CN111564661A - High-safety lithium ion battery - Google Patents
High-safety lithium ion battery Download PDFInfo
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- CN111564661A CN111564661A CN202010587003.5A CN202010587003A CN111564661A CN 111564661 A CN111564661 A CN 111564661A CN 202010587003 A CN202010587003 A CN 202010587003A CN 111564661 A CN111564661 A CN 111564661A
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- lithium ion
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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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-safety lithium ion battery, which is characterized in that a composite positive plate, a polyolefin diaphragm and a composite negative plate are overlapped to form a pole core, the pole core is placed in a battery shell, then electrolyte is injected, the battery shell is pre-sealed and placed for 24 hours to form the battery, and the battery shell is sealed after exhausting, so that the lithium ion battery is obtained. The anode of the lithium ion battery is coated by adopting the polymer emulsion, and the cathode of the lithium ion battery is coated by adopting the inorganic ceramic slurry. The polymer emulsion coating of the anode not only provides an anode protective layer, increases the wettability of electrolyte and improves the cycle performance of the battery, but also improves the safety performance of the lithium ion battery. When the temperature of the battery is increased due to short circuit and the like in the battery, the high polymer emulsion particles can be rapidly melted on the surface of the positive electrode to form a protective layer for cutting off a lithium ion transmission channel between the positive electrode and the negative electrode; after the polyolefin diaphragm melts, the anode and cathode of the cathode ceramic coating can be separated at high temperature, so that thermal runaway is prevented.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-safety lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, environmental friendliness, long service life and the like, and is widely applied to portable energy sources, energy storage power supplies and electric vehicles.
At present, the lithium ion battery is generally composed of a positive electrode, a negative electrode and a diaphragm arranged between the positive electrode and the negative electrode, and then electrolyte is added into the positive electrode and the negative electrode. The diaphragm material adopts a polypropylene or polyethylene film, the lithium ion power battery is applied to a new energy automobile in a large scale, the higher requirement on the safety of the power battery is improved, and the technology of coating a ceramic layer on a polyolefin-based film is introduced. The ceramic separator still fails to address the safety of high energy lithium ion power cells.
How to improve the safety performance of the lithium ion power battery and solve the problem of fire and explosion becomes a common target of many researchers in the field. However, the current technology does not sufficiently address the safety performance of high energy density batteries, particularly high nickel ternary system batteries. From the stability of positive and negative pole piece perspective, when the safety problem takes place, cut off the problem rapidly, be the scheme of solving this problem. The surface of the anode is coated with a polymer microsphere coating, and the surface of the cathode is coated with a ceramic material, so that the safety performance can be improved; the heat rises due to the problems of short circuit and the like in the battery, and the polymer microsphere coating can be quickly melted on the surface of the pole piece to form a protective layer and cut off a transmission channel of the positive pole and the negative pole; meanwhile, the polymer microsphere coating can inhibit the side reaction of the electrolyte and the cathode in normal use, and the cycle performance of the battery is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-safety lithium ion battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-safety lithium ion battery is prepared by stacking a composite positive plate, a polyolefin diaphragm and a composite negative plate to form a pole core, placing the pole core in a battery shell, then injecting electrolyte, placing for 24 hours, forming, exhausting and sealing the battery shell to obtain the lithium ion battery.
Further, the composite positive plate comprises a positive current collector, a positive dressing layer and a polymer microsphere coating, wherein the polymer microsphere coating and the positive dressing layer are sequentially coated on one or two surfaces of the positive current collector along a direction far away from the positive current collector, the positive dressing layer comprises a positive active material, a positive conductive agent and a positive binder, and the polymer microsphere coating comprises polymer microspheres and a coating adhesive.
Further, the composite negative plate comprises a negative current collector, a negative electrode dressing layer and an inorganic ceramic coating, wherein the inorganic ceramic coating and the negative electrode dressing layer are sequentially coated on one surface or two surfaces of the negative current collector along the direction far away from the negative current collector, the negative electrode dressing layer comprises a negative active material, a negative conductive agent and a negative binder, and the inorganic ceramic coating comprises inorganic ceramic particles and a coating adhesive.
Preferably, the thickness of the polymer microsphere coating is 0.1-30 μm, the thickness of the positive electrode dressing layer is 10-500 μm, and the thickness of the positive electrode current collector is 10-40 μm.
More preferably, the polymer microsphere coating consists of the following components in percentage by mass: 60-99.5% of polymer microspheres and 0.5-40% of coating adhesive.
More preferably, the polymer microsphere is one or more of polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl alcohol and polyethylene copolymer, and the particle size of the polymer microsphere is 0.05-15 μm.
Preferably, the positive active material is selected from one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium nickelate.
Preferably, the inorganic ceramicThe particles being Al2O3、TiO2、SiO2、MgO、ZnO、ZrO2And CaO.
Preferably, the coating adhesive is one or more of carboxymethyl cellulose, styrene butadiene rubber, polyvinylidene fluoride and polyurethane.
Preferably, the coating means is selected from one of knife coating, dip coating, spray coating and extrusion.
Compared with the prior art, the lithium ion battery provided by the invention consists of the positive and negative electrodes of the composite coating, the polyolefin diaphragm and the electrolyte. And the anode and the cathode of the composite coating are coated by adopting high-molecular emulsion, and the cathode is coated by adopting inorganic ceramic slurry. The polymer emulsion coating of the anode not only provides an anode protective layer, increases the wettability of electrolyte and improves the cycle performance of the battery, but also improves the safety performance of the lithium ion battery. When the temperature of the battery is increased due to short circuit and the like in the battery, the high polymer emulsion particles can be rapidly melted on the surface of the positive electrode to form a protective layer for cutting off a lithium ion transmission channel between the positive electrode and the negative electrode; after the polyolefin diaphragm melts, the anode and cathode of the cathode ceramic coating can be separated at high temperature, so that thermal runaway is prevented.
Drawings
Fig. 1 is a discharge curve of the cell of example 1 at 0.5C rate;
fig. 2 discharge curves of the cells of example 1 under high and low temperature conditions;
fig. 3 cycling profile of the cells of example 1 at room temperature.
Detailed Description
The following detailed description is directed to specific embodiments of the invention.
Example 1
(1) Composite positive plate
Mixing and stirring high-nickel 811 ternary multi-walled carbon nanotubes and PVDF (polyvinylidene fluoride) adhesive according to the mass percentage of 97.5:0.7:1.8, coating the mixture on an aluminum foil with the thickness of 16 mu m on a coating machine, coating the mixture with the thickness of 250 mu m, and rolling the mixture for later use;
adding a CMC solution into polyethylene microspheres with the particle size of about 1 micron of D50, mixing and stirring for 2 hours, adding Styrene Butadiene Rubber (SBR), stirring for 0.5 hour to obtain a polymer microsphere emulsion, and then coating the polymer microsphere emulsion on the rolled positive plate to finish the manufacture of the composite positive plate;
wherein the thickness of a polymer microsphere coating formed by coating the polymer microsphere emulsion is 2 mu m, and the mass percentage of the polyethylene microspheres to the styrene butadiene rubber SBR is 82.5: 17.5;
(2) composite negative plate
Mixing and stirring a silicon-carbon negative electrode, a single-arm carbon nanotube, conductive graphite SP and a PVDF adhesive according to the mass percentage of 96:0.1:1:2.9, coating the mixture on a copper foil on a coating machine, and rolling the mixture for later use;
taking inorganic ceramic particles SiO2Mixing and stirring the PVDF adhesive, the PAA acrylic resin emulsion and the additive to form slurry, and coating the slurry on the rolled negative plate to finish the manufacture of the composite negative plate;
(3) assembly
And assembling the composite positive plate, the composite negative plate and the polyolefin diaphragm into a 20Ah battery core, then packaging by using an aluminum plastic film, injecting liquid after drying, standing for 24h, forming and grading, and finishing the manufacture of the high-safety battery core.
The performance and safety performance of the battery cell of this embodiment are tested, and the results of the performance test of the battery cell are shown in table 1 below, and the results of the safety performance test are shown in fig. 1-2, where fig. 1 is a discharge curve of the battery cell at a rate of 0.5C, fig. 2 is a discharge curve of the battery cell under high and low temperature conditions, and fig. 3 is a cycle curve of the battery cell at room temperature.
TABLE 1 cell Performance test results
As can be seen from the graphs in FIGS. 1 to 3, the lithium ion battery prepared by the invention has excellent low temperature and cycle performance; as can be seen from the results in Table 1, the safety performance of the lithium ion battery prepared by the invention is superior to that of the prior art.
Example 2
(1) Composite positive plate
Mixing and stirring high-nickel 811 ternary multi-walled carbon nanotubes and PVDF (polyvinylidene fluoride) adhesive according to the mass percentage of 98:0.5:1.5, coating the mixture on an aluminum foil with the thickness of 12 mu m on a coating machine, coating the mixture with the thickness of 400 mu m, and rolling the mixture for later use;
adding a CMC solution into polyacrylonitrile microspheres with the particle size of 12 microns, mixing and stirring for 2 hours, adding polyurethane, stirring for 0.5 hour to obtain a polymer microsphere emulsion, and then coating the polymer microsphere emulsion on the rolled positive plate to finish the manufacturing of the composite positive plate;
wherein the thickness of a polymer microsphere coating formed by coating the polymer microsphere emulsion is 25 mu m, and the mass percentage of the polyacrylonitrile microspheres to the polyurethane is 95.3: 4.7;
(2) composite negative plate
Mixing and stirring a silicon-carbon negative electrode, a single-arm carbon nanotube, conductive graphite SP and a PVDF adhesive according to the mass percentage of 96:0.1:1:2.9, coating the mixture on a copper foil on a coating machine, and rolling the mixture for later use;
taking inorganic ceramic particles Al2O3Mixing and stirring the PVDF adhesive, the PAA acrylic resin emulsion and the additive to form slurry, and coating the slurry on the rolled negative plate to finish the manufacture of the composite negative plate;
(3) assembly
And superposing the composite positive plate, the composite negative plate and the polyolefin diaphragm to form a pole core, placing the pole core in a battery shell, then injecting electrolyte, placing for 24 hours, forming, and sealing the battery shell after exhausting to obtain the lithium ion battery.
Example 3
(1) Composite positive plate
Mixing and stirring high-nickel 811 ternary multi-walled carbon nanotubes and PVDF (polyvinylidene fluoride) adhesive according to the mass percentage of 95:1.7:2.8, coating the mixture on an aluminum foil with the thickness of 20 mu m on a coating machine, coating the mixture with the thickness of 150 mu m, and rolling the mixture for later use;
adding a CMC solution into polyethylene microspheres with the particle size of 5 microns, mixing and stirring for 2 hours, adding Styrene Butadiene Rubber (SBR), stirring for 0.5 hour to obtain a high-molecular microsphere emulsion, and coating the high-molecular microsphere emulsion on the rolled positive plate to finish the manufacturing of the composite positive plate;
wherein the thickness of a polymer microsphere coating formed by coating the polymer microsphere emulsion is 3 mu m, and the mass percentage of the polyethylene microspheres to the styrene butadiene rubber SBR is 78: 22;
(2) composite negative plate
Mixing and stirring the silicon-carbon negative single-arm carbon nanotube and the SP/PVDF adhesive according to the mass percentage of 96:0.1:3.9 (the mass ratio of the SP to the PVDF is 1:2.9), coating the mixture on a copper foil on a coating machine, and rolling the mixture for later use;
mixing and stirring inorganic ceramic particles MgO, PVDF (polyvinylidene fluoride) binder, PAA (poly acrylic acid) acrylic resin emulsion and additives into slurry, and coating the slurry on the rolled negative plate to finish the manufacture of the composite negative plate;
(3) assembly
And superposing the composite positive plate, the composite negative plate and the polyolefin diaphragm to form a pole core, placing the pole core in a battery shell, then injecting electrolyte, placing for 24 hours, forming, and sealing the battery shell after exhausting to obtain the lithium ion battery.
The above embodiments are merely preferred embodiments of the present invention, and any simple modification, modification and substitution changes made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A high-safety lithium ion battery is characterized in that a composite positive plate, a polyolefin diaphragm and a composite negative plate are overlapped to form a pole core, the pole core is placed in a battery shell, then electrolyte is injected, the battery shell is placed for 24 hours to form the battery, and the battery shell is sealed after exhausting, so that the lithium ion battery is obtained.
2. The lithium ion battery with high safety according to claim 1, wherein the composite positive plate comprises a positive current collector, a positive electrode dressing layer and a polymer microsphere coating, one or two surfaces of the positive current collector are coated with the polymer microsphere coating and the positive electrode dressing layer in sequence along a direction away from the positive current collector, the positive electrode dressing layer comprises a positive active material, a positive conductive agent and a positive binder, and the polymer microsphere coating comprises polymer microspheres and a coating adhesive.
3. The lithium ion battery with high safety according to claim 1, wherein the composite negative plate comprises a negative current collector, a negative electrode dressing layer and an inorganic ceramic coating, one or two surfaces of the negative current collector are coated with the inorganic ceramic coating and the negative electrode dressing layer in sequence along a direction far away from the negative current collector, the negative electrode dressing layer comprises a negative active material, a negative conductive agent and a negative binder, and the inorganic ceramic coating comprises inorganic ceramic particles and a coating binder.
4. The lithium ion battery with high safety according to claim 2, wherein the thickness of the polymer microsphere coating is 0.1-30 μm, the thickness of the positive electrode dressing layer is 10-500 μm, and the thickness of the positive electrode current collector is 10-40 μm.
5. The high-safety lithium ion battery of claim 4, wherein the polymeric microsphere coating is composed of the following components in percentage by mass: 60-99.5% of polymer microspheres and 0.5-40% of coating adhesive.
6. The high-safety lithium ion battery according to claim 5, wherein the polymer microspheres are one or more of polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl alcohol and polyethylene copolymer, and the particle size of the polymer microspheres is 0.05-15 μm.
7. The lithium ion battery of claim 2, wherein the positive electrode active material is selected from lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, and lithium nickel oxide.
8. The high-safety lithium ion battery according to claim 3, wherein the inorganic ceramic particles are Al2O3、TiO2、SiO2、MgO、ZnO、ZrO2And CaO.
9. The high-safety lithium ion battery as claimed in claim 2 or 3, wherein the coating binder is one or more of carboxymethyl cellulose, styrene-butadiene rubber, acrylate, and polyurethane.
10. A high safety lithium ion battery according to claim 2 or 3, wherein the coating is selected from one of knife coating, dip coating, spray coating and extrusion.
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| CN202010587003.5A CN111564661A (en) | 2020-06-24 | 2020-06-24 | High-safety lithium ion battery |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112072109A (en) * | 2020-09-14 | 2020-12-11 | 昆山宝创新能源科技有限公司 | Lithium ion battery and preparation method thereof |
| CN112701249A (en) * | 2021-01-04 | 2021-04-23 | 昆山宝创新能源科技有限公司 | Positive plate and preparation method and application thereof |
| CN112864352A (en) * | 2021-03-18 | 2021-05-28 | 昆山宝创新能源科技有限公司 | Pole piece and lithium ion battery |
| CN113193172A (en) * | 2021-04-28 | 2021-07-30 | 天津中能锂业有限公司 | High-temperature-resistant metal lithium negative electrode and preparation method and application thereof |
| CN114171780A (en) * | 2021-11-30 | 2022-03-11 | 蜂巢能源科技有限公司 | Lithium ion battery cell, preparation method and application thereof |
| CN114300739A (en) * | 2021-12-31 | 2022-04-08 | 洛阳储变电系统有限公司 | Lithium ion battery |
| CN114824259A (en) * | 2021-01-27 | 2022-07-29 | 郑州宇通集团有限公司 | Lithium ion battery composite positive plate, preparation method thereof and lithium ion battery |
| CN115000344A (en) * | 2022-06-23 | 2022-09-02 | 惠州锂威新能源科技有限公司 | Lithium ion battery pole piece and preparation method thereof |
| CN116315186A (en) * | 2023-05-17 | 2023-06-23 | 中创新航科技集团股份有限公司 | Battery cell |
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| CN115000344A (en) * | 2022-06-23 | 2022-09-02 | 惠州锂威新能源科技有限公司 | Lithium ion battery pole piece and preparation method thereof |
| CN115000344B (en) * | 2022-06-23 | 2023-06-13 | 惠州锂威新能源科技有限公司 | Lithium ion battery pole piece and preparation method thereof |
| CN116315186A (en) * | 2023-05-17 | 2023-06-23 | 中创新航科技集团股份有限公司 | Battery cell |
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Application publication date: 20200821 |