CN111554899A - Mixing method of electrode slurry - Google Patents
Mixing method of electrode slurry Download PDFInfo
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- CN111554899A CN111554899A CN202010393232.3A CN202010393232A CN111554899A CN 111554899 A CN111554899 A CN 111554899A CN 202010393232 A CN202010393232 A CN 202010393232A CN 111554899 A CN111554899 A CN 111554899A
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- 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
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a mixing method of electrode slurry, wherein the electrode slurry is cathode slurry, the cathode slurry comprises first graphite particles, second graphite particles and silicon particles, the average particle size D50 of the first graphite particles is 2.3-2.5 micrometers, and the D10 of the first graphite particles is 0.4-0.5 times of the D50 of the first graphite particles; the first graphite particles have a D90 of 1.8 to 2 times their D50; and the D50 of the second graphite particles is the same as the D10 of the first graphite particles, the particle size D50 of the silicon particles is 360-400nm, and the mass ratio of the first graphite particles, the second graphite particles and the silicon particles is 100:15-17: 30-35. The invention adopts a step-by-step material mixing method, the first graphite particles and the second graphite particles are firstly made into slurry, and then the silicon particles are added into the slurry to obtain the electrode slurry, the electrode slurry has long storage time, good retentivity and good coating performance, and the obtained cathode has higher energy density and stability.
Description
Technical Field
The invention relates to a mixing method of electrode slurry, and further relates to a mixing method of cathode slurry.
Background
Lithium batteries are classified into lithium batteries and lithium ion batteries. Lithium ion batteries generally use materials containing lithium as electrodes, and are representative of modern high-performance batteries. The lithium ion battery has the following characteristics: high voltage, high capacity, low consumption, no memory effect, no public hazard, small volume, small internal resistance, less self-discharge and more cycle times. Lithium ion batteries are considered to be a new type of power source that meets the increasing energy demands of portable electronic devices, electric and hybrid vehicles. Lithium ion batteries have been used in numerous civil and military applications, such as mobile phones, notebook computers, video cameras, digital cameras, and the like. The negative pole of lithium ion also has great influence to the performance of lithium ion battery, and the compounding mode of negative pole is the technological process that influences the negative pole greatly.
Disclosure of Invention
The invention provides a mixing method of electrode slurry, wherein the electrode slurry is cathode slurry, the cathode slurry comprises first graphite particles, second graphite particles and silicon particles, the average particle size D50 of the first graphite particles is 2.3-2.5 micrometers, and the D10 of the first graphite particles is 0.4-0.5 times of the D50 of the first graphite particles; the first graphite particles have a D90 of 1.8 to 2 times their D50; and the D50 of the second graphite particles is the same as the D10 of the first graphite particles, the particle size D50 of the silicon particles is 360-400nm, and the mass ratio of the first graphite particles, the second graphite particles and the silicon particles is 100:15-17: 30-35. The invention adopts a step-by-step material mixing method, the first graphite particles and the second graphite particles are firstly made into slurry, and then the silicon particles are added into the slurry to obtain the electrode slurry, the electrode slurry has long storage time, good retentivity and good coating performance, and the obtained cathode has higher energy density and stability.
The specific scheme is as follows:
a method of compounding an electrode slurry, the electrode slurry being a negative electrode slurry comprising first graphite particles, second graphite particles, and silicon particles, the first graphite particles having an average particle diameter D50 of 2.3 to 2.5 μm, the first graphite particles having a D10 of 0.4 to 0.5 times their D50; the first graphite particles have a D90 of 1.8 to 2 times their D50; the D50 of the second graphite particles is the same as the D10 of the first graphite particles, the particle size D50 of the silicon particles is 360-400nm, and the mass ratio of the first graphite particles, the second graphite particles and the silicon particles is 100:15-17: 30-35; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, adding deionized water, stirring to adjust the solid content of the slurry to be 20-25%, adding the first graphite particles, stirring uniformly, adding deionized water, and stirring to adjust the solid content of the slurry to be 50-55%;
3) adding silicon particles into the slurry obtained in the step 2, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 50-55%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:2-6: 2-6.
Further, in the slurry, the total amount of active materials: adhesive: the conductive agent is 100:3-5: 3-5. .
Further, the first graphite particles had an average particle diameter D50 of 2.4 microns and D10 of 1.1 microns; the first graphite particles have a D90 of 4.5 microns; the second graphite particles had a D50 of 1.1 microns.
Further, the particle diameter D50 of the silicon particles is 380 nm.
Further, the binder is SBR.
Further, the conductive agent is conductive carbon black, specifically, conductive furnace carbon black (CF), superconducting furnace carbon black (SCF), or superconducting furnace carbon black (XCF).
Further, the mass ratio of the first graphite particles, the second graphite particles and the silicon particles is 100:16: 32.
Further, an electrode slurry prepared by the method of claim.
The invention has the following beneficial effects:
1) the composite electrode composed of the graphite particles and the silicon particles has high energy density and rate capability, and the graphite particles and the silicon particles are mixed and arranged, so that the volume effect of the silicon particles can be effectively relieved, and the cycle life is prolonged.
2) The inventors have found that when graphite particles are distributed in two stages at a specific content and mixed with silicon particles at a specific content, the resulting slurry of the combined particle size distribution material has extremely good stability, can be left for a long period of time without delamination, and has good coating properties and a uniform and stable coating.
3) By the specific mixing sequence of the invention and by adjusting the solid content to be within the numerical range of the invention during the mixing process, the active substances can be better dispersed and stable slurry can be obtained.
4) The slurry obtained by the method has good stability, and has excellent coating performance and storage performance.
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples. The negative electrode slurry of the present invention includes first graphite particles, second graphite particles, and silicon particles. The binder is SBR. The conductive agent is superconducting furnace carbon black (SCF).
Example 1
The first graphite particles have an average particle diameter D50 of 2.4 microns and a D10 of 1.1 microns; the first graphite particles have a D90 of 4.5 microns; the second graphite particles have a D50 of 1.1 microns; the particle size D50 of the silicon particles is 380nm, and the mass ratio of the first graphite particles, the second graphite particles and the silicon particles is 100:16: 32; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and uniformly stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, adding deionized water, stirring to adjust the solid content of the slurry to be 20%, adding the first graphite particles, stirring uniformly, adding deionized water, stirring to adjust the solid content of the slurry to be 50%;
3) adding silicon particles into the slurry obtained in the step 2, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 50%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:4: 4.
Example 2
The first graphite particles have an average particle diameter D50 of 2.3 microns and a D10 of 1 micron; the first graphite particles have a D90 of 4.2 microns; and the second graphite particles have a D50 of 1 micron, the silicon particles have a particle size D50 of 360nm, and the mass ratio of the first graphite particles, second graphite particles and silicon particles is 100:15: 30; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, adding deionized water, stirring to adjust the solid content of the slurry to be 20%, adding the first graphite particles, stirring uniformly, adding deionized water, stirring to adjust the solid content of the slurry to be 50%;
3) adding silicon particles into the slurry obtained in the step 2, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 50%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:3: 3.
Example 3
The first graphite particles have an average particle diameter D50 of 2.5 microns and a D10 of 1.2 microns; the first graphite particles have a D90 of 5 microns; and the second graphite particles have a D50 of 1.2 microns, the silicon particles have a particle size D50 of 400nm, and the mass ratio of the first graphite particles, second graphite particles and silicon particles is 100:17: 35; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, adding deionized water, stirring to adjust the solid content of the slurry to be 25%, adding the first graphite particles, stirring uniformly, adding deionized water, stirring to adjust the solid content of the slurry to be 55%;
3) adding silicon particles into the slurry obtained in the step 2, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 55%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:5: 5.
Comparative example 1
The first graphite particles have an average particle diameter D50 of 2 microns and a D10 of 1 micron; the first graphite particles have a D90 of 4 microns; and the second graphite particles have a D50 of 1.5 microns, the silicon particles have a particle size D50 of 500nm, and the mass ratio of the first graphite particles, second graphite particles and silicon particles is 100:15: 30; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and uniformly stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, adding deionized water, stirring to adjust the solid content of the slurry to be 20%, adding the first graphite particles, stirring uniformly, adding deionized water, stirring to adjust the solid content of the slurry to be 50%;
3) adding silicon particles into the slurry obtained in the step 2, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 50%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:4: 4.
Comparative example 2
The first graphite particles have an average particle diameter D50 of 2.4 microns and a D10 of 1 micron; the first graphite particles have a D90 of 5.5 microns; and the second graphite particles have a D50 of 1 micron, the silicon particles have a particle size D50 of 380nm, and the mass ratio of the first graphite particles, second graphite particles and silicon particles is 100:16: 32; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and uniformly stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, adding deionized water, stirring to adjust the solid content of the slurry to be 20%, adding the first graphite particles, stirring uniformly, adding deionized water, stirring to adjust the solid content of the slurry to be 50%;
3) adding silicon particles into the slurry obtained in the step 2, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 50%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:4: 4.
Comparative example 3
The first graphite particles have an average particle diameter D50 of 2.5 microns and a D10 of 1.2 microns; the first graphite particles have a D90 of 5 microns; and the second graphite particles have a D50 of 1.2 microns, the silicon particles have a particle size D50 of 400nm, and the mass ratio of the first graphite particles, second graphite particles and silicon particles is 100:40: 20; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and uniformly stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, uniformly stirring, adding the first graphite particles and the silicon particles, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 50%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:4: 4.
Test and results
The batteries of examples 1 to 3 and comparative examples 1 to 3 were tested, stored for 12h and 24h at rest, and the solid content 5cm below the top layer was measured, and the results are shown in Table 1. Table 1 shows that when the particle size and weight ratio of the material are within the range of the present invention, the obtained slurry has high stability, can maintain good dispersibility after long-term storage, and has a positive effect on the later coating performance.
TABLE 1
| 12h(％) | 24(％) | |
| Example 1 | 49.1 | 48.3 |
| Example 2 | 48.8 | 48.5 |
| Example 3 | 54.0 | 52.4 |
| Comparative example 1 | 47.2 | 44.3 |
| Comparative example 2 | 46.8 | 42.9 |
| Comparative example 3 | 45.4 | 40.2 |
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (8)
1. A method of compounding an electrode slurry, the electrode slurry being a negative electrode slurry comprising first graphite particles, second graphite particles, and silicon particles, the first graphite particles having an average particle diameter D50 of 2.3 to 2.5 μm, the first graphite particles having a D10 of 0.4 to 0.5 times their D50; the first graphite particles have a D90 of 1.8 to 2 times their D50; the D50 of the second graphite particles is the same as the D10 of the first graphite particles, the particle size D50 of the silicon particles is 360-400nm, and the mass ratio of the first graphite particles, the second graphite particles and the silicon particles is 100:15-17: 30-35; the mixing method comprises the following steps:
1) adding deionized water into a stirring kettle, adding a binder, and stirring to obtain a glue solution;
2) adding second graphite particles and a conductive agent into the glue solution obtained in the step 1, adding deionized water, stirring to adjust the solid content of the slurry to be 20-25%, adding the first graphite particles, stirring uniformly, adding deionized water, and stirring to adjust the solid content of the slurry to be 50-55%;
3) adding silicon particles into the slurry obtained in the step 2, uniformly stirring, adding deionized water, and stirring to adjust the solid content of the slurry to be 50-55%, wherein the total amount of active materials is as follows: adhesive: the conductive agent is 100:2-6: 2-6.
2. A mixing method as defined in the preceding claim, wherein the total amount of active material in said slurry is: adhesive: the conductive agent is 100:3-5: 3-5.
3. A compounding process according to the preceding claim, said first graphite particles having an average particle size D50 of 2.4 microns, said first graphite particles having a D10 of 1.1 microns; the first graphite particles have a D90 of 4.5 microns; the second graphite particles had a D50 of 1.1 microns.
4. A compounding process according to the preceding claim, said silicon particles having a particle size D50 of 380 nm.
5. A compounding process according to the preceding claim, said binder being SBR.
6. A compounding method according to the preceding claim, wherein said conductive agent is conductive carbon black, in particular conductive furnace carbon black (CF), superconducting furnace carbon black (SCF), or superconducting furnace carbon black (XCF).
7. A compounding method as set forth in the preceding claim, wherein the mass ratio of the first graphite particles, the second graphite particles and the silicon particles is 100:16: 32.
8. An electrode slurry prepared by the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010393232.3A CN111554899A (en) | 2020-05-11 | 2020-05-11 | Mixing method of electrode slurry |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010393232.3A CN111554899A (en) | 2020-05-11 | 2020-05-11 | Mixing method of electrode slurry |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4047680A1 (en) * | 2021-02-23 | 2022-08-24 | SK Innovation Co., Ltd. | Negative electrode for secondary battery, and secondary battery including same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4047680A1 (en) * | 2021-02-23 | 2022-08-24 | SK Innovation Co., Ltd. | Negative electrode for secondary battery, and secondary battery including same |
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