CN112909249B - Three-dimensional graphene for negative electrode of quick-charging lithium ion battery and preparation method of three-dimensional graphene - Google Patents

Three-dimensional graphene for negative electrode of quick-charging lithium ion battery and preparation method of three-dimensional graphene Download PDF

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CN112909249B
CN112909249B CN202110067841.4A CN202110067841A CN112909249B CN 112909249 B CN112909249 B CN 112909249B CN 202110067841 A CN202110067841 A CN 202110067841A CN 112909249 B CN112909249 B CN 112909249B
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dimensional graphene
tdg
graphite
reaction
suspension
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CN112909249A (en
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刘巍
张昶
董雷
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ShanghaiTech University
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    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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

Abstract

The invention discloses three-dimensional graphene for a negative electrode of a quick-charging lithium ion battery and a preparation method thereof. The preparation method comprises the following steps: mixing graphite and CrO3Adding into hydrochloric acid, washing the obtained product with water to obtain intercalated graphite; putting the intercalated graphite into hydrogen peroxide for reaction; washing the obtained product with deionized water for multiple times and naturally settling until the pH value is 6-7 to obtain TDG suspension; and adding the TDG suspension into a glucose solution for hydrothermal reaction, naturally cooling, performing vacuum filtration on the reacted solution, pressing to form a film, performing vacuum freeze drying on the film, carbonizing, and cooling to obtain the three-dimensional graphene. The invention can keep the material in a regularly arranged layered structure, reduce the curvature of the electrode material, provide a rapid transmission channel for lithium ions, effectively reduce the concentration gradient of ions in the electrolyte and inhibit the growth of lithium dendrites. And the high-speed charging device has higher quick charging performance and cycling stability under the conditions of high current and high multiplying power.

Description

Three-dimensional graphene for negative electrode of quick-charging lithium ion battery and preparation method thereof
Technical Field
The invention relates to three-dimensional graphene for a negative electrode of a quick-charging lithium ion battery and a preparation method thereof, belonging to the technical field of rechargeable batteries.
Background
People have an ever-increasing need for endurance of various electronic products and electric vehicles, and rapid charging is especially important before the ultra-large capacity battery technology has not made a breakthrough progress. Therefore, the fast charging electrode material is of great interest. At present, a lithium ion battery for large-scale commercial application mainly comprises a graphite cathode, a diaphragm, an electrolyte and a lithium iron phosphate (LFP) anode. The graphite cathode is widely applied under the application condition of low multiplying power and low current, and has the advantages of large capacity, low potential and stable property. However, the slow kinetics of lithium ions during intercalation into graphite materials severely limits the charging rate of the battery system and becomes a short plate in the overall battery system. With the increase of the charging rate, the lithium storage performance of the graphite material is sharply attenuated, and the practical application value is lost. Therefore, it is important to develop a new negative electrode material having the above advantages and also having a fast charging capability.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the slow dynamic process of lithium ions in the process of being embedded into the graphite material seriously restricts the charging speed of a battery system.
In order to solve the technical problem, the invention provides a preparation method of three-dimensional graphene for a negative electrode of a fast-charging lithium ion battery, which is characterized by comprising the following steps of:
step 1): mixing graphite and CrO3Adding into hydrochloric acid, stirring, washing the obtained product with water to obtain intercalated graphite; placing the formed intercalated graphite into hydrogen peroxide, and carrying out a controllable reaction of interlayer gas release at room temperature; washing the obtained product with deionized water for many times and naturally settling until the pH value is 6-7 to obtain TDG suspension;
step 2): adding the TDG suspension into a glucose solution, uniformly mixing, transferring into a reaction kettle, carrying out hydrothermal reaction at 120 ℃, naturally cooling, carrying out vacuum filtration on the reacted solution, pressing to form a film, placing the film into a refrigerator at-25 ℃, standing, carrying out vacuum freeze drying, removing residual moisture, keeping the structure of the material stable, carbonizing at 800 ℃ under an argon atmosphere, and cooling to obtain the three-dimensional graphene.
Preferably, the graphite and CrO in the step 1)3The mass ratio of the hydrochloric acid is 1: 0.1-20: 0.2 to 50; the duration of the reaction was two days.
Preferably, the concentration of the glucose solution in the step 2) is 0.1mol/L, and the mass ratio of the TDG in the TDG suspension to the glucose in the glucose solution is 1: 0.1; the membrane was allowed to stand in a refrigerator for 12h and then vacuum freeze-dried for 24 h.
The invention also provides the three-dimensional graphene prepared by the preparation method for the three-dimensional graphene used for the negative electrode of the quick-charging lithium ion battery.
The invention also provides application of the three-dimensional graphene in a lithium ion battery cathode.
The invention prepares a regularly arranged three-dimensional graphene (TDG @ C) cathode of an in-situ grown carbon nano-dot support by utilizing the steps of intercalation expansion, hydrothermal treatment, freeze drying, high-temperature carbonization and the like.
The invention can keep the material in a regularly arranged layered structure, reduce the curvature of the electrode material, provide a rapid transmission channel for lithium ions, effectively reduce the concentration gradient of ions in the electrolyte and inhibit the growth of lithium dendrites. And the high-speed charging performance and the cycling stability are higher when the current and the multiplying power are high.
The invention utilizes the methods of intercalation expansion, hydrothermal treatment, freeze drying and high-temperature carbonization to prepare the regularly arranged three-dimensional graphene (TDG) cathode of the in-situ grown carbon nano-dot support. Taking crystalline flake graphite as a raw material, and firstly obtaining three-dimensional graphene by a chemical expansion method; then, carrying out filling intercalation of a glucose solution by utilizing hydrothermal reaction high-temperature high-pressure treatment; molding by using a vacuum filtration method, and freeze-drying; and finally, carbonizing at high temperature in an argon atmosphere to obtain the regularly arranged three-dimensional graphene (TDG @ C) negative electrode of the in-situ grown carbon nano-dot support. The invention can keep the materials in a regularly arranged layered structure, reduce the curvature of the electrode material, provide a rapid transmission channel for lithium ions, effectively reduce the concentration gradient of ions in the electrolyte, inhibit the growth of lithium dendrites and improve the rapid charging performance. The invention utilizes cheap scale graphite raw materials, has simple preparation method and lower cost, and has good commercial application prospect.
Drawings
FIG. 1 is a microstructure characterization of TDG @ C electrodes at different scales;
FIG. 2 shows the electrochemical performance of TDG @ C and CG.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
1g of graphite and 1g of CrO3Adding the mixture into 1ml of 5mol/L hydrochloric acid, stirring, and washing the obtained product with water to obtain intercalated graphite; placing the formed intercalated graphite into 2ml of 30% hydrogen peroxide, and standing for 20 minutes at room temperature; the obtained product is processed by natureAnd settling to obtain TDG suspension. 1g of the prepared TDG suspension is added into 50mL of 0.1mol/L glucose solution, mixed uniformly, transferred into a reaction kettle and subjected to hydrothermal reaction at 120 ℃. After natural cooling, the solution after reaction is vacuum filtered and pressed into a film. The membrane is placed in a refrigerator at the temperature of minus 25 ℃ for standing for 12 hours, and then vacuum freeze drying is carried out for 24 hours. Finally carbonizing the mixture for 5 hours at 800 ℃ in an argon atmosphere, and cooling to obtain the TDG @ C electrode.
The prepared TDG @ C electrode plate is used as a negative electrode, a diaphragm electrolyte and a lithium metal plate are used in a matched mode, the obtained product is packaged into a 2032 type button battery, and the obtained product is used as an experimental sample for carrying out a half-battery performance test. Using 3mg/cm2The mass-loaded TDG @ C electrode is tested under the charge-discharge multiplying power of 1C, and shows the initial specific capacity of 188.6 mAh/g. After 500 charge-discharge cycles, the specific capacity of the material is 115.4 mAh/g. Even if tested at a high rate of 6C, still exerts a higher specific capacity of 64.5 mAh/g. Use of a high mass load (10 mg/cm)2) The TDG @ C electrode is tested under the charge-discharge multiplying power of 1C, and the specific capacity is 93.0 mAh/g.
Comparative example 1
Mixing graphite (CG), Carbon black (Carbon black), carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) according to the weight ratio of 95:2:1.5:1.5, adding deionized water, and mixing and dispersing in a stirrer to form slurry. The slurry was coated on a copper foil with a doctor blade and dried in a vacuum oven at 60 ℃ for 12 hours. The dried copper foil was cut into small disks to serve as working electrodes in the cell. The prepared CG electrode plate is used as a negative electrode, a diaphragm electrolyte and a lithium metal plate are used in a matched manner, and the CG electrode plate is packaged into a 2032 type button battery and used as a comparison sample for carrying out a half-battery performance test. Using 3mg/cm2The CG electrode of mass load was tested at a charge-discharge rate of 1C. After 500 charge-discharge cycles, the specific capacity is 84.9 mAh/g. Tested at a high rate of 6C, the specific capacity of the resin is 14.3 mAh/g. Using a high quality load (10 mg/cm)2) The CG electrode of (1) is tested under the charge-discharge multiplying power of 1C, and the specific capacity of the CG electrode is 23.5 mAh/g.

Claims (1)

1. The application of the three-dimensional graphene in the negative electrode of the lithium ion battery is characterized in that the preparation method of the three-dimensional graphene comprises the following steps:
step 1): mixing graphite and CrO3Adding into hydrochloric acid, graphite, CrO3The mass ratio of the hydrochloric acid is 1: 0.1-20: 0.2-50, stirring, and washing the obtained product with water to obtain intercalated graphite; putting the formed intercalated graphite into hydrogen peroxide, and carrying out a controllable reaction of interlayer gas release at room temperature, wherein the reaction duration is two days; washing the obtained product with deionized water for multiple times and naturally settling until the pH value is 6-7 to obtain TDG suspension;
step 2): adding the TDG suspension into a glucose solution, wherein the concentration of the glucose solution is 0.1mol/L, and the mass ratio of TDG in the TDG suspension to glucose in the glucose solution is 1: 0.1, uniformly mixing, transferring into a reaction kettle, carrying out hydrothermal reaction at 120 ℃, naturally cooling, carrying out vacuum filtration on the solution after reaction, pressing to form a film, placing the film into a refrigerator at-25 ℃ for standing for 12h, then carrying out vacuum freeze drying for 24h, removing residual moisture, simultaneously keeping the structure of the material stable, then carbonizing at 800 ℃ under argon atmosphere, and cooling to obtain three-dimensional graphene; the three-dimensional graphene is in a regular arrangement of in-situ grown carbon nano-dot supporters and is in a regularly arranged layered structure.
CN202110067841.4A 2021-01-19 2021-01-19 Three-dimensional graphene for negative electrode of quick-charging lithium ion battery and preparation method of three-dimensional graphene Active CN112909249B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103570012A (en) * 2013-10-29 2014-02-12 复旦大学 Preparation method of graphene
CN105967169A (en) * 2016-05-04 2016-09-28 华南师范大学 Method for modifying three-dimensional graphene material with carbon nano-dots
CN107416811A (en) * 2017-06-21 2017-12-01 山东欧铂新材料有限公司 A kind of preparation method of high conductivity graphene
CN107601464A (en) * 2017-09-15 2018-01-19 中国科学院合肥物质科学研究院 Graphene oxide plural gel of carbon quantum dot reduction and its production and use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102238898B1 (en) * 2019-03-11 2021-04-12 연세대학교 산학협력단 Protection of lithium-dendrite growth by functionalized carbon nanodot additives
US11916223B2 (en) * 2019-05-09 2024-02-27 Global Graphene Group, Inc. Alkali metal-sulfur secondary battery containing conducting polymer network-protected cathode material particulates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103570012A (en) * 2013-10-29 2014-02-12 复旦大学 Preparation method of graphene
CN105967169A (en) * 2016-05-04 2016-09-28 华南师范大学 Method for modifying three-dimensional graphene material with carbon nano-dots
CN107416811A (en) * 2017-06-21 2017-12-01 山东欧铂新材料有限公司 A kind of preparation method of high conductivity graphene
CN107601464A (en) * 2017-09-15 2018-01-19 中国科学院合肥物质科学研究院 Graphene oxide plural gel of carbon quantum dot reduction and its production and use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Water-Stable Lithium Metal Anodes with Ultrahigh-Rate Capability Enabled by a Hydrophobic Graphene Architecture;LeiDong等;《Communication》;20200213;第32卷(第14期);第1908484(1-8)页 *

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