a sprayer, uniformly spraying the solution into a plastic container filled with liquid nitrogen, and then quickly transferring a sample into a freeze dryer for freeze drying for 40 hours at-98 ℃; freeze-drying the powder in a carbonization furnace in N2Heating to 1000 ℃ at a heating rate of 2 ℃/min in the atmosphere and preserving the heat for 2h to obtain the carbon material spherical assembly body consisting of the carbon nanowires, wherein the average diameter is 50 mu m and the average diameter of the carbon nanowires is 2 nm. The obtained carbon material spherical assembly is used as a super capacitor electrode material, and electrochemical test results show that the specific capacity of the electrode material can reach 200F/g, and 90% of the specific capacity can be maintained after 500 cycles.
Example 4
1.02g of phenolic resin powder was dissolved in 100ml of water to obtain a 10.2g/L phenolic resin solution. Adding the prepared phenolic resin solution into a sprayer, uniformly spraying the solution into a plastic container filled with liquid nitrogen, and then quickly transferring a sample into a freeze dryer for freeze drying for 40 hours at-98 ℃; freeze-drying the powder in a carbonization furnace in N2Heating to 1600 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving the heat for 1h to obtain the carbon nano sheet assembly microsphere. The obtained carbon material spherical assembly is used as a preparation material of the carbon nano-material oil absorption sponge, and experiments show that the contact angle CA of the carbon nano-material oil absorption sponge and water is 172 degrees, the rolling angle is 13 degrees, the oil absorption is 88mg/mg, and the oil absorption is 68mg/mg after oil absorption is repeated for 60 times.
Example 5
0.50g of chitosan powder was dissolved in 100ml of water to obtain 5g/L of chitosan aqueous solution, and 5ml of acetic acid solution was dropped to promote dissolution of chitosan powder. Taking the prepared chitosan waterAdding the solution into a sprayer, uniformly spraying the solution into a plastic container filled with liquid nitrogen, and then quickly transferring the sample into a freeze dryer for freeze drying for 48 hours at-98 ℃; freeze-drying the powder in a carbonization furnace in N2Heating to 2000 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving the heat for 2h to obtain the carbon material spherical assembly. Obtaining the carbon material spherical assembly body consisting of the carbon nano-sheets, wherein the average diameter is 20 mu m, and the average thickness of the carbon nano-sheets is 3 nm.
Example 6
5g of water-soluble starch powder was dissolved in 100ml of water to obtain a 50g/L starch solution. Adding the prepared starch solution into a sprayer, uniformly spraying the solution into a plastic container filled with liquid nitrogen, and then quickly transferring the sample into a freeze dryer for freeze drying for 48 hours at-98 ℃; freeze-drying the powder in a carbonization furnace in N2Heating to 2400 ℃ at the heating rate of 5 ℃/min in the atmosphere and preserving the heat for 2 hours to obtain the carbon material spherical assembly. Obtaining the carbon material spherical assembly body formed by the carbon nano-sheets, wherein the average diameter is 50 mu m, and the average thickness of the carbon nano-sheets is 30 nm.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of a nano carbon material spherical assembly is characterized by comprising the following specific steps:
the method comprises the following steps: dispersing water-soluble polymers in deionized water; the water soluble polymer is selected from phenolic resin, chitosan, gelatin, carboxymethyl cellulose, gum arabic, and hydroxyethyl starch;
step two: uniformly spraying the solution into liquid nitrogen, and then quickly freezing and drying a sample;
step three: placing the freeze-dried sample powder in a carbonization furnace in N2Carried out in the atmosphereCarbonizing;
freeze-drying for 30-50h at-20 to-100 ℃;
heating to 600-3000 ℃ at the heating rate of 1-5 ℃/min and preserving heat for 1-2 h;
the diameter of the assembled spherical carbon is 10-50 μm, and the spherical carbon is assembled by carbon nano sheets with the thickness of 3-10nm or carbon nano fibers with the diameter of 1-3 nm.
2. The method according to claim 1, wherein the concentration of the water-soluble polymer is 1g/L to 100 g/L.
3. The method according to claim 1, wherein the concentration of the water-soluble polymer is 5g/L to 15 g/L.
4. The method according to claim 1, wherein the spraying into the liquid nitrogen in step two is carried out by using a sprayer.
5. The method according to claim 1, wherein the freeze-drying temperature in the second step is-90 ℃ to-100 ℃.
6. The method as claimed in claim 1, wherein the carbonization temperature is 600-.
7. The application of the nano carbon material spherical assembly obtained by the method in claim 1 in the preparation of negative electrode materials of lithium ion batteries and sodium ion batteries, electrode materials of supercapacitors or sewage treatment materials.
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| CN102807211A (en) * | 2012-08-24 | 2012-12-05 | 北京化工大学 | Graphene spherical assembly and preparation method thereof |
| CN107827104A (en) * | 2017-11-30 | 2018-03-23 | 石狮市川大先进高分子材料研究中心 | A kind of graphene oxide microballoon, the preparation method of graphene microballoon |
| CN108666571A (en) * | 2017-03-30 | 2018-10-16 | 华中科技大学 | A kind of kalium ion battery negative material and preparation method thereof and cathode pole piece |
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| CN109179368A (en) * | 2018-09-13 | 2019-01-11 | 安庆师范大学 | It is a kind of using sodium alginate as the preparation method of the negative electrode of lithium ion battery porous carbon materials of carbon source |
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| CN102807211A (en) * | 2012-08-24 | 2012-12-05 | 北京化工大学 | Graphene spherical assembly and preparation method thereof |
| CN108666571A (en) * | 2017-03-30 | 2018-10-16 | 华中科技大学 | A kind of kalium ion battery negative material and preparation method thereof and cathode pole piece |
| CN107827104A (en) * | 2017-11-30 | 2018-03-23 | 石狮市川大先进高分子材料研究中心 | A kind of graphene oxide microballoon, the preparation method of graphene microballoon |
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