CN110482529B - Black phosphorus carbon nanotube composite material and preparation method thereof - Google Patents

Black phosphorus carbon nanotube composite material and preparation method thereof Download PDF

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CN110482529B
CN110482529B CN201910794208.8A CN201910794208A CN110482529B CN 110482529 B CN110482529 B CN 110482529B CN 201910794208 A CN201910794208 A CN 201910794208A CN 110482529 B CN110482529 B CN 110482529B
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black phosphorus
precursor
gas
metal
composite material
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CN110482529A (en
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余永龙
孔令涌
黄少真
陈彩凤
任望保
陈君
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Qujing FeiMo Technology Co.,Ltd.
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Shenzhen Dynanonic Co ltd
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/003—Phosphorus
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
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    • C01B32/162—Preparation characterised by catalysts
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • C01B2202/00—Structure or properties of carbon nanotubes
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Abstract

The invention belongs to the technical field of carbon composite materials, and particularly relates to a preparation method of a black phosphorus carbon nanotube composite material, which comprises the following steps: obtaining a metal precursor, and dissolving the metal precursor in an alcohol solution to obtain a metal precursor solution; obtaining black phosphorus, adding the black phosphorus into the metal precursor solution, performing dispersion treatment, and drying to obtain a metal black phosphorus compound; heating the metal black phosphorus compound to 500-600 ℃ under the protective gas atmosphere with the absolute pressure of 4500-5000 kPa for reaction, and then sequentially introducing hydrogen and a carbon source for reaction to obtain the black phosphorus carbon nanotube composite material. According to the preparation method provided by the invention, black phosphorus is used as a carrier, a metal precursor is used as a catalyst, carbon nanotubes grow on the surface of the black phosphorus, the carbon nanotubes are uniformly dispersed and have good combination stability with the black phosphorus, the conductivity of the black phosphorus is improved, the polarization is reduced, and the rate charge-discharge performance and the cycle stability of the battery are improved.

Description

Black phosphorus carbon nanotube composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of carbon composite materials, and particularly relates to a black phosphorus carbon nanotube composite material and a preparation method thereof.
Background
Black phosphorus has an orthogonal structure and is the lowest reactive phosphorus allotrope, and the bonding between layers is weaker than that in the layers, and has conductivity similar to graphene. Different from graphene with zero band gap, black phosphorus is a direct band gap semiconductor material, the band gap is about 0.9eV, and the size of the band gap can be changed along with the increase and decrease of the number of layers, so that the band gap of the material can be adjusted and controlled by adjusting the number of layers of the black phosphorus material. The unique geometric structure and electronic structure of black phosphorus endow the black phosphorus with excellent physicochemical properties, such as: the material can convert electronic signals into light, has high carrier mobility and the like, and has wide potential application prospect in the fields of photoelectric materials, new energy battery materials and the like. The loose layered structure of the black phosphorus is beneficial to the embedding and the separation of large-particle sodium ions, so that the black phosphorus has a better application prospect in the sodium ion battery. However, the black phosphorus material has poor stability, can be oxidized quickly in air, has poor conductivity, seriously affects the characteristics of the black phosphorus material, and also limits the application of the black phosphorus material. The carbon nano tube as a one-dimensional nano material not only has excellent mechanical, electrical and chemical properties, but also has excellent environmental stability. The carbon nano tube is compounded with the black phosphorus, the respective excellent performances of the black phosphorus and the carbon nano tube are combined, and the carbon nano tube and the black phosphorus are complementary in quality, wherein the carbon nano tube can improve the stability of the black phosphorus and the conductivity of the black phosphorus, and the black phosphorus carbon nano tube composite material has better application prospects in the fields of photoelectricity, new energy batteries and the like.
However, most of the current black phosphorus carbon nanotube composites are prepared by a ball milling method, and black phosphorus and carbon nanotubes are uniformly dispersed to be combined into the composite material, so that on one hand, the carbon nanotubes which are easy to agglomerate and have high length-diameter ratio have poor dispersion effect in the black phosphorus, and the composite effect of the carbon tubes and the black phosphorus is not obvious; on the other hand, the composite material obtained by this method is still physically composite and the stability of the composite material is not good.
Disclosure of Invention
The invention aims to provide a preparation method of a black phosphorus carbon nanotube composite material, and aims to solve the technical problems that in the existing preparation method for uniformly dispersing and combining black phosphorus and carbon nanotubes by adopting ball milling, the carbon nanotubes which are easy to agglomerate have poor dispersion effect in the black phosphorus and high length-diameter ratio, the carbon nanotubes have poor composite effect with the black phosphorus, the composite material obtained by the method is still physically composite, and the stability of the composite material is poor.
The invention also aims to provide a black phosphorus carbon nanotube composite material.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a black phosphorus carbon nanotube composite material comprises the following steps:
obtaining a metal precursor, and dissolving the metal precursor in an alcohol solution to obtain a metal precursor solution;
obtaining black phosphorus, adding the black phosphorus into the metal precursor solution, performing dispersion treatment, and drying to obtain a metal black phosphorus compound;
heating the metal black phosphorus compound to 500-600 ℃ under the protective gas atmosphere with the absolute pressure of 4500-5000 kPa for reaction, and then sequentially introducing hydrogen and a carbon source for reaction to obtain the black phosphorus carbon nanotube composite material.
Preferably, the step of heating the metal black phosphorus compound to 500-600 ℃ for reaction comprises: heating the metal black phosphorus compound to 500-600 ℃ at a heating rate of 1-5 ℃/min and reacting for 2-5 hours; and/or the presence of a gas in the gas,
the step of introducing hydrogen and carbon source in sequence for reaction comprises the following steps: and (3) heating the metal black phosphorus compound to 500-600 ℃ for reaction, introducing hydrogen for reaction for 1-5 minutes, and then closing the reaction of introducing hydrogen and a carbon source for reaction for 30-90 minutes.
Preferably, the step of introducing hydrogen for reaction for 1-5 minutes comprises: according to the volume ratio of the hydrogen to the first carrier gas of 1: (4-8), introducing the hydrogen and the first carrier into a reaction system to react for 1-5 minutes; and/or the presence of a gas in the gas,
the step of closing the reaction of introducing hydrogen into the carbon source for 30-90 minutes comprises the following steps: according to the volume ratio of the carbon source to the second carrier gas of 2: (1-5), introducing the carbon source and the second carrier gas into a reaction system to react for 30-90 minutes.
Preferably, the step of dispersion processing comprises: adding the black phosphorus into the metal precursor solution, and then carrying out ultrasonic and/or ball milling treatment for 30-60 minutes; and/or the presence of a gas in the gas,
the shielding gas, the first carrier gas and the second carrier gas are each independently selected from the group consisting of: at least one of nitrogen and argon; and/or the presence of a gas in the gas,
the carbon source is selected from: at least one of alkane, alkene and alkyne.
Preferably, the metal precursor comprises a reactive precursor selected from the group consisting of: at least one of an iron precursor, a cobalt precursor and a nickel precursor; and/or the presence of a gas in the gas,
the carbon source is selected from: at least one of methane, ethylene, propylene and acetylene.
Preferably, the loading amount of the metal element in the active precursor in the metal black phosphorus compound is 0.1-0.5%.
Preferably, the metal precursor further comprises an auxiliary precursor selected from: at least one of an aluminum precursor, a magnesium precursor, a molybdenum precursor and a complexing agent.
Preferably, the auxiliary precursor comprises the molybdenum precursor, and the molar ratio of the active precursor to the molybdenum precursor is (3-6): 1; and/or the presence of a gas in the gas,
the auxiliary precursor comprises the magnesium precursor and/or the aluminum precursor, and the molar ratio of the active precursor to the magnesium precursor or the aluminum precursor is 1 (1.5-4).
Preferably, the iron precursor is selected from: ferric nitrate nonahydrate and/or ferric chloride; and/or the presence of a gas in the gas,
the cobalt precursor is selected from: cobalt nitrate hexahydrate and/or cobalt chloride; and/or the presence of a gas in the gas,
the nickel precursor is selected from: nickel nitrate hexahydrate and/or nickel chloride; and/or the presence of a gas in the gas,
the aluminum precursor is selected from: aluminum nitrate nonahydrate and/or aluminum chloride; and/or the presence of a gas in the gas,
the magnesium precursor is selected from: magnesium nitrate hexahydrate and/or magnesium chloride; and/or the presence of a gas in the gas,
the molybdenum precursor is selected from: ammonium molybdate and/or molybdenum chloride; and/or the presence of a gas in the gas,
the complexing agent is selected from: citric acid and/or triethanolamine.
Correspondingly, the black phosphorus carbon nanotube composite material comprises black phosphorus and carbon nanotubes growing on the surface of the black phosphorus, the loading capacity of the carbon nanotubes in the black phosphorus carbon nanotube composite material is 0.18-0.9%, and the pipe diameter of the carbon nanotubes is 3-5 nanometers.
The preparation method of the black phosphorus carbon nanotube composite material provided by the invention comprises the following steps of firstly dissolving a metal precursor in an alcohol solvent to obtain a metal precursor solution; then dispersing the black phosphorus into a metal precursor solution to enable the metal precursor to be fully adsorbed on the surface of the black phosphorus, and drying to obtain a metal black phosphorus compound; and then heating the metal black phosphorus compound to 500-600 ℃ in a protective gas atmosphere with the pressure of 4500-5000 kPa for reaction, enabling the metal precursor to generate a metal precursor crystal at high temperature, introducing hydrogen to reduce the metal precursor crystal in the black phosphorus to generate a metal simple substance crystal, and finally introducing a carbon source to grow a carbon nano tube on the metal simple substance crystal to obtain the black phosphorus carbon nano tube composite material. According to the preparation method of the black phosphorus carbon nanotube composite material, black phosphorus is used as a carrier, a metal precursor is used as a catalyst, and carbon nanotubes directly grow on the surface of the black phosphorus, so that on one hand, the carbon nanotubes in the prepared black phosphorus carbon nanotube composite material are uniformly dispersed, and the carbon nanotubes and the black phosphorus are good in combination stability; on the other hand, the carbon nano tube with high length-diameter ratio is efficiently connected to the surface of the black phosphorus to form a conductive network on the surface of the black phosphorus, so that the conductivity of the composite material is improved, namely the conductivity is improved, the carbon nano tube with good mechanical property improves the stability of the black phosphorus, reduces the volume expansion and reduces the polarization, and further the multiplying power charge-discharge performance and the cycle stability of the carbon nano tube in the battery are improved.
The black phosphorus carbon nanotube composite material provided by the invention comprises black phosphorus and carbon nanotubes growing on the surface of the black phosphorus, wherein the loading capacity of the carbon nanotubes in the black phosphorus carbon nanotube composite material is 0.18-0.9%, and the pipe diameter of the carbon nanotubes is 3-5 nanometers. The carbon nanotubes in the black phosphorus carbon nanotube composite material grow on the surface of black phosphorus, and the combination stability of the carbon nanotubes and the black phosphorus is good; in addition, the carbon nano-particles with the loading capacity of 0.18-0.9%, the tube diameter of 3-5 nm, high tube diameter ratio and excellent electrochemical performance are loaded on the surface of black phosphorus, so that the electronic conductivity of the black phosphorus carbon nano-tube composite material is effectively improved, the polarization is reduced, the high-rate charge and discharge of the composite material to a battery and the improvement of the cycle performance are facilitated, and the capacity retention rate of 50 cycles of the composite material under the condition of 0.2C is more than 90%.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a black phosphorus carbon nanotube composite material according to an embodiment of the present invention.
FIG. 2 is a scanning electron microscope image of the black phosphorus carbon nanotube composite material prepared in example 1 of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a black phosphorus carbon nanotube composite material, including the following steps:
s10, obtaining a metal precursor, and dissolving the metal precursor in an alcohol solution to obtain a metal precursor solution;
s20, obtaining black phosphorus, adding the black phosphorus into the metal precursor solution, performing dispersion treatment, and drying to obtain a metal black phosphorus compound;
s30, heating the metal black phosphorus compound to 500-600 ℃ in a protective gas atmosphere with the pressure of 4500-5000 kPa for reaction, and then sequentially introducing hydrogen and a carbon source for reaction to obtain the black phosphorus carbon nanotube composite material.
The preparation method of the black phosphorus carbon nanotube composite material provided by the embodiment of the invention comprises the following steps of firstly dissolving a metal precursor in an alcohol solvent to obtain a metal precursor solution; then, dispersing loose and porous black phosphorus and black phosphorus into a metal precursor solution, enabling the black phosphorus to fully absorb the metal precursor, and drying to obtain a metal black phosphorus compound; and then heating the metal black phosphorus compound to 500-600 ℃ in a protective gas atmosphere with the pressure of 4500-5000 kPa for reaction, enabling the metal precursor to generate a metal precursor crystal at high temperature, introducing hydrogen to reduce the metal precursor crystal in the black phosphorus to generate a metal simple substance crystal, and finally introducing a carbon source to grow a carbon nano tube on the metal simple substance crystal to obtain the black phosphorus carbon nano tube composite material. According to the preparation method of the black phosphorus carbon nanotube composite material, provided by the embodiment of the invention, black phosphorus is used as a carrier, a metal precursor is used as a catalyst, and carbon nanotubes directly grow on the surface of the black phosphorus, so that on one hand, the carbon nanotubes in the prepared black phosphorus carbon nanotube composite material are uniformly dispersed, and the carbon nanotubes and the black phosphorus are good in combination stability; on the other hand, the carbon nano tube with high length-diameter ratio is efficiently connected to the surface of the black phosphorus to form a conductive network on the surface of the black phosphorus, so that the conductivity of the composite material is improved, namely the conductivity is improved, the carbon nano tube with good mechanical property improves the stability of the black phosphorus, reduces the volume expansion and reduces the polarization, and further the multiplying power charge-discharge performance and the cycle stability of the carbon nano tube in the battery are improved.
Specifically, in step S10, a metal precursor is obtained, and the metal precursor is dissolved in an alcohol solution to obtain a metal precursor solution. According to the preparation method of the black phosphorus carbon nanotube composite material, disclosed by the embodiment of the invention, the metal precursor is firstly dissolved in the alcohol solution to obtain the metal precursor solution, so that the subsequent metal precursor is favorably adsorbed to the surface of black phosphorus, and a catalytic carrier is provided for the growth of the carbon nanotube.
The embodiment of the present invention does not specifically limit the manner in which the metal precursor is dissolved in the alcohol solution, as long as the metal precursor can be completely dissolved in the solvent. In some embodiments, the metal precursor is dissolved in an alcohol solution such as ethanol or methanol, and then stirred for 1 to 12 hours to sufficiently dissolve the metal precursor in the solvent.
As a preferred embodiment, the metal precursor comprises a reactive precursor selected from the group consisting of: at least one of an iron precursor, a cobalt precursor, and a nickel precursor. The metal precursor comprises at least one active precursor of an iron precursor, a cobalt precursor and a nickel precursor, and the active precursors are main active metal catalysts for the subsequent catalytic growth of the carbon nano tube.
As a preferred embodiment, the iron precursor is selected from: ferric nitrate nonahydrate and/or ferric chloride. The ferric nitrate nonahydrate or ferric chloride precursor adopted in the embodiment of the invention has better crystallinity and reduction stability in the subsequent process, can generate stable iron simple substance crystals, and has better catalytic effect on the growth of carbon nano.
As a preferred embodiment, the cobalt precursor is selected from: cobalt nitrate hexahydrate and/or cobalt chloride. The cobalt nitrate hexahydrate and/or cobalt chloride precursor adopted by the embodiment of the invention has better crystallinity and reduction stability in the subsequent process, can generate stable cobalt simple substance crystals, and has better catalytic effect on the growth of carbon nano.
As a preferred embodiment, the nickel precursor is selected from: nickel nitrate hexahydrate and/or nickel chloride. The nickel nitrate hexahydrate and/or nickel chloride precursor adopted by the embodiment of the invention has better crystallinity and reduction stability in the subsequent process, can generate stable nickel elementary substance crystals, and has better catalytic effect on the growth of carbon nano.
In some embodiments, the metal precursor includes at least two active precursors of an iron precursor, a cobalt precursor, and a nickel precursor. The embodiment of the invention simultaneously contains more than two active precursors, which is more favorable for improving the growth effect of the carbon nano tube on the black phosphorus.
As a preferred embodiment, the metal precursor further comprises an auxiliary precursor selected from: at least one of an aluminum precursor, a magnesium precursor, a molybdenum precursor and a complexing agent. In the embodiment of the invention, the metal precursor further comprises at least one auxiliary precursor of an aluminum precursor, a magnesium precursor, a molybdenum precursor and a complexing agent, wherein the molybdenum precursor is an auxiliary catalyst and plays a role in promoting and maintaining the catalytic effect of main active precursors of iron, cobalt and nickel; the aluminum precursor and the magnesium precursor form a specific crystal structure with main active precursors of iron, cobalt and nickel, so that the stability of the crystal structure of the active precursors is improved, and the stability of the catalytic effect of the active precursors is improved; the complexing agent has a complexing effect and is beneficial to forming a stable metal simple substance crystal structure by active precursor metal. The auxiliary precursors of the embodiment of the invention have the promotion and stabilization effects on the catalytic effect of the active precursor, so that the active precursor forms more stable metal simple substance crystals in black phosphorus, and the carbon nano tube can be better grown in a catalytic manner.
As a preferred embodiment, the aluminum precursor is selected from: aluminum nitrate nonahydrate and/or aluminum chloride. The magnesium precursor is selected from: magnesium nitrate hexahydrate and/or magnesium chloride. The molybdenum precursor is selected from: ammonium molybdate and/or molybdenum chloride. The complexing agent is selected from: citric acid and/or triethanolamine. The specific substances selected by the auxiliary precursor in the embodiment of the invention are beneficial to the formation of a stable metal simple substance crystal catalyst on the black phosphorus by the active precursor, thereby improving the growth efficiency of the carbon nano tube formed on the surface of the black phosphorus.
As a preferred embodiment, the auxiliary precursor comprises the molybdenum precursor, and the molar ratio of the active precursor to the molybdenum precursor is (3-6): 1. The molar ratio of the active precursor to the molybdenum precursor is (3-6): 1, and the molybdenum precursor with the mass ratio has the best promotion effect on the stable metal simple substance crystal catalyst generated by the active precursor in black phosphorus, so that the active precursor has the best catalytic effect on the growth of the carbon nano tube on the black phosphorus surface. In some embodiments, the molar ratio of the active precursor to the molybdenum precursor can be 3:1, 4:1, 5:1, or 6: 1.
As a preferred embodiment, the auxiliary precursor comprises the magnesium precursor and/or the aluminum precursor, and the molar ratio of the active precursor to the magnesium precursor or the aluminum precursor is 1 (1.5-4). The molar ratio of the active precursor to the magnesium precursor or the aluminum precursor is 1 (1.5-4), the magnesium-aluminum precursor and the iron, cobalt and nickel active precursor in the molar ratio can form an optimal crystal structure, and the optimal crystal structure can be used as a carrier of the active precursor, so that the stability of a metal elementary substance crystal formed by the active precursor is improved, and the growth stability of the carbon nano tube on the black phosphorus is improved. In some embodiments, the molar ratio of the active precursor to the magnesium precursor or the aluminum precursor may be 1:1.5, 1:2, 1:3, or 1: 4.
In some embodiments, the metal precursor includes at least one active precursor of an iron precursor, a cobalt precursor, and a nickel precursor, and also includes auxiliary precursors such as an aluminum precursor, a magnesium precursor, a molybdenum precursor, and a complexing agent. The molar ratio of the active precursor to the molybdenum precursor is (3-6): 1, and the molar ratio of the active precursor to the magnesium precursor or the aluminum precursor is 1: (1.5-4). According to the embodiment of the invention, the metal precursor simultaneously comprises the active precursor and the auxiliary precursor, and the active precursor can generate a stable metal simple substance crystal catalyst with a proper size in black phosphorus through the auxiliary promotion effect of the auxiliary precursor on the metal of the active precursor, so that the growth stability of the carbon nano tube on the surface of the black phosphorus can be effectively improved.
Specifically, in step S20, black phosphorus is obtained, and the black phosphorus is added to the metal precursor solution, dispersed, and dried to obtain the metal black phosphorus composite. According to the preparation method of the black phosphorus carbon nanotube composite material, the black phosphorus is added into the metal precursor solution, the loose and porous black phosphorus has a good adsorption effect on the metal precursor in the solution, so that the metal precursor is adsorbed into the black phosphorus to obtain the metal black phosphorus composite, and a catalysis basis is provided for the subsequent growth of the carbon nanotube.
As a preferred embodiment, the step of the dispersion treatment includes: and (3) adding the black phosphorus into the metal precursor solution, and then carrying out ultrasonic and/or ball milling treatment for 30-60 minutes. According to the embodiment of the invention, the black phosphorus is generated into small particles through ball milling or ultrasonic treatment for 30-60 minutes, the black phosphorus particles with small particle sizes have larger comparative area, and the metal precursor in the solution has better adsorption effect, so that the metal precursor is uniformly adsorbed into the black phosphorus gaps, and carbon nanotubes uniformly distributed on the surface of the black phosphorus are favorably grown, and the black phosphorus carbon nanotube composite material has better stability and electrochemical performance. In some embodiments, after the black phosphorus is added to the metal precursor solution, the metal black phosphorus composite is obtained by performing ultrasonic and/or ball milling treatment for 30 minutes, 40 minutes, 50 minutes or 60 minutes and performing rotary evaporation drying at 80 ℃.
As a preferred embodiment, the loading amount of the metal element in the active precursor in the metal black phosphorus compound is 0.1-0.5%. According to the embodiment of the invention, the loading amount of at least one metal element of iron, cobalt and nickel in the active precursor in the metal black phosphorus composite is 0.1-0.5%, and the metal elements of iron, cobalt or nickel in the active precursor in the metal black phosphorus composite are main catalytic active substances for the subsequent growth of the carbon nano tube, so that the loading amount of the metal elements in the active precursor in the composite determines the growth amount of the carbon nano tube on the subsequent black phosphorus, and the loading amount of the metal elements in the active precursor is 0.1-0.5%, so that the growth amount of the carbon nano tube in the black phosphorus carbon nano tube composite has the best promotion effect on the stability and electrochemical performance of the composite. If the loading capacity of the metal elements in the active precursor in the black phosphorus is too high, the active precursor is more densely distributed in the black phosphorus, large-particle metal is easily fused and synthesized in the subsequent high-temperature treatment stage, and a nanoscale metal simple substance crystal cannot be generated, so that the carbon nano tube cannot be catalytically grown; if the loading capacity of the metal elements in the active precursor in the black phosphorus is too low, the growth amount of the carbon nano tube on the surface of the black phosphorus is limited, so that the overall performance of the black phosphorus-carbon nano tube composite material is influenced. In some embodiments, the loading of the metal element in the active precursor in the metal black phosphorus composite may be 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.
Specifically, in the step S30, under a protective gas atmosphere with an absolute pressure of 4500kPa-5000kPa, the temperature of the metal black phosphorus composite is raised to 500-600 ℃ for reaction, and then hydrogen and a carbon source are sequentially introduced for reaction, so as to obtain the black phosphorus carbon nanotube composite material. In the embodiment of the invention, under the protective gas atmosphere with the absolute pressure of 4500-5000 kPa, the metal black phosphorus compound is heated to 500-600 ℃ for reaction, and then hydrogen and a carbon source are sequentially introduced for reaction, so that the black phosphorus carbon nanotube composite material is obtained. Wherein, the high pressure environment of 4500kPa-5000kPa is helpful to increase the melting point of the black phosphorus, so that the black phosphorus is kept in a solid state in the high temperature environment, and the function of the carbon nano tube growth carrier is exerted to the maximum extent. The protective gas atmosphere is effective to prevent the black phosphorus from being oxidized at high temperatures, and in some embodiments, the protective gas is selected from the group consisting of: at least one of nitrogen and argon. And heating the metal black phosphorus compound to 500-600 ℃ for reaction, so that a metal precursor adsorbed in the black phosphorus forms a metal precursor crystal, introducing hydrogen to reduce the metal precursor crystal into a metal simple substance crystal, and introducing a carbon source to grow a carbon nano tube on the surface of the metal simple substance crystal, thereby obtaining the black phosphorus carbon nano tube composite material.
As a preferred embodiment, the step of heating the metal black phosphorus compound to 500-600 ℃ for reaction comprises the following steps: and heating the metal black phosphorus compound to 500-600 ℃ at a heating rate of 1-5 ℃/min, and reacting for 2-5 hours. In the embodiment of the invention, the metal black phosphorus compound is heated to 500-600 ℃ at a heating rate of 1-5 ℃/min and reacts for 2-5 hours, so that the metal precursor adsorbed in the black phosphorus forms a metal precursor crystal. The temperature rise speed of 1-5 ℃/min effectively ensures that the generated metal precursor crystal is a nanoscale crystal not greater than 10 nanometers, and provides a catalytic base for the subsequent growth of the carbon nano tube with small tube diameter. If the temperature rise rate is more than 5 ℃/min, the growth speed of the metal precursor on the surface of the black phosphorus is too high, and a metal precursor crystal with too large particle size is formed, so that the diameter of the generated carbon nano tube is too large, the length-diameter ratio of the carbon nano tube is reduced, and the electrochemical performance of the black phosphorus carbon nano tube composite material is influenced; and reacting for 2-5 hours at 500-600 ℃, wherein the reaction temperature and time further ensure that the metal precursor fully forms stable nanoscale metal precursor crystals with the particle size smaller than 10 nanometers, and the formation of the nanoscale metal precursor crystals can be influenced when the reaction temperature is too high or too low and the time is too short or too long. In some embodiments, the metal black phosphorus composite is heated to 500 ℃, 550 ℃ or 600 ℃ at a heating rate of 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min for 2 hours, 3 hours, 4 hours or 5 hours.
As a preferred embodiment, the step of sequentially introducing hydrogen and a carbon source for reaction comprises the following steps: and (3) heating the metal black phosphorus compound to 500-600 ℃ for reaction, introducing hydrogen for reaction for 1-5 minutes, and then closing the reaction of introducing hydrogen and a carbon source for reaction for 30-90 minutes. In the embodiment of the invention, hydrogen is introduced into a reaction system after the temperature of the metal black phosphorus compound is raised to 500-600 ℃ for reaction for 1-5 minutes, so that the formed metal precursor crystal is fully reduced into a metal simple substance crystal, then the hydrogen is closed to be introduced into a carbon source for reaction for 30-90 minutes, the partially molten metal on the surface of the metal simple substance crystal has a strong adsorption and dissolution effect on the carbon source at high temperature, and the carbon source adsorbed on the surface of the metal simple substance crystal is continuously dissolved and separated out to generate the carbon nano tube, so that the black phosphorus carbon nano tube composite material is obtained.
As a preferred embodiment, the step of introducing hydrogen for reaction for 1-5 minutes comprises the following steps: according to the volume ratio of the hydrogen to the first carrier gas of 1: (4-8), introducing the hydrogen and the first carrier into a reaction system to react for 1-5 minutes. In the step of introducing hydrogen to reduce the metal precursor crystal into the elemental metal crystal, the volume ratio of the hydrogen to the first carrier gas is 1: (4-8) introducing the hydrogen and the first carrier into a reaction system to react for 1-5 minutes. The hydrogen proportion influences the reduction rate of the metal precursor crystal to the metal elementary crystal, and the hydrogen proportion is too high, the reduction rate is too high, and the formation of the nanoscale metal elementary crystal smaller than 10nm is not facilitated. The reaction time of 1-5 minutes ensures that the metal precursor crystals on the surface of the black phosphorus fully reduce the metal simple substance crystals. The first carrier gases are each independently selected from: at least one of nitrogen and argon. In some embodiments, in a system in which the metal black phosphorus composite is heated to 500 ℃, 550 ℃ or 600 ℃ at a heating rate of 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min and reacted for 2 hours, 3 hours, 4 hours or 5 hours, the hydrogen and the first carrier gas are introduced into the reaction system to react for 1 minute, 2 minutes, 3 minutes, 4 minutes or 5 minutes at a volume ratio of the hydrogen to the first carrier gas of 1:4, 1:5, 1:6, 1:7 or 1: 8.
As a preferred embodiment, the step of closing the introduction of hydrogen into the carbon source for reaction for 30-90 minutes comprises the following steps: according to the volume ratio of the carbon source to the second carrier gas of 2: (1-5), introducing the carbon source and the second carrier gas into a reaction system to react for 30-90 minutes. In the embodiment of the invention, the temperature of the metal black phosphorus compound is raised to 500-600 ℃ for reaction, and hydrogen is introduced into a reaction system for reaction for 1-5 minutes, wherein the volume ratio of the carbon source to the second carrier gas is 2: (1-5) introducing the carbon source and the second carrier gas into a reaction system to react for 30-90 minutes. Wherein the volume ratio of the carbon source to the second carrier gas is 2: (1-5), the growth rate of the carbon nano tube on the black phosphorus surface is influenced by the carbon source proportion, if the carbon source content is too high, the carbon source is too fast precipitated on the surface of the metal simple substance crystal to grow into the carbon nano tube, and the carbon source is precipitated in the form of amorphous carbon; if the carbon source content is too low, the growth rate of the carbon nano-meter is affected. The reaction time of 30-90 minutes ensures the growth of the carbon nano tube, and if the reaction time is too long, the catalyst is inactivated, so that a large amount of amorphous carbon and other byproducts are generated, and the performance of the black phosphorus carbon nano tube composite material is influenced. The second carrier gases are each independently selected from: at least one of nitrogen and argon.
In some embodiments, the metal black phosphorus complex is heated to 500 ℃, 550 ℃ or 600 ℃ at a heating rate of 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min and reacted for 2 hours, 3 hours, 4 hours or 5 hours, the hydrogen and the first carrier gas are introduced into the reaction system to react for 1 minute, 2 minutes, 3 minutes, 4 minutes or 5 minutes according to the volume ratio of the carbon source to the second carrier gas of 1:4, 1:5, 1:6, 1:7 or 1:8, and the volume ratio of the carbon source to the second carrier gas is 2: 1. 2:2, 2:3, 2:4 or 2:5, and introducing the carbon source and the second carrier gas into the reaction system to react for 30 minutes, 50 minutes, 70 minutes or 90 minutes.
As a preferred embodiment, the carbon source is selected from: at least one of alkane, alkene and alkyne. As a more preferred embodiment, the carbon source is selected from the group consisting of: at least one of methane, ethylene, propylene and acetylene. The carbon source adopted by the embodiment of the invention can grow the carbon nano tube under the action of the metal simple substance crystal catalyst.
In some embodiments, a method of making a black phosphorus carbon nanotube composite comprises the steps of:
s11, dissolving ferric nitrate nonahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, aluminum nitrate nonahydrate, magnesium nitrate hexahydrate, ammonium molybdate and citric acid in alcohol, and stirring for 1-12h to mainly dissolve a metal precursor to obtain a metal precursor solution;
s21, adding black phosphorus into the obtained metal precursor solution, performing ultrasonic treatment or ball milling for 30-60min, and drying in a rotary evaporator at 80-90 ℃ to obtain a metal black phosphorus compound, wherein the loading amounts of iron, cobalt and nickel in the metal black phosphorus compound are 0.1-0.5%;
s31, placing the obtained metal black phosphorus compound in a pressure vessel under the absolute pressure of 4500-5000 kPa under N2Heating to 500-600 ℃ at a heating rate of 1-5 ℃/min in the atmosphere, keeping the temperature for 2-5h, introducing hydrogen and nitrogen according to a volume ratio of 1 (4-8), and reacting for 1-5 min; finally, hydrogen is turned off, and the volume ratio of the hydrogen to the hydrogen is 2: and (1) introducing a carbon source and nitrogen, and reacting for 30-90 min to obtain the black phosphorus carbon nanotube composite material.
The embodiment of the invention also provides a black phosphorus carbon nanotube composite material, which comprises black phosphorus and carbon nanotubes growing on the surface of the black phosphorus, wherein the loading capacity of the carbon nanotubes in the black phosphorus carbon nanotube composite material is 0.18-0.9%, and the pipe diameter of the carbon nanotubes is 3-5 nanometers.
The black phosphorus carbon nanotube composite material provided by the embodiment of the invention comprises black phosphorus and carbon nanotubes growing on the surface of the black phosphorus, wherein the loading capacity of the carbon nanotubes in the black phosphorus carbon nanotube composite material is 0.18-0.9%, and the pipe diameter of the carbon nanotubes is 3-5 nanometers. The carbon nanotubes in the black phosphorus carbon nanotube composite material of the embodiment of the invention grow on the surface of black phosphorus, and the combination stability with the black phosphorus is good; in addition, the carbon nano-particles with the loading capacity of 0.18-0.9%, the tube diameter of 3-5 nm, high tube diameter ratio and excellent electrochemical performance are loaded on the surface of black phosphorus, so that the electronic conductivity of the black phosphorus carbon nano-tube composite material is effectively improved, the polarization is reduced, the high-rate charge and discharge of the composite material on a battery and the improvement of the cycle performance are facilitated, and the capacity retention rate is more than 90% after the composite material is cycled for 50 times under the condition of 0.2C.
The black phosphorus carbon nanotube composite material provided by the embodiment of the invention can be prepared by the preparation method of the black phosphorus carbon nanotube composite material.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the progress of the preparation method of the black phosphorus carbon nanotube composite material of the embodiments of the present invention obviously manifest, the above technical solutions are illustrated by the following examples.
Example 1
A black phosphorus carbon nanotube composite material comprises the following preparation steps:
dissolving nickel nitrate hexahydrate, aluminum nitrate nonahydrate, magnesium nitrate hexahydrate, ammonium molybdate and citric acid in alcohol, stirring for 2 hours to mainly dissolve a metal precursor to obtain a metal precursor solution;
secondly, adding black phosphorus into the obtained metal precursor solution, performing ultrasonic treatment or ball milling for 40min, and drying in a rotary evaporator at 80 ℃ to obtain a metal black phosphorus compound, wherein the loading amounts of iron, cobalt and nickel in the metal black phosphorus compound are 0.5%;
thirdly, placing the obtained metal black phosphorus compound in a pressure container under the absolute pressure of 4800kPa and N2Heating to 550 ℃ at the heating rate of 2 ℃/min in the atmosphere of (1), keeping the temperature for 2 hours, introducing hydrogen and nitrogen according to the volume ratio of 1:5, and reacting for 5 minutes; finally, theClosing hydrogen according to the volume ratio of 2: and 5, introducing a carbon source and nitrogen, and reacting for 60min to obtain the black phosphorus carbon nanotube composite material.
Example 2
A black phosphorus carbon nanotube composite material comprises the following preparation steps:
dissolving ferric nitrate nonahydrate, cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, magnesium nitrate hexahydrate, ammonium molybdate and citric acid in alcohol, and stirring for 5 hours to mainly dissolve a metal precursor to obtain a metal precursor solution;
secondly, adding black phosphorus into the obtained metal precursor solution, performing ultrasonic treatment or ball milling for 60min, and drying in a rotary evaporator at 80 ℃ to obtain a metal black phosphorus compound, wherein the loading amounts of iron, cobalt and nickel in the metal black phosphorus compound are 0.1%;
thirdly, placing the obtained metal black phosphorus compound in a pressure container under the absolute pressure of 5000kPa and N2Heating to 600 ℃ at the temperature rising speed of 5 ℃/min in the atmosphere of (1), keeping the temperature for 3 hours, introducing hydrogen and nitrogen according to the volume ratio of 1:6, and reacting for 3 minutes; finally, hydrogen is turned off, and the volume ratio of the hydrogen to the hydrogen is 2:3 introducing a carbon source and nitrogen, and reacting for 90min to obtain the black phosphorus carbon nanotube composite material.
Example 3
A black phosphorus carbon nanotube composite material comprises the following preparation steps:
dissolving ferric nitrate nonahydrate, aluminum nitrate nonahydrate, magnesium nitrate hexahydrate, ammonium molybdate and citric acid in alcohol, and stirring for 10 hours to mainly dissolve a metal precursor to obtain a metal precursor solution;
secondly, adding black phosphorus into the obtained metal precursor solution, performing ultrasonic treatment or ball milling for 45min, and drying in a rotary evaporator at 80 ℃ to obtain a metal black phosphorus compound, wherein the loading amounts of iron, cobalt and nickel in the metal black phosphorus compound are 0.3%;
thirdly, placing the obtained metal black phosphorus compound in a pressure container under the absolute pressure of 4500kPa under N2Heating to 500 ℃ at the heating rate of 4 ℃/min in the atmosphere of (1), keeping the temperature for 3 hours, introducing hydrogen and nitrogen according to the volume ratio of 1:8, and reacting for 5 minutes; finally, hydrogen is turned off, and the volume ratio of the hydrogen to the hydrogen is 2: 1 introducing carbon source and nitrogen, reacting for 90min to obtainTo black phosphorus carbon nanotube composites.
Further, in order to verify the progress of the preparation method of the black phosphorus carbon nanotube composite material in the embodiment of the present invention, the performance of the prepared black phosphorus carbon nanotube composite material is tested in the embodiment of the present invention.
Test example 1
The black phosphorus carbon nanotube composite material prepared in the embodiment 1 is tested by a scanning electron microscope, and as shown in the attached figure 2, the carbon nanotubes uniformly grow and wrap the surface of black phosphorus, the tube diameter is 3-5 nanometers, and the dispersibility of the carbon nanotubes is good.
Test example 2
According to the embodiment of the invention, the load capacity of the carbon nanotubes in the black phosphorus carbon nanotube composite material of the embodiment 1-3 is tested by a thermogravimetric analysis method, wherein the load capacity of the carbon nanotubes in the black phosphorus carbon nanotube composite material of the embodiment 1 is 0.3%; the carbon nanotube loading in the black phosphorus carbon nanotube composite material of example 2 was 0.5%; the loading of carbon nanotubes in the black phosphorus carbon nanotube composite of example 3 was 0.8%.
Test example 3
The black phosphorus carbon nanotube composite material prepared in the examples 1 to 3 is prepared into a sodium ion battery, the cycling stability performance is tested, and the test results are shown in the following table 1:
TABLE 1
Capacity retention after 50 cycles at 0.2C
Example 1 90.1％
Example 2 91.2％
Example 3 90.6％
From the test results, the capacity retention rate of the battery made of the black phosphorus carbon nanotube composite material prepared by the embodiment of the invention is more than 90% after 50 cycles under the condition of 0.2C.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The preparation method of the black phosphorus carbon nanotube composite material is characterized by comprising the following steps of:
obtaining a metal precursor, and dissolving the metal precursor in an alcohol solution to obtain a metal precursor solution;
obtaining black phosphorus, adding the black phosphorus into the metal precursor solution, performing dispersion treatment, and drying to obtain a metal black phosphorus compound;
heating the metal black phosphorus compound to 500-600 ℃ under the protective gas atmosphere with the absolute pressure of 4500-5000 kPa for reaction, and then sequentially introducing hydrogen and a carbon source for reaction to obtain the black phosphorus carbon nanotube composite material.
2. The method for preparing the black phosphorus carbon nanotube composite material as claimed in claim 1, wherein the step of heating the metal black phosphorus composite to 500-600 ℃ for reaction comprises: heating the metal black phosphorus compound to 500-600 ℃ at a heating rate of 1-5 ℃/min and reacting for 2-5 hours; and/or the presence of a gas in the gas,
the step of introducing hydrogen and carbon source in sequence for reaction comprises the following steps: and (3) heating the metal black phosphorus compound to 500-600 ℃ for reaction, introducing hydrogen for reaction for 1-5 minutes, and then closing the reaction of introducing hydrogen and a carbon source for reaction for 30-90 minutes.
3. The method for preparing the black phosphorus carbon nanotube composite material as claimed in claim 2, wherein the step of introducing hydrogen gas for reaction for 1-5 minutes comprises: according to the volume ratio of the hydrogen to the first carrier gas of 1: (4-8), introducing the hydrogen and the first carrier into a reaction system to react for 1-5 minutes; and/or the presence of a gas in the gas,
the step of closing the reaction of introducing hydrogen into the carbon source for 30-90 minutes comprises the following steps: according to the volume ratio of the carbon source to the second carrier gas of 2: (1-5), introducing the carbon source and the second carrier gas into a reaction system to react for 30-90 minutes.
4. The method of preparing a black phosphorus carbon nanotube composite material according to claim 3, wherein the step of dispersion treatment comprises: adding the black phosphorus into the metal precursor solution, and then carrying out ultrasonic and/or ball milling treatment for 30-60 minutes; and/or the presence of a gas in the gas,
the shielding gas, the first carrier gas and the second carrier gas are each independently selected from the group consisting of: at least one of nitrogen and argon; and/or the presence of a gas in the gas,
the carbon source is selected from: at least one of alkane, alkene and alkyne.
5. The method for preparing a black phosphorus carbon nanotube composite material according to any one of claims 1 to 4, wherein the metal precursor comprises an active precursor selected from the group consisting of: at least one of an iron precursor, a cobalt precursor and a nickel precursor; and/or the presence of a gas in the gas,
the carbon source is selected from: at least one of methane, ethylene, propylene and acetylene.
6. The method for preparing the black phosphorus carbon nanotube composite material according to claim 5, wherein the loading amount of the metal element in the active precursor in the metal black phosphorus composite is 0.1-0.5%, and the loading amount refers to loading mass.
7. The method of preparing a black phosphorus carbon nanotube composite material of claim 5, wherein the metal precursor further comprises an auxiliary precursor selected from the group consisting of: at least one of an aluminum precursor, a magnesium precursor, a molybdenum precursor and a complexing agent.
8. The method for preparing the black phosphorus carbon nanotube composite material according to claim 7, wherein the auxiliary precursor comprises the molybdenum precursor, and the molar ratio of the active precursor to the molybdenum precursor is (3-6): 1; and/or the presence of a gas in the gas,
the auxiliary precursor comprises the magnesium precursor and/or the aluminum precursor, and the molar ratio of the active precursor to the magnesium precursor or the aluminum precursor is 1 (1.5-4).
9. The method of preparing a black phosphorus carbon nanotube composite material according to claim 7 or 8, wherein the iron precursor is selected from the group consisting of: ferric nitrate nonahydrate and/or ferric chloride; and/or the presence of a gas in the gas,
the cobalt precursor is selected from: cobalt nitrate hexahydrate and/or cobalt chloride; and/or the presence of a gas in the gas,
the nickel precursor is selected from: nickel nitrate hexahydrate and/or nickel chloride; and/or the presence of a gas in the gas,
the aluminum precursor is selected from: aluminum nitrate nonahydrate and/or aluminum chloride; and/or the presence of a gas in the gas,
the magnesium precursor is selected from: magnesium nitrate hexahydrate and/or magnesium chloride; and/or the presence of a gas in the gas,
the molybdenum precursor is selected from: ammonium molybdate and/or molybdenum chloride; and/or the presence of a gas in the gas,
the complexing agent is selected from: citric acid and/or triethanolamine.
10. A black phosphorus carbon nanotube composite material, which is prepared by the method of any one of claims 1 to 9, and comprises black phosphorus and carbon nanotubes growing on the surface of the black phosphorus, wherein the loading capacity of the carbon nanotubes in the black phosphorus carbon nanotube composite material is 0.18 to 0.9 percent, and the tube diameter of the carbon nanotubes is 3 to 5 nanometers.
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