CN113078378B - Formation method of lithium battery - Google Patents
Formation method of lithium battery Download PDFInfo
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- CN113078378B CN113078378B CN202110378803.0A CN202110378803A CN113078378B CN 113078378 B CN113078378 B CN 113078378B CN 202110378803 A CN202110378803 A CN 202110378803A CN 113078378 B CN113078378 B CN 113078378B
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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
- H01M10/052—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
- H01M10/05—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 belongs to the field of lithium battery manufacturing, and provides a lithium battery formation method for solving the problem of poor systematicness of current formation, which comprises the following steps: and (2) injecting the lithium ion battery core, standing and forming, wherein the temperature is 5-60 ℃, the surface pressure of the battery core is 0.3-0.5Mpa, and the current is 0.01-0.6C. The invention establishes corresponding relation among current, temperature and electric quantity when the battery cell is formed by a formula, so that the SEI of the formed battery cell is more stable and compact, the cycle performance is better, the formation time is shortened, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the field of lithium battery manufacturing, and particularly relates to a lithium battery formation method.
Background
With the development of society and the progress of technology, clean and efficient new energy is more and more emphasized by the nation and people. Since the lithium ion secondary battery has been commercialized, the lithium ion secondary battery has attracted attention by the public because of its advantages such as excellent cycle performance, rate capability, high power, and high energy density, and has been widely used in the fields of electric vehicles, buses, mobile phones, notebooks, electric bicycles, electric tools, energy storage, and the like.
In the production process of the lithium ion battery, the procedures of material preparation, coating, tabletting, assembly, baking, liquid injection, formation, battery sorting, PACK and the like are included, although the production procedures of each manufacturer are basically the same and different, the control parameters of the production process are far from each other. The formation process has a great influence on the performance of the lithium ion battery, and is a subject of research by various manufacturers. The current research on the formation process is mainly performed around a negative electrode SEI film (solid electrolyte interface film). Since the lithium ion battery generates a passivation film on the surface of the negative electrode during the first charge and discharge, the passivation film has the characteristics of solid electrolyte and good electronic insulation, but is a good ion conductor, Li+Can be freely inserted and removed, can prevent the co-insertion of solvent molecules, and avoids the damage to electrode materials caused by the co-insertion of the solvent molecules, thereby greatly improving the cycle performance and prolonging the service life of the electrode. Therefore, intensive research on the formation mechanism, composition structure, stability and influence factors of the SEI film and further search for an effective way for improving the performance of the SEI film are always the key points of research of various manufacturers.
At present, the formed SEI is generally considered to be more compact and stable in a low-temperature environment and during small-current formation, but polarization of a battery can be increased in the low-temperature environment, lithium precipitation of a negative electrode can be caused when the current is slightly large, lithium precipitation can be improved during small-current formation, formation time can be prolonged, and production efficiency is affected. Therefore, the main forming method at present mainly comprises: high temperature (generally 35-60 ℃), pressurization (generally 0.2-0.6Mpa), step current (the current is from small to large along with the formation), although this method has been used by various manufacturers, there is great randomness in the use process, the systematicness is not strong, the formation time is not too long, but the stability and compactness of SEI are sacrificed although the formation time is not shortened.
Patent CN108767319A discloses a formation method of a lithium ion battery, which comprises the following steps: the method comprises the steps of injecting liquid into the lithium ion battery, standing, forming, vacuumizing and then carrying out aging treatment, and effectively solves the problems of low cycle performance and battery bulging after the lithium ion battery is formed, but the added aging step consumes long time and affects the production efficiency. Accordingly, an ideal solution is needed.
Disclosure of Invention
The invention aims to solve the problem of poor systematicness of current formation, and provides a formation method of a lithium battery.
In order to achieve the above purpose, the invention adopts the following technical scheme,
a formation method of a lithium battery comprises the following steps: and (2) injecting the lithium ion battery core, standing and forming, wherein the temperature is 5-60 ℃, the surface pressure of the battery core is 0.3-0.5Mpa, and the current is 0.01-0.6C.
Preferably, the battery cell is one of lithium iron phosphate-graphite, ternary-graphite, lithium manganate-graphite, ternary composite-graphite, lithium manganate composite-graphite, lithium manganese rich base-graphite, lithium manganese phosphate-graphite, ternary-silicon carbon, lithium manganate-silicon carbon, ternary composite-silicon carbon, lithium manganese rich base-silicon carbon, lithium manganese phosphate-silicon carbon, lithium manganate composite-silicon carbon systems.
Preferably, in the formation process, the first step: constant-current charging, wherein the current I1 is 0.01-0.12 ℃, the charging state Q1 is 15-60%, and the temperature T1 is 10-25 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.1-0.4C, the charging state Q2 is 20-60%, and the temperature T2 is 20-55 ℃; the third step: constant-current charging, wherein the current I3 is 0.3-0.6C, the charging state Q3 is 40-90%, and the temperature T3 is 25-60 ℃. The sectional type charging with low current firstly and then high current is adopted, which is beneficial to reducing polarization and generating SEI film. When the formation current is larger, although the formation time is shortened, the formed SEI is not compact enough; when the formation current is small, the formed SEI is compact, but the formation time is long and the efficiency is low; when the formation temperature is low, a compact SEI film can be formed, but the battery polarization can be increased due to the low temperature, and the lithium precipitation risk exists on the surface of the negative electrode; when the formation temperature is higher, the polarization can be reduced, but when the temperature is too high, the electrolyte components can be damaged, and the battery can be inflated.
More preferably, the current i (c), the temperature T (° c), and the charge Q (%) at the time of formation satisfy the following relationships: 0.5-100In/TnNot more than 2.0(n is not less than 1) and 100In/Qn-1Less than or equal to 2(n is more than or equal to 2). The inventors found that when the current, temperature and charge amount satisfy the above relationship, the formed SEI is denser, the negative electrode interface is better, and the battery cycle performance is better.
Preferably, the formation is carried out in high-temperature pressurization formation equipment, the pressure of the equipment is firstly adjusted, then the core is placed for standing for 2-5min, and then the formation is carried out by electrifying. The first laying aside for 2-5min is to detect whether the electric core is in good contact with the formation voltage sampling equipment.
Therefore, the beneficial effects of the invention are as follows: the current, the temperature and the electric quantity when the battery core is formed are related through a formula, the formation time is shortened under the condition that the SEI film is stable and compact, the cycle performance of the battery core is improved, the production efficiency is improved, and the method is suitable for mass production.
Detailed Description
The invention is further described below with reference to specific embodiments:
in the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
General examples
A formation method of a lithium battery comprises the following steps: carrying out high-temperature or normal-temperature standing on the ternary + graphite system battery cells which are normally produced in batch and are subjected to liquid injection; placing into high temperature pressurization formation equipment after standing, setting the pressure at 0.3-0.5Mpa, placing into a battery core, standing for 2-5min, and electrifying for formation; in the formation process, the first step: constant-current charging, wherein the current I1 is 0.01-0.12 ℃, the charging state Q1 is 15-60%, and the temperature T1 is 10-25 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.1-0.4C, the charging state Q2 is 20-60%, and the temperature T2 is 20-55 ℃; the third step: constant-current charging, wherein the current I3 is 0.3-0.6C, the charging state Q3 is 40-90%, and the temperature T3 is 25-60 ℃.
Example 1
A formation method of a lithium battery comprises the following steps: carrying out high-temperature standing on the ternary + graphite system battery cells which are normally produced in batch and are subjected to liquid injection; placing the battery cell into high-temperature pressurization formation equipment after standing is finished, setting the pressure to be 0.4Mpa, placing the battery cell for standing for 3min, ensuring that the battery cell is in good contact with formation voltage sampling equipment, and then electrifying for formation; in the formation process, the first step: constant-current charging, wherein the current I1 is 0.08C, the charging state Q1 is 15%, and the temperature T1 is 10 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.22C, the charging state Q2 is 25 percent, and the temperature T2 is 25 ℃; the third step: constant-current charging, wherein the current I3 is 0.4C, the charging state Q3 is 55 percent, and the temperature T3 is 45 ℃.
Example 2
The difference between the formation method of the lithium battery and the embodiment 1 is the formation process, and the first step is as follows: constant-current charging, wherein the current I1 is 0.12 ℃, the charging state Q1 is 15%, and the temperature T1 is 10 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.25 ℃, the charging state Q2 is 35%, and the temperature T2 is 30 ℃; the third step: constant-current charging, wherein the current I3 is 0.42C, the charging state Q3 is 65%, and the temperature T3 is 50 ℃.
Example 3
The difference between the formation method of the lithium battery and the embodiment 1 is the formation process, and the first step is as follows: constant-current charging, wherein the current I1 is 0.10 ℃, the charging state Q1 is 20%, and the temperature T1 is 10 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.30 ℃, the charging state Q2 is 35%, and the temperature T2 is 40 ℃; the third step: constant-current charging, wherein the current I3 is 0.45C, the charging state Q3 is 55 percent, and the temperature T3 is 55 ℃.
Example 4
The difference between the formation method of the lithium battery and the embodiment 1 is the formation process, and the first step is as follows: constant-current charging, wherein the current I1 is 0.1 ℃, the charging state Q1 is 20%, and the temperature T1 is 10 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.30 ℃, the charging state Q2 is 40%, and the temperature T2 is 35 ℃; the third step: constant-current charging, wherein the current I3 is 0.45C, the charging state Q3 is 60 percent, and the temperature T3 is 50 ℃.
Example 5
The difference between the formation method of the lithium battery and the embodiment 1 is the formation process, and the first step is as follows: constant-current charging, wherein the current I1 is 0.10 ℃, the charging state Q1 is 20%, and the temperature T1 is 15 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.35C, the charging state Q2 is 40%, and the temperature T2 is 45 ℃; the third step: constant-current charging, wherein the current I3 is 0.50 ℃, the charging state Q3 is 60%, and the temperature T3 is 55 ℃.
Example 6
The difference between the formation method of the lithium battery and the embodiment 1 is the formation process, and the first step is as follows: constant-current charging, wherein the current I1 is 0.10 ℃, the charging state Q1 is 15%, and the temperature T1 is 5 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.40 ℃, the charging state Q2 is 30%, and the temperature T2 is 20 ℃; the third step: constant-current charging, wherein the current I3 is 0.50 ℃, the charging state Q3 is 60%, and the temperature T3 is 55 ℃.
Example 7
The difference between the formation method of the lithium battery and the embodiment 1 is that an electric core system is lithium iron phosphate + graphite.
Example 8
A formation method of a lithium battery, which is different from the embodiment 2 in that an electric core system is lithium iron phosphate + graphite.
Example 9
A formation method of a lithium battery, which is different from the embodiment 3 in that an electric core system is lithium iron phosphate + graphite.
Example 10
A formation method of a lithium battery, which is different from the embodiment 4 in that an electric core system is lithium iron phosphate + graphite.
Example 11
A formation method of a lithium battery, which is different from the embodiment 5 in that an electric core system is lithium iron phosphate + graphite.
Example 12
A formation method of a lithium battery, which is different from the embodiment 6 in that an electric core system is lithium iron phosphate + graphite.
Example 13
The difference between the formation method of the lithium battery and the embodiment 1 is that the battery core system is lithium manganate + graphite.
Example 14
The difference between the formation method of the lithium battery and the embodiment 2 is that the battery core system is lithium manganate + graphite.
Example 15
A lithium battery formation method, which is different from the embodiment 3 in that the battery core system is lithium manganate + graphite.
Example 16
The difference between the formation method of the lithium battery and the embodiment 4 is that the battery core system is lithium manganate + graphite.
Example 17
The difference between the formation method of the lithium battery and the embodiment 5 is that the battery core system is lithium manganate + graphite.
Example 18
The difference between the formation method of the lithium battery and the embodiment 6 is that the battery core system is lithium manganate + graphite.
Comparative example 1
The difference between the formation method of the lithium battery and the embodiment 1 is the formation process, and the first step is as follows: constant-current charging, wherein the current I1 is 0.15 ℃, the charging state Q1 is 10%, and the temperature T1 is 5 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.40 ℃, the charging state Q2 is 20%, and the temperature T2 is 20 ℃; the third step: constant-current charging, wherein the current I3 is 0.60 ℃, the charging state Q3 is 60%, and the temperature T3 is 30 ℃.
Comparative example 2
The formation method of the lithium battery is different from the embodiment 1 in that an electric core system is lithium iron phosphate + graphite; the formation process comprises the following steps: constant-current charging, wherein the current I1 is 0.20 ℃, the charging state Q1 is 5%, and the temperature T1 is 5 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.40 ℃, the charging state Q2 is 25%, and the temperature T2 is 20 ℃; the third step: constant-current charging, wherein the current I3 is 0.60 ℃, the charging state Q3 is 60%, and the temperature T3 is 55 ℃.
Comparative example 3
The formation method of the lithium battery is different from the embodiment 1 in that the battery core system is lithium manganate + graphite; the formation process comprises the following steps: constant-current charging, wherein the current I1 is 0.20 ℃, the charging state Q1 is 10%, and the temperature T1 is 5 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.45 ℃, the charging state Q2 is 20%, and the temperature T2 is 15 ℃; the third step: constant-current charging, wherein the current I3 is 0.60 ℃, the charging state Q3 is 60%, and the temperature T3 is 55 ℃.
Performance testing
100I calculated in examples 6, 12 and 18n/TnValue and 100In/Qn-1Values outside the preferred range, slight lithium precipitation occurred, indicating that the current was small during initialization and that the current and temperature were appropriate. As can be seen by comparing the comparative example and the examples, the current i (c), the temperature T (° c), and the charge Q (%) at the time of formation satisfy the following relationships: 0.5-100In/TnNot more than 2.0(n is not less than 1) and 100In/Qn-1When the number n is less than or equal to 2(n is more than or equal to 2), the cycle performance of the battery cell can be improved, the production efficiency is improved, and the method is suitable for mass production. This reference is a work product of the inventors and is not disclosed in the prior art, but is inventive.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (3)
1. A formation method of a lithium battery is characterized by comprising the following steps: injecting a lithium ion battery core, standing and forming, wherein the temperature is 5-60 ℃, the surface pressure of the battery core is 0.3-0.5Mpa, and the current is 0.01-0.6C; the current I (C), temperature T (DEG C), and charge Q (%) at the time of formation satisfy the following relationships: 0.5-100In/TnNot more than 2.0(n is not less than 1) and 100In/Qn-1≤2(n≥2);
The battery cell is one of lithium iron phosphate-graphite, ternary-graphite, lithium manganate-graphite, ternary composite-graphite, lithium manganate composite-graphite, lithium manganese rich base-graphite, lithium manganese phosphate-graphite, ternary-silicon carbon, lithium manganate-silicon carbon, ternary composite-silicon carbon, lithium manganese rich base-silicon carbon, lithium manganese phosphate-silicon carbon and lithium manganate composite-silicon carbon systems.
2. The formation method of the lithium battery as claimed in claim 1, wherein in the formation process, a first step of: constant-current charging, wherein the current I1 is 0.01-0.12 ℃, the charging state Q1 is 15-60%, and the temperature T1 is 10-25 ℃; the second step is that: constant-current charging, wherein the current I2 is 0.1-0.4C, the charging state Q2 is 20-60%, and the temperature T2 is 20-55 ℃; the third step: constant-current charging, wherein the current I3 is 0.3-0.6C, the charging state Q3 is 40-90%, and the temperature T3 is 25-60 ℃.
3. The method as claimed in claim 1, wherein the formation is carried out in a high-temperature pressurized formation device, the pressure of the device is adjusted, the battery cell is placed for 2-5min, and then the formation is carried out by electrifying.
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CN113948778B (en) * | 2021-10-12 | 2023-06-16 | 远景动力技术(江苏)有限公司 | Lithium ion battery core and formation method and application thereof |
CN114335769B (en) * | 2021-12-23 | 2024-01-02 | 湖北亿纬动力有限公司 | Formation aging method of battery cell and lithium ion battery |
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