CN110739095A - conductive agents prepared from polyacrylonitrile gel and preparation method thereof - Google Patents

conductive agents prepared from polyacrylonitrile gel and preparation method thereof Download PDF

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CN110739095A
CN110739095A CN201910976654.0A CN201910976654A CN110739095A CN 110739095 A CN110739095 A CN 110739095A CN 201910976654 A CN201910976654 A CN 201910976654A CN 110739095 A CN110739095 A CN 110739095A
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polyacrylonitrile
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gel
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additive
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高延敏
徐俊烽
施方长
张政
王明明
孙存思
杨红洲
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Jiangsu University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile

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Abstract

The invention discloses conductive agents prepared by polyacrylonitrile gel and a preparation method thereof, the polyacrylonitrile gel is prepared by dissolving polyacrylonitrile fiber in N' N-dimethylformamide, then dripping into deionized water, adding an additive, carrying out precipitation polymerization to obtain the polyacrylonitrile gel, then placing the obtained gel in a vacuum cracking furnace, adjusting different heat treatment parameters to carbonize the gel, thereby obtaining the conductive agents with different conductivities.

Description

conductive agents prepared from polyacrylonitrile gel and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to conductive agents prepared from polyacrylonitrile gel and a preparation method thereof.
Background
In recent years, the research interest on conductive polymers is high, and many conductive polymer products with practical value have been developed.
From the market, at present, the main conductive agents are conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and the like, the conductive carbon black has a small particle size, can be applied to the fields of various industries such as batteries, conductive adhesives, conductive slurry and the like, has a high market share, is not as practical as the conductive carbon black but has a low production cost, and the carbon nanotubes and the carbon fibers have a very large specific surface area and excellent conductivity but are difficult to use widely at due to high preparation cost.
Polyacrylonitrile is a saturated carbon skeleton high polymer with cyano groups alternately linked on carbon atoms, and can be carbonized at high temperature to obtain an active substance with good conductivity, stability to oxygen, high charge storage capacity and high charge-discharge speed. This is related to the formation of a special trapezoidal conjugated structure when polyacrylonitrile is carbonized at high temperature. The electrical property of the material is closely related to the preparation process, the conventional preparation process at present carbonizes solid polyacrylonitrile powder or fiber, the method is simple, but the particle size is larger than 5 μm, and the limited specific surface area performance is difficult to fully exert. However, in this process, the properties of the obtained material still do not achieve the desired properties, and need to be guided and controlled from the source of the raw materials.
Disclosure of Invention
which is the object of the invention is to provide conductive agents prepared by polyacrylonitrile gel, the specific technical proposal is as follows:
conductive agents prepared from polyacrylonitrile gel are prepared from an additive, polyacrylonitrile fibers, N' N-dimethylformamide and water according to the mass ratio of 1: 90-110: 4000-5000: 8000-25000, wherein the additive is iron phthalocyanine, cobalt phthalocyanine or nickel phthalocyanine (the structural formula is shown in the following formula).
Figure BDA0002233862300000021
Wherein M is a metal element Fe, Co or Ni.
The invention also aims to provide a preparation method of the conductive agent. The specific technical scheme is as follows:
A method for preparing conductive agent by polyacrylonitrile gel, comprising the following steps:
step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, and then placing the polyacrylonitrile fibers in a 75-85 ℃ oven for heat preservation for 15-25 min to obtain a polyacrylonitrile solution, wherein the mass of the N' N-dimethylformamide is 40-50 times that of the polyacrylonitrile fibers;
slowly dripping a polyacrylonitrile solution into deionized water, adding the additive while stirring, and centrifuging to obtain polyacrylonitrile gel, wherein the mass ratio of the additive to polyacrylonitrile is 1: 90-110;
and 3, performing heat treatment on the polyacrylonitrile gel: raising the temperature to 100-150 ℃, preserving the heat for 10-60 min, and carrying out gel dehydration; raising the temperature to 200-300 ℃ and preserving the heat for 1-2 h to ensure that polyacrylonitrile molecules are subjected to internal cyclization; then increasing the temperature to 400-500 ℃ and preserving the heat for 3-4 h to carbonize polyacrylonitrile at a low temperature; finally, increasing the temperature to 800-900 ℃, preserving the heat for 3-4 h, and carrying out high-temperature carbonization;
and 4, taking out the material subjected to the heat treatment in the step , and grinding the material into powder to obtain the conductive agent.
Preferably, the stirring speed in the step 2 is 1000-1500 r/min.
Preferably, the dosage of the deionized water in the step 2 is 3-4 times of the volume of the polyacrylonitrile solution.
Preferably, the heat treatment process in step 3 is as follows: raising the temperature to 100-120 ℃, preserving heat for 20-30 min, raising the temperature to 240-280 ℃, preserving heat for 1-2 h, then increasing the temperature to 400-420 ℃, preserving heat for 3-4 h, and finally increasing the temperature to 800-850 ℃, preserving heat for 3-4 h.
Preferably, the particle size of the powder in the 4 th step is less than or equal to 1 μm.
The invention has the beneficial effects that:
the conductive agents prepared by polyacrylonitrile gel and the preparation method thereof can effectively solve the problem that the large specific surface area of particles is limited, the particle size is controlled below 1 mu m, and the conductivity exceeds 100S/cm.
Drawings
FIG. 1 shows a polyacrylonitrile conductive agent and CuCo prepared in example 4 of the present invention2S4The electron microscope picture of the electrode surface assembled by nano crystal grains shows that the larger particles circled in the picture are polyacrylonitrile conductive agent, and the rest are CuCo2S4A nanocrystal particle;
FIG. 2 is a graph showing the comparison between the specific surface area and the electrical conductivity of the conductive agents obtained in examples 1 to 6.
Detailed Description
The following examples illustrate the contents of the present invention but should not be construed as limiting the invention, modifications and substitutions of the methods, procedures or conditions of the present invention are within the scope of the present invention without departing from the spirit and substance of the invention.
The synthesis route of the additive (iron phthalocyanine, cobalt phthalocyanine and nickel phthalocyanine) is as follows:
raw materials: phthalic anhydride or phthalic imide and derivatives thereof, urea is used as a nitrogen source, and ammonium molybdate or vanadyl chloride or boric acid is used as a catalyst to react at a high temperature (as shown in the following formula).
Figure BDA0002233862300000031
Example 1
The preparation method of kinds of conductive agents prepared by polyacrylonitrile gel comprises the following steps:
step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, wherein the mass of the N' N-dimethylformamide is 40 times that of the polyacrylonitrile fibers, and then placing the polyacrylonitrile fibers in a 75-DEG C oven for heat preservation for 25min to obtain a polyacrylonitrile solution;
and 2, slowly dropwise adding the polyacrylonitrile solution into deionized water, wherein the using amount of the deionized water is 3 times of the volume of the polyacrylonitrile solution, adding an additive iron phthalocyanine (M in the structural formula is Fe), and the mass of the additive and the polyacrylonitrile is 1: 100, stirring while dropwise adding, wherein the stirring speed is 1000-1500 r/min, and then centrifuging to obtain polyacrylonitrile gel;
step 3, placing polyacrylonitrile gel in a vacuum cracking furnace, raising the temperature to 100 ℃, preserving the heat for 30min, and dehydrating the gel; raising the temperature to 260 ℃ and preserving the temperature for 1h to ensure that polyacrylonitrile molecules form rings; then increasing the temperature to 420 ℃ and preserving the heat for 3h to carbonize the polyacrylonitrile at a low temperature; finally, increasing the temperature to 820 ℃ and preserving the heat for 4 hours to carry out high-temperature carbonization;
and 4, taking out the substance carbonized at the high temperature, grinding the substance into powder by using a grinding dish, and controlling the particle size to be less than 1 mu m to obtain the conductive agent.
Example 2
The preparation method of kinds of conductive agents prepared by polyacrylonitrile gel comprises the following steps:
step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, wherein the mass of the N' N-dimethylformamide is 50 times that of the polyacrylonitrile fibers, and then placing the polyacrylonitrile fibers in an oven at the temperature of 80 ℃ for heat preservation for 20min to obtain a polyacrylonitrile solution;
and 2, slowly dropwise adding the polyacrylonitrile solution into deionized water, wherein the using amount of the deionized water is 4 times of the volume of the polyacrylonitrile solution, adding an additive, namely cobalt phthalocyanine (M in the structural formula is Co), and the mass ratio of the additive to the polyacrylonitrile is 1: 100, stirring while dropwise adding, wherein the stirring speed is 1000-1500 r/min, and then centrifuging to obtain polyacrylonitrile gel;
step 3, placing polyacrylonitrile gel in a vacuum cracking furnace, raising the temperature to 120 ℃, preserving the heat for 20min, and dehydrating the gel; raising the temperature to 240 ℃ and preserving the temperature for 2h to ensure that polyacrylonitrile molecules are subjected to internal cyclization; then increasing the temperature to 400 ℃ and preserving the heat for 4h to carbonize the polyacrylonitrile at a low temperature; finally, increasing the temperature to 800 ℃, preserving the heat for 4 hours, and carrying out high-temperature carbonization;
and 4, taking out the substance carbonized at the high temperature, grinding the substance into powder by using a grinding dish, and controlling the particle size to be less than 1 mu m to obtain the conductive agent.
Example 3
The preparation method of kinds of conductive agents prepared by polyacrylonitrile gel comprises the following steps:
step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, wherein the mass of the N' N-dimethylformamide is 45 times that of the polyacrylonitrile fibers, and then placing the polyacrylonitrile fibers in an oven at 85 ℃ for heat preservation for 15min to obtain a polyacrylonitrile solution;
and 2, slowly dripping the polyacrylonitrile solution into deionized water, wherein the using amount of the deionized water is 4 times of the volume of the polyacrylonitrile solution, adding nickel phthalocyanine (M in the structural formula is Ni), and the mass ratio of the additive to the polyacrylonitrile is 1: 100, stirring while dropwise adding, wherein the stirring speed is 1000-1500 r/min, and then centrifuging to obtain polyacrylonitrile gel;
step 3, placing polyacrylonitrile gel in a vacuum cracking furnace, raising the temperature to 110 ℃, preserving the heat for 25min, and dehydrating the gel; raising the temperature to 280 ℃ and preserving the temperature for 1h to ensure that polyacrylonitrile molecules are subjected to internal cyclization; then increasing the temperature to 400 ℃ and preserving the heat for 3h to carbonize the polyacrylonitrile at a low temperature; finally, increasing the temperature to 850 ℃ and preserving the heat for 3 hours to carry out high-temperature carbonization;
and 4, taking out the substance carbonized at the high temperature, grinding the substance into powder by using a grinding dish, and controlling the particle size to be less than 1 mu m to obtain the conductive agent.
Example 4
The preparation method of kinds of conductive agents prepared by polyacrylonitrile gel comprises the following steps:
step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, wherein the mass of the N' N-dimethylformamide is 50 times that of the polyacrylonitrile fibers, and then placing the polyacrylonitrile fibers in a 75-DEG C oven for heat preservation for 20min to obtain a polyacrylonitrile solution;
and 2, slowly dropwise adding the polyacrylonitrile solution into deionized water, wherein the using amount of the deionized water is 3 times of the volume of the polyacrylonitrile solution, adding an additive, namely cobalt phthalocyanine (M in the structural formula is Co), and the mass ratio of the additive to the polyacrylonitrile is 1: 100, stirring while dropwise adding, wherein the stirring speed is 1000-1500 r/min, and then centrifuging to obtain polyacrylonitrile gel;
step 3, placing polyacrylonitrile gel in a vacuum cracking furnace, raising the temperature to 100 ℃, preserving the heat for 25min, and dehydrating the gel; raising the temperature to 260 ℃ and preserving the temperature for 2 hours to ensure that polyacrylonitrile molecules are subjected to internal cyclization; then increasing the temperature to 420 ℃ and preserving the heat for 3h to carbonize the polyacrylonitrile at a low temperature; finally, increasing the temperature to 830 ℃, preserving the heat for 4 hours, and carrying out high-temperature carbonization;
and 4, taking out the substance carbonized at the high temperature, grinding the substance into powder by using a grinding dish, and controlling the particle size to be less than 1 mu m to obtain the conductive agent.
Example 5
The preparation method of kinds of conductive agents prepared by polyacrylonitrile gel comprises the following steps:
step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, wherein the mass of the N' N-dimethylformamide is 50 times that of the polyacrylonitrile fibers, and then placing the polyacrylonitrile fibers in an oven at 85 ℃ for heat preservation for 15min to obtain a polyacrylonitrile solution;
and 2, slowly dropwise adding the polyacrylonitrile solution into deionized water, wherein the using amount of the deionized water is 3 times of the volume of the polyacrylonitrile solution, adding an additive iron phthalocyanine (M in the structural formula is Fe), and the mass ratio of the additive to the polyacrylonitrile is 1: 100, stirring while dropwise adding, wherein the stirring speed is 1000-1500 r/min, and then centrifuging to obtain polyacrylonitrile gel;
step 3, placing polyacrylonitrile gel in a vacuum cracking furnace, raising the temperature to 120 ℃, preserving the heat for 30min, and dehydrating the gel; raising the temperature to 280 ℃ and preserving the temperature for 1h to ensure that polyacrylonitrile molecules are subjected to internal cyclization; then increasing the temperature to 420 ℃ and preserving the heat for 4 hours to carbonize the polyacrylonitrile at a low temperature; finally, increasing the temperature to 800 ℃, preserving the heat for 3 hours, and carrying out high-temperature carbonization;
and 4, taking out the substance carbonized at the high temperature, grinding the substance into powder by using a grinding dish, and controlling the particle size to be less than 1 mu m to obtain the conductive agent.
Example 6
The preparation method of kinds of conductive agents prepared by polyacrylonitrile gel comprises the following steps:
step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, wherein the mass of the N' N-dimethylformamide is 45 times that of the polyacrylonitrile fibers, and then placing the polyacrylonitrile fibers in an oven at the temperature of 80 ℃ for heat preservation for 20min to obtain a polyacrylonitrile solution;
and 2, slowly dripping polyacrylonitrile solution into deionized water, wherein the using amount of the deionized water is 3 times of the volume of the polyacrylonitrile solution, adding nickel phthalocyanine (M in the structural formula is Ni), and the mass ratio of the additive to the polyacrylonitrile is 1: 100, dropwise adding while stirring, and then centrifuging to obtain polyacrylonitrile gel;
step 3, placing polyacrylonitrile gel in a vacuum cracking furnace, raising the temperature to 110 ℃, preserving the heat for 20min, and dehydrating the gel; raising the temperature to 250 ℃ and preserving the temperature for 2 hours to ensure that polyacrylonitrile molecules are subjected to internal cyclization; then increasing the temperature to 420 ℃ and preserving the heat for 3h to carbonize the polyacrylonitrile at a low temperature; finally, increasing the temperature to 850 ℃ and preserving the heat for 3 hours to carry out high-temperature carbonization;
and 4, taking out the substance carbonized at the high temperature, grinding the substance into powder by using a grinding dish, controlling the particle size to be less than 1 mu m, and stirring at the speed of 1000-1500 r/min to obtain the conductive agent.
FIG. 1 shows the polyacrylonitrile conductive agent and CuCo prepared in case 4 of the present invention2S4The electron microscope picture of the electrode surface assembled by nano crystal grains shows that the larger particles circled in the picture are polyacrylonitrile conductive agent, and the rest are CuCo2S4And (4) nano-crystalline grains. The conductive agent is uniformly distributed in the CuCo2S4On the nanocrystal particle.
The conductive agents obtained in the above examples were tested and the results are shown in the following table and fig. 2:
Figure BDA0002233862300000061
the results in the above table and figure 2 show that: the best implementation method is adopted in the embodiment 4, and the prepared electrode has the advantages of good conductivity, large specific surface area and best conductive effect.

Claims (6)

  1. The conductive agent prepared from polyacrylonitrile gel is characterized by being prepared from an additive, polyacrylonitrile fibers, N' N-dimethylformamide and water according to a mass ratio of 1: 90-110: 4000-5000: 8000-25000, wherein the additive is iron phthalocyanine, cobalt phthalocyanine or nickel phthalocyanine.
  2. 2. The method for preparing kinds of conductive agents prepared from polyacrylonitrile gel according to claim 1, comprising the following steps:
    step 1, soaking polyacrylonitrile fibers in N 'N-dimethylformamide, and then placing the polyacrylonitrile fibers in a 75-85 ℃ oven for heat preservation for 15-25 min to obtain a polyacrylonitrile solution, wherein the mass of the N' N-dimethylformamide is 40-50 times that of the polyacrylonitrile fibers;
    slowly dripping a polyacrylonitrile solution into deionized water, adding the additive while stirring, and centrifuging to obtain polyacrylonitrile gel, wherein the mass ratio of the additive to polyacrylonitrile is 1: 90-110;
    and 3, performing heat treatment on the polyacrylonitrile gel: raising the temperature to 100-150 ℃, preserving heat for 10-60 min, raising the temperature to 200-300 ℃, preserving heat for 1-2 h, then increasing the temperature to 400-500 ℃, preserving heat for 3-4 h, and finally increasing the temperature to 800-900 ℃, preserving heat for 3-4 h;
    and 4, taking out the material subjected to the heat treatment in the step , and grinding the material into powder to obtain the conductive agent.
  3. 3. The method for preparing kinds of conductive agents prepared from polyacrylonitrile gel according to claim 2, wherein the stirring speed in the step 2 is 1000-1500 r/min.
  4. 4. The method for preparing kinds of conductive agents prepared from polyacrylonitrile gel according to claim 2, wherein the amount of deionized water used in step 2 is 3-4 times of the volume of polyacrylonitrile solution.
  5. 5. The method for preparing conductive agent from polyacrylonitrile gel according to claim 2, wherein the heat treatment process in step 3 is to raise the temperature to 100-120 ℃ and keep the temperature for 20-30 min, then raise the temperature to 240-280 ℃ and keep the temperature for 1-2 h, then raise the temperature to 400-420 ℃ and keep the temperature for 3-4 h, and finally raise the temperature to 800-850 ℃ and keep the temperature for 3-4 h.
  6. 6. The method for preparing kinds of conductive agents prepared from polyacrylonitrile gel according to claim 2, wherein the particle size of the powder in step 4 is less than or equal to 1 μm.
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