CN116072848A - Electrode slurry, preparation method thereof, electrode plate and lithium ion battery - Google Patents

Electrode slurry, preparation method thereof, electrode plate and lithium ion battery Download PDF

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CN116072848A
CN116072848A CN202310120498.4A CN202310120498A CN116072848A CN 116072848 A CN116072848 A CN 116072848A CN 202310120498 A CN202310120498 A CN 202310120498A CN 116072848 A CN116072848 A CN 116072848A
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electrode slurry
cobalt
electrode
stirring
positive electrode
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张天戈
陈志伟
刘荣江
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Eve Energy Co Ltd
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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Abstract

The invention provides an electrode slurry and a preparation method thereof, an electrode plate and a lithium ion battery, wherein the electrode slurry comprises a monocrystal type nickel-cobalt-manganese ternary positive electrode material, a lithium cobalt oxide positive electrode material, a conductive agent and a binder, and the content ratio of nickel, manganese and cobalt in the monocrystal type nickel-cobalt-manganese ternary positive electrode material is (4-9): (0-4): (0-3). According to the invention, the monocrystal type nickel-cobalt-manganese ternary cathode material and the lithium cobaltate cathode material are used as the cathode material in the electrode slurry of the lithium battery, and the added monocrystal type nickel-cobalt-manganese ternary cathode material is low in cost, so that the technical problem of high preparation cost of the electrode slurry can be effectively improved on the basis of not affecting the performance of the prepared electrode slurry.

Description

Electrode slurry, preparation method thereof, electrode plate and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to electrode slurry, a preparation method thereof, an electrode plate and a lithium ion battery.
Background
With the increasing demand of consumer 3C products for lithium batteries, however, the raw material costs of lithium batteries are relatively high, especially for lithium cobaltate cathode material systems, there is an urgent need to reduce the cost of the cathode material (the cost of the cathode material is 40% or more of the total cost of the raw materials of lithium batteries), for example, to find other low-cost cathode materials that can replace lithium cobaltate cathode materials. However, replacing the lithium cobalt oxide cathode material with other low cost cathode materials is also susceptible to deterioration of the properties of the prepared electrode slurry, for example, thermal stability and energy density at high pressure are susceptible to.
Accordingly, the prior art is still in need of advancement and development.
Disclosure of Invention
The embodiment of the invention provides electrode slurry, a preparation method thereof, an electrode plate and a lithium ion battery, which can solve the technical problem of high preparation cost of the electrode slurry.
In a first aspect, an embodiment of the present invention provides an electrode slurry, including a single crystal nickel cobalt manganese ternary positive electrode material, a lithium cobalt oxide positive electrode material, a conductive agent, and a binder, where the content ratio of nickel, manganese, and cobalt in the single crystal nickel cobalt manganese ternary positive electrode material is (4-9): (0-4): (0-3).
In an embodiment, the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary cathode material is 6:3:1.
In one embodiment, the mass of the monocrystal nickel cobalt manganese ternary positive electrode material accounts for 45-49 wt% of the total mass of the electrode slurry, the mass of the lithium cobalt oxide positive electrode material accounts for 45-49 wt% of the total mass of the electrode slurry, the mass of the conductive agent accounts for 1-5 wt% of the total mass of the electrode slurry, and the mass of the binder accounts for 1-5 wt% of the total mass of the electrode slurry.
In one embodiment, the mass of the single-crystal nickel cobalt manganese ternary cathode material is 49wt% of the total mass of the electrode slurry, the mass of the lithium cobalt oxide cathode material is 49wt% of the total mass of the electrode slurry, the mass of the conductive agent is 1wt% of the total mass of the electrode slurry, and the mass of the binder is 1wt% of the total mass of the electrode slurry.
In a second aspect, an embodiment of the present invention provides a method for preparing an electrode slurry, including the steps of:
mixing the binder with an organic solvent to obtain a colloid solution;
adding a conductive agent into the colloid solution for mixing to obtain a first mixture;
mixing a lithium cobalt oxide positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material and the organic solvent to obtain a second mixture;
and mixing the first mixture, the second mixture and the organic solvent to prepare the electrode slurry.
In one embodiment, the solids content of the colloidal solution is 6-10% and the viscosity of the colloidal solution is 2000-3000 mpa.
In one embodiment, the viscosity of the electrode paste is 3000 to 5000mpa.
In an embodiment, the conductive agent is at least one of carbon nanotubes, carbon fibers, graphene and conductive carbon black, and the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, sodium alginate, polymethyl methacrylate and hydrogenated nitrile rubber.
In a third aspect, embodiments of the present invention provide an electrode sheet, including the electrode paste, or including an electrode paste prepared by using the preparation method of the electrode paste.
In a fourth aspect, an embodiment of the present invention provides a lithium ion battery, including the electrode sheet.
The embodiment of the invention has the beneficial effects that:
in the embodiment of the invention, the single-crystal nickel-cobalt-manganese ternary cathode material and the lithium cobalt oxide cathode material are used together as cathode materials in electrode slurry of a lithium battery, so that on one hand, the preparation cost of the electrode slurry can be effectively reduced, and on the other hand, the energy density of the electrode slurry can be maintained at a higher level on the basis of effectively reducing the preparation cost of the electrode slurry, the added single-crystal nickel-cobalt-manganese ternary cathode material does not influence the cycle stability and the thermal stability of the prepared electrode slurry, so that the electrode slurry can adapt to a high-pressure environment of 4.4V, and meanwhile, the energy density of the single-crystal nickel-cobalt-manganese ternary cathode material and the lithium cobalt oxide cathode material can be maintained at a higher level.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a method for preparing an electrode slurry according to an embodiment of the present invention;
FIG. 2 is a graph of a cyclic stability test at 25℃for multiple sets of electrode slurries provided by embodiments of the present invention;
fig. 3 is a graph of a cyclic stability test at 45 c for multiple sets of electrode slurries provided by embodiments of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the invention.
The embodiment of the invention provides an electrode slurry, which comprises a monocrystal type nickel-cobalt-manganese ternary positive electrode material, a lithium cobalt oxide positive electrode material, a conductive agent and a binder, wherein the content ratio of nickel, manganese and cobalt in the monocrystal type nickel-cobalt-manganese ternary positive electrode material is (4-9): (0-4): (0-3).
In this embodiment, the single-crystal nickel-cobalt-manganese ternary cathode material and the lithium cobalt oxide cathode material are used together as the cathode material in the electrode slurry of the lithium battery, and the price of the single-crystal nickel-cobalt-manganese ternary cathode material is lower than that of the lithium cobalt oxide cathode material, so that after a part of the lithium cobalt oxide cathode material is replaced by the single-crystal nickel-cobalt-manganese ternary cathode material in a certain proportion, the preparation cost of the electrode slurry is obviously reduced, thereby being beneficial to industrial production.
Figure BDA0004079829130000041
Further, the added single-crystal nickel-cobalt-manganese ternary cathode material has better cycle stability and thermal stability, so that the cycle stability and thermal stability of the prepared electrode slurry can be maintained at higher levels, the prepared electrode slurry can be adapted to a high-pressure environment of 4.4V, and meanwhile, when the single-crystal nickel-cobalt-manganese ternary cathode material and the lithium cobalt oxide cathode material are blended in a proper proportion, the energy density of the prepared electrode slurry can also be maintained at higher levels.
Therefore, the embodiment can effectively reduce the preparation cost of the electrode slurry on the premise that the circulation stability, the thermal stability and the energy density of the electrode slurry are all at higher levels.
Wherein, the content ratio of nickel, manganese and cobalt in the monocrystal type nickel-cobalt-manganese ternary positive electrode material is (4-9): (0-4): (0-3), for example, the content ratio of nickel, manganese and cobalt in the single crystal nickel-cobalt-manganese ternary cathode material may be 5:3:2. 6:3:1. 7:2:1. 8:1:1, etc.
Preferably, the content ratio of nickel, manganese and cobalt in the single-crystal nickel-cobalt-manganese ternary positive electrode material is 6:3:1.
In this embodiment, when the content ratio of nickel, manganese, and cobalt in the single-crystal nickel-cobalt-manganese ternary cathode material is 6:3:1, the chemical formula of the single-crystal nickel-cobalt-manganese ternary cathode material is LiNi 6 CoMn 3 O 2 The monocrystal type nickel-cobalt-manganese ternary positive electrode material can effectively reduce the preparation cost of the electrode slurry on the premise that the prepared electrode slurry has good circulation stability, thermal stability and energy density.
Specifically, in this embodiment, when the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary cathode material is 6:3:1, the particle diameter D50 of the single crystal type nickel-cobalt-manganese ternary cathode material is 4-5 um, and the specific surface area is 0.66m 2 Per g, tap density 2.25g/cc, gram capacity at 0.1C 190mAh/g.
In a specific embodiment, the mass of the monocrystal nickel-cobalt-manganese ternary positive electrode material accounts for 45-49 wt% of the total mass of the electrode slurry, the mass of the lithium cobalt oxide positive electrode material accounts for 45-49 wt% of the total mass of the electrode slurry, the mass of the conductive agent accounts for 1-5 wt% of the total mass of the electrode slurry, and the mass of the binder accounts for 1-5 wt% of the total mass of the electrode slurry.
In this embodiment, the adopted lithium cobalt oxide cathode material has the advantages of high energy density, high discharge voltage, good charging performance, long cycle life and the like, but is relatively expensive, while the adopted single crystal type nickel cobalt manganese ternary cathode material has relatively excellent cycle stability and thermal stability, and is relatively economical to the lithium cobalt oxide, on one hand, the preparation cost of the electrode slurry can be effectively reduced by blending the lithium cobalt oxide cathode material with the single crystal type nickel cobalt manganese ternary cathode material, on the other hand, the cycle stability and thermal stability of the electrode slurry prepared by singly adopting the lithium cobalt oxide cathode material are equivalent, the added single crystal type nickel cobalt manganese ternary cathode material does not influence the cycle stability and thermal stability of the prepared electrode slurry, so that the electrode slurry can adapt to a high-voltage environment of 4.4V, and on the other hand, the energy density of the prepared electrode slurry can be maintained at a relatively high level when the single crystal type nickel cobalt manganese ternary cathode material and the lithium cobalt oxide cathode material are blended in a proper proportion.
It is understood that in this embodiment, on the premise that the prepared electrode slurry can adapt to a high-pressure environment of 4.4V, the cycle performance and thermal stability equivalent to those of the electrode slurry prepared by singly using the lithium cobalt oxide cathode material are maintained, and the energy density is kept at a higher level, the improvement of the mass ratio of the single crystal type nickel cobalt manganese ternary cathode material is beneficial to reducing the preparation cost of the electrode slurry, wherein if the mass ratio of the single crystal type nickel cobalt manganese ternary cathode material is too small, the preparation cost of the prepared electrode slurry is influenced, resulting in too high preparation cost, and if the mass ratio of the lithium cobalt oxide cathode material is too small, the energy density, cycle performance and thermal stability of the electrode slurry are reduced. Preferably, the mass ratio of the single crystal type nickel cobalt manganese ternary positive electrode material in the electrode slurry is the same as that of the lithium cobalt oxide positive electrode material.
Preferably, the mass of the single-crystal nickel cobalt manganese ternary positive electrode material accounts for 49wt% of the total mass of the electrode slurry, the mass of the lithium cobalt oxide positive electrode material accounts for 49wt% of the total mass of the electrode slurry, the mass of the conductive agent accounts for 1wt% of the total mass of the electrode slurry, and the mass of the binder accounts for 1wt% of the total mass of the electrode slurry.
In this embodiment, the electrode slurry prepared by adopting the above ratio has good processing performance, and is beneficial to completion of subsequent preparation procedures of the lithium ion battery.
Further, as shown in fig. 1, an embodiment of the present invention provides a method for preparing an electrode slurry, including the steps of:
s10, mixing a binder with an organic solvent to obtain a colloid solution;
s20, adding a conductive agent into the colloid solution for mixing to obtain a first mixture;
s30, mixing a lithium cobaltate positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material and the organic solvent to obtain a second mixture;
and S40, mixing the first mixture, the second mixture and the organic solvent to prepare the electrode slurry.
In this embodiment, the electrode slurry may be prepared by mixing a binder, a conductive agent, lithium cobaltate, a single crystal type nickel cobalt manganese ternary cathode material, and an organic solvent. Wherein the conductive agent is at least one of carbon nanotubes, carbon fibers, graphene and conductive carbon black, and the carbon nanotubes comprise single-wall carbon nanotubes and multi-wall carbon nanotubes, preferably multi-wall carbon nanotubes; the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, sodium alginate, polymethyl methacrylate and hydrogenated nitrile rubber, and preferably polyvinylidene fluoride is adopted; the organic solvent is N-methyl pyrrolidone.
In a specific embodiment, the solid content of the colloidal solution prepared in step S10 is 6-10% and the viscosity of the colloidal solution is 2000-3000 mpa.
In this embodiment, the prepared colloidal solution is transparent and has no suspended matter, and considering that the stability of the colloidal solution may affect the subsequent preparation process of the electrode slurry, the solid content of the prepared colloidal solution is 6-10%, so as to avoid unstable electrochemical performance of the prepared electrode slurry due to insufficient stability of the colloidal solution in the subsequent processing process of the electrode slurry.
Preferably, the solids content of the colloidal solution is 8% and the viscosity of the colloidal solution is 2500mpa.
Understandably, when the solid content of the colloidal solution is 8% and the viscosity of the colloidal solution is 2500mpa, the stability of the prepared colloidal solution is high, thereby stabilizing the processability of the prepared electrode slurry.
In a specific embodiment, the viscosity of the electrode paste is 3000 to 5000mpa.
In this embodiment, in order to ensure that the prepared electrode paste has stable properties during the subsequent processing and can ensure that the battery has excellent electrical properties, the viscosity of the prepared electrode paste needs to be controlled to 3000-5000 mpa, and preferably, the viscosity of the electrode paste is 4000mpa.
Further, the embodiment of the invention also provides an electrode plate, which comprises the electrode paste or the electrode paste prepared by the preparation method of the electrode paste.
In addition, the embodiment of the invention provides a lithium ion battery, which comprises the electrode plate.
The present invention will be described in detail with reference to specific examples.
Example 1
Mixing a lithium cobalt oxide positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material, a carbon nano tube and polyvinylidene fluoride according to the following weight percentage of 49:49:1:1, preparing raw materials, wherein the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary positive electrode material is 6:3:1.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Equally dividing a lithium cobalt oxide positive electrode material and a monocrystal nickel cobalt manganese ternary positive electrode material into two parts, firstly adding one part of lithium cobalt oxide positive electrode material, one part of monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 90min again, at 25rpm and at 2500rpm, then continuously adding the other part of lithium cobalt oxide positive electrode material, monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 240min again, at 25rpm and at 2500rpm, and finally stirring for 30min, at 25rpm and at 1000rpm to obtain a second mixture;
(3) And mixing the first mixture, the second mixture and the organic solvent, and adding a proper amount of N-methyl pyrrolidone to prepare the electrode slurry 1 with the viscosity of 4000 cp.
Example 2
Mixing a lithium cobalt oxide positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material, a carbon nano tube and polyvinylidene fluoride according to the following weight percentage of 49:49:1:1, preparing raw materials, wherein the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary positive electrode material is 5:3:2.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Equally dividing a lithium cobalt oxide positive electrode material and a monocrystal nickel cobalt manganese ternary positive electrode material into two parts, firstly adding one part of lithium cobalt oxide positive electrode material, one part of monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 90min again, at 25rpm and at 2500rpm, then continuously adding the other part of lithium cobalt oxide positive electrode material, monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 240min again, at 25rpm and at 2500rpm, and finally stirring for 30min, at 25rpm and at 1000rpm to obtain a second mixture;
(3) And mixing the first mixture, the second mixture and the organic solvent, and adding a proper amount of N-methyl pyrrolidone to prepare the electrode slurry 2 with the viscosity of 4000 cp.
Example 3
Mixing a lithium cobalt oxide positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material, a carbon nano tube and polyvinylidene fluoride according to the following weight percentage of 49:49:1:1, preparing raw materials, wherein the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary positive electrode material is 7:2:1.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Equally dividing a lithium cobalt oxide positive electrode material and a monocrystal nickel cobalt manganese ternary positive electrode material into two parts, firstly adding one part of lithium cobalt oxide positive electrode material, one part of monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 90min again, at 25rpm and at 2500rpm, then continuously adding the other part of lithium cobalt oxide positive electrode material, monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 240min again, at 25rpm and at 2500rpm, and finally stirring for 30min, at 25rpm and at 1000rpm to obtain a second mixture;
(3) And mixing the first mixture, the second mixture and the organic solvent, and adding a proper amount of N-methyl pyrrolidone to prepare the electrode slurry 3 with the viscosity of 4000 cp.
Example 4
Mixing a lithium cobalt oxide positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material, a carbon nano tube and polyvinylidene fluoride according to the following weight percentage of 49:49:1:1, preparing raw materials, wherein the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary positive electrode material is 8:1:1.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Equally dividing a lithium cobalt oxide positive electrode material and a monocrystal nickel cobalt manganese ternary positive electrode material into two parts, firstly adding one part of lithium cobalt oxide positive electrode material, one part of monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 90min again, at 25rpm and at 2500rpm, then continuously adding the other part of lithium cobalt oxide positive electrode material, monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 240min again, at 25rpm and at 2500rpm, and finally stirring for 30min, at 25rpm and at 1000rpm to obtain a second mixture;
(3) And mixing the first mixture, the second mixture and the organic solvent, and adding a proper amount of N-methyl pyrrolidone to prepare the electrode slurry 4 with the viscosity of 4000 cp.
Example 5
Mixing a lithium cobalt oxide positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material, a carbon nano tube and polyvinylidene fluoride according to a ratio of 48:48:2:2, preparing raw materials, wherein the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary positive electrode material is 6:3:1.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Equally dividing a lithium cobalt oxide positive electrode material and a monocrystal nickel cobalt manganese ternary positive electrode material into two parts, firstly adding one part of lithium cobalt oxide positive electrode material, one part of monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 90min again, at 25rpm and at 2500rpm, then continuously adding the other part of lithium cobalt oxide positive electrode material, monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 240min again, at 25rpm and at 2500rpm, and finally stirring for 30min, at 25rpm and at 1000rpm to obtain a second mixture;
(3) And mixing the first mixture, the second mixture and the organic solvent, and adding a proper amount of N-methyl pyrrolidone to prepare the electrode slurry 5 with the viscosity of 4000 cp.
Example 6
Lithium cobaltate anode material, monocrystal nickel cobalt manganese ternary anode material, carbon nano tube and polyvinylidene fluoride are mixed according to the following ratio of 47:47:3:3, preparing raw materials, wherein the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary positive electrode material is 6:3:1.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Equally dividing a lithium cobalt oxide positive electrode material and a monocrystal nickel cobalt manganese ternary positive electrode material into two parts, firstly adding one part of lithium cobalt oxide positive electrode material, one part of monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 90min again, at 25rpm and at 2500rpm, then continuously adding the other part of lithium cobalt oxide positive electrode material, monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 240min again, at 25rpm and at 2500rpm, and finally stirring for 30min, at 25rpm and at 1000rpm to obtain a second mixture;
(3) And mixing the first mixture, the second mixture and the organic solvent, and adding a proper amount of N-methyl pyrrolidone to prepare the electrode slurry 6 with the viscosity of 4000 cp.
Example 7
The lithium cobalt oxide anode material, the monocrystal nickel cobalt manganese ternary anode material, the carbon nano tube and polyvinylidene fluoride are mixed according to the following ratio of 46:46:4:4, preparing raw materials, wherein the content ratio of nickel, manganese and cobalt in the single crystal type nickel-cobalt-manganese ternary positive electrode material is 6:3:1.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Equally dividing a lithium cobalt oxide positive electrode material and a monocrystal nickel cobalt manganese ternary positive electrode material into two parts, firstly adding one part of lithium cobalt oxide positive electrode material, one part of monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 90min again, at 25rpm and at 2500rpm, then continuously adding the other part of lithium cobalt oxide positive electrode material, monocrystal nickel cobalt manganese ternary positive electrode material and N-methyl pyrrolidone, mixing for 10min, stirring at 20rpm, stirring for 240min again, at 25rpm and at 2500rpm, and finally stirring for 30min, at 25rpm and at 1000rpm to obtain a second mixture;
(3) The first mixture, the second mixture and the organic solvent are mixed, and an appropriate amount of N-methylpyrrolidone is added to prepare electrode slurry 7 with a viscosity of 4000 cp.
Comparative example 1
Lithium cobaltate anode material, carbon nano tube and polyvinylidene fluoride are prepared according to the following steps: 1: the mass ratio of 1 was used for preparing the raw materials.
(1) Mixing polyvinylidene fluoride and N-methyl pyrrolidone, stirring for 30min at a stirring speed of 20rpm, scraping off polyvinylidene fluoride on a stirring shaft, stirring for 600min at a stirring speed of 30rpm at a dispersing speed of 2500rpm to obtain a colloid solution, uniformly dividing the carbon nano tubes into two parts, adding one part of carbon nano tubes into the colloid solution for mixing, stirring for 10min at a stirring speed of 10rpm, adding another part of carbon nano tubes, stirring for 10min at a stirring speed of 10rpm, stirring for 80min at a stirring speed of 30rpm and at a dispersing speed of 2500rpm to obtain a first mixture;
(2) Uniformly dividing a lithium cobalt oxide positive electrode material into two parts, firstly adding one part of the lithium cobalt oxide positive electrode material and N-methylpyrrolidone to mix, stirring for 10min, wherein the stirring speed is 20rpm, stirring for 90min again, the stirring speed is 25rpm, the dispersing speed is 2500rpm, then continuously adding the other part of the lithium cobalt oxide positive electrode material and N-methylpyrrolidone to mix, stirring for 10min, the stirring speed is 20rpm, stirring for 240min again, the stirring speed is 25rpm, the dispersing speed is 2500rpm, and finally stirring for 30min, the stirring speed is 25rpm, and the dispersing speed is 1000rpm to obtain a second mixture;
(3) And mixing the first mixture, the second mixture and the organic solvent, and adding a proper amount of N-methyl pyrrolidone to prepare the electrode slurry 8 with the viscosity of 4000 cp.
In this example, the electrode pastes prepared in examples 1 to 7 and comparative example 1 were subjected to a cyclic stability test at 25 ℃ and a cyclic stability test at 45 ℃ in a cyclic test cabinet, wherein the test conditions for the cyclic stability test at 25 ℃ were: the test conditions for the 0.8C charge/1.25C discharge to 3V, cycle 500 weeks, 45℃cycle stability test were: 1C charge/1C discharge, cycle 300 weeks.
Specifically, as shown in fig. 2 and 3, it can be seen from fig. 2 that the cycling stability of the electrode paste prepared in example 1 was not lower than that of the electrode paste prepared in comparative example 1 at 25 ℃, and in fig. 2, the capacity retention rate of the electrode paste prepared in other examples was higher than that of the electrode paste prepared in comparative example 1 except that the capacity retention rate of the electrode paste prepared in example 5 was lower than that of the electrode paste prepared in comparative example 1 when the cycle number was within 400. Meanwhile, as can also be seen from fig. 3, the cycling stability of the electrode paste prepared in example 1 was not lower than that of the electrode paste prepared in comparative example 1 at 45 ℃.
Further, taking the electrode paste prepared in example 1 as an example, the capacity retention rate of the electrode paste prepared in example 1 in fig. 2 after being circulated at 25 ℃ for 300 weeks is 95%, the capacity retention rate of the electrode paste prepared in example 1 in fig. 3 after being circulated at 45 ℃ for 300 weeks is 90%, which means that the circulation temperature is increased, the capacity retention rate of the electrode paste is not greatly changed, and the prepared electrode paste has better thermal stability.
Therefore, the single-crystal nickel-cobalt-manganese ternary cathode material and the lithium cobaltate cathode material are used as the cathode material in the electrode slurry of the lithium battery, and the added single-crystal nickel-cobalt-manganese ternary cathode material has low cost on the premise of not affecting the cycle stability, the thermal stability and the energy density of the prepared electrode slurry, so that the technical problem of high preparation cost of the electrode slurry can be effectively solved.
The foregoing has outlined rather broadly the more detailed description of embodiments of the invention, wherein the principles and embodiments of the invention are explained in detail using specific examples, the above examples being provided solely to facilitate the understanding of the method and core concepts of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present invention, the present description should not be construed as limiting the present invention.

Claims (10)

1. The electrode slurry is characterized by comprising a monocrystal type nickel-cobalt-manganese ternary positive electrode material, a lithium cobaltate positive electrode material, a conductive agent and a binder, wherein the content ratio of nickel, manganese and cobalt in the monocrystal type nickel-cobalt-manganese ternary positive electrode material is (4-9): (0-4): (0-3).
2. The electrode slurry of claim 1, wherein the content ratio of nickel, manganese, cobalt in the single crystal nickel cobalt manganese ternary cathode material is 6:3:1.
3. The electrode slurry according to any one of claims 1 or 2, wherein the mass of the single crystal nickel cobalt manganese ternary cathode material is 45 to 49wt% of the total mass of the electrode slurry, the mass of the lithium cobalt oxide cathode material is 45 to 49wt% of the total mass of the electrode slurry, the mass of the conductive agent is 1 to 5wt% of the total mass of the electrode slurry, and the mass of the binder is 1 to 5wt% of the total mass of the electrode slurry.
4. The electrode slurry of claim 3, wherein the mass of the single crystal nickel cobalt manganese ternary cathode material is 49wt% of the total mass of the electrode slurry, the mass of the lithium cobalt oxide cathode material is 49wt% of the total mass of the electrode slurry, the mass of the conductive agent is 1wt% of the total mass of the electrode slurry, and the mass of the binder is 1wt% of the total mass of the electrode slurry.
5. A method for preparing an electrode slurry, comprising the steps of:
mixing the binder with an organic solvent to obtain a colloid solution;
adding a conductive agent into the colloid solution for mixing to obtain a first mixture;
mixing a lithium cobalt oxide positive electrode material, a monocrystal nickel cobalt manganese ternary positive electrode material and the organic solvent to obtain a second mixture;
and mixing the first mixture, the second mixture and the organic solvent to prepare the electrode slurry.
6. The method of producing an electrode paste according to claim 5, wherein the solid content of the colloidal solution is 6 to 10% and the viscosity of the colloidal solution is 2000 to 3000mpa.
7. The method of producing an electrode paste according to claim 5, wherein the viscosity of the electrode paste is 3000 to 5000mpa.
8. The method according to claim 5, wherein the conductive agent is at least one of carbon nanotubes, carbon fibers, graphene, and conductive carbon black, and the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, sodium alginate, polymethyl methacrylate, and hydrogenated nitrile rubber.
9. An electrode sheet comprising the electrode slurry according to any one of claims 1 to 4, or comprising the electrode slurry prepared by the electrode slurry preparation method according to any one of claims 5 to 8.
10. A lithium ion battery comprising the electrode sheet of claim 9.
CN202310120498.4A 2023-02-15 2023-02-15 Electrode slurry, preparation method thereof, electrode plate and lithium ion battery Pending CN116072848A (en)

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