CN113300058B - Liquid injection method of lithium battery, manufacturing method of lithium battery and lithium battery - Google Patents
Liquid injection method of lithium battery, manufacturing method of lithium battery and lithium battery Download PDFInfo
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- CN113300058B CN113300058B CN202110464266.1A CN202110464266A CN113300058B CN 113300058 B CN113300058 B CN 113300058B CN 202110464266 A CN202110464266 A CN 202110464266A CN 113300058 B CN113300058 B CN 113300058B
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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
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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
- H01M10/058—Construction or manufacture
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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
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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
- 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
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Abstract
The invention discloses a liquid injection method of a lithium battery, which comprises the following steps: the method comprises the following steps: adding PVDF powder into electrolyte, and uniformly mixing to obtain a mixed glue solution of the electrolyte and the PVDF powder; step two: adding the ceramic particles into the mixed glue solution for high-speed uniform dispersion to obtain an electrolyte glue solution containing the ceramic particles; step three: and (3) injecting electrolyte glue solution from the end face of the battery core in a vacuum manner, so that the electrolyte in the electrolyte glue solution enters the battery core, and ceramic particles are deposited on the end faces of two ends of the battery core. According to the invention, the ceramic particles are deposited on the end faces of the two ends of the battery cell to form the protective layers, so that when the diaphragm is heated, the heat applied to the end part of the diaphragm can be isolated, and when the diaphragm is heated and contracted, the ceramic particles form the insulating layers on the end faces, so that the contact between a positive electrode and a negative electrode is avoided, the short circuit is avoided, the thickness of the diaphragm is not increased, and the energy density of the lithium battery is not reduced.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a liquid injection method of a lithium battery, a manufacturing method of the lithium battery and the lithium battery.
Background
Lithium ion batteries are widely used in daily life because of their advantages such as high voltage, high energy density, small self-discharge, no memory effect, and wide working range.
As shown in fig. 2, the separator covers the negative electrode between the positive electrode and the negative electrode and in the width to prevent the positive electrode and the negative electrode of the battery cell from short-circuiting, but the separator of the battery cell is thinner and thinner due to the increasing energy density, and the coating of the separator on the pole piece is less and less. As shown in fig. 3, the diaphragm inside the battery cell is not significantly shrunk by heat due to the bonding with the pole piece under the action of pressure, and the diaphragm at the end face of the diaphragm is not bonded with the pole piece and is easily shrunk under the heating condition, so that the two ends of the positive and negative electrodes are contacted to cause a short circuit.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the liquid injection method of the lithium battery, the manufacturing method of the lithium battery and the lithium battery are provided, after the diaphragm is heated and shrunk, the two ends of the positive and negative pole pieces can still be isolated, the two ends of the positive and negative pole pieces are prevented from being in contact short circuit, and meanwhile, the energy density of the battery cannot be influenced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a liquid injection method of a lithium battery, which comprises the following steps:
the method comprises the following steps: adding PVDF powder into an electrolyte, and uniformly mixing to obtain a mixed glue solution of the electrolyte and the PVDF powder;
step two: adding ceramic particles into the mixed glue solution for high-speed uniform dispersion to obtain an electrolyte glue solution containing the ceramic particles;
step three: and enabling the electrolyte in the electrolyte glue solution to enter the electric core from the end face of the electric core in a vacuum liquid injection mode, and depositing the ceramic particles on the end faces of two ends of the electric core.
The PVDF powder can enable the ceramic particles to stably exist in electrolyte, a vacuum liquid injection mode is adopted in the liquid injection of the battery core, the electrolyte can rapidly enter the battery core from the end face position under the negative pressure condition, and the ceramic particles can be accumulated along with the electrolyte at an electrolyte inlet. When the electricity core is heated, the ceramic particle can effectually slow down the diaphragm shrink, the diaphragm of electricity core inside is because it is not obvious to be heated the shrink with the pole piece to have the adhesion nature, and the diaphragm of terminal surface position does not have the atress and is heated the shrink easily, the ceramic particle is because having good heat-proof quality can the separation most heat to the shrink of the diaphragm of terminal surface position slows down, forms the insulating layer at the tip at diaphragm and pole piece both ends simultaneously, prevents positive plate and negative pole piece contact short circuit.
As an improvement of the invention, in the step one, the mass percentage concentration of the PVDF powder in the mixed glue solution is 0.1-1%. The PVDF powder can well stabilize the ceramic particles within the mass percentage range, has low content, and cannot influence the chemical reaction of the electrolyte in the battery core.
As a modification of the present invention, in the first step, the electrolyte includes a lithium salt, an organic solvent, and an additive.
As an improvement of the invention, in the second step, the mass percentage concentration of the ceramic particles in the electrolyte solution is 0.1-8%. Within the mass percentage range, enough ceramic particles can form isolation layers at two ends of the battery core, and the solubility of the electrolyte in the battery core is not influenced.
As an improvement of the present invention, in the second step, the ceramic fine particles include SiO 2 、CaO、TiO 2 、MgO、ZnO、SnO 2 、ZrO 2 Any one or more of them. The ceramic particles do not react with the electrolyte, the property is stable, and meanwhile, the ceramic particles have a good heat insulation effect and can insulate most of heat received by the diaphragm at the end face position.
As a modification of the present invention, the ceramic fine particles have a particle size ranging from 0.1 μm to 3.39 μm. Preferably 1.65 to 3.39 μm. Ceramic particle can be fine in this particle diameter range electric core both ends terminal surface carries out the deposit, and can not along with electrolyte gets into inside the electric core, avoided the deposit to be in electric core both ends the reduction of ceramic particle has also been avoided ceramic miropowder gets into electric core internal disturbance chemical reaction has guaranteed simultaneously can be when the diaphragm is heated the shrink electric core both ends form the protective layer, prevent positive negative pole piece contact.
As an improvement of the present invention, in step three, the specific operation flow of the vacuum liquid injection is as follows:
s1, placing the battery cell into an injection chamber, vacuumizing the injection chamber by a vacuum pump, and forming a vacuum environment in the battery cell; the gas in the battery cell can be effectively removed, and the volume of the battery cell is reduced.
S2, inserting an electrolyte injection nozzle into the battery cell electrolyte injection port, opening an electrolyte injection valve, pressurizing an electrolyte chamber to 0.2-1.0MPa by using nitrogen, and maintaining the pressure for a certain time; the electrolyte can rapidly enter the interior of the battery core through pressurization, and meanwhile, the ceramic particles are prevented from entering the interior of the battery core along with the electrolyte and are deposited at two ends of the battery core.
And S3, discharging gas from the liquid injection chamber to normal pressure, and finally standing for 12-36h for a long time to enable the electrolyte to be fully infiltrated with the positive and negative materials and the diaphragm of the battery cell, so that the ceramic particles are deposited on the end faces of the two ends of the battery cell.
As an improvement of the present invention, in S3, the cell filling ports are disposed at the top end and the bottom end of the cell. And the liquid injection port of the battery cell is arranged at the top end and the bottom end of the battery cell, so that the ceramic particles can be better deposited on the end surfaces of the two ends of the battery cell.
The invention also discloses a manufacturing method of the lithium battery, which comprises the following manufacturing steps in sequence: the method comprises the steps of electrode paste preparation, coating, pole piece punching, lamination, battery assembly, any one of the liquid injection methods of the lithium battery and battery sealing.
In addition, the invention also discloses a lithium battery which is prepared by the preparation method of the lithium battery. The lithium battery manufactured by the method can well prevent the short circuit of the positive electrode and the negative electrode, and simultaneously ensures the energy density of the lithium battery.
Compared with the prior art, the invention has the following beneficial effects: compared with the prior art that the coating is added on the diaphragm to increase the heat resistance of the diaphragm, so that the thickness of the diaphragm is increased, and the energy density of the lithium battery is reduced, the PVDF and the ceramic particles are added into the electrolyte, the electrolyte is injected into the battery cell by a vacuum injection method, the ceramic particles are accumulated at two ends of the battery cell, and the accumulated ceramic particles form protective layers on end faces at two ends of the battery cell, so that the heating temperature of the diaphragm can be reduced when the diaphragm is heated, and the insulating effect can be realized after the diaphragm 1 is heated and shrunk, so that the short circuit caused by the contact of a positive electrode and a negative electrode can be prevented. Because the ceramic particles deposited at the two ends of the battery core play an isolation role, the thickness of the diaphragm or the pole piece is not increased, and the energy density of the lithium battery is not influenced.
Drawings
Fig. 1 is a schematic flow chart of a liquid injection method for a lithium battery according to the present application;
fig. 2 is a schematic structural diagram of a battery cell in the prior art;
fig. 3 is a schematic diagram of a heat-shrinkable structure of a diaphragm of a battery cell in the prior art;
fig. 4 is a schematic diagram of the internal structure of a cell with ceramic particles added;
FIG. 5 is a schematic diagram of a thermal contraction structure of a diaphragm of a battery cell with ceramic particles added;
in the figure: 1-a separator; 2-a negative electrode; 3-a positive electrode; 4-ceramic particles.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
Detailed exemplary embodiments are disclosed below. However, specific structural and functional details disclosed herein are merely for purposes of describing example embodiments. It should be understood, however, that the intention is not to limit the invention to the particular exemplary embodiments disclosed, but to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure. Like reference numerals refer to like elements throughout the description of the figures. Unless otherwise specified, the preparation methods are those commonly used in the art, and the equipment and detection methods used are also those commonly used in the art.
As shown in fig. 1 and fig. 4 to 5, the present embodiment provides a liquid injection method for a lithium battery, including the following steps:
the method comprises the following steps: adding PVDF powder into electrolyte, and uniformly mixing to obtain a mixed glue solution of the electrolyte and the PVDF powder;
step two: adding the ceramic particles 4 into the mixed glue solution for high-speed uniform dispersion to obtain an electrolyte glue solution containing the ceramic particles;
step three: and injecting the electrolyte glue solution from the end face of the battery cell in a vacuum manner, so that the electrolyte in the electrolyte glue solution enters the battery cell, and the ceramic particles 4 are deposited on the end faces of two ends of the battery cell.
The PVDF powder can enable the ceramic particles 4 to stably exist in electrolyte, a vacuum liquid injection mode is adopted in the liquid injection of the battery core, the electrolyte can rapidly enter the battery core from the end face position under the negative pressure condition, and the ceramic particles 4 can be accumulated along with the electrolyte at an electrolyte inlet. When the electricity core is heated, ceramic particle 4 can effectually slow down 1 shrink of diaphragm, the inside diaphragm 1 of electricity core is because it is not obvious to be heated the shrink with the pole piece to have the adhesion nature, and the diaphragm 1 of terminal surface position does not have the atress and is heated the shrink easily, ceramic particle 4 is owing to have good heat-proof quality and can the separation most heat to the shrink of diaphragm 1 of terminal surface position slows down, forms the insulating layer at the tip at diaphragm 1, positive plate 3 and 2 both ends of negative pole piece simultaneously, prevents positive plate 3 and 2 contact short circuits of negative pole piece.
Preferably, in the step one, the mass percentage concentration of the PVDF powder in the mixed glue solution is 0.1-1%. The PVDF powder can well stabilize the ceramic particles 4 within the mass percentage range, and meanwhile, the content of the PVDF powder is not high, so that the chemical reaction of the electrolyte in the battery core is not influenced.
Preferably, in the step one, the electrolyte includes a lithium salt, an organic solvent, and an additive.
Preferably, in the second step, the mass percentage concentration of the ceramic particles 4 in the electrolyte glue solution is 0.1-8%. Within this mass percentage range, the ceramic particles 4 can be sufficiently isolated at both ends of the battery cell without affecting the solubility of the electrolyte in the battery cell.
Preferably, in step two, the ceramic particles 4 comprise SiO 2 、CaO、TiO 2 、MgO、ZnO、SnO 2 、ZrO 2 Any one or more of them. The ceramic particles 4 are selected not to react with the electrolyte, so that the ceramic particles are stable in property, have a good heat insulation effect and can insulate most of heat received by the diaphragm 1 at the end face position.
Preferably, the ceramic fine particles 4 have a particle size in the range of 0.1 to 3.39 μm. Preferably 1.65 to 3.39 μm. Ceramic particle 4 can be fine in this particle diameter range electric core both ends terminal surface deposit, and can not along with electrolyte gets into inside the electric core, avoided the deposit to be in the electric core both ends ceramic particle 4's reduction has also been avoided ceramic miropowder 4 gets into the internal interference chemical reaction of electric core has guaranteed simultaneously can be in when diaphragm 1 is heated the shrink electric core both ends form the protective layer, prevent positive plate 3 and negative pole piece 2 contact.
Preferably, in step three, the specific operation flow of the vacuum liquid injection is as follows:
s1, placing the battery cell into an injection chamber, vacuumizing the injection chamber by a vacuum pump, and forming a vacuum environment in the battery cell; the gas in the battery cell can be effectively removed, and the volume of the battery cell is reduced.
S2, inserting an electrolyte injection nozzle into the battery cell electrolyte injection port, opening an electrolyte injection valve, pressurizing an electrolyte chamber to 0.2-1.0MPa by using nitrogen, and maintaining the pressure for a certain time; the electrolyte can rapidly enter the interior of the battery core through pressurization, and meanwhile, the ceramic particles 4 are ensured not to enter the interior of the battery core along with the electrolyte but to be deposited at two ends of the battery core.
And S3, discharging gas from the liquid injection chamber to normal pressure, and finally standing for 12-36h for a long time to fully infiltrate the electrolyte, the positive and negative materials of the battery cell and the diaphragm, so that the ceramic particles 4 are deposited on the end faces of the two ends of the battery cell.
Preferably, in S3, the battery cell injection port is disposed at the top end and the bottom end of the battery cell. The top end and the bottom end of the battery cell are provided with the battery cell liquid injection port, so that the ceramic particles 4 can be better deposited on the end faces of the two ends of the battery cell.
The embodiment also provides a manufacturing method of the lithium battery, which sequentially comprises the following manufacturing steps: preparing electrode slurry, coating, punching pole pieces, laminating, assembling batteries, and sealing the batteries by any one of the liquid injection methods of the lithium batteries.
In addition, the embodiment also provides a lithium battery which is prepared by the manufacturing method of the lithium battery. The battery core manufactured by the method can well prevent the short circuit of the positive electrode and the negative electrode, and simultaneously ensures the energy density of the lithium battery.
Compared with the prior art, the invention has the following beneficial effects: compared with the prior art that a coating is added on a diaphragm 1 to increase the heat resistance of the diaphragm 1, so that the thickness of the diaphragm 1 is increased, and the energy density of a lithium battery is reduced, the PVDF and the ceramic particles 4 are added into the electrolyte, the electrolyte is injected into the battery core by a vacuum liquid injection method, the ceramic particles 4 are accumulated at two ends of the battery core, and the accumulated ceramic particles 4 form protective layers on the end faces at two ends of the battery core, so that the heating temperature of the diaphragm 1 can be reduced when the diaphragm 1 is heated, and the insulating effect can be achieved after the diaphragm 1 is heated and shrunk, and the short circuit caused by the contact of a positive electrode and a negative electrode can be prevented. Because the ceramic particles 4 deposited at the two ends of the battery core play an isolation role, the thickness of the diaphragm 1 or the pole piece is not increased, and the energy density of the lithium battery is not influenced.
While specific embodiments of the invention have been illustrated and described, it will be appreciated, as described above, that the invention is not limited to the forms disclosed herein, but is to be construed in all aspects as excluding other embodiments and may be used in various other combinations, modifications, and environments and is capable of modifications within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A liquid injection method of a lithium battery is characterized by comprising the following steps:
the method comprises the following steps: adding PVDF powder into electrolyte, and uniformly mixing to obtain a mixed glue solution of the electrolyte and the PVDF powder;
step two: adding ceramic particles into the mixed glue solution for high-speed uniform dispersion to obtain an electrolyte glue solution containing the ceramic particles;
step three: and enabling the electrolyte in the electrolyte glue solution to enter the electric core from the end face of the electric core in a vacuum liquid injection mode, and depositing the ceramic particles on the end faces of two ends parallel to the laminating direction of the electric core pole pieces.
2. The liquid injection method of the lithium battery according to claim 1, wherein in the first step, the mass percentage concentration of the PVDF powder in the mixed glue solution is 0.1-1%.
3. The method for injecting the lithium battery as claimed in claim 1, wherein in the first step, the electrolyte comprises a lithium salt, an organic solvent and an additive.
4. The liquid injection method of a lithium battery as claimed in claim 1, wherein in the second step, the mass percentage concentration of the ceramic particles in the electrolyte liquid is 0.1-8%.
5. The method for injecting the lithium battery as claimed in claim 1, wherein in the second step, the ceramic fine particles comprise SiO 2 、Al 2 O 3 、CaO、TiO 2 、MgO、ZnO、SnO 2 、ZrO 2 Any one or more of them.
6. The method for injecting a lithium battery as defined in claim 1, wherein the ceramic fine particles have a particle size in a range of 0.1 to 3.39 μm.
7. The liquid injection method of a lithium battery as claimed in claim 1, wherein the specific operation flow of the vacuum liquid injection in step three is as follows:
s1, placing the battery cell into an injection chamber, vacuumizing the injection chamber by a vacuum pump, and forming a vacuum environment in the battery cell;
s2, inserting an electrolyte injection nozzle into the battery cell electrolyte injection port, opening an electrolyte injection valve, pressurizing an electrolyte chamber to 0.2-1.0Mpa by using nitrogen, and maintaining the pressure for a certain time;
and S3, discharging air to normal pressure in the liquid injection chamber, and standing for 12-36 hours for a long time to enable the electrolyte to be fully soaked with the positive and negative materials and the diaphragm of the battery cell, wherein the ceramic particles are arranged on the end faces of two ends parallel to the laminating direction of the pole pieces of the battery cell.
8. The method of injecting the lithium battery as claimed in claim 7, wherein in S3, the cell injection ports are provided at top and bottom ends of the cell.
9. A method of manufacturing a lithium battery, comprising the method of charging a lithium battery according to any one of claims 1 to 8.
10. A lithium battery produced by the method for producing a lithium battery according to claim 9.
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| CN101908645A (en) * | 2010-07-30 | 2010-12-08 | 哈尔滨工业大学 | A ceramic/solid polymer electrolyte composite material with continuous and directional distribution of reinforced phase and its preparation method |
| CN103337660A (en) * | 2013-07-01 | 2013-10-02 | 彩虹集团公司 | Lithium ion electrolyte solution |
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| JP2003203620A (en) * | 2002-01-08 | 2003-07-18 | Matsushita Electric Ind Co Ltd | Lithium-ion battery and its injection method |
| JP5382496B2 (en) * | 2008-09-19 | 2014-01-08 | トヨタ自動車株式会社 | Battery unit |
| WO2014092121A1 (en) * | 2012-12-13 | 2014-06-19 | エリーパワー株式会社 | Method for producing non-aqueous electrolyte secondary battery |
| KR20150014637A (en) * | 2013-07-30 | 2015-02-09 | 주식회사 엘지화학 | Secondary Battery Capable of Additional Supplying of Electrolyte |
| KR20170091149A (en) * | 2014-12-05 | 2017-08-08 | 셀가드 엘엘씨 | Improved coated separators for lithium batteries and related methods |
| JP6588716B2 (en) * | 2015-03-24 | 2019-10-09 | 日立造船株式会社 | Metal air battery |
| CN109004263B (en) * | 2018-07-25 | 2022-08-26 | 湖南立方新能源科技有限责任公司 | Electrolyte and high-safety lithium ion battery containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908645A (en) * | 2010-07-30 | 2010-12-08 | 哈尔滨工业大学 | A ceramic/solid polymer electrolyte composite material with continuous and directional distribution of reinforced phase and its preparation method |
| CN103337660A (en) * | 2013-07-01 | 2013-10-02 | 彩虹集团公司 | Lithium ion electrolyte solution |
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Denomination of invention: A liquid injection method for lithium batteries, a production method for lithium batteries, and a lithium battery Effective date of registration: 20230829 Granted publication date: 20221104 Pledgee: Agricultural Bank of China Limited Zhuzhou branch Pledgor: HUNAN LIFANG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2023980054119 |
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Granted publication date: 20221104 Pledgee: Agricultural Bank of China Limited Zhuzhou branch Pledgor: HUNAN LIFANG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2023980054119 |
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Denomination of invention: A liquid injection method for lithium batteries, a manufacturing method for lithium batteries, and lithium batteries Granted publication date: 20221104 Pledgee: Agricultural Bank of China Limited Zhuzhou branch Pledgor: HUNAN LIFANG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2024980042821 |
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