CN113506860A - Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof - Google Patents

Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof Download PDF

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CN113506860A
CN113506860A CN202110660794.4A CN202110660794A CN113506860A CN 113506860 A CN113506860 A CN 113506860A CN 202110660794 A CN202110660794 A CN 202110660794A CN 113506860 A CN113506860 A CN 113506860A
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selenium
carbon nanotube
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杨秋合
袁永锋
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Hangzhou Vocational and Technical College
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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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

The invention discloses a carbon nanotube-in-tube @ selenium composite material, a preparation method thereof and application of the composite material in preparation of a sodium ion battery anode. In the carbon nanotube-in-tube @ selenium composite material, the carbon nanotube-in-tube is a tube-in-tube structure in which a carbon nanotube is used as an inner tube and an amorphous carbon nanotube is used as an outer tube to form an outer tube sleeved with the inner tube; selenium is compounded in the gap between the inner tube and the outer tube of the carbon nano tube. The preparation method comprises the following steps: firstly growing ZIF-8 nano-particles on the surface of a carbon nano-tube, treating with tannic acid to obtain a precursor of the carbon nano-tube, carbonizing to obtain the carbon nano-tube, finally mixing with selenium, heating until the selenium is melted, and sucking the selenium into the carbon nano-tube to obtain a final product. The invention can improve the conductivity and structural stability of selenium and improve the reversible capacity and cycle performance of selenium. The carbon nanotube-in-tube @ selenium composite material is a sodium ion battery anode material with important application value.

Description

Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a carbon nanotube-in-tube @ selenium composite material and a preparation method and application thereof.
Background
In recent years, with the rapid development of electric vehicles and electric tools, higher requirements are put on new energy devices. The shortage of lithium resources limits the space for further development of lithium ion batteries. The reserve of sodium is 4-5 orders of magnitude more than that of lithium, and the development of sodium ion batteries to replace lithium ion batteries has become a main direction of new energy development in recent years.
As a sodium storage material, selenium (Se) has higher theoretical specific capacity (675mAh g)-1) The theoretical volume energy density is equivalent to sulfur, but selenium is a semiconductor material and has higher conductivity compared with almost insulating sulfur, so that the research on the application of selenium in the sodium ion battery attracts high attention of scholars at home and abroad.
At present, the main problem hindering the application of selenium in sodium ion batteries is that the conductivity of selenium is not high enough, resulting in lower specific capacity; and due to the serious volume expansion and shuttle effect, the specific capacity of the selenium is rapidly reduced, and the cycle performance is poor.
In order to improve the sodium storage performance of selenium, the selenium is compounded with various carbon materials to form a current main research strategy. The invention patent with publication number CN109360959A discloses a selenium-carbon composite material. The invention patent with publication number CN109817920A discloses a selenium-coated carbon nanotube/graphene material. However, most of the selenium-carbon composite structures cannot effectively prevent the shuttle effect of selenium at present; when the selenium content is low, the specific capacity of the composite material is also low; when the selenium content is high, the selenium is easy to be distributed unevenly, so that the electrochemical performance of the material is unstable. Therefore, the development of high-performance selenium-carbon composite structures is still under intensive study.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides a carbon nanotube-in-tube @ selenium composite material. The invention can improve the conductivity and the structural stability of the selenium, inhibit the shuttle effect of the selenium and improve the reversible capacity and the cycle performance of the selenium. The carbon nanotube-in-tube @ selenium composite material has important application value in the field of sodium ion batteries.
A carbon nanotube-in-tube @ selenium composite material is characterized in that a carbon nanotube-in-tube structure is formed by using Carbon Nanotubes (CNTs) as inner tubes and amorphous carbon nanotubes as outer tubes and sleeving the inner tubes; the selenium is compounded in the gap between the inner tube and the outer tube of the carbon nano tube.
Preferably, the outer diameter of the inner tube of the carbon nano tube is 10-100nm, the outer diameter of the outer tube is 30-300nm, the wall thickness of the outer tube is 2-30nm, and the gap between the inner tube and the outer tube is 5-140 nm.
The outer tube of the carbon nanotube tube is preferably formed by carbonizing tannic acid.
Preferably, the mass percentage of the selenium in the carbon nanotube-in-tube @ selenium composite material is 20% -80%.
The invention also provides a preparation method of the carbon nanotube-in-tube @ selenium composite material, which comprises the following steps:
(1)60-240mg Zn(NO3)2·6H2dissolving O in 10mL of methanol, and stirring for 10min to obtain a solution 1; 162-650mg of dimethyl imidazole and 20mg of acidified carbon nanotube are added into 10mL of methanol, and the solution is subjected to ultrasonic treatment for 4 times, each time for 5min, to be used as a solution 2; pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; transferring the mixed solution to a 50mL Teflon high-pressure kettle, sealing, and then putting the kettle into a 90 ℃ oven for heat preservation for 6 hours; after natural cooling, washing the product for three times by using methanol, centrifugally collecting, and drying at 80 ℃ to obtain CNTs @ ZIF-8;
(2) dispersing 50mg of CNTs @ ZIF-8 in 25mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; dissolving 50mg of tannic acid in 25mL of deionized water, and stirring for 15min to form a uniform mixed solution serving as a solution 4; pouring the solution 4 into the solution 3, stirring for 5min, washing the product with deionized water for three times, centrifugally collecting, and drying at 80 ℃. Heating the obtained product to 600 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, preserving the heat for 2 hours, and soaking the cooled product with 0.2M HCl to remove residual zinc to obtain a carbon nano tube;
(3) fully and uniformly mixing 20mg of the carbon nano tube and 10-80mg of selenium powder through a micro-vibration ball mill; and transferring the mixture into a 15mL Teflon autoclave in a glove box, sealing, taking out the mixture from the glove box, putting the mixture into a muffle furnace, heating to 260 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 12h, and cooling to room temperature to obtain the carbon nano tube-in-tube @ selenium composite material.
The preparation method comprises the steps of firstly growing ZIF-8 nano particles on the surface of a carbon nano tube to form a structure similar to a sugarcoated haws string, then treating with tannic acid to obtain a precursor of a carbon nano tube-in-tube, carbonizing to obtain the carbon nano tube-in-tube, finally mixing with selenium, heating until the selenium is melted, and sucking the selenium into the carbon nano tube-in-tube, thereby obtaining a final product.
The invention also provides application of the carbon nanotube-in-tube @ selenium composite material in preparation of a sodium ion battery anode.
The positive electrode of the sodium-ion battery is made of the material of the invention: respectively weighing the carbon nano tube-in-tube selenium composite material, the acetylene black conductive agent and the polyvinylidene fluoride (PVDF) binder in a mass ratio of 80:10:10, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground carbon nano tube-in-tube selenium composite material and the acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer aluminum foil (the diameter is 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode slice.
Assembling the prepared electrode plate, a metal sodium sheet and a diaphragm into a CR2025 button type sodium ion battery, wherein the electrolyte is 1mol L-1NaClO4The EC-DMC-FEC electrolyte adopts a Xinwei battery test system to test the charge-discharge performance and the cycle performance of the sodium ion battery.
The invention can improve the conductivity and structural stability of selenium and improve the reversible capacity and cycle performance of selenium.
Compared with the prior art, the invention has the main advantages that:
1) selenium is stored in the gaps in the carbon nano tube, and can be contacted with the inner and outer carbon nano tube walls, so that the conductivity of the carbon nano tube is obviously improved, and the specific capacity of the carbon nano tube is improved; compared with the traditional porous structure and the coating structure, the near-closed structure of the tube in the carbon nano tube can effectively inhibit the shuttle effect of selenium and improve the circulating stability of the selenium; selenium is stored in the gap along the axial direction of the middle tube of the carbon nano tube, so that the selenium is more uniformly distributed, and the electrochemical performance of the selenium is more stable; the electrolyte can penetrate into the gaps in the carbon nano tube to meet the requirement of electrochemical reaction for storing selenium inside; the selenium is clamped by the inner and outer carbon nano tubes, and the structure can obviously inhibit the volume expansion of the selenium and improve the structural stability of the selenium. The carbon nanotube-middle tube @ selenium composite material is used for manufacturing the electrode, and the carbon nanotube-middle tubes are mutually wound in the electrode, so that the conductivity of the electrode is improved, and the structural strength of the electrode is enhanced.
2) Based on the reaction of the tannic acid and the ZIF-8, the dissolution of the ZIF-8 and the formation of the external carbon nano tube are synchronously carried out, and the synthesis method of the carbon nano tube is simplified. The selenium is melted into liquid and then adsorbed in the gaps in the carbon nano tube based on the capillary action, and the selenium compounding method is mild, simple to operate, low in cost, low in equipment requirement and beneficial to industrial production.
Drawings
FIG. 1 is a TEM photograph of CNTs @ ZIF-8 prepared in example 1;
FIG. 2 is a TEM photograph of a tube of the carbon nanotube prepared in example 1;
fig. 3 is a TEM photograph of the carbon nanotube-in-tube @ selenium composite prepared in example 1;
FIG. 4 is a graph of the current density of 0.5Ag of the carbon nanotube-in-tube @ selenium composite prepared in example 1-1Cycle performance map of (c).
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1)120mg Zn(NO3)2·6H2Dissolving O in 10mL of methanol, and stirring for 10min to obtain a solution 1; 325mg of dimethylimidazole and 20mg of acidified carbon nanotubes (outer diameter 30-50nm)10mL of methanol was added and the solution was sonicated 4 times for 5min each time as solution 2. Quickly pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; and transferring the mixed solution to a 50mL Teflon autoclave, sealing the autoclave, and then putting the autoclave into a 90 ℃ oven for heat preservation for 6 hours. After natural cooling, the product is washed for three times by methanol, centrifugally collected and dried at 80 ℃ to obtain CNTs @ ZIF-8.
(2) Dispersing 50mg of CNTs @ ZIF-8 in 25mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; 50mg of tannic acid was dissolved in 25mL of deionized water and stirred for 15min to form a uniform mixed solution as solution 4. And quickly pouring the solution 4 into the solution 3, stirring for 5min, washing the product for three times by using deionized water, centrifugally collecting, and drying at 80 ℃. And heating the obtained product to 600 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, preserving the heat for 2 hours, and soaking the cooled product with 0.2M HCl to remove residual zinc to obtain the carbon nano tube.
(3) Fully and uniformly mixing 20mg of the carbon nano tube and 40mg of selenium powder through a micro-vibration ball mill; and transferring the mixture into a 15mL Teflon autoclave in a glove box, sealing, taking out the mixture from the glove box, putting the mixture into a muffle furnace, heating to 260 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 12h, and cooling to room temperature to obtain the carbon nanotube-in-tube @ selenium composite material.
FIG. 1 is a TEM photograph of prepared CNTs @ ZIF-8, and it can be seen that some ZIF-8 nanoparticles having a size of about 30nm are closely and uniformly coupled to the surface of CNT, and the surface of CNTs is substantially completely covered. FIG. 2 is a TEM photograph of the prepared carbon nanotube tube, which shows that the ZIF-8 nanoparticles are completely disappeared, a new carbon nanotube is formed outside the original CNTs, and the carbon nanotube is formed by carbonizing tannic acid, has an amorphous structure, and forms a tube-in-tube structure of an outer tube sleeve inner tube. The outer diameter of the novel carbon nano tube is about 80nm, and the wall thickness is about 10 nm; the outer diameter of the carbon nano tube inner tube is about 37 nm; the gap between the inner tube and the outer tube of the carbon nanotube tube is about 11 nm. Fig. 3 is a TEM photograph of the tube-in-tube @ selenium composite material of carbon nanotubes, wherein the voids in the tube of the carbon nanotubes are filled with selenium, and the shadow of the inner carbon nanotubes can be seen at the central axis. No obvious particles exist on the outer surface of the carbon nano tube, which shows that the selenium basically permeates into the carbon nano tube. And carrying out thermogravimetric analysis under nitrogen, wherein in the heating process, because the boiling point of selenium is lower until selenium is completely volatilized, the content of selenium in the composite material is calculated to be 65.6 wt% and the balance is carbon through the mass difference before and after reaction.
The positive electrode of the sodium-ion battery is made of the material of the invention: respectively weighing the carbon nano tube-in-tube selenium composite material, the acetylene black conductive agent and the polyvinylidene fluoride (PVDF) binder in a mass ratio of 80:10:10, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground carbon nano tube-in-tube selenium composite material and the acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer aluminum foil (the diameter is 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode slice.
Assembling the prepared electrode plate, a metal sodium sheet and a diaphragm into a CR2025 button type sodium ion battery, wherein the electrolyte is 1mol L-1NaClO4The EC-DMC-FEC electrolyte adopts a Xinwei battery test system to test the charge-discharge performance and the cycle performance of the sodium ion battery.
FIG. 4 shows the current density of the prepared carbon nanotube-in-tube @ selenium composite material at 0.5Ag-1The cycle performance of (c). The charging and discharging voltage range is 1.0-3.0V. The specific discharge capacity of the 2 nd cycle is 652mAh g-1Then the discharge capacity slowly decreased to 472mAh g at the 200 th cycle-1The high-performance lithium ion battery has high specific capacity and good cycling stability. The specific capacity and the cycle performance of the carbon nanotube-tube @ selenium composite material are superior to those of the carbon-selenium composite material with the publication number of CN109360959A at the current density of 0.1Ag-1After 200 times of circulation, 320mAh g-1The discharge capacity of the composite material is also superior to that of the selenium/graphene nano composite material with the publication number of CN107910536A in the current density of 0.4Ag-1About 400mAh g after 200 times of circulation-1The discharge capacity of (2).
Example 2
(1)120mg Zn(NO3)2·6H2Dissolving O in 10mL of methanol, and stirring for 10min to obtain a solution 1; 325mg of dimethylimidazole and 20mg of acidification10mL of methanol was added to a carbon nanotube (outer diameter 30-50nm), and the solution was sonicated 4 times for 5min each time to give solution 2. Quickly pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; and transferring the mixed solution to a 50mL Teflon autoclave, sealing the autoclave, and then putting the autoclave into a 90 ℃ oven for heat preservation for 6 hours. After natural cooling, the product is washed for three times by methanol, centrifugally collected and dried at 80 ℃ to obtain CNTs @ ZIF-8.
(2) Dispersing 50mg of CNTs @ ZIF-8 in 25mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; 50mg of tannic acid was dissolved in 25mL of deionized water and stirred for 15min to form a uniform mixed solution as solution 4. And quickly pouring the solution 4 into the solution 3, stirring for 5min, washing the product for three times by using deionized water, centrifugally collecting, and drying at 80 ℃. And heating the obtained product to 600 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, preserving the heat for 2 hours, and soaking the cooled product with 0.2M HCl to remove residual zinc to obtain the carbon nano tube.
(3) Fully and uniformly mixing 20mg of the carbon nano tube and 20mg of selenium powder through a micro-vibration ball mill; and transferring the mixture into a 15mL Teflon autoclave in a glove box, sealing, taking out the mixture from the glove box, putting the mixture into a muffle furnace, heating to 260 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 12h, and cooling to room temperature to obtain the carbon nanotube-in-tube @ selenium composite material.
The structure of the product carbon nanotube-in-tube @ selenium composite material is similar to that of example 1, with the main difference that the mass percentage of selenium in the composite material is changed to 49 wt%.
The positive electrode of the sodium ion battery is manufactured by the same process as the example 1, and the sodium ion battery is assembled by using the current density of 0.5Ag-1And carrying out cyclic charge and discharge test in the voltage range of 1.0-3.0V. The cycle performance trend is similar to that of example 1, and the specific discharge capacity of the 2 nd cycle is 667mAh g-1Then the discharge capacity slowly decreases, and at the 200 th cycle, the discharge capacity decreases to 494mAh g-1。
Example 3
(1)180mg Zn(NO3)2·6H2Dissolving O in 10mL of methanol, and stirring for 10min to obtain a solution 1; 487.5mg of dimethylimidazole and 20The solution 2 was prepared by adding 10mL of methanol to mg of acidified carbon nanotubes (outer diameter 30-50nm) and sonicating the solution 4 times for 5min each. Quickly pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; and transferring the mixed solution to a 50mL Teflon autoclave, sealing the autoclave, and then putting the autoclave into a 90 ℃ oven for heat preservation for 6 hours. After natural cooling, the product is washed for three times by methanol, centrifugally collected and dried at 60 ℃ to obtain CNTs @ ZIF-8.
The subsequent steps were the same as in example 1.
The structure of the product carbon nanotube-in-tube @ selenium composite material is similar to that of example 1, and the main difference is that the outer diameter of the outer tube of the carbon nanotube-in-tube is increased to 90-120nm, and the gap between the inner tube and the outer tube is increased to about 16-30 nm.
The positive electrode of the sodium ion battery is manufactured by the same process as the example 1, and the sodium ion battery is assembled by using the current density of 0.5Ag-1And carrying out cyclic charge and discharge test in the voltage range of 1.0-3.0V. The cycle performance trend is similar to that of example 1, and the specific discharge capacity of the 2 nd cycle is 669mAh g-1Then the discharge capacity is slowly reduced, and at the 200 th cycle, the discharge capacity is reduced to 487mAh g-1。
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (6)

1. The carbon nanotube-in-tube @ selenium composite material is characterized in that the carbon nanotube-in-tube is of a tube-in-tube structure in which a carbon nanotube is used as an inner tube and an amorphous carbon nanotube is used as an outer tube, and the outer tube is sleeved with the inner tube; the selenium is compounded in the gap between the inner tube and the outer tube of the carbon nano tube.
2. The carbon nanotube-in-tube @ selenium composite material as claimed in claim 1, wherein an outer diameter of an inner tube of the carbon nanotube-in-tube is 10-100nm, an outer diameter of an outer tube is 30-300nm, a wall thickness of the outer tube is 2-30nm, and a gap between the inner tube and the outer tube is 5-140 nm.
3. The carbon nanotube-in-tube @ selenium composite of claim 1, wherein an outer tube of the carbon nanotube-in-tube is formed by tannic acid carbonization.
4. The carbon nanotube-in-tube @ selenium composite material as claimed in claim 1, wherein the mass percentage of selenium in the carbon nanotube-in-tube @ selenium composite material is 20% -80%.
5. The preparation method of the carbon nanotube-in-tube @ selenium composite material as claimed in any one of claims 1 to 4, comprising the steps of:
(1)60-240mg Zn(NO3)2·6H2dissolving O in 10mL of methanol, and stirring for 10min to obtain a solution 1; 162-650mg of dimethyl imidazole and 20mg of acidified carbon nanotube are added into 10mL of methanol, and the solution is subjected to ultrasonic treatment for 4 times, each time for 5min, to be used as a solution 2; pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; transferring the mixed solution to a 50mL Teflon high-pressure kettle, sealing, and then putting the kettle into a 90 ℃ oven for heat preservation for 6 hours; after natural cooling, washing the product for three times by using methanol, centrifugally collecting, and drying at 80 ℃ to obtain CNTs @ ZIF-8;
(2) dispersing 50mg of CNTs @ ZIF-8 in 25mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; dissolving 50mg of tannic acid in 25mL of deionized water, and stirring for 15min to form a uniform mixed solution serving as a solution 4; pouring the solution 4 into the solution 3, stirring for 5min, washing the product with deionized water for three times, centrifugally collecting, and drying at 80 ℃; heating the obtained product to 600 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, preserving the heat for 2 hours, and soaking the cooled product with 0.2M HCl to remove residual zinc to obtain a carbon nano tube;
(3) fully and uniformly mixing 20mg of the carbon nano tube and 10-80mg of selenium powder through a micro-vibration ball mill; and transferring the mixture into a 15mL Teflon autoclave in a glove box, sealing, taking out the mixture from the glove box, putting the mixture into a muffle furnace, heating to 260 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 12h, and cooling to room temperature to obtain the carbon nano tube-in-tube @ selenium composite material.
6. The application of the carbon nanotube-in-tube @ selenium composite material as claimed in any one of claims 1 to 4 in preparation of a positive electrode of a sodium ion battery.
CN202110660794.4A 2021-06-15 2021-06-15 Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof Withdrawn CN113506860A (en)

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CN114177195A (en) * 2021-11-13 2022-03-15 广东暨创硒源纳米研究院有限公司 Method for efficiently preparing metal organic framework selenium atom-loaded nanocomposite and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114099704A (en) * 2021-11-13 2022-03-01 广东暨创硒源纳米研究院有限公司 Simple preparation method and application of ultra-small nano selenium metal framework composite material
CN114177195A (en) * 2021-11-13 2022-03-15 广东暨创硒源纳米研究院有限公司 Method for efficiently preparing metal organic framework selenium atom-loaded nanocomposite and application
CN114099704B (en) * 2021-11-13 2023-10-03 广东暨创硒源纳米研究院有限公司 Simple preparation method and application of ultra-small nano selenium metal frame composite material

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