CN112072186A - Method for improving formation wettability and SEI film stability of soft package battery - Google Patents
Method for improving formation wettability and SEI film stability of soft package battery Download PDFInfo
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- CN112072186A CN112072186A CN201910502725.3A CN201910502725A CN112072186A CN 112072186 A CN112072186 A CN 112072186A CN 201910502725 A CN201910502725 A CN 201910502725A CN 112072186 A CN112072186 A CN 112072186A
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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
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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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 relates to the technical field of lithium ion batteries, and provides a method for improving the wettability and the stability of an SEI (solid electrolyte interphase) film of a soft package battery, aiming at solving the problem that the wettability and the stability of the SEI film are poor due to the fact that an aluminum plastic film at a roll core is prone to bulging in the traditional soft package battery formation process. The method carries out pre-sealing treatment near the junction of the roll core and the air bag of the soft package battery, plays a role in shaping the roll core, ensures that the battery cell keeps a better infiltration effect in the formation process, and is favorable for forming a stable SEI film through high-temperature aging.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a method for improving the formation wettability and SEI film stability of a soft package battery.
Background
In the first charge and discharge process of the liquid lithium ion battery, the electrode material and the electrolyte react on a solid-liquid phase interface to form a passivation layer covering the surface of the electrode material. The passivation layer is an interfacial layer, characterized by a solid electrolyte, which is an electronic insulator but Li+Of good electrical conductivity, Li+Can be freely inserted into and removed from the passivation layer, so that the passivation film is called a Solid Electrolyte Interface (SEI) film.
The formation of the SEI film has a crucial influence on the performance of the electrode material. On one hand, the formation of the SEI film consumes part of lithium ions, so that the first charge-discharge irreversible capacity is increased, and the charge-discharge efficiency of the electrode material is reduced; on the other hand, the SEI film has organic solvent insolubility and can stably exist in an organic electrolyte solution, and solvent molecules cannot pass through the passivation film, so that the co-intercalation of the solvent molecules can be effectively prevented, the damage to an electrode material caused by the co-intercalation of the solvent molecules is avoided, the cycle performance of the electrode is greatly improved, and the service life of the electrode is greatly prolonged. Therefore, intensive research on the formation mechanism, composition structure, stability and influence factors thereof of the SEI film and further search for effective ways to improve the performance of the SEI film are always hot spots of research in the world electrochemical world.
The soft package lithium ion battery generally adopts an aluminum plastic film as a packaging material, and the material is composed of a polypropylene layer, an aluminum layer and a nylon layer, and has the advantages of flexibility, light weight and flexible design. During the formation process, various gases, such as C, are produced2H4CO, etc., in order to store the gas, air bag regions are usually reserved on the aluminum plastic film bag for storing the generated gas, and the air bag regions are flexible and flexible.
The battery core can lead to laminate polymer battery's bulging in the gas that produces in soaking and formation, and this kind of phenomenon is especially obvious in high Ni ternary battery, and the bulging of rolling up core department plastic-aluminum membrane can lead to the electrolyte liquid level to hang down, influences the infiltration nature of the pole piece on one side upper portion to the battery all can carry out high temperature ageing after the preliminary filling formation, and the purpose lets the SEI membrane that forms dissolve regeneration, if electrolyte can not soak the pole piece completely, also can influence the SEI filming of pole piece.
The Chinese patent literature discloses a method for infiltrating electrolyte of a soft package lithium ion battery and a method for forming the soft package lithium ion battery, and the application publication number is CN 106876792A. However, the infiltration effect of the pole piece and the electrolyte in the charging and discharging process of the battery cannot be ensured, because the gas generation is more in the formation process of the battery core (especially in a high nickel system), the gas causes the swelling of the battery core, the liquid level of the electrolyte is reduced therewith, and the infiltration of the pole piece at the side of the air bag and the SEI film formation become insufficient due to the consumption of the electrolyte. May cause black spots, lithium deposition, etc. (see fig. 1).
Disclosure of Invention
The invention provides a method for improving the formation wettability and the stability of a soft package battery, aiming at solving the problem that an aluminum plastic film at a roll core is easy to bulge in the traditional formation process of the soft package battery, so that the wettability and the stability of an SEI film are poor.
In order to achieve the purpose, the invention adopts the following technical scheme:
before vacuum liquid injection of a battery core, primary pre-sealing treatment is carried out at least two positions at the junction of a roll core and an air bag to obtain a first pre-sealing area, then the liquid is injected in vacuum, the air bag is sealed at an opening of the air bag, and the battery core is obtained through formation, air extraction, heat sealing and cutting.
According to the invention, the shape stability (no bulging) of the battery core in the formation process is kept by performing the pre-sealing treatment near the junction of the winding core and the air bag of the soft package battery, so that most of gas is discharged to the air bag area, and the liquid level of the electrolyte is maintained, thereby improving the wettability of the electrolyte and the SEI film forming stability in the formation aging process.
Preferably, the first pre-sealing area is 2-5mm away from the final seal.
Preferably, the first pre-sealing region has a dimension of 75mm in length and 8mm in width.
Preferably, before the formation, the packaged airbag is subjected to primary air suction and then secondary pre-sealing treatment to obtain a second pre-sealing area.
Preferably, the second pre-sealed region is located at a bevel angle to the open end of the gas pouch.
Preferably, the formation process comprises the following steps:
(1) standing the battery cell for 24 hours at the normal temperature of 25 +/-2 ℃;
(2) puncturing the air bag to perform primary air extraction and sealing;
(3) charging with 0.05C constant current for 140min, and continuing to charge with 0.1C constant current for 110 min;
(4) standing at high temperature for 18h, then performing secondary air extraction and sealing;
(5) after being charged to 4.2V by using a 0.3C constant current, the constant voltage is charged to 0.05C.
Preferably, in the step (4), the temperature of the high-temperature standing is controlled to be 36-40 ℃.
Therefore, the invention has the following beneficial effects: carry out the pre-sealing near the core and the air pocket juncture of laminate polymer battery core, play the effect of putting into shape to the core of rolling up for electric core all keeps better infiltration effect in the formation process, and help high temperature ageing to form stable SEI membrane.
Drawings
Fig. 1 is a real image of black spots and lithium deposition in a soft package battery in the prior art.
FIG. 2 is a process flow diagram of the present invention.
Fig. 3 is a process flow diagram of a comparative example.
Fig. 4 is a state diagram of a cell offline disassembled negative electrode interface obtained in embodiment 1.
Fig. 5 is a state diagram of a disassembled negative electrode interface after the battery cell obtained in example 1 is cycled at normal temperature for 100 weeks.
In the figure: the air bag comprises an aluminum plastic film punching pit 1, an air bag 2, a first pre-sealing area 3, a second pre-sealing area 4 and a heat sealing area 5.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
Referring to the process flow shown in fig. 2, position 1 is where the plastic-aluminum film punching pit is located for placing a roll core and storing electrolyte, and position 2 is a reserved air bag;
(1) before the vacuum liquid injection of the battery core, performing two-position pre-sealing treatment near the junction of the winding core 1 and the air bag 2 to obtain two parallel first packaging areas 3, wherein the pre-sealing position is 2mm away from the final seal, and the length is 75mm and the width is 8 mm;
(2) sealing and soaking for a period of time after vacuum liquid injection, then performing primary air suction and sealing at the oblique angle of the opening end of the air bag to obtain a second pre-sealing area 4;
(3) carrying out formation charging and high-temperature soaking on the battery cell:
(a) standing the battery cell for 24 hours at the normal temperature of 25 ℃;
(b) puncturing the air bag to perform primary air suction and sealing;
(c) charging with 0.05C constant current for 140min, and continuing to charge with 0.1C constant current for 110 min;
(d) standing at the high temperature of 38 ℃ for 18h, then performing secondary air suction and sealing;
(e) charging to 4.2V by using a 0.3C constant current, and then charging to 0.05C by using a constant voltage;
(4) after formation, secondary air exhaust is carried out and finally heat sealing is carried out to obtain a heat sealing area 5;
(5) and cutting to obtain the final battery core.
The soft-package battery of the embodiment is taken off line and fully disassembled after being cycled for 100 weeks at normal temperature, the state of the negative electrode interface is shown in fig. 4 and 5, the interface film is dense, and no black spots and lithium deposition exist.
Example 2
Referring to the process flow shown in fig. 2, position 1 is where the plastic-aluminum film punching pit is located for placing a roll core and storing electrolyte, and position 2 is a reserved air bag;
(1) before the vacuum liquid injection of the battery core, two pre-sealing treatments are carried out near the junction of the winding core 1 and the air bag 2 to obtain two parallel first packaging areas 3, wherein the pre-sealing positions are 5mm away from the final seal, and the length is 70mm and the width is 10 mm;
(2) sealing and soaking for a period of time after vacuum liquid injection, then performing primary air suction and sealing at the oblique angle of the opening end of the air bag to obtain a second pre-sealing area 4;
(3) carrying out formation charging and high-temperature soaking on the battery cell:
(a) standing the battery cell for 24 hours at 23 ℃;
(b) puncturing the air bag to perform primary air suction and sealing;
(c) charging with 0.05C constant current for 140min, and continuing to charge with 0.1C constant current for 110 min;
(d) standing at the high temperature of 40 ℃ for 18h, then performing secondary air suction and sealing;
(e) charging to 4.2V by using a 0.3C constant current, and then charging to 0.05C by using a constant voltage;
(4) after formation, secondary air exhaust is carried out and finally heat sealing is carried out to obtain a heat sealing area 5;
(5) and cutting to obtain the final battery core.
The soft-package battery of the embodiment is offline and fully disassembled after being cycled for 100 weeks at normal temperature, and the interface of the negative electrode interface state is formed into a compact film without black spots and lithium precipitation.
Example 3
Referring to the process flow shown in fig. 2, position 1 is where the plastic-aluminum film punching pit is located for placing a roll core and storing electrolyte, and position 2 is a reserved air bag;
(1) before the vacuum liquid injection of the battery core, performing two-position pre-sealing treatment near the junction of the winding core 1 and the air bag 2 to obtain two parallel first packaging areas 3, wherein the pre-sealing position is 2-5mm away from the final seal, and the length is 65mm and the width is 10 mm;
(2) sealing and soaking for a period of time after vacuum liquid injection, then performing primary air suction and sealing at the oblique angle of the opening end of the air bag to obtain a second pre-sealing area 4;
(3) carrying out formation charging and high-temperature soaking on the battery cell:
(a) standing the battery cell for 24 hours at 27 ℃;
(b) puncturing the air bag to perform primary air suction and sealing;
(c) charging with 0.05C constant current for 140min, and continuing to charge with 0.1C constant current for 110 min;
(d) standing at the high temperature of 36 ℃ for 18h, then performing secondary air suction and sealing;
(e) charging to 4.2V by using a 0.3C constant current, and then charging to 0.05C by using a constant voltage;
(4) after formation, secondary air exhaust is carried out and finally heat sealing is carried out to obtain a heat sealing area 5;
(5) and cutting to obtain the final battery core.
The soft-package battery of the embodiment is offline and fully disassembled after being cycled for 100 weeks at normal temperature, and the interface of the negative electrode interface state is formed into a compact film without black spots and lithium precipitation.
Comparative example
The comparative example differs from example 1 in that the first encapsulation zone without step (1) employs the process flow shown with reference to fig. 3, and the rest of the process is identical. The soft package battery of the comparative example is taken off line and fully disassembled after being cycled for 100 weeks at normal temperature, and the interface of the negative electrode interface state has black spots and lithium precipitation.
The performance indexes of the battery cells obtained in examples 1 to 3 and the comparative example were measured, and the results are shown in table 1:
TABLE 1 test results
| Performance index | Example 1 | Example 2 | Example 3 | Comparative example |
| High temperature soak time | 18h | 16h | 17h | 24h |
| SEI film | No black spot and no lithium deposition | No black spot and no lithium deposition | No black spot and no lithium deposition | Black spot and separated lithium |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. A method for improving the wettability and the stability of an SEI film of a soft package battery is characterized in that before vacuum liquid injection of a battery core, primary pre-sealing treatment is carried out at least two positions at the junction of a winding core and an air bag to obtain a first pre-sealing area, then the liquid is injected in vacuum, the air bag is sealed at the opening of the air bag, and the battery core is obtained through formation, air extraction, heat sealing and cutting.
2. The method for improving the wettability of the soft package battery and the stability of the SEI film according to claim 1, wherein the distance between the first pre-sealing area and the final seal is 2-5 mm.
3. The method for improving the wettability of soft-packed battery and the stability of SEI film according to claim 1, wherein the size of the first pre-sealing area is 75mm long by 8mm wide, but not limited thereto.
4. The method for improving the wettability and the SEI film stability of the soft package battery as claimed in claim 1, wherein before formation, the encapsulated airbag is subjected to a first air-exhaust process and then a second pre-encapsulation process to obtain a second pre-encapsulation region.
5. The method for improving the wettability of soft package battery and the stability of the SEI film according to claim 4, wherein the second pre-sealing region is located at a bevel angle of the opening end of the gas bag.
6. The method for improving the formation wettability and the SEI film stability of the soft package battery according to claim 1, wherein the formation process comprises the following steps:
(a) standing the battery cell for 24 hours at normal temperature;
(b) puncturing the air bag to perform primary air suction and sealing;
(c) charging with 0.05C constant current for 140min, and continuing to charge with 0.1C constant current for 110 min;
(d) standing at high temperature for 18h, then performing secondary air extraction and sealing;
(e) after being charged to 4.2V by using a 0.3C constant current, the constant voltage is charged to 0.05C.
7. The method for improving the chemical wettability and the SEI film stability of the soft package battery according to claim 6, wherein the temperature of the high-temperature standing in the step (4) is controlled to be 36-40 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113036230A (en) * | 2021-03-18 | 2021-06-25 | 广东邦普循环科技有限公司 | Preparation method and application of lithium cobaltate soft package battery |
| CN114069020A (en) * | 2021-10-18 | 2022-02-18 | 深圳市首通新能源科技有限公司 | Lithium battery manufacturing method and lithium battery |
| CN114361598A (en) * | 2021-12-04 | 2022-04-15 | 万向一二三股份公司 | Unequal-wall double-pit shell punching method for external package of soft package battery and battery thereof |
| CN114551971A (en) * | 2021-11-30 | 2022-05-27 | 万向一二三股份公司 | Heat packaging method for soft package battery |
| CN116544316A (en) * | 2023-07-07 | 2023-08-04 | 四川大学 | Deliquescence inhibition method for AlSb thin-film solar cell |
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| CN116544316A (en) * | 2023-07-07 | 2023-08-04 | 四川大学 | Deliquescence inhibition method for AlSb thin-film solar cell |
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Effective date of registration: 20211109 Address after: No.855, Jianshe 2nd Road, Xiaoshan Economic and Technological Development Zone, Hangzhou City, Zhejiang Province Applicant after: Wanxiang A123 Co.,Ltd. Address before: No.855 Jianshe Er Road, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: Wanxiang A123 Co.,Ltd. Applicant before: WANXIANG GROUP Co.,Ltd. |
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