CN113054270A - Soft package lithium ion battery formation process - Google Patents
Soft package lithium ion battery formation process Download PDFInfo
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- CN113054270A CN113054270A CN202110314513.XA CN202110314513A CN113054270A CN 113054270 A CN113054270 A CN 113054270A CN 202110314513 A CN202110314513 A CN 202110314513A CN 113054270 A CN113054270 A CN 113054270A
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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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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
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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 formation process of a soft package lithium ion battery. Belongs to the technical field of lithium ion battery manufacture. The method mainly solves the problem that the subsequent charge and discharge gas generation is serious due to insufficient formation of the lithium titanate system battery by adopting normal temperature formation or 45 ℃ high temperature formation. It is mainly characterized by comprising the following steps: preheating the mixture to 75-85 ℃; the method comprises the first-stage formation of firstly carrying out first formation and then carrying out first air-extraction sealing after the temperature is restored to room temperature; performing first-time electricity emptying, performing second-time formation, recovering to room temperature, and performing second-time air-extraction and second-time formation after sealing; and (5) carrying out secondary electric quantity emptying to finish the third formation after secondary air extraction of the whole formation process. The invention enables the lithium titanate negative electrode material to fully react with the electrolyte, eliminates the influence of subsequent side reaction on the battery performance, prolongs the service life of the battery, and is mainly used for the formation process after the liquid injection aging process of the lithium titanate system lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a soft package lithium ion battery formation process.
Background
The formation of the soft package lithium ion battery is a process of activating the battery, a battery prepared by taking a lithium titanate material as a negative electrode active material and taking a conventional ternary material as a positive electrode active material needs a long time in the formation process, and if the formation is insufficient, the prepared finished product battery can continuously generate gas in the charging, discharging and circulating processes, so that the performance of the battery is reduced, and the cycle life is shortened.
In the prior art, soft package lithium ion batteries are formed at normal temperature or at high temperature of 45 ℃, but the formation method is not suitable for lithium titanate system batteries. Therefore, there are problems that the formation of a lithium titanate-based battery is insufficient, and gas generation is severe after subsequent charge and discharge.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a formation process of a soft package lithium ion battery, which can enable a lithium titanate system battery to be fully formed.
The above object of the present invention is achieved by the following technical solutions: a soft package lithium ion battery formation process is used for a formation process after a lithium titanate system lithium ion battery liquid injection aging process, and is characterized in that: the method comprises four process steps of preheating, first-stage formation, second-stage formation after primary air extraction and third-stage formation after secondary air extraction, so that the lithium titanate negative electrode material and electrolyte are fully reacted, the influence of subsequent side reactions on the performance of the battery is eliminated, and the service life of the battery is prolonged.
In the preheating process step in the technical scheme of the invention, the soft package lithium ion battery after the liquid injection aging process is heated to 75-85 ℃; in the first-stage formation process step, the soft package lithium ion battery is firstly subjected to first formation, and is subjected to first air extraction and sealing after being recovered to room temperature; in the second-stage formation process step after the primary air extraction, the first-time electric quantity emptying is carried out on the soft package lithium ion battery, then the second-time formation is carried out, and the air extraction and sealing are carried out for the second time after the room temperature is recovered; and in the third formation process step after secondary air extraction, secondary electric quantity emptying is carried out on the soft package lithium ion battery, and the whole formation process is completed.
In the preheating process step in the technical scheme of the invention, the preheating pressure is 0.4-0.6 MPa; in the first-stage formation process step, the first formation is carried out in a step-and-step charging mode within the current range of 0.02-0.3C; in the second-stage formation process step after the primary air extraction, the constant current discharge is carried out by 0.5-1C current, and the first-time electric quantity emptying is carried out within 60-120min of discharge time; the second formation is carried out in a current range of 0.02-0.3C in a step sectional charging mode, and the second air extraction and sealing are carried out after the temperature is restored to the room temperature; in the third-stage formation process step after the secondary air extraction, the secondary electric quantity is discharged with a constant current of 0.5-1C within 60-120 min.
In the preheating process step in the technical scheme of the invention, the soft package lithium ion battery is preheated in the formation cabinet; in the first-stage formation process step and the second-stage formation process step after primary air extraction, the first formation and the second formation are carried out in a formation cabinet; in the first-stage formation process step and the second-stage formation process step after the primary air extraction, the primary air extraction sealing and the secondary air extraction sealing are carried out on air extraction sealing equipment.
In the first-stage formation process step in the technical solution of the present invention, a step-stage charging manner is:
s1: performing a first stage of constant current charging at a current of 0.02-0.03 ℃ for 300 min;
s2: performing second-stage constant current charging at a current of 0.05-0.07C for 300 min;
s3: performing third-stage constant current charging at a current of 0.08-0.12 ℃ for 100-150 min;
s4: and performing constant current charging at the fourth stage with a current of 0.15-0.24 ℃ for 100-150 min.
In the second-stage formation process step after primary air extraction in the technical scheme of the invention, a stepped sectional charging mode is adopted as follows:
s1: constant current discharging of the 0.5-0.1C battery cell for 60-120 min;
s2: carrying out first-stage constant current charging at the current of 0.02-0.03 ℃ for 300 min;
s3: carrying out second-stage constant current charging at the current of 0.05-0.07 ℃, wherein the charging time is 240-;
s4: and carrying out third-stage constant current charging at the current of 0.08-0.12 ℃, wherein the charging time is 240-300 min.
According to the technical scheme, the positive active material of the soft package lithium ion battery is one or more of lithium manganate, lithium nickel cobalt manganese oxide and lithium manganese iron phosphate.
According to the technical scheme, the negative active material of the soft package lithium ion battery is lithium titanate.
The invention has the beneficial effects that:
1. the soft package lithium ion battery formation process adopts three-stage stepwise formation, prolongs the charging time and enables the side reactions in the battery to fully occur; the lithium titanate negative electrode material, the electrolyte and trace moisture are fully reacted, so that the possibility of secondary reaction in the charge-discharge cycle process of the finished battery is eliminated;
2. the soft package lithium ion battery formation process adopts a two-time air extraction mode to extract the gas generated in the lithium ion battery formation process, so that the side reaction in the battery moves forward.
Drawings
FIG. 1 is a flow chart of the manufacturing process of the present invention.
Detailed Description
The invention relates to a formation process of a soft package lithium ion battery, which is used for a formation process after a liquid injection aging process of a lithium titanate system lithium ion battery and comprises four process steps of preheating, first-stage formation, second-stage formation after primary air extraction and third-stage formation after secondary air extraction. In the preheating process step, the soft package lithium ion battery after the liquid injection and aging process is heated to 75-85 ℃, and the preheating pressure is 0.4-0.6 MPa; in the first-stage formation process step, the soft-package lithium ion battery is firstly formed for the first time, the first-stage formation is carried out in a stepped segmented charging mode within the current range of 0.02-0.3 ℃, and the first-stage air extraction and sealing are carried out after the temperature is restored to the room temperature; in the second-stage formation process step after primary air extraction, first-time electric quantity emptying is carried out on the soft-package lithium ion battery, constant current discharging is carried out at the current of 0.5-1C, the discharging time is 60-120min, then second formation is carried out, the second-time formation is carried out in a step segmented charging mode within the current range of 0.02-0.3C, and secondary air extraction and sealing are carried out after the temperature is restored to the room temperature; and in the third stage formation process step after secondary air extraction, carrying out secondary electric quantity emptying on the soft package lithium ion battery, and carrying out constant current discharge at a current of 0.5-1C for 60-120min to finish the whole formation process.
The concrete formation steps are shown in fig. 1 and comprise: the aging of the battery is completed → 75-85 ℃, 0.4-0.6MPa preheating → the first stage of one-section low current charging 0.02-0.03C constant current charging 240- Electrifying for 60-80min → formation is completed.
Example 1
The positive electrode material of the soft package lithium ion battery is nickel cobalt lithium manganate, and the negative electrode is lithium titanate. And after the battery is subjected to liquid injection and aging, transferring the battery into a hot pressing formation cabinet, pressing the battery to 0.4MPa, preheating the battery after the battery is compressed, and finishing preheating after the temperature of the equipment is raised to 75 ℃.
The first stage is that:
s1: charging at constant current of 0.02C for 300 min;
s2: charging at constant current of 0.05C for 300 min;
s3: charging at constant current of 0.08C for 120 min;
s4: and charging at constant current of 0.15C for 120 min.
And after the first-stage formation is finished, taking down the battery from the formation cabinet, recovering to room temperature, performing primary air extraction on air extraction sealing equipment, and completely extracting gas generated in the formation of the battery and then sealing.
After finishing once exhausting and sealing, putting the battery into a hot-pressing formation cabinet, and carrying out second-stage formation:
s1: discharging at constant current of 0.5C for 100 min;
s2: charging at constant current of 0.02C for 300 min;
s3: charging at constant current of 0.06C for 300 min;
s4: and charging the battery for 300min at a constant current of 0.08C.
And (5) finishing the second-stage formation, taking down the battery from the formation cabinet, recovering to room temperature, performing secondary air extraction on air extraction sealing equipment, and sealing after exhausting the gas generated in the formation of the battery.
After secondary air extraction and sealing, the battery is placed into a hot-pressing formation cabinet, and is discharged for 100min at a constant current of 0.5C, so that the whole formation process is completed.
Example 2
The positive electrode material of the soft package lithium ion battery is lithium manganese iron phosphate, and the negative electrode is lithium titanate. And after the battery is subjected to liquid injection and aging, transferring the battery into a hot pressing formation cabinet, pressing the battery to 0.6MPa, preheating the battery after the battery is compressed, and finishing preheating after the temperature of the equipment is raised to 85 ℃.
The first stage is that:
s1: charging at constant current of 0.03C for 240 min;
s2: charging at constant current of 0.07C for 240 min;
s3: charging at constant current of 0.12C for 150 min;
s4: and charging at constant current of 0.24C for 150 min.
And after the first-stage formation is finished, taking down the battery from the formation cabinet, recovering to room temperature, performing primary air extraction on air extraction sealing equipment, and completely extracting gas generated in the formation of the battery and then sealing.
After finishing once exhausting and sealing, putting the battery into a hot-pressing formation cabinet, and carrying out second-stage formation:
s1: discharging with 1C current for 60 min;
s2: charging at 0.03C for 240 min;
s3: charging at 0.07C current for 240 min;
s4: and (5) constant current charging at 0.12 ℃ for 240 min.
And (5) finishing the second-stage formation, taking down the battery from the formation cabinet, recovering to room temperature, performing secondary air extraction on air extraction sealing equipment, and sealing after exhausting the gas generated in the formation of the battery.
And after secondary air extraction and sealing, putting the battery into a hot-pressing formation cabinet, and discharging for 60min at a constant current of 1C to complete the whole formation process.
Claims (10)
1. A soft package lithium ion battery formation process is used for a formation process after a lithium titanate system lithium ion battery liquid injection aging process, and is characterized in that: the method comprises four process steps of preheating, first stage formation, second stage formation after primary air extraction and third stage formation after secondary air extraction.
2. The soft package lithium ion battery formation process according to claim 1, characterized in that:
in the preheating process step, the soft package lithium ion battery after the liquid injection and aging process is heated to 75-85 ℃;
in the first-stage formation process step, the soft package lithium ion battery is firstly subjected to first formation, and is subjected to first air extraction and sealing after being recovered to room temperature;
in the second-stage formation process step after the primary air extraction, the first-time electric quantity emptying is carried out on the soft package lithium ion battery, then the second-time formation is carried out, and the air extraction and sealing are carried out for the second time after the room temperature is recovered;
and in the third formation process step after secondary air extraction, secondary electric quantity emptying is carried out on the soft package lithium ion battery, and the whole formation process is completed.
3. The soft package lithium ion battery formation process according to claim 2, characterized in that:
in the preheating process step, the preheating pressure is 0.4-0.6 MPa;
in the first-stage formation process step, the first formation is carried out in a step-and-step charging mode within the current range of 0.02-0.3C;
in the second-stage formation process step after the primary air extraction, the constant current discharge is carried out by 0.5-1C current, and the first-time electric quantity emptying is carried out within 60-120min of discharge time; the second formation is carried out in a current range of 0.02-0.3C in a step sectional charging mode, and the second air extraction and sealing are carried out after the temperature is restored to the room temperature;
in the third-stage formation process step after the secondary air extraction, the secondary electric quantity is discharged with a constant current of 0.5-1C within 60-120 min.
4. The soft package lithium ion battery formation process according to claim 3, characterized in that:
in the preheating process step, the soft package lithium ion battery is preheated in the formation cabinet;
in the first-stage formation process step and the second-stage formation process step after primary air extraction, the first formation and the second formation are carried out in a formation cabinet;
in the first-stage formation process step and the second-stage formation process step after the primary air extraction, the primary air extraction sealing and the secondary air extraction sealing are carried out on air extraction sealing equipment.
5. The soft package lithium ion battery formation process according to claim 4, characterized in that: in the first-stage formation process step, a step-stage sectional charging mode is as follows:
s1: performing a first stage of constant current charging at a current of 0.02-0.03 ℃ for 300 min;
s2: performing second-stage constant current charging at a current of 0.05-0.07C for 300 min;
s3: performing third-stage constant current charging at a current of 0.08-0.12 ℃ for 100-150 min;
s4: and performing constant current charging at the fourth stage with a current of 0.15-0.24 ℃ for 100-150 min.
6. The soft package lithium ion battery formation process according to claim 4 or 5, characterized in that: in the second stage formation process step after primary air extraction, a step sectional charging mode is as follows:
s1: constant current discharging of the 0.5-0.1C battery cell for 60-120 min;
s2: carrying out first-stage constant current charging at the current of 0.02-0.03 ℃ for 300 min;
s3: carrying out second-stage constant current charging at the current of 0.05-0.07 ℃, wherein the charging time is 240-;
s4: and carrying out third-stage constant current charging at the current of 0.08-0.12 ℃, wherein the charging time is 240-300 min.
7. The soft-package lithium ion battery formation process according to any one of claims 1 to 5, characterized in that: the positive active substance of the soft package lithium ion battery is one or more of lithium manganate, lithium nickel cobalt manganese oxide and lithium manganese iron phosphate.
8. The soft-package lithium ion battery formation process according to any one of claims 1 to 5, characterized in that: the negative active material of the soft package lithium ion battery is lithium titanate.
9. The soft package lithium ion battery formation process according to claim 6, characterized in that: the negative active material of the soft package lithium ion battery is lithium titanate.
10. The soft package lithium ion battery formation process according to claim 7, characterized in that: the negative active material of the soft package lithium ion battery is lithium titanate.
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