CN112467066A - Pulping method of high-nickel ternary material - Google Patents
Pulping method of high-nickel ternary material Download PDFInfo
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- CN112467066A CN112467066A CN202011337522.2A CN202011337522A CN112467066A CN 112467066 A CN112467066 A CN 112467066A CN 202011337522 A CN202011337522 A CN 202011337522A CN 112467066 A CN112467066 A CN 112467066A
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- ternary material
- nickel ternary
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/48—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
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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
- H01M4/48—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a pulping method of a high-nickel ternary material, which is characterized in that CO is introduced from the bottom of a high-speed stirring dispersion tank before feeding of high-nickel ternary main powder2Gas, so that the mixed liquid of the tank body, the glue and the conductive agent is filled with CO2A gas. While stirring and dispersing the slurry, continuously introducing CO2Gas, CO2Reacts with LiOH on the surface of the high-nickel ternary material to generate alkalescent Li2CO3. The slurry prepared by the method has good fluidity, and has good overcharge resistance after being prepared into a battery cell.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a pulping method of a high-nickel ternary material.
Background
Lithium ion batteries have high energy density and long life and are therefore ideal energy sources for electric vehicles and other power tools. Among layered transition metal oxide positive electrode materials, lithium nickel cobalt manganese oxide (NCM) or lithium Nickel Cobalt Aluminate (NCA) has a high specific capacity, and thus has attracted many researches.
With the improvement of the endurance requirement of the lithium ion battery, the development of the anode material with higher specific capacity is required. Therefore, in recent years, a high nickel ternary positive electrode material has received much attention. Compared with the low-nickel ternary cathode material, the high-nickel ternary cathode material has higher nickel content, so that the high-nickel ternary cathode material has higher specific capacity. However, the increase of the nickel content effectively increases the specific capacity and brings many disadvantages, for example, the surface of the high-nickel ternary material has more LiOH, which is easily reacted with the binder PVDF, so that the binder PVDF loses activity, and the viscosity of the material during slurry preparation is increased, even a gel phenomenon occurs, and the material does not have coating performance. Therefore, in order to enable the high-nickel ternary material slurry to have better rheological property, most industry practitioners start with the control of LiOH of the raw material, and adopt ion doping, cladding and water washing modes to reduce residual alkali; or the temperature and the humidity during pulping are controlled to improve the performance of the pulp. But all add to the complexity and cost of pulping.
Disclosure of Invention
The invention aims to solve the problem of overhigh viscosity of the high-nickel ternary material during pulping and improve the overcharge performance of a battery, and provides a pulping method of the high-nickel ternary material to solve the technical problem.
In order to achieve the technical effects, the invention provides the following technical scheme:
a pulping method of a high-nickel ternary material comprises the following steps:
(1) dissolving a binder in an NMP solvent, and stirring and dispersing to prepare a viscose solution;
(2) adding the carbon tube conductive slurry into the viscose solution, and stirring and mixing by using a high-speed stirring dispersion tank;
(3) introducing CO into the high-speed stirring dispersion tank2Gas, so that the mixed liquid of the tank body, the glue and the conductive agent is filled with CO2A gas;
(4) adding the high-nickel ternary material into the high-speed stirring dispersion tank, and continuously introducing CO2And stirring and dispersing at high speed to obtain slurry.
The further technical scheme is that the binder is PVDF or PVDF copolymer, and the binder has the number average molecular weight of 800000-1500000.
The further technical scheme is that the mass fraction of the binder in the viscose solution is 0.9-2%.
The further technical scheme is that the mass fraction of the carbon tube conductive slurry in the slurry is 3% -10%, and the mass fraction of the conductive agent in the conductive slurry is 3% -10%.
The further technical scheme is that the high-nickel ternary material is a ternary material with the nickel content of more than 80%.
The further technical scheme is that the high-nickel ternary material is selected from NCA, NCM811 or a cobalt-free high-nickel positive electrode material.
More preferably, the high nickel ternary material is selected from NCA or NCM 811.
The further technical proposal is that the high-speed stirring dispersion tank is any one of a double-planet stirrer, a double-screw stirrer and a plow stirrer.
The further technical proposal is that a gas feed inlet is arranged at the bottom of the high-speed stirring dispersion tank, and CO is continuously introduced before the high-nickel ternary material is added and during the stirring dispersion of the slurry2A gas.
The further technical proposal is that the CO is2The gas purity is more than 99.9%.
The further technical proposal is that the CO is2The gas is introduced at a speed of 0.01-10 m 3/h.
The further technical scheme is that the rotating speed of stirring and dispersing in the step (3) is 800-1200 r/min, the mixing time is 20-30 min, the rotating speed of stirring and dispersing in the step (4) is 1000-1500 r/min, and the stirring time is 100-150 min.
Compared with the prior art, the invention has the following beneficial effects: for the high-nickel ternary material, LiOH on the surface can react with PVDF (polyvinylidene fluoride) as a binder to cause irreversible inactivation of the binder, and the viscosity of the slurry is increased sharply and has no fluidity and coating performance. Li2Decomposition of CO3 at high potentials in the charged state to produce CO2The battery explosion-proof valve can be opened in advance, and the battery is opened, so that the battery has good overcharge performance. Introducing CO from the bottom of the high-speed stirring dispersion tank before feeding the high-nickel ternary main powder2Gas, so that the mixed liquid of the tank body, the glue and the conductive agent is filled with CO2Gas, CO is continuously introduced while stirring and dispersing the slurry2Gas, CO2Reacts with LiOH on the surface of the high-nickel ternary material to generate alkalescent Li2CO3. Therefore, the prepared finished slurry has good fluidity, and has good overcharge performance after being prepared into a battery core.
Detailed Description
Example 1
(1) Controlling the ambient temperature: 25 ± 3 ℃, dew point temperature: -10 ℃. Dissolving 12kg of PVDF4300 in 200kg of solvent NMP according to the proportion of a binder, and stirring and dispersing for 100min at a rotating speed of 1000r/min by double planets to prepare a viscose solution;
(2) controlling the ambient temperature: 25 ± 3 ℃, dew point temperature: -10 ℃. Adding 30kg of CNT carbon nanotube conductive slurry with the mass fraction of 4% into the viscose solution, and mixing for 20min at the rotating speed of 1000r/min by using a double-planet stirrer;
(3) controlling the ambient temperature: 25 ± 3 ℃, dew point temperature: -10 ℃. To the above solution, 5m3CO with the purity of 99.99 percent is introduced at the flow rate of/h2Gas for 1 min. 400kg of a high nickel ternary material NCM811 as a positive electrode active material was added to the above can body at 1m3CO with the purity of 99.99 percent is continuously introduced at the flow rate of/h2Introducing gas for the time consistent with the stirring and dispersing time of the slurry, and stirring and dispersing the slurry at a high speed of 1200r/min by double planets for 120 min;
comparative example 1
Comparative example 1The difference from example 1 is that: comparative example 1 in which CO was not introduced2A gas.
Example 2
Example 2 differs from example 1 in that: while stirring the dispersed slurry, introducing CO2The flow rate of the gas is 5m3/h。
Example 3
Example 3 differs from example 1 in that: while stirring the dispersed slurry, introducing CO2The flow rate of the gas is 10m3/h。
Example 4
Example 4 differs from example 1 in that: before the high-nickel ternary material is added and when the slurry is stirred and dispersed, introducing CO2The purity of the gas was 99.9%.
The finished slurries of the above examples and comparative examples were taken and tested for viscosity. The test data for the slurry viscosity are shown in table 1:
TABLE 1 viscosity data for finished slurries of examples and comparative examples
The positive electrode slurry prepared by the above examples and comparative examples is subjected to defoaming, iron removal, coating, rolling and die cutting, then assembled with a graphite negative plate to form a 50Ah square aluminum shell battery cell with a safety explosion-proof valve, and subjected to liquid injection and formation, and then the battery cell is subjected to overcharge performance test. The overcharge performance of the cells is shown in table 2:
table 2 results of overcharge performance test of examples and comparative examples
| Sample (I) | Overcharge performance |
| Example 1 | The safety explosion-proof valve is opened, and the electric core does not catch fire or explode |
| Comparative example 1 | Fire and explosion |
| Example 2 | The safety explosion-proof valve is opened, and the electric core does not catch fire or explode |
| Example 3 | The safety explosion-proof valve is opened, and the electric core does not catch fire or explode |
| Example 4 | The safety explosion-proof valve is opened, and the electric core does not catch fire or explode |
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. The pulping method of the high-nickel ternary material is characterized by comprising the following steps:
(1) dissolving a binder in an NMP solvent, and stirring and dispersing to prepare a viscose solution;
(2) adding the carbon tube conductive slurry into the viscose solution, and stirring and mixing by using a high-speed stirring dispersion tank;
(3) introducing CO into the high-speed stirring dispersion tank2Gas, so that the mixed liquid of the tank body, the glue and the conductive agent is filled with CO2A gas;
(4) high nickel IIIAdding the raw materials into the high-speed stirring dispersion tank, and continuously introducing CO2And stirring and dispersing at high speed to obtain slurry.
2. The method for pulping a high-nickel ternary material according to claim 1, wherein the binder is PVDF or PVDF copolymer, and the binder has a number average molecular weight of 800000-1500000.
3. The method for pulping a high-nickel ternary material according to claim 1, wherein the mass fraction of the binder in the viscose solution is 0.9-2%.
4. The method for pulping a high-nickel ternary material according to claim 1, wherein the mass fraction of the carbon tube conductive paste in the paste is 3-10%, and the mass fraction of the conductive agent in the conductive paste is 3-10%.
5. The method of claim 1, wherein the high nickel ternary material is a ternary material having a nickel content of greater than 80%.
6. The method for pulping high-nickel ternary material according to claim 1, wherein the high-speed stirring dispersion tank is any one of a double planetary stirrer, a double screw stirrer and a plow stirrer.
7. The method for pulping the high-nickel ternary material according to claim 6, wherein a gas inlet is formed at the bottom of the high-speed stirring dispersion tank, and CO is continuously introduced before the high-nickel ternary material is added and during stirring and dispersing the slurry2A gas.
8. The method of pulping of a high nickel ternary material according to claim 1, wherein the CO is2The gas purity is more than 99.9%.
9. The method of pulping of a high nickel ternary material according to claim 1, wherein the CO is2The gas is introduced at a speed of 0.01 to 10m3/h。
10. The pulping method of the high-nickel ternary material according to claim 1, wherein the rotation speed of stirring and dispersing in the step (3) is 800-1200 r/min, the mixing time is 20-30 min, the rotation speed of stirring and dispersing in the step (4) is 1000-1500 r/min, and the stirring time is 100-150 min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011337522.2A CN112467066A (en) | 2020-11-25 | 2020-11-25 | Pulping method of high-nickel ternary material |
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| CN202011337522.2A CN112467066A (en) | 2020-11-25 | 2020-11-25 | Pulping method of high-nickel ternary material |
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Citations (10)
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| CN101504978A (en) * | 2009-03-19 | 2009-08-12 | 厦门钨业股份有限公司 | Lithium ionic cell positive plate made from ternary material and production method thereof |
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| US20150034862A1 (en) * | 2012-03-16 | 2015-02-05 | Hitachi Automotive Systems, Ltd. | Process for producing a positive electrode mix and a lithium ion secondary battery |
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| CN109742377A (en) * | 2019-01-17 | 2019-05-10 | 浙江工业大学 | A kind of method that nickelic tertiary cathode material surface is modified |
| CN109980224A (en) * | 2019-03-06 | 2019-07-05 | 天津力神电池股份有限公司 | A kind of anode sizing agent and preparation method and positive plate, lithium ion battery |
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| CN110915031A (en) * | 2017-07-19 | 2020-03-24 | 日本斯频德制造株式会社 | Method and apparatus for producing slurry for positive electrode of nonaqueous electrolyte secondary battery |
| CN111933923A (en) * | 2020-08-18 | 2020-11-13 | 苏州精诚智造智能科技有限公司 | Method for preparing ternary lithium ion battery |
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2020
- 2020-11-25 CN CN202011337522.2A patent/CN112467066A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101504978A (en) * | 2009-03-19 | 2009-08-12 | 厦门钨业股份有限公司 | Lithium ionic cell positive plate made from ternary material and production method thereof |
| KR20110136723A (en) * | 2010-06-15 | 2011-12-21 | 닛산 지도우샤 가부시키가이샤 | Manufacturing method for active material and active material slurry |
| US20150034862A1 (en) * | 2012-03-16 | 2015-02-05 | Hitachi Automotive Systems, Ltd. | Process for producing a positive electrode mix and a lithium ion secondary battery |
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Application publication date: 20210309 |