CN114914564B - Lithium ion battery formation method, secondary battery and preparation method thereof - Google Patents
Lithium ion battery formation method, secondary battery and preparation method thereof Download PDFInfo
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- CN114914564B CN114914564B CN202210607931.2A CN202210607931A CN114914564B CN 114914564 B CN114914564 B CN 114914564B CN 202210607931 A CN202210607931 A CN 202210607931A CN 114914564 B CN114914564 B CN 114914564B
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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
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- 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
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Abstract
According to the lithium ion battery formation method, the secondary battery and the preparation method thereof, the lithium ion battery is charged to 50% -80% of the state of charge through 0.3-1C high current in the first formation stage, the battery is easier to undergo interfacial oxidation-reduction reaction, so that a porous rough SEI film is formed initially under the condition of being held by a first clamp force, and in the second formation stage, 0.05-0.3C is utilized for multiple shallow cycles in the 80% -90% of the high state of charge, so that the reaction of a silicon negative electrode and electrolyte can be promoted more effectively, a reduction product can fully fill the SEI film formed in the first formation stage, meanwhile, because the positive electrode is in a high potential in the charging process, interface oxidation reaction is easier to occur, the recombination and the repair compression of a surface product can be realized, the quality of the SEI film is improved, the capacity of inhibiting the volume expansion of a silicon negative electrode material is improved, the produced gas of the battery in the high state of charge can be discharged more rapidly by adopting the constraint of a larger clamp force in the second formation stage, the SEI film is more compact, the battery performance is prolonged, and the service life of the battery is prolonged.
Description
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a lithium ion battery formation method, a secondary battery and a preparation method thereof.
Background
The energy density requirement of the market for a power battery is increased more and more due to the rapid development of new energy automobiles, the ultrahigh nickel anode material and the silicon-based anode material are rapidly increased in the process of carrying out charge-discharge cycle on the subsequent battery, and further, the side reaction of electrolyte solvent and lithium salt is continuously increased, so that the lithium content in the lithium ion battery is greatly consumed, the service life is reduced, and when the service life is more serious, the battery core is severely swelled due to the fact that the battery core is produced by the electrolyte.
In view of this, it is necessary to provide a formation process suitable for high energy density lithium ion batteries to form a good quality SEI film, thereby prolonging the service life of the battery.
Disclosure of Invention
The invention aims to provide a lithium ion battery formation method, a secondary battery and a preparation method thereof, which can form an SEI film with good quality and prolong the service life of the battery.
The invention is realized in the following way:
in a first aspect, the present invention provides a lithium ion battery formation method, comprising:
a first formation stage: under the condition of a first clamp force, the lithium ion battery is charged to 50-80% of charge state at 0.3-1C;
a second formation stage: under the condition of a second clamp force, the lithium ion battery is shallow cycled for x times between 80% -90% of charge states at 0.05-0.3 ℃, wherein x is positively correlated with the silicon doped content y of the negative electrode of the lithium ion battery, and the first clamp force is smaller than the second clamp force.
In an alternative embodiment, x and y satisfy the following condition:
x＝[10.86y+0.6]+1。
in an alternative embodiment, y is 5% to 30%.
In an alternative embodiment, the first formation stage is carried out at a temperature of 50 ℃ to 60 ℃.
In an alternative embodiment, the second chemical conversion stage is carried out at a temperature of 20 ℃ to 30 ℃.
In an alternative embodiment, the first clamp force is between 0.05MPa and 0.15MPa.
In an alternative embodiment, the second clamp force is between 0.1MPa and 0.35MPa.
In an alternative embodiment, the second clamp force is positively correlated with x.
In a second aspect, the present invention provides a method for preparing a secondary battery, comprising a lithium ion battery formation method according to any of the preceding embodiments.
In a third aspect, the present invention provides a secondary battery manufactured by the secondary battery manufacturing method according to the foregoing embodiment.
The invention has the following beneficial effects:
according to the method, the lithium ion battery is charged to 50% -80% of the state of charge by 0.3-1C high current in the first formation stage, the battery is easier to undergo interfacial redox reaction, so that a porous rough SEI film is preliminarily formed under the condition that the first clamp force is applied, the reaction of a silicon negative electrode and electrolyte can be more effectively promoted by utilizing 0.05-0.3C in the 80% -90% high state of charge in the second formation stage in a plurality of shallow cycles, the SEI film formed in the first formation stage can be fully filled with a reduction product, meanwhile, the positive electrode is at a high potential in the charging process, interfacial oxidation reaction is easier to occur, surface product recombination and repair compression can be realized, the quality of the SEI film is improved, the capacity of inhibiting the volume expansion of a silicon negative electrode material is improved, the produced gas of the battery in the high state of charge can be more rapidly discharged by adopting the constraint of larger clamp force in the second formation stage, the SEI film is more compact, the performance of the battery can be effectively improved, and the service life is longer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a lithium ion battery formation method of the present application;
FIG. 2 is a graph of a linear fit relationship for x and y of the present application;
FIG. 3 is a graph showing comparison of cycle retention rates of the batteries of the examples and the comparative examples;
fig. 4 is a graph showing the storage capacity recovery ratio of the batteries of the examples and the comparative examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Referring to fig. 1, the present invention provides a lithium ion battery formation method, which includes the following steps:
a first formation stage: under the condition of a first clamp force, the lithium ion battery is charged to 50-80% of charge state at 0.3-1C;
a second formation stage: under the condition of a second clamp force, the lithium ion battery is shallow cycled for x times between 80% -90% of charge states at 0.05-0.3 ℃, wherein x is positively correlated with the silicon doped content y of the negative electrode of the lithium ion battery, and the first clamp force is smaller than the second clamp force. State of charge (SOC), which characterizes the ratio of the remaining capacity of a battery after a period of use or prolonged rest to the capacity of its fully charged state, is often expressed as a percentage. The value range is 0-1, and the battery is completely discharged when the state of charge=0, and the battery is completely full when the state of charge=1.
According to the method, the lithium ion battery is charged to 50% -80% of the state of charge by 0.3-1C high current in the first formation stage, the battery is easier to undergo interfacial redox reaction, so that a porous rough SEI film is preliminarily formed under the condition that the first clamp force is applied, the reaction of a silicon negative electrode and electrolyte can be more effectively promoted by utilizing 0.05-0.3C in the 80% -90% high state of charge in the second formation stage in a plurality of shallow cycles, the SEI film formed in the first formation stage can be fully filled with a reduction product, meanwhile, the positive electrode is at a high potential in the charging process, interfacial oxidation reaction is easier to occur, surface product recombination and repair compression can be realized, the quality of the SEI film is improved, the capacity of inhibiting the volume expansion of a silicon negative electrode material is improved, the produced gas of the battery in the high state of charge can be more rapidly discharged by adopting the constraint of larger clamp force in the second formation stage, the SEI film is more compact, the performance of the battery can be effectively improved, and the service life is longer.
In some embodiments of the invention, the first formation stage is carried out at a temperature of 50 ℃ to 60 ℃, which may be, for example, 50 ℃, 52 ℃, 55 ℃, 57 ℃, 59 ℃, 60 ℃. Therefore, the characteristic of high lithium ion activity of the electrolyte at high temperature can be effectively utilized, the reaction is easier to occur, a thicker porous SEI film is formed, the porous SEI film is filled in a second formation stage, and the high temperature is favorable for violent exhaust of a high-nickel and silicon-doped system, so that the finally obtained SEI is more compact, and the problem of swelling of a lithium ion battery in the later period of recycling is avoided.
The second formation stage is performed at 20-30deg.C, such as 20deg.C, 22deg.C, 25deg.C, 28deg.C, 30deg.C, to reduce lithium ion activity, and preferably to form SEI film filling repair for the first formation stage.
The inventor researches show that the linear fitting relation of x and y is shown in fig. 2, and x and y meet the condition of x= [10.86y+0.6] +1, namely the function value of x is equal to the sum of the maximum integer of not more than 10.86y+0.6 and one, and y is 5% -30%, such as 5%, 10%, 15%, 20%, 25% and 30%, so as to ensure that the silicon anode and the electrolyte react sufficiently.
The first clamping force is 0.05-0.15 MPa, such as 0.05MPa, 0.08MPa, 0.12MPa and 0.15MPa, the second clamping force is positively correlated with x and is 0.1-0.35 MPa, such as 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa and 0.35MPa, so as to ensure the discharge of the generated gas of the battery.
It should be further noted that the formation of the lithium ion battery is performed in the fixture formation cabinet, so that the first fixture force and the second fixture force are both provided by the fixture formation cabinet, and the temperature of the lithium ion battery is also realized by adjusting the temperature of the fixture formation cabinet.
Therefore, before the first formation stage, the lithium ion battery formation method of the present invention further includes:
and placing the lithium ion battery in a clamp formation cabinet, and heating to 50-60 ℃ to stabilize the temperature of the lithium ion battery at 50-60 ℃.
Similarly, after the first formation stage and before the second formation stage, the lithium ion battery formation method of the present invention further includes:
the temperature of the clamp formation cabinet is regulated to 20-30 ℃ so as to stabilize the temperature of the lithium ion battery at 20-30 ℃.
The invention also provides a preparation method of the secondary battery, which comprises the formation method of the secondary battery, so that after the preparation method of the lithium ion battery is utilized, the aging process is not continued, the subsequent capacity-dividing process can be directly carried out, the time for producing the battery is shortened, and the cost is indirectly reduced.
The invention also provides a secondary battery which is manufactured by the manufacturing method of the secondary battery, and therefore, the secondary battery has corresponding beneficial effects and is not described in detail herein.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Examples
In the embodiment of the invention, the negative electrode active material of the lithium ion battery is a graphite silicon-doped mixed material, the silicon-doped content y is 20wt%, and the positive electrode active material is a high nickel material;
(1) And placing the lithium ion battery in a clamp formation cabinet, heating to 55 ℃, standing for 3 hours, and keeping the temperature of the lithium ion battery stable at 55 ℃.
(2) Under the condition that the first clamp force is 0.1MPa, charging the lithium ion battery for 30min at the current of 0.5C so as to enable the state of charge to reach 50%;
(3) And regulating the temperature of the clamp formation cabinet to 25 ℃ until the temperature of the lithium ion battery is stabilized at 25 ℃.
(4) And under the condition that the second clamp force is 0.3MPa, the lithium ion battery is charged for 60min at the current of 0.1C and discharged for 30min at the current of 0.2C, and the charge and discharge are repeatedly circulated for 3 times between 80% and 90% of the charge states.
(5) And after the formation is finished, the production process is consistent with the conventional production process, and the two-shot-welding sealing nail-capacity-separating-OCV-off-line is realized.
Comparative example
In the comparative example, the lithium ion battery anode active material is a graphite silicon-doped mixed material, the silicon-doped content y is 20wt%, and the cathode active material is a high nickel material;
(1) And placing the lithium ion battery in a clamp formation cabinet, heating to 45 ℃, standing for 3 hours, and keeping the temperature of the lithium ion battery stable at 45 ℃.
(2) Conventional low current multistage formation stage: under the pressure of 0.1MPa, the lithium ion battery is charged for 60min, 150min and 60min respectively at the current of 0.05C, 0.1C and 0.2C so as to enable the charge states to reach 5%, 30% and 50% respectively;
(3) And after the formation is finished, the production process is consistent with the conventional production process, and the two-shot-welding sealing nail-capacity-separating-OCV-off-line is realized.
Battery performance test
1. The lithium ion batteries obtained by the formation of the examples and the comparative examples are subjected to cyclic test at 45 ℃, the test conditions are 2.5-4.2V, and the test current is 1C/1C; the initial efficiency and capacity retention of the two lithium ion batteries are compared, and the performance test results are shown in table 1 and fig. 2.
TABLE 1 Performance test results
| Battery cell | First effect (%) | Cycle retention @90% |
| Examples | 87.55％ | 950 turns |
| Comparative example | 88.06％ | 430 circles |
According to the data in table 1 and as shown in fig. 3, the first effect of the lithium ion battery obtained by the formation method provided by the embodiment of the invention is higher, the cycle number of the capacity retention rate reduced to 90% is doubled, the service life of the battery is longer, and the performance is better.
2. The lithium ion batteries obtained by the formation of the comparative example and the example are fully charged to 4.2V and then are stored in a baking oven at 60 ℃, the storage capacity recovery rate of the two lithium ion batteries is calculated respectively, the performance test results are shown in fig. 4, and as can be seen from fig. 4, the storage capacity recovery rate of the lithium ion battery obtained by the formation method of the example is higher than that of the lithium ion battery obtained by the formation method of the comparative example, so that the battery performance is better.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method of forming a lithium ion battery, comprising:
a first formation stage: under the condition of a first clamp force, the lithium ion battery is charged to 50-80% of charge state at 0.3-1C;
a second formation stage: under the condition of a second clamp force, the lithium ion battery is shallow cycled for x times between 80% -90% of charge states at 0.05-0.3 ℃, wherein x is positively correlated with the silicon content y of the negative electrode of the lithium ion battery, and the first clamp force is smaller than the second clamp force;
wherein x and y satisfy the following condition:
x＝[10.86y+0.6]+1；
y is 5% -30%.
2. The lithium ion battery formation method according to claim 1, wherein the first formation stage is performed at a temperature of 50 ℃ to 60 ℃.
3. The lithium ion battery formation method according to claim 1, wherein the second formation stage is performed at a temperature of 20 ℃ to 30 ℃.
4. The lithium ion battery formation method according to claim 1, wherein the first clamp force is 0.05MPa to 0.15MPa.
5. The lithium ion battery formation method according to claim 1, wherein the second clamp force is 0.1MPa to 0.35MPa.
6. The lithium ion battery formation method of claim 1, wherein the second clamp force is positively correlated with x.
7. A method for producing a secondary battery, characterized by comprising the lithium ion battery formation method according to any one of claims 1 to 6.
8. A secondary battery, characterized by being produced by the secondary battery production method according to claim 7.
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| CN114284587A (en) * | 2021-12-27 | 2022-04-05 | 惠州亿纬锂能股份有限公司 | Cell formation and capacity grading method |
| KR20220052703A (en) * | 2020-10-21 | 2022-04-28 | 에스케이온 주식회사 | Method, battery management system, charging apparatus for charging secondary battery using silicon based negative electrode |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108258347A (en) * | 2017-12-28 | 2018-07-06 | 国联汽车动力电池研究院有限责任公司 | A kind of chemical synthesizing method of silicium cathode soft bag lithium ionic cell |
| CN110858671A (en) * | 2018-08-22 | 2020-03-03 | 中信国安盟固利动力科技有限公司 | Formation method of lithium titanate battery |
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| CN114284587A (en) * | 2021-12-27 | 2022-04-05 | 惠州亿纬锂能股份有限公司 | Cell formation and capacity grading method |
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