CN113594400B - Method for preparing sodium ion battery cathode material by magnetic filtration technology - Google Patents

Method for preparing sodium ion battery cathode material by magnetic filtration technology Download PDF

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CN113594400B
CN113594400B CN202110793972.0A CN202110793972A CN113594400B CN 113594400 B CN113594400 B CN 113594400B CN 202110793972 A CN202110793972 A CN 202110793972A CN 113594400 B CN113594400 B CN 113594400B
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walled carbon
carbon nanotube
acidified
chemical vapor
radio frequency
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CN113594400A (en
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刘显慧
陈子博
顾旻
杨威威
卜雅丽
何倩
吴强
焦云飞
刘瑞卿
应世强
李谊
马延文
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Nanjing Yipu Advanced Materials Research Institute Co ltd
Nanjing University of Posts and Telecommunications
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Nanjing Yipu Advanced Materials Research Institute Co ltd
Nanjing University of Posts and Telecommunications
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    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/28—Deposition of only one other non-metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
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Abstract

The invention discloses a method for preparing a sodium ion battery cathode material by a magnetic filtration technology, and particularly relates to a method for preparing a composite material carrier of a functionalized multi-walled carbon nanotube and a semi-metal target source by a chemical vapor codeposition technology of pre-functionalizing treating the multi-walled carbon nanotube, taking the multi-walled carbon nanotube as a substrate and screening radio frequency plasma by magnetic filtration. The functionalized multi-walled carbon nanotube in the structure is used as a conductive framework to improve the structural stability and the conductive performance of the coating carrier, the semimetal target material source is used as an active material, selenium and phosphorus on the semimetal target material source have high chemical bonding force with the functionalized multi-walled carbon nanotube framework, and the selenium and phosphorus fixing performance, the multi-selenide and phosphide conversion kinetics and the cycle life of the electrode are improved.

Description

Method for preparing sodium ion battery cathode material by magnetic filtration technology
Technical Field
The invention relates to a method for preparing a sodium ion battery cathode material by a magnetic filtration technology, which can be used in the technical field of preparation of sodium ion battery electrode materials.
Background
Lithium Ion Batteries (LIBs) have been widely used in electric vehicles, portable electronic devices, and large-scale stationary energy storage for the past few decades. Recently, sodium ion batteries (NIBs) have attracted considerable attention for their low cost and abundant natural resource reserves for potential use in large-scale energy storage systems. However, the further development of the NIB is limited by the insufficient energy density, and the dendrite problem of sodium ions also becomes a safety hazard for its application.
Carbon nanotubes are attractive as sodium ion battery negative electrode materials, with single-walled carbon nanotubes typically about 0.1nm in diameter, which can be considered as a single graphite roll. Multi-walled carbon nanotubes consist of multiple concentric graphite cylinders, and thus their diameter varies according to the number of cylinder walls. The spacing between each concentric cylinder is typically about 0.334nm. The carbon nano tube has remarkable mechanical property (tensile strength is up to 63 GPa) and electrochemical property (electric conductivity is 10,000cm) 2 V -1 s -1 ) While being extremely light in weight and easy to make into self-supporting films. However, the use of carbon nanotubes as negative electrode materials for sodium ion batteries is limited by their poor binding to sodium ions and their hydrophobic nature.
The preparation method of the active material coated on the cathode material of the traditional sodium ion battery mainly comprises a wet chemical coating method and a chemical vapor deposition method, wherein although a sample prepared by the wet chemical coating method can obtain a high-load electrode, the binding force between the prepared active material and a substrate material is poor; the chemical vapor deposition can obtain a more uniform covering layer, but the purity of a deposition sample with the thickness difficult to control is generally poor, and the electrochemical stability of a subsequently prepared electrode is influenced.
The magnetic filtration screening radio frequency plasma deposition technology is one of the advanced material surface treatment technologies at present, and the technology is a deposition technology which utilizes radio frequency to generate plasma under a vacuum environment, filters large particles through a magnetic filtration device and then deposits the large particles on the surface of a substrate material. The magnetic filtration radio frequency plasma deposition technology is how to utilize the technology due to the high ion ionization rate and the high ion energy, and the capability of preparing various high-mechanical strength covering layers with high quality, compactness, good binding force and smoothness. However, how to utilize this technology to develop a new cathode material with low cost, higher capacity and high rate cycling stability is the key point of the current research, so it is a great challenge to design a composite material with strong chemical adsorption capacity and fast conversion reaction kinetics to active substances, and simultaneously, the coating layer has adjustable thickness, good binding force and uniform distribution.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for preparing a sodium-ion battery cathode material by using a magnetic filtration technology.
The purpose of the invention is realized by the following technical scheme: a method for preparing a sodium ion battery cathode material by a magnetic filtration technology is characterized in that a multi-walled carbon nanotube is subjected to functionalization treatment in advance, the multi-walled carbon nanotube is used as a substrate, and a composite material carrier of the functionalized multi-walled carbon nanotube and a semi-metal target source is prepared by a chemical vapor codeposition technology for screening radio frequency plasma by magnetic filtration.
Preferably, the multi-walled carbon nanotube is firstly functionalized, the multi-walled carbon nanotube is used as a carrier, then a radio frequency plasma technology, a magnetic filtration technology and a chemical vapor deposition technology are combined for use, a radio frequency discharge target material source is introduced into the magnetic filtration tube for screening, the purpose of controlling and screening the chemical vapor deposition source is achieved, the chemical vapor deposition is carried out, vacuum is extracted from a chemical vapor deposition device, and plasma after magnetic filtration and screening can be deposited on a base material to form a uniform and stable coating.
Preferably, the method comprises the steps of:
s1: pre-functionalizing a multi-walled carbon nanotube to obtain a functionalized multi-walled carbon nanotube;
s2: preparing the functionalized multi-walled carbon nano-tube obtained in the step S1 into a film and drying the film
S3: cleaning a functionalized multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition chamber;
s4: vacuumizing the chemical vapor deposition device;
s5: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s6: introducing a radio frequency discharge target source into a magnetic filter tube for screening;
s7: controlling the current and the negative bias of the magnetic filtering bent pipe;
s8: controlling the temperature of a reaction chamber of the chemical vapor deposition device;
s9: opening a gas inlet path of the chemical gas phase reaction chamber;
s10: and after the deposition is finished, closing the radio frequency discharge and magnetic filtration power supply, and releasing the vacuum degree to obtain the functionalized multi-walled carbon nanotube/semimetal composite material.
Preferably, the multi-walled carbon nanotube is firstly functionalized and used as a carrier, and then the chemical vapor deposition technology is used for controlling the internal parameters of the chemical vapor deposition device, including the current of a magnetic filtration elbow, negative bias, radio frequency power, a target material source, vacuum degree, reaction chamber temperature, gas species, flow rate and deposition time, wherein the current of the magnetic filtration elbow is 1-3A, the negative bias is 150-350V, the radio frequency power is 500W-900W, the target material source is semimetal, the vacuum degree is 1 x 10 < -4 > to 4 x 10 < -4 > Pa, the temperature of the reaction chamber is 400 ℃ T800 ℃, and the gas is in the temperature range of 400 ℃ T800 DEG CSpecies Ar or hydrogen H 2 And H 2 The flow rate of the/Ar mixed gas is 150 ppm-500 ppm, and the deposition time is 10min-40min.
Preferably, said H 2 The molar flow ratio of the/Ar mixed gas is 3:4 to 1:10, and the target material source is one of selenium and phosphorus semi-metal materials.
Preferably, the carbon nanotubes are pre-acidified, and selenium is used as the semi-metal target material, and the method comprises the following steps:
s1: weighing 200mg of multi-walled carbon nanotubes in 100mL of strong acid solution, fully stirring for 5-10min at the rotation speed of 550rpm, and uniformly distributing the multi-walled carbon nanotubes in the mixed solution; the strong acid solution is a mixed solution of 75mL of concentrated nitric acid and 25mL of concentrated sulfuric acid;
s2: after the multi-walled carbon nano-tube is dispersed uniformly, the container is moved to a water bath kettle, a condenser tube is connected to the mouth of a burning bottle, and the temperature is kept for 3.5 hours at 85 ℃ at the rotating speed of 100rpm;
s3: after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multiwalled carbon nanotube-ethanol dispersion liquid according to a certain proportion, carrying out suction filtration to obtain a corresponding proportion of acidified multiwalled carbon nanotube film (CNTs film), washing with ultrapure water and ethanol for several times, placing the suction-filtered film in a vacuum drying oven, and drying at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: the chemical vapor deposition device is vacuumized to reach a vacuum degree of 1 x 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8: introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 900W;
s9: controlling the current of the magnetic filtering bent pipe to be 1A and the negative bias to be 150V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 600 ℃;
s11: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas type is argon, and the gas flow rate is 150ppm;
s12: and after the deposition is finished for 10min, closing the radio frequency discharge and magnetic filtration power supply, and releasing the vacuum degree to obtain the acidified multi-walled carbon nanotube/selenium composite material.
Preferably, the method for pre-acidifying carbon nanotubes and using phosphorus as a semi-metal target material comprises the following steps:
s1: weighing 200mg of multi-walled carbon nanotubes in 100mL of strong acid solution, and fully stirring at the rotating speed of 550rpm for 5-10min until the multi-walled carbon nanotubes are uniformly distributed in the mixed solution; the strong acid solution is a mixed solution of 75mL of concentrated nitric acid and 25mL of concentrated sulfuric acid;
s2: after the multi-walled carbon nano-tube is uniformly dispersed, moving the container into a water bath kettle, connecting a condenser pipe to the mouth of a burning bottle, and preserving heat for 3.5 hours at 85 ℃ at the rotating speed of 100rpm;
s3: after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multi-walled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain an acidified multi-walled carbon nanotube film (CNTs film) with a corresponding proportion, washing the acidified multi-walled carbon nanotube film (CNTs film) for a plurality of times by using ultrapure water and ethanol, placing the suction-filtered film in a vacuum drying oven, and drying the film at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8: introducing a radio frequency discharge target material phosphorus source into a magnetic filter tube for screening, wherein the radio frequency power is 700W;
s9: controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V;
s10: controlling the temperature of a reaction chamber of a chemical vapor deposition device to be 400 ℃;
s11: opening a gas inlet circuit of the chemical gas phase reaction chamber, wherein the gas is argon and the gas flow rate is 500ppm;
s12: and after depositing for 20min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the acidified multi-walled carbon nanotube/phosphorus composite material.
Preferably, the method comprises the steps of pre-functionalizing the multi-walled carbon nanotubes, pre-fluorinating the carbon nanotubes, and using selenium as a semi-metal target material, and specifically comprises the following steps:
s1: weighing acidified multi-walled carbon nanotubes and polytetrafluoroethylene, mixing according to the ratio of 6:1, and grinding for about 20min until no obvious white substance exists;
s2: pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at the heating rate of 2 ℃/min, and annealing for 4 hours;
s3, taking out the porcelain boat after the porcelain boat is cooled to obtain a fluorinated multi-walled carbon nanotube, grinding for about 5 minutes, performing suction filtration to obtain a thin film, and drying;
s4: cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition chamber;
s5: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 1 multiplied by 10 -4 Pa；
S6: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s7: introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 800W;
s8: controlling the current of the magnetic filtering bent pipe to be 1A and the negative bias to be 150V;
s9: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 700 ℃;
s10: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is argon, and the gas flow rate is 200ppm;
s11: and after depositing for 30min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the fluorinated multi-walled carbon nanotube/selenium composite material.
Preferably, the method preferably comprises the steps of:
s1: weighing 200mg of multi-walled carbon nanotubes in 100mL of strong acid solution, and fully stirring at the rotating speed of 550rpm for 5-10min until the multi-walled carbon nanotubes are uniformly distributed in the mixed solution; the strong acid solution is a mixed solution of 75mL of concentrated nitric acid and 25mL of concentrated sulfuric acid;
s2: after the multi-wall carbon nano tubes are uniformly dispersed, the container is moved into a water bath kettle, and the condenser tube is connected to the mouth of the burning bottle. Keeping the temperature for 3.5h at the rotating speed of 100rpm and the temperature of 85 ℃;
s3: after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multi-walled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain an acidified multi-walled carbon nanotube film (CNTs film) with a corresponding proportion, washing the acidified multi-walled carbon nanotube film (CNTs film) for a plurality of times by using ultrapure water and ethanol, placing the suction-filtered film in a vacuum drying oven, and drying the film at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 4 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8, introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 850W;
s9: controlling the current of the magnetic filtering bent pipe to be 3A and the negative bias to be 350V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 550 ℃;
s11: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is a hydrogen/argon mixed gas, the molar flow ratio is 1:10, and the gas flow rate is 600ppm;
s12: and after depositing for 40min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the acidified multi-walled carbon nanotube/selenium composite material.
Preferably, the carbon nanotube is subjected to fluorination treatment in advance, and phosphorus is used as a semi-metal target material, and the method specifically comprises the following steps:
s1: weighing acidified multi-walled carbon nanotubes and polytetrafluoroethylene, mixing according to the ratio of 6:1, and grinding for about 20min until no obvious white substance exists;
s2, pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at a heating rate of 2 ℃/min, and annealing for 4 hours;
s3: taking out the ceramic boat after cooling to obtain fluorinated multi-walled carbon nanotubes, grinding for about 5 minutes, performing suction filtration to obtain a film, and drying;
s4: cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the cleaned fluorinated multi-walled carbon nanotube film substrate on a rotatable base in a deposition chamber;
s5: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa；
S6: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s7: introducing a radio frequency discharge target material phosphorus source into a magnetic filter tube for screening, wherein the radio frequency power is 600W;
s8: controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V;
s9: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 500 ℃;
s10: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is argon, and the gas flow rate is 450ppm;
s11: and after depositing for 20min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the fluorinated multi-walled carbon nanotube/phosphorus composite material.
Compared with the prior art, the technical scheme adopted by the invention has the following technical effects: the invention provides a method for functionalizing a multi-walled carbon nanotube and a method for preparing a sodium ion battery cathode material on the surface of the functionalized carbon nanotube by a controllable magnetic filtration and radio frequency plasma screening chemical vapor codeposition technology.
The innovation of the invention is that the magnetic filtration screening radio frequency plasma is adopted, the solid source is deposited on the surface of the substrate of the functionalized multi-wall carbon nanotube by the controllable magnetic filtration screening radio frequency plasma technology, the functionalized multi-wall carbon nanotube in the structure is used as a conductive framework to improve the structural stability and the conductive performance of the selenium-containing or phosphorus-containing carrier, and the chemical vapor deposition technology is introduced into the method to achieve the aim of codeposition of the plasma and the chemical vapor. The design of the technology can not only give play to the magnetic filtration screening of the plasma to obtain a covering layer with higher quality, but also introduce chemical vapor deposition to increase different gas sources, thereby providing a new synthesis path for preparing the covering layer with different components.
The radio frequency plasma technology, the magnetic filtration technology and the chemical vapor deposition technology are combined, the radio frequency discharge target material source is introduced into the magnetic filtration tube for screening, the chemical vapor deposition source is controlled to be screened, the chemical vapor deposition is carried out, the vacuum is extracted from the chemical vapor deposition device, and the plasma after the magnetic filtration screening can be deposited on the base material to form a uniform and stable coating. The functionalized multi-walled carbon nanotube in the structure is used as a conductive framework to improve the structural stability and the conductive performance of the coating carrier, the semimetal target material source is used as an active material, selenium and phosphorus on the semimetal target material source have high chemical bonding force with the functionalized multi-walled carbon nanotube framework, and the selenium and phosphorus fixing performance, the multi-selenide and phosphide conversion kinetics and the cycle life of the electrode are improved.
Drawings
FIG. 1 is a SEM image structure schematic of an acidified MWCNT/Se composite material prepared in example 1 of the present invention.
FIG. 2 is a TEM image of an acidified MWCNT/Se composite as prepared in example 1 of the present invention.
FIG. 3 is a plot of the coulombic efficiency at 1C current density for the acidified MWCNT/Se composite prepared in example 1 of the present invention.
Detailed Description
Objects, advantages and features of the present invention will be illustrated and explained by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or converting the equivalent thereof falls within the scope of the present invention claimed.
The invention discloses a method for preparing a sodium ion battery cathode material by a magnetic filtration technology, and particularly relates to a method for preparing a composite material carrier of a functionalized multi-walled carbon nanotube and a semi-metal target source by a chemical vapor codeposition technology of pre-functionalizing treating the multi-walled carbon nanotube, taking the multi-walled carbon nanotube as a substrate and screening radio frequency plasma by magnetic filtration.
Specifically, in the technical scheme, a multi-walled carbon nanotube is firstly functionalized and used as a carrier, then a radio frequency plasma technology, a magnetic filtration technology and a chemical vapor deposition technology are combined to introduce a radio frequency discharge target source into the magnetic filtration tube for screening so as to control and screen the chemical vapor deposition source for chemical vapor deposition, vacuum is pumped in a chemical vapor deposition device, and plasma after magnetic filtration and screening can be deposited on a substrate to form a uniform and stable coating. The deposition substrate is one of functionalized multi-walled carbon nanotubes (such as acidified multi-walled carbon nanotubes and fluorinated multi-walled carbon nanotubes), multi-walled carbon nanotubes, single-walled carbon nanotubes and the like, and the deposition semimetal target is one of selenium and phosphorus.
A method for preparing a sodium ion battery cathode material by a magnetic filtration technology comprises the following steps:
s1: pre-functionalizing a multi-walled carbon nanotube;
s2: preparing the functionalized multi-walled carbon nano-tube into a film and drying the film
S3: cleaning a functionalized multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition chamber;
s4: vacuumizing the chemical vapor deposition device;
s5: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s6: introducing a radio frequency discharge target source into a magnetic filter tube for screening;
s7: controlling the current and the negative bias of the magnetic filtering bent pipe;
s8: controlling the temperature of a reaction chamber of the chemical vapor deposition device;
s9: opening a gas inlet path of the chemical gas phase reaction chamber;
s10: and after the deposition is finished, closing the radio frequency discharge and magnetic filtration power supply, and releasing the vacuum degree to obtain the functionalized multi-walled carbon nanotube/semimetal composite material.
In the technical scheme, multi-walled carbon nanotubes are firstly functionalized and used as a carrier, and then the chemical vapor deposition technology is used for controlling the internal parameters of a chemical vapor deposition device and comprises magnetic filtration elbow current, negative bias, radio frequency power, a target material source, vacuum degree, reaction chamber temperature, gas types, flow rate and deposition time, wherein the magnetic filtration elbow current is 1-3A, the negative bias is 150-350V, the radio frequency power is 500-900W, the target material source is semimetal, and the vacuum degree is 1 multiplied by 10 -4 ～4×10 -4 Pa, the temperature of the reaction chamber is 400-800 ℃, and the gas is argon (Ar) or hydrogen (H) 2 ) And argon (H) 2 Ar) mixed gas with the flow rate of 150 ppm-500 ppm and the deposition time of 10min-40min. In this embodiment, H 2 The molar flow ratio of the/Ar mixed gas is 3: 4-1: 10, and the target material source is one of selenium and phosphorus semimetal materials.
In the technical scheme, the method for pre-acidifying the carbon nano tube and taking selenium as the semimetal target comprises the following steps:
s1: weighing 200mg of multi-walled carbon nanotubes, fully stirring the multi-walled carbon nanotubes in 100mL of strong acid solution (75 mL of concentrated nitric acid and 25mL of concentrated sulfuric acid) at the rotating speed of 550rpm for 5-10min, and uniformly distributing the multi-walled carbon nanotubes in the mixed solution;
s2: after the multi-walled carbon nano-tube is uniformly dispersed, moving the container into a water bath kettle, connecting a condenser pipe to the mouth of a burning bottle, and preserving heat for 3.5 hours at 85 ℃ at the rotating speed of 100rpm;
s3: after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multiwalled carbon nanotube-ethanol dispersion liquid according to a certain proportion, carrying out suction filtration to obtain a corresponding proportion of acidified multiwalled carbon nanotube film (CNTs film), washing with ultrapure water and ethanol for several times, placing the suction-filtered film in a vacuum drying oven, and drying at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: the chemical vapor deposition device is vacuumized to reach a vacuum degree of 1 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8: introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 900W;
s9: controlling the current of the magnetic filtering bent pipe to be 1A and the negative bias to be 150V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 600 ℃;
s11: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas type is argon, and the gas flow rate is 150ppm;
s12: and after the deposition is finished for 10min, closing the radio frequency discharge and magnetic filtration power supply, and releasing the vacuum degree to obtain the acidified multi-walled carbon nanotube/selenium composite material.
In the technical scheme, the method for pre-acidifying the carbon nano tube and taking phosphorus as the semi-metal target material comprises the following steps
S1: weighing 200mg of multi-walled carbon nanotubes, fully stirring the multi-walled carbon nanotubes in 100mL of strong acid solution (75 mL of concentrated nitric acid and 25mL of concentrated sulfuric acid) at the rotation speed of 550rpm for 5-10min, and uniformly distributing the multi-walled carbon nanotubes in the mixed solution;
s2: after the multi-walled carbon nano-tube is dispersed uniformly, the container is moved to a water bath kettle, a condenser tube is connected to the mouth of a burning bottle, and the temperature is kept for 3.5 hours at 85 ℃ at the rotating speed of 100rpm;
s3: after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multi-walled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain an acidified multi-walled carbon nanotube film (CNTs film) with a corresponding proportion, washing the acidified multi-walled carbon nanotube film (CNTs film) for a plurality of times by using ultrapure water and ethanol, placing the suction-filtered film in a vacuum drying oven, and drying the film at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8: introducing a radio frequency discharge target material phosphorus source into a magnetic filter tube for screening, wherein the radio frequency power is 700W;
s9: controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 400 ℃;
s11: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is argon, and the gas flow rate is 500ppm;
s12: and after depositing for 20min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the acidified multi-walled carbon nanotube/phosphorus composite material.
In the technical scheme, the method comprises the steps of functionalizing the multi-walled carbon nanotube in advance, fluorinating the carbon nanotube in advance, and taking selenium as a semi-metal target material, and specifically comprises the following steps:
s1: weighing acidified multi-walled carbon nanotubes and polytetrafluoroethylene, mixing according to the ratio of 6:1, and grinding for about 20min until no obvious white substance exists;
s2: pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at the heating rate of 2 ℃/min, and annealing for 4 hours;
s3: taking out the ceramic boat after cooling to obtain fluorinated multi-walled carbon nanotubes, grinding for about 5 minutes, performing suction filtration to obtain a film, and drying;
s4: cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the cleaned fluorinated multi-walled carbon nanotube film substrate on a rotatable base in a deposition chamber;
s5: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 1 multiplied by 10 -4 Pa；
S6: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s7: introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 800W;
s8: controlling the current of the magnetic filtering bent pipe to be 1A and controlling the negative bias voltage to be 150V;
s9: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 700 ℃;
s10: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is argon, and the gas flow rate is 200ppm;
s11: and after depositing for 30min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the fluorinated multi-walled carbon nanotube/selenium composite material.
Specifically, in the present technical solution, the method preferably includes the following steps:
s1: weighing 200mg of multi-walled carbon nanotubes, fully stirring the multi-walled carbon nanotubes in 100mL of strong acid solution (75 mL of concentrated nitric acid and 25mL of concentrated sulfuric acid) at the rotation speed of 550rpm for 5-10min, and uniformly distributing the multi-walled carbon nanotubes in the mixed solution;
s2: after the multi-walled carbon nano-tubes are uniformly dispersed, the container is moved into a water bath kettle, and the condenser tube is connected to the mouth of the burning bottle. Keeping the temperature for 3.5h at the rotating speed of 100rpm and the temperature of 85 ℃;
s3: after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multi-walled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain an acidified multi-walled carbon nanotube film (CNTs film) with a corresponding proportion, washing the acidified multi-walled carbon nanotube film (CNTs film) for a plurality of times by using ultrapure water and ethanol, placing the suction-filtered film in a vacuum drying oven, and drying the film at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 4 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8, introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 850W;
s9: controlling the current of the magnetic filtering bent pipe to be 3A and the negative bias to be 350V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 550 ℃;
s11: opening a gas inlet circuit of the chemical gas phase reaction chamber, wherein the gas is hydrogen/argon mixed gas, the molar flow ratio is 1:10, and the gas flow rate is 600ppm;
s12: and after depositing for 40min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the acidified multi-walled carbon nanotube/selenium composite material.
In the technical scheme, the method comprises the following steps of carrying out fluorination treatment on carbon nanotubes in advance and taking phosphorus as a semi-metal target material:
s1: weighing acidified multi-walled carbon nanotubes and polytetrafluoroethylene, mixing according to the ratio of 6:1, and grinding for about 20min until no obvious white substance exists;
s2: pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at a heating rate of 2 ℃/min, and annealing for 4 hours;
s3: taking out the ceramic boat after cooling to obtain fluorinated multi-walled carbon nanotubes, grinding for about 5 minutes, performing suction filtration to obtain a film, and drying;
s4: cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the cleaned fluorinated multi-walled carbon nanotube film substrate on a rotatable base in a deposition chamber;
s5: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa；
S6: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s7: introducing a radio frequency discharge target material phosphorus source into a magnetic filter tube for screening, wherein the radio frequency power is 600W;
s8: controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V;
s9: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 500 ℃;
s10: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is argon, and the gas flow rate is 450ppm;
s11: and after depositing for 20min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the fluorinated multi-walled carbon nanotube/phosphorus composite material.
Example 1:
the method for preparing the acidified MWCNT/Se composite material by using the functionalized multi-walled carbon nano-tubes and the chemical vapor codeposition technology for controllable magnetic filtration screening of the radio frequency plasma, which is provided by the technical scheme, comprises the steps of weighing 200mg of multi-walled carbon nano-tubes, fully stirring the multi-walled carbon nano-tubes in 100mL of strong acid solution (75 mL of concentrated nitric acid and 25mL of concentrated sulfuric acid) for 5-10min at the rotation speed of 550rpm, and uniformly distributing the multi-walled carbon nano-tubes in the mixed solution.
Then after the multi-walled carbon nano-tube is uniformly dispersed, the container is moved to a water bath, a condenser tube is connected to the mouth of a beaker, the temperature is kept for 3.5 hours at 85 ℃ at the rotation speed of 100rpm, after the reaction is finished, the solution and the like are poured into the beaker together, diluted to 1L by ultrapure water, the acidified multi-walled carbon nano-tube is obtained after the suction filtration treatment, the acidified multi-walled carbon nano-tube is placed into the beaker, added with 200mL of magnetons and ethanol, rapidly stirred and ultrasonically dispersed, and finally a certain amount of acidified multi-walled carbon nano-tube-ethanol dispersion liquid is weighed in proportion.
Carrying out suction filtration to obtain an acidified multi-walled carbon nanotube film (CNTs film) with a corresponding proportion, washing the acidified multi-walled carbon nanotube film (CNTs film) for a plurality of times by using ultrapure water and ethanol, and placing the suction-filtered film in a vacuum drying oven to be dried at 60 ℃; then the acidified carbon nanotube substrate is cleaned and fixed on a rotatable base in the deposition cavity; vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 1 multiplied by 10 -4 Pa; and cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate.
Introducing a radio frequency discharge target material Se source into a magnetic filter tube for screening, and controlling the radio frequency power to be 900W; controlling the current of the magnetic filtering bent pipe to be 1A and the negative bias to be 150V; controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 600 ℃; opening a gas inlet path of the chemical gas phase reaction chamber, wherein Ar is used as gas, and the gas flow rate is 150ppm; and after deposition is carried out for 10min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after the normal pressure state is recovered, and taking out a sample to obtain the acidified MWCNT/Se composite material.
As shown in fig. 1, 2 and 3, fig. 1 is an SEM image of the acidified MWCNT/Se composite prepared in example 1. As can be seen from fig. 1, a layer of Se was uniformly deposited on the surface of the acidified MWCNT by the chemical vapor co-deposition technique of magnetic filtration screen rf plasma.
Fig. 2 is a TEM image of the acidified MWCNT/Se composite prepared in example 1, and it can be seen from fig. 2 that the acidified MWCNT/Se composite well maintained its tubular structure after acidification.
FIG. 3 is a plot of the coulombic efficiency at 1C current density for the acidified MWCNT/Se composite prepared in example 1. As can be seen from fig. 3, the coulombic efficiency at the first discharge is close to 100%, and after 200 cycles, the coulombic efficiency remains substantially unchanged, and the good cycle stability is shown.
The preparation process of the acidified MWCNT/Se composite material prepared by the technology comprises the steps of firstly acidifying a multiwalled carbon nanotube, then utilizing a magnetic filtration screening radio frequency plasma chemical vapor co-deposition device, introducing a solid selenium source to generate plasma under the action of radio frequency under the vacuum condition, screening and removing large particles through the magnetic filtration device to form selenium plasma, and simultaneously introducing Ar through the chemical vapor deposition device to finally deposit Se plasma on the surface of the acidified multiwalled carbon nanotube to form the acidified MWCNT/Se composite material.
The material is used as a novel selenium-fixing carrier, so that the sodium battery shows excellent electrochemical performance. Se is deposited on the surface of porous carbon by using a magnetic filtration radio frequency plasma technology, and the electrochemical performance of the sodium battery is improved by using the acidified MWCNT as a conductive framework and a selenium-limiting carrier. The acidified MWCNT has high chemical binding force on the polyselenide, and improves the selenium fixation performance of the electrode, the conversion kinetics of the polyselenide and the cycle life of the battery.
Example 2:
the method for preparing the acidified MWCNT/P composite material by using the chemical vapor codeposition technology of the controllable magnetic filtration screening radio frequency plasma comprises the steps of firstly weighing 200mg of multi-wall carbon nano-tubes, fully stirring the multi-wall carbon nano-tubes in 100mL of strong acid solution (75 mL of concentrated nitric acid and 25mL of concentrated sulfuric acid) at the rotation speed of 550rpm for 5-10min, and uniformly distributing the multi-wall carbon nano-tubes in a mixed solution; after the multi-walled carbon nano-tubes are uniformly dispersed, the container is moved into a water bath kettle, and the condenser tube is connected to the mouth of the burning bottle.
Keeping the temperature for 3.5h at the rotating speed of 100rpm and the temperature of 85 ℃; after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion; finally weighing a certain amount of acidified multiwalled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain acidified multiwalled carbon nanotube films (CNTs films) with a corresponding proportion, washing the acidified multiwalled carbon nanotube films (CNTs films) with ultrapure water and ethanol for a plurality of times, placing the suction-filtered films in a vacuum drying oven, and drying the films at 60 ℃; and cleaning the acidified carbon nanotube substrate and fixing the acidified carbon nanotube substrate on a rotatable base in the deposition chamber.
Vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa; cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate; radio frequency discharge targetIntroducing a material P source into the magnetic filter tube for screening, wherein the radio frequency power is 700W; controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V; controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 400 ℃; opening a gas inlet path of the chemical gas phase reaction chamber, wherein Ar is used as gas, and the gas flow rate is 500ppm; and after 20min of deposition, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the acidified MWCNT/P composite material.
Example 3:
the method for preparing the fluorinated MWCNT/Se composite material by using the chemical vapor codeposition technology for screening the radio frequency plasma through controllable magnetic filtration provided by the invention is characterized in that the acidified multiwalled carbon nanotube and polytetrafluoroethylene are weighed and mixed according to the ratio of 6:1, and the mixture is ground for about 20min until no obvious white substance exists; pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at a heating rate of 2 ℃/min, and annealing for 4 hours; and taking out the ceramic boat after cooling to obtain the fluorinated multi-walled carbon nanotube, grinding for about 5 minutes, performing suction filtration to obtain a film, and drying.
Cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the cleaned fluorinated multi-walled carbon nanotube film substrate on a rotatable base in a deposition chamber; vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 1 multiplied by 10 -4 Pa; cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate; introducing a radio frequency discharge target material Se source into a magnetic filter tube for screening, wherein the radio frequency power is 800W; controlling the current of the magnetic filtering bent pipe to be 1A and controlling the negative bias voltage to be 150V; controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 700 ℃; opening a gas inlet circuit of the chemical gas phase reaction chamber, wherein the gas is argon and the gas flow rate is 200ppm; and after deposition is carried out for 30min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after the normal pressure state is recovered, and taking out a sample to obtain the fluorinated MWCNT/Se composite material.
Example 4:
the method for preparing the fluorinated MWCNT/P composite material by using the chemical vapor codeposition technology for filtering and screening radio frequency plasma by controllable magnetism provided by the invention is characterized in that acidified multi-walled carbon nanotubes and polytetrafluoroethylene are weighed and mixed according to the ratio of 6:1, and are ground for about 20min until no obvious white substance exists; pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at the heating rate of 2 ℃/min, and annealing for 4 hours; and taking out the ceramic boat after cooling to obtain the fluorinated multi-walled carbon nanotube, grinding for about 5 minutes, performing suction filtration to obtain a film, and drying.
Cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the cleaned fluorinated multi-walled carbon nanotube film substrate on a rotatable base in a deposition chamber; vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa; cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate; introducing a radio frequency discharge target material phosphorus source into a magnetic filter tube for screening, wherein the radio frequency power is 600W; controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V; controlling the temperature of a reaction chamber of a chemical vapor deposition device to be 500 ℃; opening a gas inlet circuit of the chemical gas phase reaction chamber, wherein the gas is argon and the gas flow rate is 450ppm; and after depositing for 20min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the fluorinated multi-walled carbon nanotube/phosphorus composite material.
Example 5:
the method for preparing the acidified MWCNT/Se composite material by using the chemical vapor codeposition technology of the controllable magnetic filtration screening radio frequency plasma comprises the steps of firstly weighing 200mg of multi-wall carbon nano-tubes, fully stirring the multi-wall carbon nano-tubes in 100mL of strong acid solution (75 mL of concentrated nitric acid and 25mL of concentrated sulfuric acid) at the rotation speed of 550rpm for 5-10min, and uniformly distributing the multi-wall carbon nano-tubes in a mixed solution; after the multi-wall carbon nano tubes are uniformly dispersed, the container is moved into a water bath kettle, and the condenser tube is connected to the mouth of the burning bottle.
Preserving the heat for 3.5 hours at the rotating speed of 100rpm and the temperature of 85 ℃; after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion; finally weighing a certain amount of acidified multiwalled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain acidified multiwalled carbon nanotube films (CNTs films) with a corresponding proportion, washing the acidified multiwalled carbon nanotube films (CNTs films) with ultrapure water and ethanol for a plurality of times, placing the suction-filtered films in a vacuum drying oven, and drying the films at 60 ℃; and then the acidified carbon nanotube substrate is cleaned and fixed on a rotatable base in the deposition chamber.
Vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 4 multiplied by 10 -4 Pa; cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate; introducing a radio frequency discharge target material W source into a magnetic filter tube for screening, wherein the radio frequency power is 850W; controlling the current of the magnetic filtering bent pipe to be 3A and the negative bias to be 350V; controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 550 ℃; opening the gas inlet path of the chemical gas phase reaction chamber, wherein the gas is H 2 The mol flow ratio of the/Ar mixed gas is 1:10, and the gas flow rate is 600ppm; and after depositing for 40min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the acidified MWCNT/Se composite material.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference signs in the claims are not to be construed as limiting the claims.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art. The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.

Claims (10)

1. A method for preparing a sodium ion battery cathode material by a magnetic filtration technology is characterized by comprising the following steps: the composite material of the functionalized multi-walled carbon nanotube and a target material source is prepared by taking the multi-walled carbon nanotube which is subjected to functionalization treatment in advance as a substrate and then adopting a chemical vapor co-deposition technology of magnetic filtration and screening of radio-frequency plasma, wherein the chemical vapor co-deposition technology of the magnetic filtration and screening of the radio-frequency plasma is to combine a radio-frequency plasma technology, a magnetic filtration technology and a chemical vapor deposition technology, introduce a radio-frequency discharge target material source into a magnetic filtration tube for screening so as to control and screen the chemical vapor deposition source and carry out chemical vapor deposition; the functionalization treatment comprises acidification treatment and/or fluorination treatment; the target source comprises a selenium source or a phosphorus source.
2. The method for preparing the negative electrode material of the sodium-ion battery by using the magnetic filtration technology according to claim 1, wherein the method comprises the following steps: firstly, functionalizing multi-walled carbon nanotubes, taking the multi-walled carbon nanotubes as a carrier, then, combining a radio frequency plasma technology, a magnetic filtration technology and a chemical vapor deposition technology, introducing a radio frequency discharge target material source into the magnetic filtration tube for screening, controlling and screening the chemical vapor deposition source, carrying out chemical vapor deposition, extracting vacuum in a chemical vapor deposition device, and depositing plasma screened by magnetic filtration on a base material to form a uniform and stable coating.
3. The method for preparing the negative electrode material of the sodium-ion battery by the magnetic filtration technology as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
s1: pre-functionalizing a multi-walled carbon nanotube to obtain a functionalized multi-walled carbon nanotube;
s2: preparing the functionalized multi-walled carbon nanotubes obtained in the step S1 into a film and drying the film;
s3: cleaning a functionalized multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition chamber;
s4: vacuumizing the chemical vapor deposition device;
s5: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s6: introducing a radio frequency discharge target material source into a magnetic filter tube for screening;
s7: controlling the current and the negative bias of the magnetic filtering bent pipe;
s8: controlling the temperature of a reaction chamber of the chemical vapor deposition device;
s9: opening a gas inlet path of the chemical gas phase reaction chamber;
s10: and after the deposition is finished, closing the radio frequency discharge and magnetic filtration power supply, and releasing the vacuum degree to obtain the functionalized multi-walled carbon nanotube/semimetal composite material.
4. The method for preparing the negative electrode material of the sodium-ion battery by the magnetic filtration technology as claimed in claim 3, wherein the method comprises the following steps: firstly, performing functional treatment on a multi-walled carbon nanotube, using the multi-walled carbon nanotube as a carrier, and then controlling internal parameters of a chemical vapor deposition device by using a chemical vapor deposition technology, wherein the internal parameters comprise magnetic filtration elbow current, negative bias, radio frequency power, a target source, vacuum degree, reaction chamber temperature, gas type, flow rate and deposition time, the magnetic filtration elbow current is 1 to 3A, the negative bias is 150 to 350V, the radio frequency power is 500W to 900W, the vacuum degree is 1 multiplied by 10 < -4 > to 4 multiplied by 10 < -4 > Pa, the reaction chamber temperature is 400 to 800 ℃, and the gas type is Ar gas or H gas 2 The flow rate of the/Ar mixed gas is 150ppm to 500ppm, and the deposition time is 10min to 40min.
5. The method for preparing the negative electrode material of the sodium-ion battery by the magnetic filtration technology as claimed in claim 4, wherein the magnetic filtration technology comprises the following steps: said H 2 The molar flow ratio of the Ar mixed gas is 3 to 1.
6. The method for preparing the negative electrode material of the sodium-ion battery by the magnetic filtration technology as claimed in claim 1, wherein the method comprises the following steps: pre-acidifying carbon nanotubes, and using selenium as a target, comprising the following steps:
s1: weighing 200mg of multi-walled carbon nanotubes, fully stirring the multi-walled carbon nanotubes in 100mL of strong acid solution at the rotation speed of 550rpm for 5-10min, and uniformly distributing the multi-walled carbon nanotubes in the mixed solution; the strong acid solution is a mixed solution of 75mL of concentrated nitric acid and 25mL of concentrated sulfuric acid;
s2: after the multi-walled carbon nano-tube is uniformly dispersed, moving the container into a water bath kettle, connecting a condenser pipe to the mouth of a burning bottle, and preserving heat for 3.5 hours at 85 ℃ at the rotating speed of 100rpm;
s3: after the reaction is finished, pouring the obtained dispersion liquid into a beaker, diluting the dispersion liquid to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multiwalled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain an acidified multiwalled carbon nanotube film with a corresponding proportion, washing the acidified multiwalled carbon nanotube film for a plurality of times by using ultrapure water and ethanol, placing the film obtained by suction filtration in a vacuum drying oven, and drying at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 1 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8: introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 900W;
s9: controlling the current of the magnetic filtering bent pipe to be 1A and the negative bias voltage to be 150V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 600 ℃;
s11: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas type is argon, and the gas flow rate is 150ppm;
s12: and after the deposition is finished for 10min, closing the radio frequency discharge and magnetic filtration power supply, and releasing the vacuum degree to obtain the acidified multi-wall carbon nano tube/selenium composite material.
7. The method for preparing the negative electrode material of the sodium-ion battery by using the magnetic filtration technology according to claim 1, wherein the method comprises the following steps: pre-acidifying carbon nanotubes, and using phosphorus as a target, comprising the following steps:
s1: weighing 200mg of multi-walled carbon nanotubes in 100mL of strong acid solution, and fully stirring at the rotating speed of 550rpm for 5-10min until the multi-walled carbon nanotubes are uniformly distributed in the mixed solution; the strong acid solution is a mixed solution of 75mL of concentrated nitric acid and 25mL of concentrated sulfuric acid;
s2: after the multi-walled carbon nano-tube is dispersed uniformly, the container is moved to a water bath kettle, a condenser tube is connected to the mouth of a burning bottle, and the temperature is kept for 3.5 hours at 85 ℃ at the rotating speed of 100rpm;
s3: after the reaction is finished, pouring the obtained dispersion liquid into a beaker, diluting the dispersion liquid to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multiwalled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain an acidified multiwalled carbon nanotube film with a corresponding proportion, washing the acidified multiwalled carbon nanotube film for a plurality of times by using ultrapure water and ethanol, placing the film obtained by suction filtration in a vacuum drying oven, and drying the film at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8: introducing a radio frequency discharge target material phosphorus source into a magnetic filter tube for screening, wherein the radio frequency power is 700W;
s9: controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 400 ℃;
s11: opening a gas inlet circuit of the chemical gas phase reaction chamber, wherein the gas is argon and the gas flow rate is 500ppm;
s12: after depositing for 20min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree,
and opening the deposition cavity after the normal pressure state is recovered, and taking out the sample to obtain the acidified multi-walled carbon nanotube/phosphorus composite material.
8. The method for preparing the negative electrode material of the sodium-ion battery by the magnetic filtration technology as claimed in claim 1, wherein the method comprises the following steps: the method comprises the steps of functionalizing a multi-walled carbon nanotube in advance, fluorinating the carbon nanotube in advance, and taking selenium as a target, and specifically comprises the following steps:
s1: weighing acidified multi-walled carbon nanotubes and polytetrafluoroethylene according to the weight ratio of 6:1, mixing and grinding for about 20min until no obvious white substance exists;
s2: pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at the heating rate of 2 ℃/min, and annealing for 4 hours;
s3: taking out the ceramic boat after cooling to obtain fluorinated multi-walled carbon nanotubes, grinding for about 5 minutes, performing suction filtration to obtain a film, and drying;
s4: cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition chamber;
s5: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 1 multiplied by 10 -4 Pa；
S6: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s7: introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 800W;
s8: controlling the current of the magnetic filtering bent pipe to be 1A and controlling the negative bias voltage to be 150V;
s9: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 700 ℃;
s10: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is argon, and the gas flow rate is 200ppm;
s11: and after deposition is carried out for 30min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after the normal pressure state is recovered, and taking out a sample to obtain the fluorinated multi-walled carbon nanotube/selenium composite material.
9. The method for preparing the negative electrode material of the sodium-ion battery by using the magnetic filtration technology according to claim 1, wherein the method comprises the following steps: the method preferably comprises the steps of:
s1: weighing 200mg of multi-walled carbon nanotubes in 100mL of strong acid solution, and fully stirring at the rotation speed of 550rpm for 5-10min until the multi-walled carbon nanotubes are uniformly distributed in the mixed solution; the strong acid solution is a mixed solution of 75mL of concentrated nitric acid and 25mL of concentrated sulfuric acid;
s2: after the multi-walled carbon nano-tube is uniformly dispersed, moving the container into a water bath kettle, connecting a condenser pipe to the mouth of a burning bottle, and preserving heat for 3.5 hours at 85 ℃ at the rotating speed of 100rpm;
s3: after the reaction is finished, pouring the solution and the like into a beaker, diluting the solution to 1L by using ultrapure water, performing suction filtration treatment to obtain an acidified multi-walled carbon nanotube, placing the acidified multi-walled carbon nanotube into the beaker, adding 200mL of magnetons and ethanol, and performing rapid stirring and ultrasonic dispersion;
s4: weighing a certain amount of acidified multiwalled carbon nanotube-ethanol dispersion liquid according to a proportion, carrying out suction filtration to obtain an acidified multiwalled carbon nanotube film with a corresponding proportion, washing the acidified multiwalled carbon nanotube film for a plurality of times by using ultrapure water and ethanol, placing the suction-filtered film in a vacuum drying oven, and drying the film at 60 ℃;
s5: cleaning an acidified multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition cavity;
s6: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 4 multiplied by 10 -4 Pa；
S7: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s8: introducing a radio frequency discharge target selenium source into a magnetic filter tube for screening, wherein the radio frequency power is 850W;
s9: controlling the current of the magnetic filtering bent pipe to be 3A and the negative bias to be 350V;
s10: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 550 ℃;
s11: opening a gas inlet circuit of the chemical gas phase reaction chamber, wherein the gas is a hydrogen/argon mixed gas, the molar flow ratio is 1;
s12: and after depositing for 40min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the acidified multi-walled carbon nanotube/selenium composite material.
10. The method for preparing the negative electrode material of the sodium-ion battery by using the magnetic filtration technology according to claim 1, wherein the method comprises the following steps: the method comprises the following steps of carrying out fluorination treatment on carbon nanotubes in advance and taking phosphorus as a target material:
s1: weighing acidified multi-walled carbon nanotubes and polytetrafluoroethylene according to the weight ratio of 6:1, mixing and grinding for about 20min until no obvious white substance exists;
s2: pouring the ground mixture into a porcelain boat, placing the porcelain boat into a tube furnace, heating the porcelain boat to 400 ℃ at a heating rate of 2 ℃/min, and annealing for 4 hours;
s3: taking out the ceramic boat after cooling to obtain fluorinated multi-walled carbon nanotubes, grinding for about 5 minutes, performing suction filtration to obtain a film, and drying;
s4: cleaning a fluorinated multi-walled carbon nanotube film substrate and fixing the substrate on a rotatable base in a deposition chamber;
s5: vacuum pumping is carried out in the chemical vapor deposition device, and the vacuum degree reaches 2 multiplied by 10 -4 Pa；
S6: cleaning the surface of the deposition substrate by adopting plasma to remove oil stains and impurities on the surface of the deposition substrate;
s7: introducing a radio frequency discharge target material phosphorus source into a magnetic filter tube for screening, wherein the radio frequency power is 600W;
s8: controlling the current of the magnetic filtering bent pipe to be 2A and the negative bias to be 280V;
s9: controlling the temperature of a reaction chamber of the chemical vapor deposition device to be 500 ℃;
s10: opening a gas inlet path of the chemical gas phase reaction chamber, wherein the gas is argon, and the gas flow rate is 450ppm;
s11: and after depositing for 20min, closing the radio frequency discharge and magnetic filtration power supply, releasing the vacuum degree, opening the deposition cavity after recovering to the normal pressure state, and taking out a sample to obtain the fluorinated multi-walled carbon nanotube/phosphorus composite material.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1811414A (en) * 2006-03-31 2006-08-02 中山大学 Active protective membrane, preparing method and biological testing element thereof
CN102090923A (en) * 2009-12-14 2011-06-15 冷博 Anti-adhesion surgical device
CN109817881A (en) * 2019-01-22 2019-05-28 陕西科技大学 A kind of preparation method and application of copper foil load anode material of lithium-ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1811414A (en) * 2006-03-31 2006-08-02 中山大学 Active protective membrane, preparing method and biological testing element thereof
CN102090923A (en) * 2009-12-14 2011-06-15 冷博 Anti-adhesion surgical device
CN109817881A (en) * 2019-01-22 2019-05-28 陕西科技大学 A kind of preparation method and application of copper foil load anode material of lithium-ion battery

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