CN108615867B - Organic macromolecular negative electrode material for secondary battery and preparation method thereof - Google Patents

Organic macromolecular negative electrode material for secondary battery and preparation method thereof Download PDF

Info

Publication number
CN108615867B
CN108615867B CN201810420792.6A CN201810420792A CN108615867B CN 108615867 B CN108615867 B CN 108615867B CN 201810420792 A CN201810420792 A CN 201810420792A CN 108615867 B CN108615867 B CN 108615867B
Authority
CN
China
Prior art keywords
graphene oxide
metal phthalocyanine
secondary battery
organic macromolecular
negative electrode
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
CN201810420792.6A
Other languages
Chinese (zh)
Other versions
CN108615867A (en
Inventor
薛卫东
王源
杨琪
赵睿
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.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
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 University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN201810420792.6A priority Critical patent/CN108615867B/en
Publication of CN108615867A publication Critical patent/CN108615867A/en
Application granted granted Critical
Publication of CN108615867B publication Critical patent/CN108615867B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses an organic macromolecular negative electrode material for a secondary battery and a preparation method thereof, wherein the organic macromolecular negative electrode material is a multilayer composite structure formed by alternately overlapping metal phthalocyanine tetrasulfonic acid tetrasalt lamella and graphene oxide lamella, the mass ratio of the metal phthalocyanine tetrasulfonic acid tetrasalt lamella to the graphene oxide lamella is (1-4): 1, and the thickness of the multilayer composite structure is 2-20 mu m. The metal phthalocyanine tetrasulfonate is adopted, graphene oxide is used as a template agent, and the metal phthalocyanine tetrasulfonate is synthesized in one step by a hydrothermal ultrasonic oscillation method. The product can solve the problem of dissolving in electrolyte in the electrochemical reaction process, and simultaneously greatly enhances the conductivity after compounding; and the energy storage performance of the material for the secondary battery system is excellent and exceeds that of most organic electrode materials.

Description

Organic macromolecular negative electrode material for secondary battery and preparation method thereof
Technical Field
The invention relates to the technical field of cathode materials of secondary batteries, in particular to an organic macromolecular cathode material for a secondary battery and a preparation method thereof.
Background
Secondary batteries, represented by lithium ion batteries, are considered as the most promising energy storage devices in electric vehicles and portable electronic devices, and have excellent energy storage performance and high energy density. Currently, most secondary batteries employ inorganic materials as commercial electrode materials, such as LiCoO2And LiFePO4. However, the exhaustion of resources and the serious environmental pollution make the energy resources incapable of being continuously or circularly utilized, and the energy resources far from meeting the increasing demands of the energy market. Ever since williams et al used organic electrode materials for the first time in 1969, they have attracted much attention due to their abundant natural resources, environmental friendliness, and organic molecular diversity. Organic battery materials may be the best choice for the next generation of green sustainable low cost batteries.
Organic electrode Materials such as reducing agent green (W Ai, W Zhou, Z Du, et al. (2017) heated High Energy Organic catalysts for Li-Ion Batteries: A Case Study of Vat Dye/Graphene Composites Advanced Functional Materials 27.), Organic Nanohybrids (M Lee, J Hong, H Kim, et al. (2014) Organic Nanohybrids for Fast and stable Energy Storage Adv. Material 26:2558.), quinone derivatives (T Nokami, T Matsuo, Y Inatomi, et al. (2012) Polymer-Bound Dye-4, 5,9,10-tetra for Fast-channel media and calcium additive 134. the invention is not limited to the above-mentioned Materials. However, organic battery materials still have some common problems that prevent them from further development. First, organic electrode materials have poor chemical stability, and due to similar compatibility, they are very easily dissolved in organic electrolytes, resulting in gradual capacity fading of batteries during long-term electrochemical reaction, making it difficult to meet the commercialization requirements; second, most organic materials have poor conductivity in a battery system, and the actual specific capacity of the organic battery cannot be fully utilized in an electrochemical reaction system.
Disclosure of Invention
Aiming at the problems that the organic electrode material has poor chemical stability, the battery capacity is gradually attenuated, and the actual specific capacity of the organic battery cannot be fully utilized due to poor conductivity, the invention provides an organic macromolecular negative electrode material for a secondary battery and a preparation method thereof.
The technical scheme of the first aspect of the invention is that the organic macromolecular negative electrode material for the secondary battery is a multilayer composite structure formed by alternately overlapping metal phthalocyanine tetrasulfonate lamella and graphene oxide lamella, the mass ratio of the metal phthalocyanine tetrasulfonate lamella to the graphene oxide lamella is (1-4): 1, and the thickness of the multilayer composite structure is 2-20 um.
The metal phthalocyanine tetrasulfonic acid tetrasodium salt is a phthalocyanine derivative which is used as one of organic macromolecular dyes, has a special two-dimensional conjugated pi electron structure and high photo-thermal stability. The method is widely applied to the fields of optical devices, electrochemical reduction of carbon dioxide, electrochemical sensors, coloring agents and the like. The applicant creatively discovers that the metal phthalocyanine tetrasulfonic acid tetrasulfonate not only can be applied to the field, but also can be used for a secondary battery system, and the problem that the metal phthalocyanine tetrasulfonate is dissolved in an electrolyte in the electrochemical reaction process is radically solved as the metal phthalocyanine tetrasulfonate is an organic salt and is not dissolved in an organic solvent; the graphene oxide/graphene composite material is compounded with graphene oxide to form a multilayer composite structure, so that the conductivity of the graphene oxide/graphene composite material can be greatly enhanced while the original structure is not damaged, the graphene oxide/graphene composite material can be in contact with more active sites in an electrochemical reaction, the capacity of the graphene oxide/graphene composite material can be fully utilized, and the graphene oxide/graphene composite material is used for a secondary battery system, has excellent energy storage performance and exceeds most organic electrode materials.
According to the second technical scheme, the preparation method of the organic macromolecular negative electrode material for the secondary battery comprises the steps of taking metal phthalocyanine tetrasulfonate, taking graphene oxide as a template agent, and adopting a hydrothermal ultrasonic oscillation method to synthesize a metal phthalocyanine tetrasulfonate and graphene oxide compound in one step to obtain the organic macromolecular negative electrode material.
Preferably, the one-step synthesis of the metal phthalocyanine tetrasulfonate and graphene oxide compound by the hydrothermal ultrasonic oscillation method specifically comprises the following steps: adding metal phthalocyanine tetrasulfonate into deionized water to be completely dissolved to obtain a metal phthalocyanine tetrasulfonate solution, adding oxidized graphene into a mixed solution of ethanol and water, uniformly oscillating by ultrasonic waves to obtain a graphene oxide mixed solution, uniformly mixing the metal phthalocyanine tetrasulfonate solution and the graphene oxide mixed solution, carrying out hydrothermal compounding, and carrying out freeze drying to obtain the metal phthalocyanine tetrasulfonate and graphene oxide compound.
Wherein, the graphene oxide is prepared by a flake graphite freeze-drying method.
Preferably, the metal phthalocyanine tetrasulfonic acid tetrasodium salt is any one of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and nickel II phthalocyanine tetrasulfonic acid tetrapotassium salt.
Preferably, the mass ratio of the metal phthalocyanine tetrasulfonic acid tetrasalt to the graphene oxide is (1-4): 1.
Preferably, the mixed solution of ethanol and water is prepared by mixing (1-8): 1 and water.
Preferably, the temperature of the ultrasonic oscillation is 20-50 ℃, and the time is 0.3-0.5 h.
Preferably, the temperature of the hydrothermal compounding is 120-250 ℃, and the time is 12-24 h.
More preferably, the temperature of the hydrothermal compounding is 160-200 ℃, and the time is 12-24 h.
Preferably, the mixing time of the metal phthalocyanine tetrasulfonic acid tetrasulfonate solution and the graphene oxide mixed solution is 4-5 h.
Preferably, the secondary battery is any one of a lithium battery, a sodium battery, and a potassium battery.
Based on the above explanation, compared with the prior art, the invention has the beneficial effects that: (1) the metal phthalocyanine tetrasulfonic acid tetrasulfonate is an organic salt and is insoluble in an organic solvent, so that the problem that the metal phthalocyanine tetrasulfonate is dissolved in electrolyte in the electrochemical reaction process is radically solved; (2) the original structure is not damaged in the process of physical compounding with the graphene oxide, the conductivity of the graphene oxide is greatly enhanced after compounding, the graphene oxide can be contacted with more active sites in an electrochemical reaction, and the capacity of the graphene oxide can be fully utilized; (3) the metal phthalocyanine tetrasulfonate is firstly proposed to be used for a secondary battery system, and the energy storage performance of the metal phthalocyanine tetrasulfonate is excellent and exceeds that of most organic electrode materials.
Drawings
FIG. 1 is a schematic molecular structure diagram of the tetrasodium salt of nickel II phthalocyanine tetrasulfonic acid in example 1;
FIG. 2 is an XPS spectrum of a complex of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide of example 1;
FIG. 3 is an SEM image of a composite of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide of example 1;
fig. 4 is a graph of the magnification of the composite of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide at different current densities in example 1.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to specific embodiments.
Example 1
The organic macromolecular negative electrode material for the secondary battery is of a multilayer composite structure formed by alternately overlapping metal phthalocyanine tetrasulfonate lamella and graphene oxide lamella, and the thickness of the organic macromolecular negative electrode material is 2-20 um. The preparation method comprises the following steps:
the method comprises the following steps: respectively measuring 180m of concentrated sulfuric acid and 20ml of concentrated phosphoric acid, and then weighing 1.5g of flake graphite;
step two: placing concentrated sulfuric acid, concentrated phosphoric acid and flake graphite into a three-neck flask, slowly and mechanically stirring, then adding 6-10 g of potassium permanganate 3-5 times, keeping the temperature to be controlled to be not higher than 50 ℃, mechanically stirring the generated mixture at 40-55 ℃ for 12-24 hours until the dark green liquid is changed into brown liquid, and finally slowly adding hydrogen peroxide into the mixed liquid until the color is changed from brown to bright yellow and no redundant bubbles are generated;
step three: repeatedly cleaning the obtained yellow precipitate with deionized water until the pH value is neutral, freezing the yellow precipitate into ice blocks, and putting the ice blocks into a freeze drying box to obtain black graphene oxide finally;
step four: 160mg of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt (TsNiPc, the molecular structure is shown in figure 1) is weighed and dissolved in 40ml of deionized water solution, and the solution is stirred for 0.5h until the nickel II phthalocyanine tetrasulfonic acid tetrasodium salt is completely dissolved; weighing 40mg of graphene oxide, dissolving the graphene oxide in 30ml of mixed solution (ethanol: water is 2: 1), performing ultrasonic oscillation at 30 ℃ for 0.5h, uniformly mixing the two solutions, and stirring for 4 h;
step five: putting the mixed solution into a polytetrafluoroethylene lining crystallization kettle, and carrying out hydrothermal treatment at a high temperature of 180 ℃ for 24 hours;
step six: the mixed solution is put into a refrigerator to be frozen into ice blocks, and then the ice blocks are put into a freeze dryer until the black ice blocks are completely changed into purple black powder, so that a compound (TsNiPc @ GO) of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide is obtained, namely the organic macromolecular anode material in the embodiment.
The organic macromolecular negative electrode material is made into a lithium battery:
step seven: mixing the prepared organic macromolecular negative electrode material with acetylene black and PVDF in a ratio of 7: 2: 1, uniformly coating the copper foil with the mixture in a ratio of 1, drying the copper foil in vacuum at the temperature of 110 ℃ for 12-24 hours, cutting the dried electrode slice into small wafers with the diameter of 14mm by using a cutting machine, and putting the small wafers into a glove box which contains less than 0.5ppm of oxygen and less than 0.5ppm of water and is filled with argon;
step eight: adopting a button cell mould of CR2032 model, taking Celgard 2500 as a diaphragm and 1M LiPF6Dissolving in a solvent with the volume ratio of 1: 1: 1 EC: DEC: and (3) taking the DMC mixed solution as an electrolyte, taking a metal lithium sheet as a counter electrode, and assembling the button cell in a glove box.
The XPS spectrum, SEM spectrum and magnification spectrum of the composite of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide described in this example under different current densities are shown in fig. 2 to 4.
After the battery is cycled for 100 cycles, the reversible capacity of the battery is 460mAh/g under the current density of 100 mA/g.
Example 2
The organic macromolecular negative electrode material for the secondary battery is a multilayer composite structure formed by alternately overlapping metal phthalocyanine tetrasulfonate lamella and graphene oxide lamella, and the thickness of the organic macromolecular negative electrode material is 2-20 um. The preparation method comprises the following steps:
step one to step three, as in example 1;
step four: weighing 80mg of nickel II phthalocyanine tetrasulfate, dissolving in 40ml of deionized water solution, and stirring for 0.5h until complete dissolution; weighing 40mg of graphene oxide, dissolving the graphene oxide in 30ml of mixed solution (ethanol: water is 1: 1), performing ultrasonic oscillation at 20 ℃ for 0.5h, uniformly mixing the two solutions, and stirring for 4 h;
step five: putting the mixed solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal treatment at a high temperature of 120 ℃ for 24 hours;
step six: and (3) freezing the mixed solution in a refrigerator to form ice blocks, and then putting the ice blocks in a freeze dryer until the black ice blocks are completely changed into purple black powder to obtain a compound of nickel II phthalocyanine tetrasulfate and graphene oxide, namely the organic macromolecular negative electrode material in the embodiment.
The organic macromolecular negative electrode material is made into a lithium battery as in example 1.
The cell was tested by a blue tester to have a reversible capacity of 420mAh/g at a current density of 100mA/g after 100 cycles.
Example 3
The organic macromolecular negative electrode material for the secondary battery is of a multilayer composite structure formed by alternately overlapping metal phthalocyanine tetrasulfonate lamella and graphene oxide lamella, and the thickness of the organic macromolecular negative electrode material is 2-20 um. The preparation method comprises the following steps:
step one to step three, as in example 1;
step four: weighing 40mg of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt, dissolving in 40ml of deionized water solution, and stirring for 0.5h until the nickel II phthalocyanine tetrasulfonic acid tetrasodium salt is completely dissolved; weighing 40mg of graphene oxide, dissolving the graphene oxide in 30ml of mixed solution (ethanol: water is 8: 1), performing ultrasonic oscillation at 50 ℃ for 0.3h, uniformly mixing the two solutions, and stirring for 4 h;
step five: putting the mixed solution into a polytetrafluoroethylene lining crystallization kettle, and carrying out hydrothermal treatment at a high temperature of 250 ℃ for 12 hours;
step six: and (3) freezing the mixed solution in a refrigerator to form ice blocks, and then putting the ice blocks in a freeze dryer until the black ice blocks are completely changed into purple black powder to obtain a compound of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide, namely the organic macromolecular negative electrode material in the embodiment.
The organic macromolecular negative electrode material is made into a lithium battery as in example 1.
The cell was tested by a blue tester to have a reversible capacity of 404mAh/g at a current density of 100mA/g after 100 cycles.
Comparative example 1
The preparation method of the organic electrode material of the comparative example comprises the following steps:
the method comprises the following steps: weighing 70mg of nickel II phthalocyanine tetrasodium salt tetrasodium sulfonate, 20mg of acetylene black and 10mg of PVDF, uniformly mixing and coating the mixture on a copper foil, drying the mixture in vacuum at the temperature of 110 ℃ for 12-24 hours, cutting the dried electrode slice into small wafers with the diameter of 14mm by using a cutting machine, and putting the small wafers into a glove box which has the oxygen and water contents lower than 0.5ppm and is filled with argon;
step two: adopting a button cell mould of CR2032 model, taking Celgard 2500 as a diaphragm and 1M LiPF6Dissolving in a solvent with the volume ratio of 1: 1: 1 EC: DEC: and (3) taking the DMC mixed solution as an electrolyte, taking a metal lithium sheet as a counter electrode, and assembling the button cell in a glove box.
After the cell is cycled for 100 cycles through a blue tester, the reversible capacity of the cell is 230mAh/g under the condition of 100mA/g of current density.
As can be seen from examples 1 to 3 and comparative example 1, the reversible capacity of the lithium battery prepared from the organic macromolecular negative electrode material of the present invention reaches 450mAh/g or more, and the energy storage performance thereof is excellent and exceeds that of most organic electrode materials, and meanwhile, the lithium battery prepared from the metal phthalocyanine tetrasulfonate and the graphene oxide composite has a greatly improved reversible capacity compared with the lithium battery prepared from only the metal phthalocyanine tetrasulfonate, and the conductivity thereof is greatly enhanced after the metal phthalocyanine tetrasulfonate and the graphene oxide are compounded, and the lithium battery can contact with more active sites in an electrochemical reaction, so that the capacity thereof can be fully utilized.
Example 4
In this example, the same as the first seven steps of example 1, and the prepared organic macromolecular negative electrode material is made into a sodium battery, that is, in step eight, a button battery mold of the type CR2032 is adopted, glass fiber is used as a diaphragm, and 0.8M NaPF is used as a membrane6Dissolving in a solvent with the volume ratio of 1: 1 EC: and (3) using a DEC mixed solution as an electrolyte and a metal sodium sheet as a counter electrode, and assembling the button cell in a glove box.
After the cell is cycled for 100 cycles through a blue tester, the reversible capacity of the cell is 203mAh/g under the condition of 100mA/g of current density.
Example 5
In this example, the same as the first seven steps of example 1, and the prepared organic macromolecular anode material is made into a potassium battery, that is, in step eight, a button battery mold of CR2032 type is adopted, glass fiber is used as a separator, and 0.8M KPF6 is dissolved in a solvent with a volume ratio of 1: 1 EC: and (3) using a DEC mixed solution as an electrolyte, using a potassium metal sheet as a counter electrode, and assembling the button cell in a glove box.
After the cell is cycled for 100 cycles through a blue tester, the cell has a reversible capacity of 107mAh/g under the condition of a current density of 100 mA/g.
As can be seen from the data of the embodiments 4 to 5, the organic macromolecular negative electrode material can also be used for preparing sodium batteries and potassium batteries, and the reversible capacity of the prepared sodium batteries and potassium batteries is greatly improved compared with that of the conventional sodium batteries and potassium batteries.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (5)

1. A preparation method of an organic macromolecular negative electrode material for a secondary battery is characterized by comprising the following steps: the secondary battery is any one of a lithium battery, a sodium battery and a potassium battery, the organic macromolecular negative electrode material is a multilayer composite structure formed by alternately overlapping metal phthalocyanine tetrasulfonic acid tetrasodium salt lamella and graphene oxide lamella, the metal phthalocyanine tetrasulfonic acid tetrasodium salt is any one of nickel II phthalocyanine tetrasulfonic acid tetrasodium salt and nickel II phthalocyanine tetrasulfonic acid tetrapotassium salt, the mass ratio of the metal phthalocyanine tetrasulfonic acid tetrasodium salt lamella to the graphene oxide lamella is (1-4): 1, the thickness of the multilayer composite structure is 2-20um, and the preparation method comprises the following steps: taking metal phthalocyanine tetrasulfonate and graphene oxide as a template agent, and adopting a hydrothermal ultrasonic oscillation method to synthesize a metal phthalocyanine tetrasulfonate and graphene oxide compound in one step to obtain the organic macromolecular negative electrode material, wherein the hydrothermal ultrasonic oscillation method for synthesizing the metal phthalocyanine tetrasulfonate and graphene oxide compound in one step specifically comprises the following steps: adding metal phthalocyanine tetrasulfonate into deionized water to be completely dissolved to obtain a metal phthalocyanine tetrasulfonate solution, adding oxidized graphene into a mixed solution of ethanol and water, uniformly oscillating by ultrasonic waves to obtain a graphene oxide mixed solution, uniformly mixing the metal phthalocyanine tetrasulfonate solution and the graphene oxide mixed solution, carrying out hydrothermal compounding, and carrying out freeze drying to obtain the metal phthalocyanine tetrasulfonate and graphene oxide compound.
2. The method of producing an organic macromolecular anode material for a secondary battery according to claim 1, characterized in that: the mixed solution of the ethanol and the water is prepared from the following components in a volume ratio of (1-8): 1 and water.
3. The method of producing an organic macromolecular anode material for a secondary battery according to claim 1, characterized in that: the temperature of the ultrasonic oscillation is 20-50 ℃, and the time is 0.3-0.5 h.
4. The method of producing an organic macromolecular anode material for a secondary battery according to claim 1, characterized in that: the temperature of the hydrothermal compounding is 120-250 ℃, and the time is 12-24 h.
5. The method of producing an organic macromolecular anode material for a secondary battery according to claim 1, characterized in that: the mixing time of the metal phthalocyanine tetrasulfonic acid tetrasodium salt solution and the graphene oxide mixed solution is 4-5 h.
CN201810420792.6A 2018-05-04 2018-05-04 Organic macromolecular negative electrode material for secondary battery and preparation method thereof Active CN108615867B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810420792.6A CN108615867B (en) 2018-05-04 2018-05-04 Organic macromolecular negative electrode material for secondary battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810420792.6A CN108615867B (en) 2018-05-04 2018-05-04 Organic macromolecular negative electrode material for secondary battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108615867A CN108615867A (en) 2018-10-02
CN108615867B true CN108615867B (en) 2021-03-19

Family

ID=63661730

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810420792.6A Active CN108615867B (en) 2018-05-04 2018-05-04 Organic macromolecular negative electrode material for secondary battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108615867B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546117B (en) * 2018-11-19 2020-06-16 中南大学 Layered metal organic phosphate framework sodium ion positive electrode material and preparation method thereof
CN110148750A (en) * 2019-04-08 2019-08-20 东莞天予天正新能源科技有限公司 A kind of cathode material of lithium ion battery and preparation method thereof
CN111446428B (en) * 2020-03-23 2021-04-20 珠海冠宇电池股份有限公司 Lithium negative electrode material and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101950593B (en) * 2010-09-21 2012-10-10 中国科学院苏州纳米技术与纳米仿生研究所 Composite material and application thereof serving as super capacitor electrode material
CN102815696B (en) * 2012-08-09 2014-07-23 广西师范大学 Preparation and application of copper phthalocyanine functionalized graphenes and layer assembly membrane thereof
US9362555B2 (en) * 2012-09-07 2016-06-07 Nanotek Instruments, Inc. Rechargeable lithium cell having a chemically bonded phthalocyanine compound cathode
CN102935382B (en) * 2012-11-15 2014-05-28 广西师范大学 Method for preparing metal phthalocyanine functional grapheme Pt supported catalyst of direct methanol fuel cell
CN106935825A (en) * 2017-03-21 2017-07-07 桂林电子科技大学 A kind of graphene oxide/metal organic frame composite and its preparation method and application

Also Published As

Publication number Publication date
CN108615867A (en) 2018-10-02

Similar Documents

Publication Publication Date Title
CN107591511A (en) Composite film material for lithium battery and its preparation method and application
CN104300123A (en) Mixed positive electrode material, positive plate using the same, and lithium ion battery
CN108615867B (en) Organic macromolecular negative electrode material for secondary battery and preparation method thereof
CN105655642A (en) Electrolyte and high-nickel anode lithium ion battery containing same
CN108288728A (en) It is a kind of adaptation silicon carbon material lithium-ion battery electrolytes and its application
JP2001146427A (en) Coated lithium-mixed oxide particle and use thereof
CN110112419A (en) It can the MXene aeroge cathode of lithium collector and preparation method thereof of high magnification fast charging and discharging, application
KR20150036432A (en) Lithium-air battery and preparation method therefor
CN108539142A (en) A kind of preparation method of lithium sulfur battery anode material
CN105789561B (en) A kind of preparation method of lithium-polysulfide secondary cell
CN106299263A (en) A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery
CN110061289A (en) Manufacturing method, nonaqueous electrolytic solution and the nonaqueous electrolytic solution secondary battery of nonaqueous electrolytic solution
CN109167063A (en) A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection
CN114284475B (en) Preparation method of three-dimensional structured composite lithium metal anode and product thereof
CN106299264A (en) A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery
CN110844945A (en) High-nickel ternary cathode material and preparation method and application thereof
CN113540468A (en) Negative plate and battery
CN109119687A (en) electrolyte and electrochemical energy storage device
CN111755735B (en) Porous organic compound electrolyte and preparation method and application thereof
CN106299371A (en) A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery
CN115395013A (en) Preparation method of positive electrode material of double-ion sodium battery
CN114204118A (en) PVDF (polyvinylidene fluoride) -based composite solid electrolyte and preparation method thereof
CN114361573A (en) Non-aqueous eutectic electrolyte and preparation method and application thereof
CN114188605A (en) Lithium ion battery electrolyte for silicon-carbon cathode and lithium ion battery containing electrolyte
CN113451547A (en) Composite metal lithium cathode and lithium ion battery comprising same

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