CN110148720B - Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof - Google Patents

Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof Download PDF

Info

Publication number
CN110148720B
CN110148720B CN201910393397.8A CN201910393397A CN110148720B CN 110148720 B CN110148720 B CN 110148720B CN 201910393397 A CN201910393397 A CN 201910393397A CN 110148720 B CN110148720 B CN 110148720B
Authority
CN
China
Prior art keywords
schiff base
electrode material
composite electrode
crystal structure
base polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910393397.8A
Other languages
Chinese (zh)
Other versions
CN110148720A (en
Inventor
杨应奎
张建业
韩小彦
李红
章庆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South Central Minzu University
Original Assignee
South Central University for Nationalities
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South Central University for Nationalities filed Critical South Central University for Nationalities
Priority to CN201910393397.8A priority Critical patent/CN110148720B/en
Publication of CN110148720A publication Critical patent/CN110148720A/en
Application granted granted Critical
Publication of CN110148720B publication Critical patent/CN110148720B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a Schiff base polymer/carbon nano tube composite electrode material with a string crystal structure and a preparation method thereof, the composite electrode material is prepared by one-step solvothermal reaction of dialdehyde, diamine and acidified carbon nano tubes, the dialdehyde and the diamine are used as monomers for synthesizing the Schiff base polymer, the total solubility is 0.001-2 mol/L, and the content of the carbon nano tubes in the product is 2.5-50 wt.%. The method has simple reaction and high yield, does not pollute the environment by-product water, can particularly promote Schiff base to uniformly embed and grow on the carbon nano tube to form a polymer with a string crystal structure, exposes more lithium ion binding sites, greatly increases the specific surface area of the material, ensures that the electrolyte is more fully contacted with the material, increases the conductive capacity of the material after the carbon nano tube is compounded, and has the advantages of good structural stability, high specific capacity, good rate capability and the like.

Description

Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof
Technical Field
The invention belongs to the field of electrode materials, and particularly relates to a Schiff base polymer/carbon nanotube composite electrode material with a string crystal structure and a preparation method thereof.
Background
In recent years, the use of fossil fuels in large quantities has caused great damage to the environment. Therefore, it is particularly important to develop clean new energy storage and conversion technology. In recent years, secondary batteries have attracted extensive attention and research. Among them, the lithium ion battery, as a novel secondary battery, has the advantages of environmental protection, long cycle life, good rate performance, no memory effect, high energy density, etc., and has been widely used commercially. At present, the lithium ion battery is not only applied to small electronic products, but also widely applied to new energy electric vehicles and military industries.
Currently, commercial lithium ion batteries basically use graphite as a negative electrode material. The graphite material has good conductivity, higher crystallinity and good layered structure, and is suitable for the intercalation-deintercalation of lithium. However, the theoretical specific capacity of graphite is low (372mAh/g), which greatly restricts the development of lithium ion batteries. Traditional inorganic materials can also be used as negative electrode materials of lithium batteries, but the electrode materials have poor flexibility and can cause crystal structure damage during large-current discharge, so that poor cycle and rate performance is caused, and the materials belong to non-renewable resources and can cause harm to the environment during mining.
In contrast, the organic material with electrochemical activity belongs to renewable resources, and has the advantages of good molecular flexibility, adjustable structure and the like, thereby being a good electrode material. However, these molecules are readily soluble in organic electrolytes and have slow reaction kinetics. Therefore, the high polymer with electrochemical activity obtained by design synthesis is a good method. Among the high polymers, the Schiff base has the advantages of simple synthesis, good thermodynamic stability and the like, and can be widely applied to lithium ion battery cathode materials. However, current research shows that schiff base polymers have poor conductivity and are easy to stack, so that the specific surface area of the polymers is small, the utilization rate of functional groups is low, and therefore, the capacity is low, and the application of the schiff base polymers is limited.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a schiff base polymer/carbon nanotube composite electrode material having a string crystal structure with excellent electrical properties, and a method for preparing the same.
In order to achieve the purpose, the invention adopts the following scheme:
< composite electrode Material >
The invention provides a Schiff base polymer/carbon nano tube composite electrode material with a string crystal structure, which is characterized in that: the preparation method comprises the steps of carrying out solvothermal reaction on dialdehyde, diamine and an acidified carbon nano tube to obtain the Schiff base polymer, wherein in a reaction solution, the dialdehyde and the diamine are used as monomers for synthesizing the Schiff base polymer, and the total solubility of the monomers is 0.001-2.0 mol/L; in the composite electrode material, the content of the carbon nano tube is 2.5-50 wt.%.
Preferably, the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: the dialdehyde is any one of terephthalaldehyde, m-phthalaldehyde, o-phthalaldehyde and 2, 3-naphthaldehyde.
Preferably, the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: the diamine is at least one of 2, 6-diaminoanthraquinone, p-phenylenediamine, ethylenediamine, 1, 3-diaminopropane, 1, 2-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 8-diaminooctane and 1, 10-diaminodecane.
Preferably, the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube.
Preferably, the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: the reaction solvent is at least one of water, ethanol, p-xylene, toluene, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and acetic acid.
< preparation method >
The invention also provides a preparation method of the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure, which is characterized by comprising the following steps of: the preparation method comprises the steps of carrying out solvothermal reaction on dialdehyde, diamine and an acidified carbon nano tube to obtain the polymer, wherein in a reaction solution, the dialdehyde and the diamine in equal molar ratio are used as monomers for synthesizing the Schiff base polymer, and the total solubility of the monomers is 0.001-2.0 mol/L; the content of the carbon nano tube in the composite electrode material is 2.5-50 wt.%.
Preferably, the preparation method of the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: ultrasonically dispersing the acidified carbon nano tube in a solvent for a period of time, then filling inert gas for protection, adding dialdehyde under stirring, and adding diamine after the dialdehyde is dissolved; and then carrying out solvothermal reaction, carrying out suction filtration separation after the reaction is finished, and drying to obtain the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure. The inert gas may be nitrogen or argon.
Preferably, the preparation method of the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: the time of ultrasonic dispersion is 1-60 min.
Preferably, the preparation method of the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: the drying temperature is 60-120 ℃.
Preferably, the preparation method of the schiff base polymer/carbon nanotube composite electrode material with the string crystal structure provided by the invention can also have the following characteristics: the reaction temperature of the solvothermal reaction is 0-180 ℃, and the reaction time is 1-72 h.
Action and Effect of the invention
The invention provides a Schiff base polymer/carbon nano tube composite electrode material with a string crystal structure, which is synthesized by solvothermal reaction in one step, and has the advantages of simple reaction, high yield and no pollution of byproduct water to the environment. The Schiff base is uniformly embedded and grown on the carbon nano tube to form the polymer with the string crystal structure. The structure not only exposes more lithium ion binding sites, but also greatly increases the specific surface area of the material, so that the electrolyte is more fully contacted with the material, and the conductivity of the material is increased after the carbon nano tube is compounded, so that the lithium ion battery can be used. The Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure prepared by the invention has the advantages of good structural stability, high specific capacity, good rate capability and the like.
Drawings
Fig. 1 is a scanning electron microscope image of the schiff base polymer/carbon nanotube composite electrode material with a tandem crystal structure prepared in the first embodiment;
fig. 2 is a graph of electrochemical test cycle performance of the schiff base polymer/carbon nanotube composite electrode material with the tandem structure prepared in the first example and the pure schiff base prepared in the comparative example;
fig. 3 is a pure schiff base electrochemical test rate performance graph of the schiff base polymer/carbon nanotube composite electrode material with the tandem structure prepared in the first embodiment and the pure schiff base prepared in the comparative example;
FIG. 4 is a scanning electron micrograph of pure Schiff base prepared in the comparative example.
Detailed Description
The following describes in detail specific embodiments of the schiff base polymer/carbon nanotube composite electrode material with a string crystal structure according to the present invention with reference to the accompanying drawings.
< example one >
The preparation method comprises the following steps:
1) 0.0608 acidified carbon nanotubes were weighed into a 250mL round bottom flask, 80mL toluene was added, and the mixture was sonicated for 30min to fully disperse the carbon nanotubes.
2) 0.3357g of terephthalaldehyde was added to the round bottom flask and the stirring was turned on to dissolve the terephthalaldehyde completely.
3) 0.2708g of p-phenylenediamine were added, and the mixture was heated to 150 ℃ under reflux for 6 hours while stirring under argon.
4) After the reaction is finished, the heating is closed, the stirring is stopped after the solution is cooled to the room temperature, the pressure reduction and the suction filtration are carried out, and the product is fully washed by ethanol; and drying the product at 80 ℃ for 12h, and collecting the product as black solid powder, namely the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure.
In the composite electrode material prepared in the first embodiment, the mass ratio of the schiff base polymer to the carbon nanotubes is about 10: 1.
And (3) performance characterization:
as shown in fig. 1, from the scanning electron microscope picture of the composite electrode material, it can be found that schiff base shish is uniformly coated on the surface of the carbon nanotube. The structure is beneficial to improving the specific surface area, increasing the ion transmission speed and the electrochemical reaction active sites, improving the utilization rate of the active material and further improving the rate capability and the specific capacity of the active material.
In addition, in order to test the electrochemical performance of the composite electrode material, the prepared composite electrode material, a conductive additive (SP) and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 6:3:1, the mixture is uniformly ground, then a proper amount of N-methyl-2-pyrrolidone (NMP) is added, the mixture is ground again to enable the slurry concentration to be proper, the mixture is uniformly coated on a carbon-coated copper foil (current collector) by an automatic coating machine, the thickness of a coating film is adjusted according to actual conditions, and the mass of a polymer on a pole piece is controlled to be about 1.0 mg. The coated film was pre-dried at 50 ℃ and then dried in a vacuum oven at 80 ℃ for 12 h. After drying, the sample film is compressed by a roller press to avoid the sample falling off. The films were cut into 10mm diameter pole pieces using a microtome, and then assembled in an empty glove box using 1M LiPF6 as the electrolyte for the assembled cell (EC: DMC 2: 1). And packaging the assembled battery by using a button cell automatic sealing machine, standing for 12 hours, and then carrying out electrochemical test.
The test results are shown in fig. 2 and 3, and after 60 cycles, the specific capacity of the schiff base/carbon nanotube composite electrode material with the tandem structure is 395mAh/g (the current density is 100mA/g), and the retention rate is 32.3% (100 mA/g-5A/g).
< example two >
The preparation method comprises the following steps:
1) 0.1212 of acidified carbon nano-tube is weighed and added into a 250mL round-bottom flask, 80mL toluene is added, and the carbon nano-tube is fully dispersed by ultrasonic treatment for 30 min.
2) 0.3357g of terephthalaldehyde was added to the round bottom flask and the stirring was turned on to dissolve the terephthalaldehyde completely.
3) 0.2708g of p-phenylenediamine were added, and the mixture was heated to 150 ℃ under reflux for 6 hours while stirring under argon.
4) After the reaction is finished, the heating is closed, the stirring is stopped after the solution is cooled to the room temperature, the pressure reduction and the suction filtration are carried out, and the product is fully washed by ethanol; and drying the product at 80 ℃ for 12h, and collecting the product as black solid powder, namely the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure.
In the composite electrode material prepared in the second embodiment, the mass ratio of the schiff base polymer to the carbon nanotubes is about 10: 2.
Performance characterization (test method same as example one):
scanning electron microscope pictures of the composite electrode material can confirm that Schiff base crystal strings are uniformly coated on the surface of the carbon nano tube.
After the composite electrode material is assembled into a battery, the electrochemical performance of the battery is tested, and the specific capacity of the battery after 60 cycles is 520mAh/g (the current density is 100mA/g), and the retention rate is 35.3% (100 mA/g-5A/g).
As shown in table 1 below, the data of the above examples one and two and the following comparative examples are compared: compared with pure Schiff base polymers, the Schiff base/carbon nanotube composite has better electrochemical performance, and the specific capacity and rate capability of the composite are greatly improved along with the increase of the content of the carbon nanotubes.
Figure BDA0002057339290000081
< example three >
The preparation method comprises the following steps:
1) 0.0971g of acidified carbon nanotubes were weighed into a 250mL round bottom flask, 80mL of ethanol was added, and the mixture was sonicated for 30min to fully disperse the carbon nanotubes.
2) 0.3357g of terephthalaldehyde was added to the round bottom flask and the stirring was turned on to dissolve the terephthalaldehyde completely.
3) Then 170. mu.L of ethylenediamine was added, the argon gas was turned on under stirring, and the mixture was heated to 80 ℃ and refluxed for 6 hours.
4) After the reaction is finished, the heating is closed, the stirring is stopped after the solution is cooled to the room temperature, the pressure reduction and the suction filtration are carried out, and the product is fully washed by ethanol; and drying the product at 80 ℃ for 12h, and collecting the product as black solid powder, namely the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure.
< example four >
The preparation method comprises the following steps:
1) 0.1109g of carbon nanotubes are weighed into a 250mL round bottom flask, 80mL of ethanol is added, and the mixture is subjected to ultrasonic treatment for 30min to fully disperse the carbon nanotubes.
2) 0.3357g of terephthalaldehyde was added to the round bottom flask and the stirring was turned on to dissolve the terephthalaldehyde completely.
3) Then 255 μ L of butanediamine was added, argon was turned on under stirring, and the mixture was heated to 60 ℃ and refluxed for 6 hours.
4) After the reaction is finished, the heating is closed, the stirring is stopped after the solution is cooled to the room temperature, the pressure reduction and the suction filtration are carried out, and the product is fully washed by ethanol; and drying the product at 80 ℃ for 12h, and collecting the product as black solid powder, namely the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure.
< example five >
The preparation method comprises the following steps:
1) 1.0112g of carbon nanotubes are weighed into a 250mL round bottom flask, 140mL of dimethyl sulfoxide is added, and the mixture is subjected to ultrasonic treatment for 30min to fully disperse the carbon nanotubes.
2) 0.4154g of 2, 5-dihydroxy terephthalaldehyde was added to the round bottom flask and the stirring was started to dissolve the 2, 5-dihydroxy terephthalaldehyde completely.
3) 0.5956g of 2, 6-diaminoanthraquinone are then added, the argon shield is turned on with stirring, and the mixture is heated to 180 ℃ and refluxed for 72 hours.
4) After the reaction is finished, the heating is closed, the stirring is stopped after the solution is cooled to the room temperature, the pressure reduction and the suction filtration are carried out, and the product is fully washed by ethanol; and drying the product at 80 ℃ for 12h, and collecting the product as black solid powder, namely the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure.
< example six >
The preparation method comprises the following steps:
1) 0.2130g of carbon nanotubes are weighed into a 250mL round bottom flask, 100mL of N, N-dimethylformamide is added, and the mixture is sonicated for 30min to fully disperse the carbon nanotubes.
2) 0.4154g of 2, 5-dihydroxy terephthalaldehyde was added to the round bottom flask and the stirring was started to dissolve the 2, 5-dihydroxy terephthalaldehyde completely.
3) 0.5960g of 2, 6-diaminoanthraquinone is added, argon protection is started under stirring, and reaction is carried out for 6h at 150 ℃.
4) After the reaction is finished, the heating is closed, the stirring is stopped after the solution is cooled to the room temperature, the pressure reduction and the suction filtration are carried out, and the product is fully washed by ethanol; and drying the product at 60 ℃ for 15h, and collecting the product as black solid powder, namely the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure.
< example seven >
The preparation method comprises the following steps:
1) 0.1532g of carbon nanotubes are weighed into a 250mL round bottom flask, 80mL of ethanol is added, and the mixture is subjected to ultrasonic treatment for 30min to fully disperse the carbon nanotubes.
2) 0.3357g of terephthalaldehyde was added to the round bottom flask and the stirring was turned on to dissolve the terephthalaldehyde completely.
3) 0.4308g of sebacic diamine are added, argon protection is turned on under stirring, and reaction is carried out for 6h at 0 ℃.
4) After the reaction is finished, stopping stirring, performing vacuum filtration, and fully washing the product by using ethanol; and drying the product at 60 ℃ for 12h, and collecting the product as black solid powder, namely the Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure.
< comparative example >
The comparative example is a Schiff base polymer synthesized by a solvothermal method.
The preparation method comprises the following steps:
1) 0.3354g of terephthalaldehyde was weighed into a 250mL round bottom flask, 80mL of toluene was added, and stirring was started to dissolve the terephthalaldehyde completely.
2) 0.2708g of p-phenylenediamine were weighed into a round bottom flask, and heated to 150 ℃ under reflux for 6 hours with stirring and argon blanketing turned on.
3) After the reaction is finished, the heating is closed, the stirring is stopped after the solution is cooled to the room temperature, the pressure reduction and the suction filtration are carried out, and the product is fully washed by ethanol; and drying the product at 80 ℃ for 12h, and collecting the product as bright yellow solid powder, namely the pure Schiff base polymer.
And (3) performance characterization:
mixing the prepared pure Schiff base polymer with a conductive additive (SP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 6:3:1, grinding uniformly, adding a proper amount of N-methyl-2-pyrrolidone (NMP), grinding again to enable the concentration of slurry to be proper, uniformly coating the slurry on a carbon-coated copper foil (current collector) by using an automatic coating machine, adjusting the thickness of a coating film according to actual conditions, and controlling the mass of the polymer on a pole piece to be about 1.0 mg. The coated film was pre-dried at 50 ℃ and then dried in a vacuum oven at 80 ℃ for 12 h. After drying, the sample film is compressed by a roller press to avoid the sample falling off. The films were cut into 10mm diameter pole pieces using a microtome, and then assembled in an empty glove box using 1M LiPF6 as the electrolyte for the assembled cell (EC: DMC 2: 1). And packaging the assembled battery by using a button cell automatic sealing machine, standing for 12 hours, and then carrying out electrochemical test.
As shown in fig. 4, the pure schiff base polymer sheet is relatively thick, which is not favorable for its effective utilization. The specific capacity after 60 cycles is 230mAh/g (the current density is 100mA/g), and the retention rate is only 17.7% (100 mA/g-5A/g).
The above embodiments are merely illustrative of the technical solutions of the present invention. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure and the preparation method thereof according to the present invention are not limited to the description in the above embodiments, but are subject to the scope defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.

Claims (8)

1. The Schiff base polymer/carbon nano tube composite electrode material with the string crystal structure for the lithium ion battery is characterized in that:
ultrasonically dispersing the acidified carbon nano tube in a solvent for a period of time, then filling inert gas for protection, adding dialdehyde under stirring, and adding diamine after the dialdehyde is dissolved; then, dialdehyde, diamine and acidified carbon nano-tubes are subjected to solvothermal reaction to prepare the polymer, Schiff bases are uniformly embedded and grow on the carbon nano-tubes to form a polymer with a string crystal structure,
in the reaction solution, dialdehyde and diamine are used as monomers for synthesizing the Schiff base polymer, and the total solubility of the monomers is 0.001-2.0 mol/L; in the composite electrode material, the content of the carbon nano tube is 2.5-50 wt.%.
2. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure for a lithium ion battery according to claim 1, wherein:
wherein the dialdehyde is any one of terephthalaldehyde, m-phthalaldehyde, o-phthalaldehyde and 2, 3-naphthaldehyde.
3. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure for a lithium ion battery according to claim 1, wherein:
wherein the diamine is at least one of 2, 6-diaminoanthraquinone, p-phenylenediamine, ethylenediamine, 1, 3-diaminopropane, 1, 2-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 8-diaminooctane and 1, 10-diaminodecane.
4. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure for a lithium ion battery according to claim 1, wherein:
wherein the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube.
5. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure for a lithium ion battery according to claim 1, wherein:
wherein, in the reaction solution, at least one of water, ethanol, p-xylene, toluene, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and acetic acid is adopted as a solvent.
6. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure for a lithium ion battery according to claim 1, wherein:
wherein the time of ultrasonic dispersion is 1-60 min.
7. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure for a lithium ion battery according to claim 1, wherein:
wherein, after the solvothermal reaction is finished, the mixture is filtered and dried, and the drying temperature is 60-120 ℃.
8. The schiff base polymer/carbon nanotube composite electrode material with a string crystal structure for a lithium ion battery according to claim 1, wherein:
wherein the reaction temperature of the solvothermal reaction is 0-180 ℃, and the reaction time is 1-72 h.
CN201910393397.8A 2019-05-13 2019-05-13 Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof Active CN110148720B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910393397.8A CN110148720B (en) 2019-05-13 2019-05-13 Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910393397.8A CN110148720B (en) 2019-05-13 2019-05-13 Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110148720A CN110148720A (en) 2019-08-20
CN110148720B true CN110148720B (en) 2021-07-06

Family

ID=67595181

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910393397.8A Active CN110148720B (en) 2019-05-13 2019-05-13 Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110148720B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114075346A (en) * 2020-08-17 2022-02-22 安徽璜峪电磁技术有限公司 Preparation method of poly-Schiff base cerium salt hybrid graphene composite foam wave-absorbing material containing quinone structure

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070053825A1 (en) * 2005-04-29 2007-03-08 Li Christopher Y Modified carbon nanotubes using controlled polymer crystallization
CN101177527B (en) * 2007-11-16 2010-07-07 东华大学 Method for preparing carbon nano-tube/polyimide composite material
CN102134342B (en) * 2010-12-07 2013-01-02 杭州福膜新材料科技有限公司 Crosslinking polyolefin microporous membrane and preparation method thereof
CN102175732B (en) * 2010-12-08 2013-06-19 桂林理工大学 Preparation method of carbon nano tube electrode modified by Schiff base coordination compounds
CN102295775B (en) * 2011-06-09 2012-10-10 黑龙江大学 Carbon nanotube/poly Schiff base polymer, preparation method thereof, and application thereof
CN105482051A (en) * 2015-12-11 2016-04-13 中国科学院化学研究所 Schiff base-type conjugated polymer thermoelectric material, and preparation method thereof

Also Published As

Publication number Publication date
CN110148720A (en) 2019-08-20

Similar Documents

Publication Publication Date Title
CN103199258B (en) Anode material for lithium-ion batteries, anode preparation method and lithium ion battery
US9437870B2 (en) Nano-silicon composite lithium ion battery anode material coated with poly (3,4-ethylenedioxythiophene) as carbon source and preparation method thereof
CN109103399B (en) Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery
CN106848202B (en) Preparation method of lithium ion battery negative plate
WO2013097553A1 (en) Lithium ion battery composite electrode material immersed and coated by conducting polymer and preparation method thereof
CN109546137B (en) Carbon-based supported polyimide array and preparation method and energy storage application thereof
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN110190284B (en) Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof
CN103074007A (en) Water-based adhesive used in silicon anode of lithium ion battery and preparation method of silicon anode
CN110061239A (en) Lignin-based binder, preparation method thereof and lithium ion battery
CN111697231B (en) Natural aqueous sulfur positive electrode binder, preparation method thereof and application of binder in preparation of sulfur positive electrode of lithium-sulfur battery
CN112038637B (en) Composite conductive agent, preparation method thereof and lithium ion battery
CN113690420B (en) Nitrogen-sulfur doped silicon-carbon composite material and preparation method and application thereof
CN112751008B (en) Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof
CN110148720B (en) Schiff base polymer/carbon nano tube composite electrode material with string crystal structure and preparation method thereof
CN103730664A (en) Positive electrode material of lithium sulfur battery and preparation method and application of material
CN104393299B (en) Nano-silicon polythiophene conductive composite for lithium ion battery and preparation method thereof
CN113562719A (en) Nano SnO2Preparation method of water-soluble asphalt carbon composite electrode negative electrode material
CN105895878A (en) Lithium titanate modified material and preparation method thereof
CN112736234A (en) Novel lithium ion battery cathode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof
CN109167024A (en) The graphene oxide and preparation method thereof that more carbonyls for electrode material of lithium battery are modified
Liang et al. N-doped C/Si@ damo composite material using PVP as the carbon source for lithium-ion batteries anode
CN112310398A (en) Electrode binder and silicon composite electrode
CN1597781A (en) Nano composite of polypyrrole / carbon black and preparation process thereof
CN113054182B (en) Graft copolymer coated silicon-based material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant