CN114614007A - Lithium ion battery anode slurry and preparation method thereof - Google Patents

Lithium ion battery anode slurry and preparation method thereof Download PDF

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CN114614007A
CN114614007A CN202210147769.0A CN202210147769A CN114614007A CN 114614007 A CN114614007 A CN 114614007A CN 202210147769 A CN202210147769 A CN 202210147769A CN 114614007 A CN114614007 A CN 114614007A
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lithium ion
ion battery
deionized water
mixture
positive electrode
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CN114614007B (en
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梅晨
黄善鹏
徐宁
高旭光
其他发明人请求不公开姓名
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Dongguan K Tech New Energy Co ltd
Guangdong Greenway Technology Co Ltd
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Guangdong Greenway Technology 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive 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

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Abstract

The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode slurry and a preparation method thereof, wherein the anode slurry comprises NCM, a binder, a conductive agent, a dispersing agent and deionized water, and the binder is prepared from the following components in percentage by mass (7-9): PVA-COOH and CMC of (1-3). The positive electrode slurry prepared by the invention can solve the problem that NCM is used as a positive electrode active substance to cause the positive electrode slurry to form gel or settle easily, ensure the stability of the positive electrode slurry and ensure the cycle life and safety of a lithium ion battery using the positive electrode slurry.

Description

Lithium ion battery anode slurry and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode slurry and a preparation method thereof.
Background
Lithium ion battery has long service life, the voltage is high, advantages such as energy density is high, at present, all use lithium ion battery supply energy among a great deal of electronic product, lithium ion battery includes positive plate, negative pole piece and locates the diaphragm between positive plate and the negative pole piece, positive plate includes anodal mass flow body and the anodal diaphragm of coating on anodal mass flow body, the negative pole piece includes the negative pole mass flow body and the negative pole diaphragm of coating on the negative pole mass flow body, anodal diaphragm is formed by anodal thick liquids coating, stoving.
In order to meet the requirement of high energy density, at present, the cathode slurry often selects an NCM (nickel cobalt lithium manganate) ternary cathode material as a cathode active material, wherein the higher the nickel content is, the higher the energy density of the lithium ion battery is, and at the same time, the Li/Ni mixed-out phenomenon is aggravated. In order to form a layered structure well, an excess lithium source is required to be put in the NCM synthesis process, and Li is generated after synthesis2Unreacted lithium oxide in O state, which reacts with water and carbon dioxide in the air to form LiOH and Li2CO3The pH value of the slurry can be increased, so that gel is formed or sedimentation occurs, the stability of the slurry is poor, and the lithium ion battery has serious gas generation problem in the charging and discharging process, so that the expansion deformation and the cycle life of the lithium ion battery are shortened.
Disclosure of Invention
The invention aims to provide a lithium ion battery anode slurry and a preparation method thereof, aiming at overcoming the defects of the prior art, solving the problem that NCM (non-volatile organic compound) is used as an anode active material to cause the anode slurry to form gel or settle easily, ensuring the stability of the anode slurry and ensuring the cycle life and the safety of a lithium ion battery using the anode slurry.
Based on the above, the invention provides a lithium ion battery positive electrode slurry, which comprises NCM, a binder, a conductive agent, a dispersing agent and deionized water, wherein the binder is prepared from the following components in percentage by mass (7-9): (1-3) PVA-COOH and CMC (carboxymethyl cellulose).
Preferably, the weight percentage of each raw material of the positive electrode slurry is as follows:
Figure BDA0003509023430000021
further preferably, the weight percentage of each raw material of the positive electrode slurry is as follows:
Figure BDA0003509023430000022
preferably, the binder consists of PVA-COOH and CMC in a mass ratio of 8: 2.
Preferably, the conductive agent is at least one of Super P, acetylene black, and CNT (carbon nanotube).
Preferably, the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion or polyvinyl acrylate.
Preferably, the NCM is NCM 523.
The invention also provides a preparation method of the lithium ion battery anode slurry, which comprises the following steps:
s1, mixing and stirring PVA-COOH, NCM and a first part of deionized water according to the formula amount for a period of time, and adjusting the pH value to 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and stirring for a period of time to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and stirring for a period of time to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and stirring for a period of time to obtain a fourth mixture;
and S5, adding the dispersant and the rest deionized water in the formula amount into the fourth mixture, and stirring for a period of time to obtain the lithium ion battery anode slurry.
Preferably, in step S1, the mixture is stirred in a double planetary stirrer at a speed of 15-30rpm of revolution for 15-30 min.
Preferably, in step S2, the revolution stirring speed of the double planetary stirrer is 15-30rpm, the rotation stirring speed is 1000-1500rpm, and the stirring time is 60-80 min.
Preferably, in step S3, the revolution stirring speed of the double planetary stirrer is 15-30rpm, and the stirring time is 5-10 min.
Preferably, in step S4, the revolution stirring speed of the double planetary stirrer is 15-30rpm, the rotation stirring speed is 1000-1500rpm, and the stirring time is 60-90 min.
Preferably, in step S5, the revolution stirring speed of the double planetary stirrer is 15-30rpm, the rotation stirring speed is 1000-1500rpm, and the stirring time is 30-60 min.
Preferably, the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is (2-8): (8-2).
Preferably, the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is (50-60): (15-20): (15-20)(5-10).
Preferably, steps S1 to S5 are all performed at a negative pressure of 0 to-20 kPa.
The invention has the beneficial effects that:
the positive electrode slurry prepared by the invention can solve the problem that NCM is used as a positive electrode active substance to cause the positive electrode slurry to form gel or settle easily, ensure the stability of the positive electrode slurry and ensure the cycle life and safety of a lithium ion battery using the positive electrode slurry.
The invention uses the following components in the mass ratio of (7-9): (1-3) PVA-COOH and CMC as binders, PVA-COOH being capable of reacting with LiOH, Li2CO3The PVA-COOLi is generated through reaction, on one hand, the pH value of the anode slurry can be adjusted to 8-10, the slurry is prevented from forming gel or settling due to overhigh pH value, and the stability of the slurry is improved; meanwhile, LiOH, Li2CO3The reduction of the positive electrode slurry can reduce the gas generation of the lithium ion battery using the positive electrode slurry in the charging and discharging process, thereby avoiding the expansion deformation of the lithium ion battery and ensuring the service life. On the other hand, the PVA-COOLi can be used as a lithium supplement agent to prolong the cycle life of the battery in the charging and discharging processes. In addition, the positive electrode slurry is coated and dried on the positive electrode current collector to form a positive electrode diaphragm which is combined with the positive electrode current collectorAfter the positive plate, part of carboxyl which is not completely substituted in the CMC may react with hydroxyl in PVA-COOH in the baking process of the positive plate, so that the stability of the positive plate is further increased, and the stripping force of the positive plate on the positive plate is improved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood, however, that the description herein of specific embodiments is intended to illustrate and not limit the invention.
Example 1
The lithium ion battery anode slurry of the embodiment comprises the following raw materials in percentage by weight:
Figure BDA0003509023430000041
wherein the binder consists of PVA-COOH and CMC in a mass ratio of 8: 2.
Wherein the conductive agent consists of Super P and CNT in a mass ratio of 3: 1.
Wherein the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion.
The preparation method of the lithium ion battery anode slurry of the embodiment comprises the following steps:
s1, putting PVA-COOH, NCM and a first part of deionized water with the formula ratio into a double-planet stirrer, adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, and stirring for 15min to enable the pH value to be 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 60min to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm and the stirring time to be 5min to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm, the rotation stirring speed to be 1500rpm and the stirring time to be 60min to obtain a fourth mixture;
and S5, adding the dispersant and the residual deionized water in the formula amount into the fourth mixture, and adjusting the revolution stirring speed of a double-planet stirrer to be 30rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 30min to obtain the lithium ion battery anode slurry.
Wherein the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is 1: 1.
Wherein the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is 5:2:2: 1.
The positive electrode slurry of this example was prepared at a negative pressure of 0 to-20 kPa.
Example 2
The lithium ion battery anode slurry of the embodiment comprises the following raw materials in percentage by weight:
Figure BDA0003509023430000051
wherein the binder consists of PVA-COOH and CMC in a mass ratio of 7: 3.
Wherein the conductive agent consists of Super P and CNT in a mass ratio of 3: 1.
Wherein the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion.
The preparation method of the lithium ion battery anode slurry of the embodiment comprises the following steps:
s1, putting PVA-COOH, NCM and a first part of deionized water with the formula ratio into a double-planet stirrer, adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, and stirring for 15min to enable the pH value to be 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 60min to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm and the stirring time to be 5min to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm, the rotation stirring speed to be 1500rpm and the stirring time to be 60min to obtain a fourth mixture;
and S5, adding the dispersant and the residual deionized water in the formula amount into the fourth mixture, and adjusting the revolution stirring speed of a double-planet stirrer to be 30rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 30min to obtain the lithium ion battery anode slurry.
Wherein the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is 1: 1.
Wherein the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is 5:2:2: 1.
The positive electrode slurry of this example was prepared at a negative pressure of 0 to-20 kPa.
Example 3
The lithium ion battery anode slurry of the embodiment comprises the following raw materials in percentage by weight:
Figure BDA0003509023430000061
wherein the binder consists of PVA-COOH and CMC in a mass ratio of 8: 2.
Wherein the conductive agent consists of Super P and CNT in a mass ratio of 4: 1.
Wherein the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion.
The preparation method of the lithium ion battery anode slurry of the embodiment comprises the following steps:
s1, putting PVA-COOH, NCM and a first part of deionized water with the formula ratio into a double-planet stirrer, adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, and stirring for 15min to enable the pH value to be 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 60min to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm and the stirring time to be 5min to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm, the rotation stirring speed to be 1500rpm and the stirring time to be 60min to obtain a fourth mixture;
and S5, adding the dispersant and the residual deionized water in the formula amount into the fourth mixture, and adjusting the revolution stirring speed of a double-planet stirrer to be 30rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 30min to obtain the lithium ion battery anode slurry.
Wherein the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is 1: 1.
Wherein the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is 5:2:2: 1.
The positive electrode slurry of this example was prepared at a negative pressure of 0 to-20 kPa.
Example 4
The lithium ion battery anode slurry of the embodiment comprises the following raw materials in percentage by weight:
Figure BDA0003509023430000071
Figure BDA0003509023430000081
wherein the binder consists of PVA-COOH and CMC in a mass ratio of 8: 2.
Wherein the conductive agent consists of Super P and CNT in a mass ratio of 3: 2.
Wherein the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion.
The preparation method of the lithium ion battery anode slurry of the embodiment comprises the following steps:
s1, putting PVA-COOH, NCM and a first part of deionized water into a double-planet stirrer, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, wherein the stirring time is 15min, so that the pH value is 8-10, and a first mixture is obtained;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 60min to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm and the stirring time to be 5min to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm, the rotation stirring speed to be 1500rpm and the stirring time to be 60min to obtain a fourth mixture;
and S5, adding the dispersant and the rest deionized water according to the formula ratio into the fourth mixture, and adjusting the revolution stirring speed of a double-planet stirrer to be 30rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 30min to obtain the lithium ion battery anode slurry.
Wherein the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is 1: 1.
Wherein the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is 5:2:2: 1.
The positive electrode slurry of this example was prepared at a negative pressure of 0 to-20 kPa.
Example 5
The lithium ion battery anode slurry of the embodiment comprises the following raw materials in percentage by weight:
Figure BDA0003509023430000082
Figure BDA0003509023430000091
wherein the binder consists of PVA-COOH and CMC in a mass ratio of 8: 2.
Wherein the conductive agent consists of Super P and CNT in a mass ratio of 3: 1.
Wherein the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion.
The preparation method of the lithium ion battery anode slurry of the embodiment comprises the following steps:
s1, putting PVA-COOH, NCM and a first part of deionized water with the formula ratio into a double-planet stirrer, adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, and stirring for 15min to enable the pH value to be 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 60min to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm and the stirring time to be 5min to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm, the rotation stirring speed to be 1500rpm and the stirring time to be 60min to obtain a fourth mixture;
and S5, adding the dispersant and the residual deionized water in the formula amount into the fourth mixture, and adjusting the revolution stirring speed of a double-planet stirrer to be 30rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 30min to obtain the lithium ion battery anode slurry.
Wherein the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is 1: 1.
Wherein the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is 5:2:2: 1.
The positive electrode slurry of this example was prepared at a negative pressure of 0 to-20 kPa.
Comparative example 1
The lithium ion battery anode slurry of the embodiment comprises the following raw materials in percentage by weight:
Figure BDA0003509023430000101
wherein the binder consists of PVA-COOH and CMC in a mass ratio of 8: 2.
Wherein the conductive agent consists of Super P and CNT in a mass ratio of 3: 1.
Wherein the dispersant is vinyl acetate-butyl acrylate copolymer emulsion.
The preparation method of the lithium ion battery anode slurry of the embodiment comprises the following steps:
s1, putting PVA-COOH, NCM and a first part of deionized water with the formula ratio into a double-planet stirrer, adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, and stirring for 15min to enable the pH value to be 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 60min to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm and the stirring time to be 5min to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm, the rotation stirring speed to be 1500rpm and the stirring time to be 60min to obtain a fourth mixture;
and S5, adding the dispersant and the residual deionized water in the formula amount into the fourth mixture, and adjusting the revolution stirring speed of a double-planet stirrer to be 30rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 30min to obtain the lithium ion battery anode slurry.
Wherein the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is 1: 1.
Wherein the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is 5:2:2: 1.
The positive electrode slurry of this example was prepared at a negative pressure of 0 to-20 kPa.
Comparative example 2
The lithium ion battery anode slurry of the embodiment comprises the following raw materials in percentage by weight:
Figure BDA0003509023430000111
wherein the binder consists of PVA-COOH and CMC in a mass ratio of 1: 9.
Wherein the conductive agent consists of Super P and CNT in a mass ratio of 3: 1.
Wherein the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion.
The preparation method of the lithium ion battery anode slurry of the embodiment comprises the following steps:
s1, putting PVA-COOH, NCM and a first part of deionized water with the formula ratio into a double-planet stirrer, adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, and stirring for 15min to enable the pH value to be 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 15rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 60min to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm and the stirring time to be 5min to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and adjusting the revolution stirring speed of the double-planet stirrer to be 30rpm, the rotation stirring speed to be 1500rpm and the stirring time to be 60min to obtain a fourth mixture;
and S5, adding the dispersant and the residual deionized water in the formula amount into the fourth mixture, and adjusting the revolution stirring speed of a double-planet stirrer to be 30rpm, the rotation stirring speed to be 1000rpm and the stirring time to be 30min to obtain the lithium ion battery anode slurry.
Wherein the mass ratio of the partial CMC in the step S2 to the residual CMC in the step S3 is 1: 1.
Wherein the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is 5:2:2: 1.
The positive electrode slurry of this example was prepared at a negative pressure of 0 to-20 kPa.
Performance testing and analysis
The initial viscosity, the viscosity after 8 hours, the number of times of folding and light-tight of the coated positive electrode sheet, the peeling force of the coated positive electrode sheet, the ultimate compaction density, the resistance and the capacity of the positive electrode sheet of the positive electrode slurry prepared in the examples 1 to 5 and the positive electrode slurry prepared in the comparative examples 1 to 2 are respectively carried out, and the test results are shown in table 1.
TABLE 1
Figure BDA0003509023430000121
Figure BDA0003509023430000131
Referring to the test data in table 1, the following analysis was performed:
(1) the difference between the example 1 and the examples 3-5 is that the percentage of each raw material is different, so that the performances are different, but the performances are all at the better level, and the comprehensive comparison shows that the performance of the example 1 is optimal.
(2) Example 1 is different from example 2 in the mass ratio of PVA-COOH to CMC, and compared with the test data of the two examples, example 1 is superior to example 2, which shows that the positive electrode slurry prepared by using PVA-COOH and CMC in the mass ratio of 8:2 has the best effect.
(3) Example 1 differs from comparative example 1 in that the raw material solid content of comparative example 1 is increased, resulting in a significant increase in the positive electrode paste viscosity and the positive electrode sheet resistance, while the positive electrode sheet peel force, ultimate compacted density, and capacity are reduced.
(4) Example 1 differs from comparative example 2 in that comparative example 2, to which only a small amount of PVA-COOH was added, the positive electrode slurry sagged after 8 h. This is because too little PVA-COOH was added to maintain the pH in the appropriate range (8-10), which resulted in settling of the slurry with the binder CMC being the predominant amount. The PVA-COOLi is generated through the reaction of the PVA-COOH and the lithium carbonate and the lithium hydroxide which are remained on the surface of the anode material, the pH value of a slurry system is reduced, the slurry sedimentation is prevented, and the formation of the PVA-COOLi is more beneficial to the exertion of capacity; in addition, when the addition amount of the CMC was too large, the positive electrode sheet showed a decrease in ultimate compacted density, and the ratio of 1: the ultimate compacted density of PVA-COOH and CMC at a 9 mass ratio was only 3.25g.cm-3Peel force 0.3N, whereas example 1 8: ultimate compacted density of PVA-COOH and CMC at 2 mass ratio of 3.65g.cm-3And the stripping force is 0.61N, which shows that the addition of a large amount of PVA-COOH is favorable for improving the binding force and the compaction density of the positive plate, thereby further improving the electrochemical performance of the battery. The PVA-COOH has strong mechanical processing performance and adhesive force, and due to the addition of the CMC, a part of carboxyl which is not completely substituted in the CMC can possibly react with hydroxyl in the PVA-COOH in the baking process of the positive plate, so that the stability of the positive plate is further improved, the stripping force of the positive plate on the positive plate is improved, and the positive plate is ensured to be strippedThe positive plate can not be broken and fall powder under the condition of higher compaction density.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The positive electrode slurry of the lithium ion battery is characterized in that: the conductive adhesive comprises NCM, an adhesive, a conductive agent, a dispersing agent and deionized water, wherein the adhesive is prepared from the following components in percentage by mass (7-9): (1-3) PVA-COOH and CMC.
2. The lithium ion battery positive electrode slurry according to claim 1, wherein: the binder consists of PVA-COOH and CMC in a mass ratio of 8: 2.
3. The lithium ion battery anode slurry according to claim 1, wherein the anode slurry comprises the following raw materials in percentage by weight:
Figure FDA0003509023420000011
4. the lithium ion battery anode slurry according to claim 3, wherein the anode slurry comprises the following raw materials in percentage by weight:
Figure FDA0003509023420000012
5. the lithium ion battery positive electrode slurry according to claim 1, wherein: the conductive agent is at least one of Super P, acetylene black and CNT;
the dispersing agent is vinyl acetate-butyl acrylate copolymer emulsion or polyvinyl acrylate.
6. The method for preparing the positive electrode slurry of the lithium ion battery according to any one of claims 1 to 5, characterized by comprising the following steps:
s1, mixing and stirring PVA-COOH, NCM and a first part of deionized water in a formula amount in a double-planet stirrer for a period of time, and adjusting the pH value to 8-10 to obtain a first mixture;
s2, adding the conductive agent, part of CMC and the second part of deionized water in the formula amount into the first mixture, and stirring for a period of time to obtain a second mixture;
s3, adding the residual CMC into the second mixture, and stirring for a period of time to obtain a third mixture;
s4, adding a third part of deionized water into the third mixture, and stirring for a period of time to obtain a fourth mixture;
and S5, adding the dispersant and the rest deionized water in the formula amount into the fourth mixture, and stirring for a period of time to obtain the lithium ion battery anode slurry.
7. The method for preparing the positive electrode slurry of the lithium ion battery according to claim 6, wherein the method comprises the following steps: in step S1, the revolution stirring speed of the double planetary stirrer is 15-30rpm, and the stirring time is 15-30 min;
in step S3, the revolution stirring speed of the double planetary stirrer is 15-30rpm, and the stirring time is 5-10 min.
8. The method for preparing the positive electrode slurry of the lithium ion battery according to claim 6, wherein the method comprises the following steps: in step S2, the revolution stirring speed of the double planetary stirrer is 15-30rpm, the rotation stirring speed is 1000-1500rpm, and the stirring time is 60-80 min;
in step S4, the revolution stirring speed of the double planetary stirrer is 15-30rpm, the rotation stirring speed is 1000-1500rpm, and the stirring time is 60-90 min;
in step S5, the revolution stirring speed of the double planetary stirrer is 15-30rpm, the rotation stirring speed is 1000-1500rpm, and the stirring time is 30-60 min.
9. The method for preparing the positive electrode slurry of the lithium ion battery according to claim 6, wherein the method comprises the following steps: the mass ratio of the part of the CMC added to the first mixture in step S2 to the remaining CMC in step S3 is (2-8): (8-2);
the mass ratio of the first part of deionized water in the step S1, the second part of deionized water in the step S2, the third part of deionized water in the step S4 and the rest of deionized water in the step S5 is (50-60): (15-20): (15-20)(5-10).
10. The method for preparing the positive electrode slurry of the lithium ion battery according to claim 6, wherein the method comprises the following steps: steps S1 to S5 are all performed under a negative pressure of 0 to-20 kPa.
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