CN111384430B - Preparation method of high-safety polymer ternary lithium power battery - Google Patents
Preparation method of high-safety polymer ternary lithium power battery Download PDFInfo
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- CN111384430B CN111384430B CN202010031492.6A CN202010031492A CN111384430B CN 111384430 B CN111384430 B CN 111384430B CN 202010031492 A CN202010031492 A CN 202010031492A CN 111384430 B CN111384430 B CN 111384430B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- 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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- 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
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Abstract
The invention provides a preparation method of a high-safety polymer ternary lithium power battery, and belongs to the technical field of lithium ion batteries. According to the invention, AT9 is coated on the blank part of the positive electrode current collector, so that internal short circuit caused by point discharge in the charging and discharging process and under the limit conditions of needling, extrusion and the like of the battery is prevented, and the safety of the battery is improved. According to the invention, 5% of lithium titanate material is further added into the negative electrode graphite, so that the characteristics of the lithium titanate battery on a low voltage platform and high safety coefficient are fully utilized, especially in the process of overcharging the battery, the lithium titanate material starts to generate gas continuously along with the rise of voltage, the explosion-proof device can be opened by the internal gas of the battery under relatively safe voltage, the safety protection effect is further achieved, and the high safety performance of the nickel cobalt lithium manganate polymer power battery is realized.
Description
The present application claims priority of chinese patent application with the application number CN201910215579.6 entitled "a method for manufacturing a high safety polymer ternary lithium power battery" filed by chinese patent office on 21.03.2019, which is incorporated herein by reference in its entirety.
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a cylindrical nickel cobalt lithium manganate power battery capable of passing safety tests such as overcharge and needling.
Background
The nickel-cobalt lithium manganate lithium ion power battery has excellent performances of low cost, high energy density, long cycle life and the like, is widely popularized and applied to the field of new energy automobiles, but the safety performance of the ternary material lithium ion power battery is poorer than that of other material systems, and particularly the overcharge and needling performances need to be further improved to meet the safety performance requirement. Common methods for improving safety performance include structural improvement of cell pole pieces, improvement of active materials, and adoption of high-safety materials. For example, the surface of the pole piece is coated with an alumina ceramic coating for electronic isolation and ion conduction, and a coating process is adopted in the manufacturing of the ternary lithium ion battery, or electrolyte with overcharge-proof and flame-retardant additives is used. At present, the requirements of power batteries on energy density and safety are very strict, the energy density of the batteries can be greatly sacrificed by the common method, in addition, various safety improving materials are mutually matched, and if the safety improving materials are not proper, the effect of improving the safety performance of a battery core cannot be achieved, and the performance of the batteries can be deteriorated.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a high-safety polymer ternary lithium power battery, and AT9 is coated on the blank part of the positive electrode current collector, so that the internal short circuit caused by point discharge of the battery in the charging and discharging process and under the limit conditions of needling, extrusion and the like is prevented, and the safety of the battery is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a high-safety polymer ternary lithium power battery, which comprises the following steps:
a) dry mixing the ternary positive active substance, the conductive agent and PVDF in a stirring tank, adding an NMP solvent, and uniformly mixing by using a vacuum high-speed stirrer to prepare positive slurry;
b) uniformly coating the positive electrode slurry on a positive electrode current collector by using an extrusion, spraying or transfer coating machine, coating AT9 with the width of 0.5-1 mm AT the tab blank position, and forming a positive electrode piece after drying, rolling, slitting and welding the electrode tab;
c) dry-mixing a negative electrode active material and a conductive agent, adding a binder which is well stirred by taking deionized water as a solvent, and uniformly mixing by using a vacuum high-speed stirrer to prepare negative electrode slurry;
d) uniformly coating the negative electrode slurry on a negative electrode current collector by using an extrusion, spraying or transfer coating machine, and forming a negative electrode plate after drying, rolling, slitting and welding electrode lugs;
e) and winding the prepared positive and negative pole pieces and the wet-process ceramic diaphragm, entering a shell, performing bottom welding, rolling a groove, baking, injecting liquid, welding a cover cap, sealing, forming and grading to obtain the polymer nickel ternary lithium power battery.
Preferably, the ternary positive active material is nickel cobalt lithium manganate or nickel cobalt lithium aluminate, the AT9 is powdery or liquid alpha-alumina, and the mass ratio of the alpha-alumina: PVDF 9: 1; the negative active material is a mixture of artificial graphite and lithium titanate, and the mass ratio of the artificial graphite: lithium titanate 9.5: 0.5.
preferably, the positive electrode slurry is prepared by mixing the following positive electrode active materials in percentage by mass: conductive agent: PVDF 96.5: 2: 1.5, the solid content of the slurry is 60 percent, and the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 8000 +/-2000 mpa & s.
Preferably, the negative electrode slurry is prepared by mixing the following negative electrode active materials in mass ratio: conductive agent: binder 96: 2: 2, the solid content of the slurry is 40 percent, the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 4000 +/-2000 mpa & s.
Compared with the prior art, the manufactured lithium ion battery has excellent electrochemical performance and high safety performance, and the AT9 is coated AT the blank part of the positive electrode current collector, so that the internal short circuit caused by point discharge in the charging and discharging process and under the limit conditions of needling, extrusion and the like of the battery is prevented, and the safety of the battery is improved.
Preferably, the lithium titanate material is added into the negative electrode active material, so that the characteristics of a low voltage platform and high safety coefficient of the lithium titanate material are fully utilized, particularly, in the process of overcharging of the battery, the lithium titanate material starts to generate gas continuously along with the rise of voltage, the explosion-proof device can be opened by the internal gas of the battery under relatively safe voltage, the safety protection effect is further achieved, and the cycle life of the battery can be prolonged; in addition, the lithium titanate material has the advantages of simple preparation, good processing performance, high cost performance and the like.
Detailed Description
The invention provides a preparation method of a high-safety polymer ternary lithium power battery, which comprises the following steps:
a) dry mixing the ternary positive active substance, the conductive agent and PVDF in a stirring tank, adding an NMP solvent, and uniformly mixing by using a vacuum high-speed stirrer to prepare positive slurry;
b) uniformly coating the positive electrode slurry on a positive electrode current collector by using an extrusion, spraying or transfer coating machine, coating AT9 with the width of 0.5-1 mm AT the tab blank position, and forming a positive electrode piece after drying, rolling, slitting and welding the electrode tab;
c) dry-mixing a negative electrode active material and a conductive agent, adding a binder which is well stirred by taking deionized water as a solvent, and uniformly mixing by using a vacuum high-speed stirrer to prepare negative electrode slurry;
d) uniformly coating the negative electrode slurry on a negative electrode current collector by using an extrusion, spraying or transfer coating machine, and forming a negative electrode plate after drying, rolling, slitting and welding electrode lugs;
e) and winding the prepared positive and negative pole pieces and the wet-process ceramic diaphragm, entering a shell, performing bottom welding, rolling a groove, baking, injecting liquid, welding a cover cap, sealing, forming and grading to obtain the polymer nickel ternary lithium power battery.
The ternary positive active substance, the conductive agent and the PVDF are dry-mixed in a stirring tank, then the NMP (N-methyl pyrrolidone) solvent is added, and the mixture is uniformly mixed by a vacuum high-speed stirrer to prepare the positive slurry.
In the present invention, the ternary positive electrode active material is preferably lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate, and the conductive agent is not particularly limited in the present invention, and may be any conductive agent known to those skilled in the art, such as Carbon Nanotubes (CNTs). In the present invention, the preparation of the cathode slurry is preferably a positive electrode active material in a mass ratio of: conductive agent: PVDF 96.5: 2: 1.5, the solid content of the slurry is 60 percent (the solvent is NMP), the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 8000 +/-2000 mpa & s. The method is not specially limited for the specific operation conditions in the process of preparing the anode slurry, and can realize the uniform mixing of all the components.
After the positive pole slurry is obtained, the positive pole slurry is uniformly coated on a positive pole current collector by using an extrusion, spraying or transfer coating machine, AT9 with the width of 0.5-1 mm is coated AT the tab blank position, and the positive pole piece is formed after drying, rolling, slitting and welding the tab.
In the invention, the AT9 is preferably a powdery or liquid α -alumina, and the mass ratio of α -alumina: PVDF 9: 1. the invention preferably coats AT9 slurry on the tab blank part to form an AT9 coating with the width of 0.5-1 mm. In the present invention, the preparation method of the AT9 slurry preferably comprises: adopting NMP as a solvent, wherein the weight ratio of alpha-aluminum oxide: PVDF 9: 1, the solid content of the slurry is 50 percent, the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 4000 +/-1000 mpa-s. The method is not specially limited for the specific operation conditions in the process of preparing the AT9 slurry, and can realize uniform mixing of all the components. The specific coating mode of the AT9 slurry and the coating thickness of the AT9 coating are not specially limited and can be selected according to actual needs. The specific operations of drying, rolling, slitting and welding the tab are not particularly limited, and the method known by the technical personnel in the field can be adopted.
The invention dry-mixes the negative active material and the conductive agent, then adds the adhesive which is well stirred by using deionized water as the solvent, and evenly mixes the mixture by using a vacuum high-speed stirrer to prepare the negative slurry.
In the present invention, the negative electrode active material is preferably a mixture of artificial graphite and lithium titanate, where the mass ratio of artificial graphite: lithium titanate 9.5: 0.5. the present invention is not particularly limited to the kind of the adhesive, and any adhesive known to those skilled in the art may be used. In the invention, the preparation of the cathode slurry preferably takes deionized water as a solvent, and the cathode active material is prepared by the following components in percentage by mass: conductive agent: binder 96: 2: 2, the solid content of the slurry is 40 percent, the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 4000 +/-2000 mpa & s. The method is not specially limited for the specific operation conditions in the process of preparing the cathode slurry, and can realize the uniform mixing of all the components.
After the negative electrode slurry is obtained, the negative electrode slurry is uniformly coated on a negative electrode current collector by using an extrusion, spraying or transfer coating machine, and a negative electrode pole piece is formed after drying, rolling, slitting and welding electrode lugs. The specific operations of coating, drying, rolling, slitting and welding the tab are not particularly limited in the invention, and the method known to those skilled in the art can be adopted.
The preparation sequence of the positive pole piece and the negative pole piece is not specially limited.
After the positive pole piece and the negative pole piece are obtained, the positive pole piece and the negative pole piece and the wet-process ceramic diaphragm are wound, placed into a shell, subjected to bottom welding, subjected to groove rolling, baked, injected with liquid, subjected to cap welding, sealed, formed and subjected to capacity grading, and the polymer nickel ternary lithium power battery is obtained. The specific operations of winding, entering a shell, bottom welding, rolling a groove, baking, injecting liquid, welding a cap, sealing, forming and grading are not particularly limited, and the method known by the technical personnel in the field can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the nickel cobalt lithium manganate power battery with the specification of 9.4 × 155.5 × 208-22Ah (capacity) comprises the following steps:
NMP is adopted as a solvent, and according to the mass proportion, the nickel cobalt lithium manganate: CNT (carbon nanotube): PVDF 96.5: 2: 1.5, the solid content of the slurry is 60 percent, the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 8000 +/-1000 mpa-s, namely the anode slurry;
NMP is used as a solvent, AT9 adopts powdery alpha-alumina, and the powdery alpha-alumina is prepared from the following components in percentage by mass: PVDF 9: 1, uniformly mixing the slurry with a solid content of 50% by using a high-speed vacuum mixer, and preparing AT9 slurry with the viscosity of the mixed slurry of 4000 +/-1000 mpa & s;
uniformly coating the positive electrode slurry on a positive electrode current collector by using an extrusion or transfer coating machine, coating AT9 slurry with the width of 0.5-1 mm AT the tab blank position, and forming a positive electrode piece after drying, rolling, slitting and welding the electrode tab;
deionized water is used as a solvent, and the mass ratio of the negative electrode active material: conductive agent: binder 96: 2: 2, the solid content of the slurry is 40%, the slurry is uniformly mixed by a high-speed vacuum mixer, the viscosity of the mixed slurry is 4000 +/-1000 mpa.s, and the mixed slurry is cathode slurry, wherein the cathode active substance is a mixture of artificial graphite and lithium titanate, and the mass ratio of the mixture is artificial graphite: lithium titanate 9.5: 0.5;
uniformly coating the negative electrode slurry on a negative electrode current collector by using an extrusion or transfer coating machine, and forming a negative electrode plate after drying, rolling, slitting and welding electrode lugs;
and winding the prepared positive and negative pole pieces and the wet-process ceramic diaphragm, putting into a shell, performing bottom welding, rolling a groove, baking, injecting liquid, welding a cover cap, sealing, forming and grading to obtain the cylindrical lithium ion battery.
The cylindrical lithium ion battery obtained in the embodiment 1 is used as a sample, the safety of the battery is tested according to the requirements of GBT 31485-2015, 2 samples are tested in parallel in each test item, 10 samples are obtained in total and are respectively numbered from 1# to 10#, and the test results are shown in Table 1. As can be seen from table 1, after destructive tests such as short circuit, overcharge, thermal shock, needle prick, and weight impact, the battery did not explode or ignite, which indicates that the method provided by the present invention can improve the safety of the battery.
Table 1 safety test results of the cylindrical lithium ion battery prepared in example 1
Comparative example 1
A cylindrical lithium ion battery was manufactured by referring to the method of example 1, except that the steps of preparing the AT9 slurry and coating the AT9 slurry AT the tab margin were omitted.
The cylindrical lithium ion battery obtained in the comparative example 1 is used as a sample, the safety of the battery is tested according to the GBT 31485-2015 requirement, 2 samples are tested in parallel in each test item, 10 samples are obtained in total and are respectively numbered from 1# to 10#, and the test results are shown in Table 2. As can be seen from table 2, after destructive tests such as short circuit, thermal shock, and heavy impact, the battery did not explode or ignite, but after overcharge and needle punching tests, the battery ignited and exploded, which indicates that the lithium ion battery prepared in comparative example 1 has a certain potential safety hazard.
Table 2 safety test results of the cylindrical lithium ion battery prepared in comparative example 1
Comparative example 2
A cylindrical lithium ion battery was manufactured with reference to the method of example 1, except that the composition of the negative active material was only artificial graphite.
The cylindrical lithium ion battery obtained in the comparative example 2 is used as a sample, the safety of the battery is tested according to the GBT 31485-2015 requirement, 2 samples are tested in parallel in each test item, 10 samples are obtained in total and are respectively numbered from 1# to 10#, and the test results are shown in Table 3. As can be seen from table 3, after the destructive tests of short circuit, thermal shock and heavy impact, the battery did not explode or ignite, but after the overcharge and needle-punch tests, the battery was exploded, which indicates that the lithium ion battery prepared in comparative example 2 has a certain potential safety hazard.
Table 3 safety test results of the cylindrical lithium ion battery prepared in comparative example 2
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (1)
1. A preparation method of a high-safety polymer ternary lithium power battery is characterized by comprising the following steps:
a) dry mixing the ternary positive active substance, the conductive agent and PVDF in a stirring tank, adding an NMP solvent, and uniformly mixing by using a vacuum high-speed stirrer to prepare positive slurry;
b) uniformly coating the positive electrode slurry on a positive electrode current collector by using an extrusion, spraying or transfer coating machine, coating AT9 with the width of 0.5-1 mm AT the tab blank position, and forming a positive electrode piece after drying, rolling, slitting and welding the electrode tab;
c) dry-mixing a negative electrode active material and a conductive agent, adding a binder which is well stirred by taking deionized water as a solvent, and uniformly mixing by using a vacuum high-speed stirrer to prepare negative electrode slurry;
d) uniformly coating the negative electrode slurry on a negative electrode current collector by using an extrusion, spraying or transfer coating machine, and forming a negative electrode plate after drying, rolling, slitting and welding electrode lugs;
e) winding the prepared positive and negative pole pieces and the wet-process ceramic diaphragm, entering a shell, performing bottom welding, rolling a groove, baking, injecting liquid, welding a cover cap, sealing, forming and grading to obtain the polymer nickel ternary lithium power battery;
the ternary positive active substance is nickel cobalt lithium manganate or nickel cobalt lithium aluminate, the AT9 is powdery or liquid alpha-alumina, and the mass ratio of the alpha-alumina: PVDF 9: 1; the negative active material is a mixture of artificial graphite and lithium titanate, and the mass ratio of the artificial graphite: lithium titanate 9.5: 0.5;
the preparation of the anode slurry comprises the following steps of preparing an anode active material according to the mass ratio: conductive agent: PVDF 96.5: 2: 1.5, the solid content of the slurry is 60 percent, the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 8000 +/-2000 mpa & s;
the preparation of the cathode slurry comprises the following steps of preparing a cathode active material according to the mass ratio: conductive agent: binder 96: 2: 2, the solid content of the slurry is 40 percent, the slurry is uniformly mixed by a high-speed vacuum mixer, and the viscosity of the mixed slurry is 4000 +/-2000 mpa & s.
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| CN108604708A (en) * | 2016-02-29 | 2018-09-28 | 松下知识产权经营株式会社 | Non-aqueous electrolyte secondary battery |
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| US20080138699A1 (en) * | 2006-12-07 | 2008-06-12 | Jinhee Kim | Jelly roll electrode assembly and secondary battery using the assembly |
| CN101431169A (en) * | 2008-10-29 | 2009-05-13 | 东莞新能源科技有限公司 | Lithium ion cell and cell body |
| JP5837884B2 (en) * | 2010-10-27 | 2015-12-24 | 協立化学産業株式会社 | Conductive undercoat agent composition |
| WO2018179900A1 (en) * | 2017-03-31 | 2018-10-04 | パナソニックＩｐマネジメント株式会社 | Secondary battery |
| CN107959021A (en) * | 2017-10-31 | 2018-04-24 | 湖北猛狮新能源科技有限公司 | A kind of preparation method of cylinder nickle cobalt lithium manganate power battery |
| CN109473729B (en) * | 2018-11-05 | 2020-11-13 | 宁德新能源科技有限公司 | Electrochemical device |
| CN109449478A (en) * | 2018-11-05 | 2019-03-08 | 宁德新能源科技有限公司 | Electrochemical appliance |
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| CN105703010A (en) * | 2014-11-28 | 2016-06-22 | 宁德时代新能源科技股份有限公司 | Electrode slice and electrochemical energy storage device |
| CN108604708A (en) * | 2016-02-29 | 2018-09-28 | 松下知识产权经营株式会社 | Non-aqueous electrolyte secondary battery |
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