CN111342143B - Preparation method of flexible package polymer lithium ion battery and battery - Google Patents
Preparation method of flexible package polymer lithium ion battery and battery Download PDFInfo
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- CN111342143B CN111342143B CN202010170602.7A CN202010170602A CN111342143B CN 111342143 B CN111342143 B CN 111342143B CN 202010170602 A CN202010170602 A CN 202010170602A CN 111342143 B CN111342143 B CN 111342143B
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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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- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0404—Machines for assembling 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
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
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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
Abstract
The invention discloses a preparation method of a flexible package polymer lithium ion battery, which comprises the following steps: obtaining an aluminum-plastic film, wherein one side of the aluminum-plastic film is a battery box main body wrapping a battery core, and the other side of the aluminum-plastic film is an air bag which is communicated with the battery box main body; putting the water absorption unit into an air bag with a top side sealed electric core and carrying out vacuum baking; injecting electrolyte into the battery box main body and then sequentially packaging and forming the battery for the first time; removing the air bag and the water absorption unit and carrying out secondary packaging; and obtaining the flexible package polymer lithium ion battery. The invention also discloses a battery prepared by the preparation method, and the preparation method of the battery disclosed by the invention can greatly improve the performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a flexible package polymer lithium ion battery and the battery.
Background
At present, polymer flexible package lithium ion batteries have entered into various aspects of people's daily life by virtue of the characteristics of variable models, good safety performance and the like, and people have stricter requirements on the type of batteries just because of the improvement of the universality of the use of the batteries, and besides the improvement of battery materials and manufacturing processes, the battery structure is further optimized.
Moisture has a crucial influence on the performance of the lithium ion battery, the quality of the performance of the battery is determined by the amount of the moisture inside the lithium ion battery, and the moisture directly influences various electrical properties of the battery cell in the later period.
Therefore, there is a need for a method for effectively reducing the internal moisture of a lithium ion battery, which can completely remove the internal moisture of the lithium ion battery or maintain the internal moisture at an extremely low content, thereby greatly improving the performance of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a preparation method of a flexibly-packaged polymer lithium ion battery and the battery, which are used for solving the technical problem that the performance of the lithium ion battery is rapidly attenuated due to high water content in the lithium ion battery obtained by the conventional preparation method.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a flexible package polymer lithium ion battery comprises the following steps:
obtaining an aluminum-plastic film, wherein one side of the aluminum-plastic film is a battery box main body wrapping a battery core, and the other side of the aluminum-plastic film is an air bag which is communicated with the battery box main body;
putting the water absorption unit into an air bag with a top side sealed electric core and carrying out vacuum baking;
injecting electrolyte into the battery box main body and then sequentially packaging and forming the battery for the first time;
removing the air bag and the water absorption unit and carrying out secondary packaging;
and obtaining the flexible package polymer lithium ion battery.
Preferably, the injecting of the electrolyte into the case body includes:
the water absorption unit is replaced, and electrolyte is injected into the battery box main body through the replaced water absorption unit, or,
removing the water absorbing unit, injecting an electrolyte into the battery case main body, or,
the electrolyte is injected into the battery case body by the existing water absorbing unit in the air bag.
Preferably, the number of the water absorption units is one or more.
Preferably, the water absorption unit is a macromolecular water absorption resin bag.
Preferably, the water absorption unit contains a high molecular material which is insoluble in water and organic solution.
Preferably, the water absorbing unit comprises one or a mixture of polyvinyl alcohol, polyacrylic acid or a copolymer thereof.
Preferably, the electrolyte is injected into the case body in a glove box having a humidity of 0.1% or less.
Preferably, the temperature of the vacuum baking is 80-90 ℃, and the baking time is 20-30 h.
Preferably, the temperature of the vacuum baking is 85 ℃, and the baking time is 26 h.
Compared with the prior art, the preparation method of the flexibly packaged polymer lithium ion battery provided by the invention has the advantages that the water absorption unit is placed in the air bag before the battery cell is baked, and the water in the positive and negative electrode plates and the diaphragm in the battery cell is absorbed and removed in the high-temperature baking process; on the other hand, when the electrolyte is injected, the electrolyte can pass through the water absorption unit, and the water contained in the electrolyte is absorbed and removed, no new equipment is added in the embodiment of the invention, the original production process flow is basically maintained, the water content in the battery cell can be in an extremely low or even moisture-free state, the battery cell SEI film (solid electrolyte interface (film)) formed in the later period is very compact, the cycle life of the battery is greatly prolonged, and meanwhile, a series of electrical properties such as the first charge-discharge efficiency, the self-discharge and the discharge multiplying power of the battery are obviously improved.
In another aspect, the invention also provides a flexibly packaged polymer lithium ion battery, which is prepared by any one of the preparation methods of the flexibly packaged polymer lithium ion battery.
Compared with the prior art, the beneficial effects of the flexible package polymer lithium ion battery provided by the invention are the same as the beneficial effects of the preparation method of the flexible package polymer lithium ion battery provided by the first aspect, and are not repeated herein.
Drawings
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings.
Fig. 1 is a schematic diagram of a placement position of a water absorption unit in a battery cell disclosed in an embodiment of the present invention;
FIG. 2 is a method for preparing a polymer lithium ion battery with flexible package according to an embodiment of the present invention;
fig. 3 is a comparison of 0.5C 500 cycle curves for lithium ion batteries made according to the methods of the present invention (group a, examples) versus conventional methods (group B, comparative).
Detailed Description
In order to make the technical solutions of the embodiments of the present invention better understood, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of the embodiments of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the embodiments of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein.
The drawings are for illustrative purposes only and are presented in the form of illustrations rather than physical illustrations and are not to be construed as limiting the invention; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The following will further explain the specific implementation and the implementation effect of the technical solution of the present invention by combining the comparative example and the embodiment of the present invention.
The applicant researches and discovers that moisture in the battery core can react with lithium salt (such as lithium hexafluorophosphate and the like) in the electrolyte to produce HF, and the HF can damage an SEI (solid electrolyte interface) film, generate LiF (lithium iron) precipitate and consume lithium ions in the electrolyte; in addition, the moisture can generate a complex reaction or react with hydroxyl groups and metastable double bonds in a solvent of the electrolyte to generate alcohol and the like, which affects the first charge-discharge efficiency of the battery cell and the formation of an SEI film, thereby causing the rapid degradation of the performance of the lithium battery.
In order to solve the problems, the invention provides a method for preparing a flexible package polymer lithium ion battery, wherein a water absorption unit is placed in an air bag before a battery cell is baked, and water in a positive electrode plate, a negative electrode plate and a diaphragm in the battery cell is absorbed and removed in the high-temperature baking process; on the other hand, when the electrolyte is injected, the water contained in the electrolyte can be absorbed and removed through the water absorption unit, and on the premise that no new equipment is added and the original production process flow is basically maintained, the water in the positive and negative electrode plates, the diaphragm or the electrolyte in the battery cell is removed to the greatest extent, so that the influence of the water on various electrical properties of the battery cell is reduced, and the comprehensive performance of the battery cell is improved.
In order to achieve the above effects, the embodiment of the present invention adopts the following technical solutions:
as shown in fig. 1, the method comprises the following steps:
and step S01, obtaining an aluminum-plastic film, wherein one side of the aluminum-plastic film is a battery box main body wrapping the battery core, and the other side of the aluminum-plastic film is an air bag which is communicated with the battery box main body.
It should be noted that, as shown in fig. 2, the embodiment of the present invention is mainly optimized for a flexible package polymer lithium ion battery, the packaging material of the flexible package polymer battery is an aluminum-plastic composite film, the inner layer of the film is a polypropylene adhesive layer, the outer package sealing of the battery is realized by adhering two layers of composite film adhesive surfaces to each other, tightly squeezing the two layers of films by using two metal seal heads with good flatness, and melting the composite film adhesive by heating, so as to ensure that the adhesive is tightly adhered together after being melted, thereby realizing the state of the sealed opening. Therefore, one side of the aluminum plastic film is a battery box main body for wrapping the battery core, the other side of the aluminum plastic film is an air bag 2, the air bag 2 is communicated with the battery box main body 1, and as the gas generation is more in the battery formation process, an empty aluminum plastic packaging film connected with the battery body is required to load the gas in the production process, and the empty aluminum plastic packaging film is called as a lithium ion battery air bag in the industry.
And step S02, placing the water absorption unit into the air bag with the top side sealed with the battery core and carrying out vacuum baking.
The present invention provides a method for manufacturing a gas bag, which comprises placing a water absorbing unit into the gas bag through a side opening of the gas bag, and performing vacuum baking, wherein the number of the water absorbing unit may be one or more, and the embodiment of the present invention is not limited thereto, and is set according to a specific application, preferably, the water absorbing unit may be a polymer water absorbing resin bag, preferably, the water absorbing unit contains a polymer material insoluble in water and an organic solution, preferably, the water absorbing unit contains one or a mixture of polyvinyl alcohol, polyacrylic acid or a copolymer thereof; the vacuum baking is carried out in inert gas at 80-90 deg.C for 20-30h, preferably 85 deg.C for 26 h.
Through the steps, the water absorption unit is placed in the air bag before the battery cell is baked, and in the high-temperature baking process, moisture in positive and negative pole pieces and diaphragms inside the battery cell is absorbed and removed, so that the moisture content inside the battery cell is in an extremely low or even moisture-free state, a battery cell SEI film (solid electrolyte interface (film)) formed in the later period is very compact, the cycle life of the battery is greatly prolonged, and meanwhile, a series of electrical properties such as the first charge-discharge efficiency, the self-discharge and the discharge multiplying power of the battery are obviously improved.
In step S03, the electrolyte is injected into the battery case main body, and then the battery is packaged and formed into a battery in this order.
The method of injecting the electrolyte into the battery case main body includes:
1. the method of the embodiment includes that the electrolyte is not subjected to dehydration through the absorption unit, the water absorption unit which is used in the vacuum baking process needs to be removed before the electrolyte is injected, then the electrolyte is injected into the battery box body, and the electrolyte is injected into the battery box body in a glove box with the humidity being less than or equal to 0.1%.
2. In order to further remove the moisture in the electrolyte, the electrolyte is injected into the battery box main body through the water absorption unit, so that the moisture in the electrolyte can be removed, if the water absorption unit used in the baking process is injected with the electrolyte through the water absorption unit, the effect of the electrolyte is prevented from being influenced, so the water absorption unit used in the baking process is replaced before the electrolyte is injected, then the electrolyte is injected into the battery box main body, and the electrolyte is injected into the battery box main body in a glove box with the humidity of less than or equal to 0.1%.
3. In order to further remove the moisture in the electrolyte, the electrolyte is injected into the battery box main body through the water absorption unit, so that the moisture in the electrolyte can be removed, the water absorption unit used in the baking process does not need to be replaced, therefore, when the electrolyte is injected, the electrolyte is injected into the battery box main body through the water absorption unit used in the baking process, and the electrolyte is injected into the battery box main body in a glove box with the humidity of less than or equal to 0.1%.
The above-mentioned need to remove the moisture in the electrolyte, whether need change the water absorption unit that has used in the baking process before pouring into the electrolyte, this depends on the characteristic and the specific application scenario of water absorption unit.
Through the steps, when the electrolyte is injected, the electrolyte can pass through the water absorption unit, water contained in the electrolyte is absorbed and removed, the water content in the battery cell can be in an extremely low or even no-water state, the battery cell SEI film (solid electrolyte interface (film)) formed in the later period is very compact, the cycle life of the battery is greatly prolonged, and meanwhile, a series of electrical properties such as the first charge-discharge efficiency, the self-discharge and the discharge multiplying power of the battery are obviously improved.
And step S04, removing the air bag and the water absorption unit and packaging for the second time.
And step S05, obtaining the flexible package polymer lithium ion battery.
According to the preparation method of the flexible package polymer lithium ion battery, the water absorption unit is placed in the air bag before the battery cell is baked, and in the high-temperature baking process, the water in the positive and negative electrode plates and the diaphragm inside the battery cell is absorbed and removed; on the other hand, when the electrolyte is injected, the electrolyte can pass through the water absorption unit, and the water contained in the electrolyte is absorbed and removed, no new equipment is added in the embodiment of the invention, the original production process flow is basically maintained, the water content in the battery cell can be in an extremely low or even moisture-free state, the battery cell SEI film (solid electrolyte interface (film)) formed in the later period is very compact, the cycle life of the battery is greatly prolonged, and meanwhile, a series of electrical properties such as the first charge-discharge efficiency, the self-discharge and the discharge multiplying power of the battery are obviously improved.
The following are specific examples:
the battery core is made of a polymer lithium ion battery with the model number of 523450P-1000mAh, the positive electrode adopts lithium cobaltate, the negative electrode adopts artificial graphite, the diaphragm adopts a polypropylene PP diaphragm, the electrolyte adopts Ethylene Carbonate (EC) or methyl ethyl carbonate (EMC) or dimethyl carbonate (DMC) common electrolyte, and a DNP113 type aluminum plastic film is adopted for production.
The method comprises the steps of respectively stirring and coating the positive and negative raw materials of a conventional polymer lithium ion battery to obtain positive and negative pole pieces, baking the water content of the positive and negative pole pieces, winding the positive pole, a diaphragm and the negative pole into a winding core, punching a shell by using an aluminum-plastic film to perform top side sealing and packaging, and dividing the battery into A, B groups after the top side sealing, wherein the group A is an embodiment, and the group B is a comparative example.
Putting a macromolecule water-absorbent resin bag (composed of polyvinyl alcohol, polyacrylic acid or copolymer thereof and other macromolecule synthetic materials which are insoluble in water and organic solution) into the air bag of the group A, then baking for 26h at high temperature of 85 ℃ in a vacuum inert gas environment, injecting liquid into a glove box with the humidity less than or equal to 0.1%, wherein during liquid injection, electrolyte needs to be filtered through the macromolecule water-absorbent resin bag to enter the interior of the battery cell, or the macromolecule water-absorbent resin bag is removed, then the electrolyte is injected, or the macromolecule water-absorbent resin bag is replaced, the electrolyte is injected into the battery box main body through the replaced macromolecule water-absorbent resin bag, and the macromolecule water-absorbent resin bag needs to be encapsulated into the battery cell air bag during primary encapsulation.
And directly carrying out high-temperature vacuum baking for 26h at 85 ℃ in the group B under the vacuum inert gas environment, and carrying out liquid injection and primary packaging in a glove box with the humidity less than or equal to 0.1%.
And then, simultaneously aging and forming A, B two groups of batteries, removing the air bags and the high-molecular water-absorbent resin bag from the A group of batteries for secondary packaging, and directly cutting the air bags from the B group of batteries according to normal procedures for secondary packaging.
And finally, simultaneously shaping and aging the A, B two groups of batteries, and finally finishing all the manufacture of the batteries.
And (3) testing the battery: the manufactured A, B two groups of single batteries are respectively tested for the 0.5C (500mA) 100% charge-discharge 500-cycle life and the first charge-discharge efficiency of the two groups of batteries by using the same test cabinet in a room temperature environment, and a comparison is made.
A. The capacity retention rates at 500 weeks at 0.5C cycle of the two groups B of unit cells are shown in table 1 below and fig. 3; A. the first charge-discharge efficiency of the two groups of single batteries B is shown in the following table 2, and the test result numerical values are intermediate values except the optimal and the worst values of the same group.
TABLE 1
TABLE 2
As can be seen from the comparison of data of A, B two groups of batteries with 0.5C (500mA) current charge-discharge cycle for 500 weeks and the comparison of data of first charge-discharge efficiency, the capacity retention rate of the battery cell group A adopting the technical scheme of the invention after 0.5C 500 cycle is obviously higher than that of the battery cell group B not adopting the technical scheme of the invention, and the average capacity retention rate is higher by about 5%; meanwhile, the first charge-discharge efficiency of the battery cell group A adopting the technical scheme of the invention is obviously higher than that of the battery cell group B not using the embodiment of the invention, and is about 5% higher on average.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A preparation method of a flexible package polymer lithium ion battery is characterized by comprising the following steps:
obtaining an aluminum-plastic film, wherein one side of the aluminum-plastic film is a battery box main body wrapping a battery core, and the other side of the aluminum-plastic film is an air bag which is communicated with the battery box main body;
putting the water absorption unit into an air bag with a top side sealed electric core and carrying out vacuum baking;
injecting electrolyte into the battery box main body and then sequentially packaging and forming the battery for the first time;
removing the air bag and the water absorption unit and carrying out secondary packaging;
obtaining a flexible package polymer lithium ion battery;
the electrolyte is injected into the battery case main body, and the electrolyte injection device comprises:
the water absorption unit is replaced, electrolyte is injected into the battery box main body through the replaced water absorption unit, or,
removing the water absorbing unit, injecting an electrolyte into the battery case main body, or,
the electrolyte is injected into the battery case body by the existing water absorbing unit in the air bag.
2. The method for preparing the polymer lithium ion battery with flexible package according to claim 1, wherein the number of the water absorbing units is one or more.
3. The method for preparing the flexibly packaged polymer lithium ion battery according to claim 1, wherein the water absorbing unit is a high molecular water absorbing resin bag.
4. The method of claim 3, wherein the water-absorbing unit comprises a polymer material that is insoluble in water and organic solutions.
5. The method for preparing a polymer lithium ion battery with flexible package according to claim 4, wherein the water absorbing unit comprises one or a mixture of polyvinyl alcohol, polyacrylic acid or a copolymer thereof.
6. The method of claim 1, wherein the electrolyte is injected into the battery case body in a glove box having a humidity of 0.1% or less.
7. The method for preparing a polymer lithium ion battery with flexible package according to claim 1, wherein the temperature of vacuum baking is 80-90 ℃ and the baking time is 20-30 h.
8. The method for preparing the polymer lithium ion battery with flexible package according to claim 1, wherein the temperature of vacuum baking is 85 ℃ and the baking time is 26 h.
9. A flexibly packaged polymer lithium ion battery, which is prepared by the preparation method of the flexibly packaged polymer lithium ion battery as claimed in any one of claims 1 to 8.
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