CN113248672A - Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof - Google Patents

Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof Download PDF

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Publication number
CN113248672A
CN113248672A CN202110711222.4A CN202110711222A CN113248672A CN 113248672 A CN113248672 A CN 113248672A CN 202110711222 A CN202110711222 A CN 202110711222A CN 113248672 A CN113248672 A CN 113248672A
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schiff base
electrode material
base polymer
preparation
polymer electrode
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聂王焰
张智
徐颖
周艺峰
陈鹏鹏
曾少华
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Anhui University
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Anhui University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention discloses a Schiff base polymer electrode material with increased capacity in a circulation process and a preparation method thereof. The preparation method of the organic electrode material provided by the invention has the advantages of simple process, environmental friendliness, low cost and easiness in large-scale production, and has great potential in application of slowing down the capacity fading effect in the cycle process of the lithium ion battery.

Description

Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a preparation method and application of an organic electrode material.
Background
Lithium ion batteries have dominated the portable electronics market and show great promise for large-scale applications, such as electric vehicles and smart grids. At present, the development of lithium ion batteries mainly relies on metal-containing electrode materials such as transition metal oxides. However, these transition metal oxides, including transition metal elements such as cobalt, nickel, and manganese, are limited due to their low abundance and high price, and may cause serious environmental problems. Therefore, the development of environment-friendly lithium ion battery electrode materials is always a research hotspot in the field of energy.
The organic electrode material has the advantages of low cost, environmental protection, adjustable structure and the like. The existing organic electrode material for the lithium ion battery has the problems of serious cycle performance and capacity attenuation, overhigh cost, low yield and the like caused by complex preparation process. Lithium ions react on redox active sites of the organic electrode material, so that the organic electrode material with a specific structure can be obtained by different preparation methods, and the lithium storage performance of the organic electrode material is further improved.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a Schiff base polymer electrode material with increased capacity in a circulation process and a preparation method thereof, and aims to obtain a lithium ion battery cathode material with excellent circulation stability and electrochemical performance.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of Schiff base polymer electrode material with increased capacity in the circulation process is characterized in that: the Schiff base polymer electrode material is prepared by taking melamine and monomers containing benzene ring aldehyde as raw materials and dimethyl sulfoxide as a solvent through Schiff base reaction. The method specifically comprises the following steps:
step 1, adding melamine and benzene-ring-containing aldehyde monomers into dimethyl sulfoxide, and performing ultrasonic treatment until the melamine and benzene-ring-containing aldehyde monomers are dissolved to obtain a mixed solution;
step 2, adding the mixed solution into a high-pressure reaction kettle, and carrying out a solvothermal reaction to obtain a reaction product;
and 3, freezing and drying the reaction product to obtain the Schiff base polymer electrode material.
Further, the benzene ring aldehyde monomer is benzaldehyde, terephthalaldehyde or m-phthalaldehyde.
Further, the molar ratio of the melamine to the aldehyde monomer is 1:0.75 to 1: 1.5.
Further, the temperature of the solvothermal reaction is 160-180 ℃ and the time is 12-24 h.
Further, the temperature of the freeze drying is-50 ℃ and the time is 24 hours.
The Schiff base polymer electrode material prepared by the preparation method can be used as a lithium ion battery cathode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method is simple and easy to operate, environment-friendly, low in cost and easy for large-scale production, and the organic electrode material prepared by the preparation method has the advantages of high specific surface area and multiple active sites, so that the cycling stability and the electrochemical performance of the organic electrode material when the organic electrode material is used as a lithium ion battery cathode material are greatly improved.
2. The organic electrode material provided by the invention is a polymer with a three-dimensional network structure formed by connecting the triazine ring and the benzene ring through Schiff base reaction, so that the solubility of the organic electrode material in an electrolyte is reduced, and the polymer has double reaction active sites of the triazine ring and the benzene ring, so that the lithium storage can be effectively realized, the irreversible capacity loss of a battery is reduced, the stability of the organic material is improved, and the electrode activation can be realized, so that the organic electrode material has the characteristic of continuously improving the specific capacity in the battery circulation process.
Drawings
FIG. 1 is an infrared spectrum of a Schiff base polymer in example 1 of the present invention;
FIG. 2 is a structural formula of Schiff base polymer obtained by the present invention;
FIG. 3 is a transmission electron micrograph of a Schiff base polymer in example 1 of the present invention;
FIG. 4 is a graph of rate capability of Schiff base polymers in example 1 of the present invention;
FIG. 5 is a graph of the cycling performance of the Schiff base polymer at a current density of 1A/g in example 1 of the present invention.
FIG. 6 is a cyclic voltammogram of a Schiff base polymer at a scan rate of 1mV/s in example 2 of the present invention;
FIG. 7 is a graph of rate capability of Schiff base polymers in example 2 of the present invention;
FIG. 8 is a graph of the cycling performance of the Schiff base polymer at a current density of 0.5A/g in example 2 of the present invention.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
Example 1
Weighing melamine and terephthalaldehyde according to a molar ratio of 1:0.75, adding the melamine and the terephthalaldehyde into a beaker filled with dimethyl sulfoxide, carrying out ultrasonic treatment for 1 hour to form a transparent solution, transferring the transparent solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and heating in a 160 ℃ oven for 12 hours to obtain a reaction product.
And after the reaction kettle is cooled to room temperature, transferring the reaction product into a watch glass, freezing the reaction product in a refrigerator, putting the reaction product into a freeze dryer, and freeze-drying the reaction product at-50 ℃ for 24 hours to obtain the Schiff base polymer.
FIG. 1 is an infrared spectrum of a Schiff base polymer obtained in this example, 1600cm-1～1400cm-1And 810cm-1The nearby peaks are characteristic signals of triazine ring and benzene ring structures respectively, which proves that the structural formula of the polymer of the alkali of Schiff in the embodiment is shown in FIG. 2.
Fig. 3 is a transmission electron microscope image of the schiff base polymer obtained in this embodiment, and it can be seen that the schiff base polymer is formed by aggregation of particles to form a three-dimensional porous network, which is beneficial to improvement of electrochemical performance.
The Schiff base polymer prepared in the embodiment is uniformly mixed with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 5:4:1, and a proper amount of N-methylpyrrolidone is added to be prepared into slurry. And uniformly coating the slurry on a copper foil by using a 200-micron scraper, and performing vacuum drying at 80 ℃ for 12 hours to obtain the Schiff base polymer pole piece.
Punching the prepared Schiff base polymer pole piece into a circular sheet with the diameter of 12 mm; taking a metal lithium sheet with the diameter of 16mm as a positive electrode and taking Celgard2400 as a diaphragm; dissolving electrolyte lithium hexafluorophosphate in a mixed solution of dimethyl carbonate and ethylene carbonate with the volume ratio of 1:1 to prepare 1mol/L electrolyte; and assembling the button cell in a glove box filled with argon. The button cell is tested in a charge-discharge voltage of 0.01-3V by adopting a NEWARE-CT-4008T cell testing system and a CHI660E electrochemical workstation.
Fig. 4 is a rate performance diagram of the button cell battery in this embodiment, and after cycling is performed at a plurality of different current densities of 0.1A/g, 0.3A/g, 0.5A/g, 1A/g, 3A/g, 5A/g and 10A/g, the capacity of the button cell battery can still be recovered to 453.6mAh/g, which indicates that the material has excellent cycling stability and rate performance.
Fig. 5 is a cycle performance diagram of the button cell in this embodiment at a current density of 1A/g, and it can be observed that the cycle performance is continuously improved, the first-cycle charge and discharge specific capacities are 85.1mAh/g and 102.5mAh/g, respectively, and the capacity is increased to 341mAh/g after 1000 cycles of cycle, which indicates that the schiff base polymer is activated in the cycle process, and the benzene ring and the triazine ring can provide more lithium intercalation sites, so that the schiff base polymer is different from a general electrode material in that the capacity is attenuated in the cycle process, but is continuously improved.
Example 2
Weighing melamine and terephthalaldehyde according to a molar ratio of 1:1.5, adding the melamine and the terephthalaldehyde into a beaker filled with dimethyl sulfoxide, carrying out ultrasonic treatment for 1 hour to form a transparent solution, transferring the transparent solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and heating the reaction kettle in an oven at 180 ℃ for 24 hours to obtain a reaction product.
And after the reaction kettle is cooled to room temperature, transferring the reaction product into a watch glass, freezing the reaction product in a refrigerator, putting the reaction product into a freeze dryer, and freeze-drying the reaction product at-50 ℃ for 24 hours to obtain the Schiff base polymer.
The Schiff base polymer prepared in the embodiment is uniformly mixed with conductive carbon black and polyvinylidene fluoride according to the mass ratio of 5:4:1, and a proper amount of N-methylpyrrolidone is added to be prepared into slurry. And uniformly coating the slurry on a copper foil by using a 200-micron scraper, and performing vacuum drying at 80 ℃ for 12 hours to obtain the Schiff base polymer pole piece.
Punching the prepared Schiff base polymer pole piece into a circular sheet with the diameter of 12 mm; taking a metal lithium sheet with the diameter of 16mm as a positive electrode and taking Celgard2400 as a diaphragm; dissolving electrolyte lithium hexafluorophosphate in a mixed solution of dimethyl carbonate and ethylene carbonate with the volume ratio of 1:1 to prepare 1mol/L electrolyte; and assembling the button cell in a glove box filled with argon. The button cell is tested in a charge-discharge voltage of 0.01-3V by adopting a NEWARE-CT-4008T cell testing system and a CHI660E electrochemical workstation.
Fig. 6 is a cyclic voltammetry curve of the button cell in this example, it can be observed that the CV curves almost overlap after the second cycle, and there is a pair of oxidation peak and reduction peak around 1V, which indicates that the redox reaction occurring on the schiff base polymer has high stability and reversibility.
Fig. 7 is a rate performance graph of the button cell battery in this embodiment, and after cycling is performed at a plurality of different current densities of 0.1A/g, 0.3A/g, 0.5A/g, 1A/g, 3A/g, 5A/g, and 10A/g, the capacity of the button cell battery can still be recovered to 322.8mAh/g, which indicates that the material has excellent cycling stability and rate performance.
Fig. 8 is a cycle performance diagram of the button cell in this embodiment at a current density of 0.5A/g, from which it can be observed that the cycle performance shows an oscillatory increase, which indicates that the schiff base polymer is activated during the cycle, and the double active sites of the benzene ring and the triazine ring can provide more lithium intercalation sites, so that the schiff base polymer is different from a general electrode material in that the capacity of the schiff base polymer is attenuated during the cycle, but is continuously increased.
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 (8)

1. A preparation method of Schiff base polymer electrode material with increased capacity in the circulation process is characterized in that: the Schiff base polymer electrode material is prepared by taking melamine and monomers containing benzene ring aldehyde as raw materials and dimethyl sulfoxide as a solvent through Schiff base reaction.
2. The method of claim 1, comprising the steps of:
step 1, adding melamine and benzene-ring-containing aldehyde monomers into dimethyl sulfoxide, and performing ultrasonic treatment until the melamine and benzene-ring-containing aldehyde monomers are dissolved to obtain a mixed solution;
step 2, adding the mixed solution into a high-pressure reaction kettle, and carrying out a solvothermal reaction to obtain a reaction product;
and 3, freezing and drying the reaction product to obtain the Schiff base polymer electrode material.
3. The production method according to claim 1 or 2, characterized in that: the benzene ring aldehyde monomer is benzaldehyde, terephthalaldehyde or m-phthalaldehyde.
4. The production method according to claim 1 or 2, characterized in that: the molar ratio of the melamine to the aldehyde monomer is 1: 0.75-1: 1.5.
5. The method of claim 2, wherein: the temperature of the solvothermal reaction is 160-180 ℃, and the time is 12-24 h.
6. The method of claim 2, wherein: the temperature of the freeze drying is-50 ℃ and the time is 24 hours.
7. A Schiff base polymer electrode material prepared by the preparation method of any one of claims 1 to 6.
8. Use of the schiff base polymer electrode material of claim 7 in a negative electrode material of a lithium ion battery.
CN202110711222.4A 2021-06-25 2021-06-25 Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof Pending CN113248672A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773555A (en) * 2022-05-19 2022-07-22 安徽大学 Pre-lithiation modified Schiff base polymer electrode material and preparation method thereof

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CN104332596A (en) * 2014-10-22 2015-02-04 国家纳米科学中心 Nitrogen-enriched porous material/carbon nano structure composite material as well as preparation method and application thereof
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CN111205460A (en) * 2020-01-08 2020-05-29 吉林大学 Polyimide-structured organic Schiff base polymer lithium ion battery cathode material, and preparation method and application thereof

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CN104332596A (en) * 2014-10-22 2015-02-04 国家纳米科学中心 Nitrogen-enriched porous material/carbon nano structure composite material as well as preparation method and application thereof
CN106882783A (en) * 2015-12-10 2017-06-23 中科派思储能技术有限公司 A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis
CN111205460A (en) * 2020-01-08 2020-05-29 吉林大学 Polyimide-structured organic Schiff base polymer lithium ion battery cathode material, and preparation method and application thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773555A (en) * 2022-05-19 2022-07-22 安徽大学 Pre-lithiation modified Schiff base polymer electrode material and preparation method thereof
CN114773555B (en) * 2022-05-19 2024-03-26 安徽大学 Pre-lithiation modified Schiff base polymer electrode material and preparation method thereof

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