CN112909249A - Three-dimensional graphene for negative electrode of quick-charging lithium ion battery and preparation method thereof - Google Patents
Three-dimensional graphene for negative electrode of quick-charging lithium ion battery and preparation method thereof Download PDFInfo
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- CN112909249A CN112909249A CN202110067841.4A CN202110067841A CN112909249A CN 112909249 A CN112909249 A CN 112909249A CN 202110067841 A CN202110067841 A CN 202110067841A CN 112909249 A CN112909249 A CN 112909249A
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- dimensional graphene
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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
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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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 many times and naturally settling until the pH value is 6-7 to obtain TDG suspension; adding the TDG suspension into a glucose solution for hydrothermal reaction, naturally cooling, carrying out vacuum filtration on the reacted solution, pressing to form a film, carrying out vacuum freeze drying on the film, carbonizing, and cooling to obtain the three-dimensional graphene. 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, and effectively reduce ions in the electrolyteThe concentration gradient inhibits 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.
Description
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
The continuous voyage demand of people for various electronic products and electric automobiles is continuously increased, and the rapid charging is very important before the ultra-large capacity battery technology is not developed in a breakthrough way. Therefore, the fast charging electrode material has received great attention. 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 the graphite material 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 kinetic process of lithium ions in the process of embedding the lithium ions 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:
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 solution after reaction, pressing to form a film, placing the film into a refrigerator at-25 ℃, standing, then carrying out vacuum freeze drying, removing residual moisture, simultaneously keeping the structure of the material stable, then 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 the regularly arranged three-dimensional graphene (TDG @ C) cathode of the 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 intercalation expansion, hydrothermal treatment, freeze drying and high-temperature carbonization methods 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, filling and intercalating the glucose solution by 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 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 ion concentration gradient 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; and naturally settling the obtained product to obtain the 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 was placed in a refrigerator at-25 ℃ for 12h and then vacuum freeze-dried for 24 h. Finally carbonizing the obtained product 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 mixingMixing 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. And (3) taking the prepared CG electrode plate as a negative electrode, using a diaphragm electrolyte and a lithium metal plate in a matching manner, packaging into a 2032 type button battery, and performing a half-battery performance test as a control sample. Using 3mg/cm2Mass loaded CG electrodes, tested at 1C charge-discharge rate. 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. Use of a high mass 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 (5)
1. A preparation method of three-dimensional graphene for a negative electrode of a fast-charging lithium ion battery is characterized by comprising the following steps:
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 solution after reaction, pressing to form a film, placing the film into a refrigerator at-25 ℃, standing, then carrying out vacuum freeze drying, removing residual moisture, simultaneously keeping the structure of the material stable, then carbonizing at 800 ℃ under an argon atmosphere, and cooling to obtain the three-dimensional graphene.
2. The method for preparing the three-dimensional graphene for the negative electrode of the fast-charging lithium ion battery according to claim 1, wherein in the step 1), graphite and CrO are used3The mass ratio of the hydrochloric acid is 1: 0.1-20: 0.2 to 50; the duration of the reaction was two days.
3. The method for preparing the three-dimensional graphene for the negative electrode of the fast-charging lithium ion battery according to claim 1, wherein 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.
4. The three-dimensional graphene prepared by the preparation method of the three-dimensional graphene for the negative electrode of the fast-charging lithium ion battery according to any one of claims 1 to 3.
5. The use of the three-dimensional graphene of claim 4 in a lithium ion battery negative electrode.
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Citations (6)
| 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 |
| KR20200108596A (en) * | 2019-03-11 | 2020-09-21 | 연세대학교 산학협력단 | Protection of lithium-dendrite growth by functionalized carbon nanodot additives |
| US20200358084A1 (en) * | 2019-05-09 | 2020-11-12 | Nanotek Instruments, Inc. | Alkali metal-sulfur secondary battery containing conducting polymer network-protected cathode material particulates |
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- 2021-01-19 CN CN202110067841.4A patent/CN112909249B/en active Active
Patent Citations (6)
| 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 |
| KR20200108596A (en) * | 2019-03-11 | 2020-09-21 | 연세대학교 산학협력단 | Protection of lithium-dendrite growth by functionalized carbon nanodot additives |
| US20200358084A1 (en) * | 2019-05-09 | 2020-11-12 | Nanotek Instruments, Inc. | Alkali metal-sulfur secondary battery containing conducting polymer network-protected cathode material particulates |
Non-Patent Citations (1)
| Title |
|---|
| LEIDONG等: "Water-Stable Lithium Metal Anodes with Ultrahigh-Rate Capability Enabled by a Hydrophobic Graphene Architecture", 《COMMUNICATION》 * |
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