CN108321435B - Formation method of lithium ion battery - Google Patents
Formation method of lithium ion battery Download PDFInfo
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- CN108321435B CN108321435B CN201711338702.0A CN201711338702A CN108321435B CN 108321435 B CN108321435 B CN 108321435B CN 201711338702 A CN201711338702 A CN 201711338702A CN 108321435 B CN108321435 B CN 108321435B
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000007600 charging Methods 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000000523 sample Substances 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000010277 constant-current charging Methods 0.000 description 19
- 238000010280 constant potential charging Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a formation method of a lithium ion battery, which relates to the technical field of lithium ion batteries and is characterized in that the battery is charged to 4.2V by adopting preset current and then discharged to 3.6-3.85V, and the battery is vacuumized in the formation process. The invention utilizes high voltage formation to ensure that the side reaction in the SEI film formation process is completely reacted, and the formed SEI film is more compact and stable. Experimental results show that the lithium ion battery obtained by the formation method has smaller internal resistance, thinner battery thickness and excellent high-temperature cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a formation method of a lithium ion battery.
Background
The modern society pays more and more attention to the safety performance and the cycle performance of the power battery. The safety performance and the cycle performance of the power battery are related to the safety coefficient and the service life of the new energy vehicle, and the power battery is an important index for people to select the new energy vehicle.
Formation is an important link in the battery manufacturing process, plays a role in starting and stopping, and is used for forming a layer of solid electrolyte interface film (SEI) on an electrode material in the battery in the first charging and discharging process of the battery, wherein the good and the bad of the SEI film are related to the safety performance and the high-temperature cycle performance of the battery in use. The existing formation process mostly adopts the method of directly charging the battery to 3.6-3.8V, and the SEI film formed in the method is not compact and stable enough, so that the safety performance and the high-temperature cycle performance of the battery at the later stage are influenced.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a formation method of a lithium ion battery, and the method can form a compact and stable SEI film in the battery.
The invention provides a formation method of a lithium ion battery, which is characterized in that the battery is charged to 4.2V by adopting preset current and then discharged to 3.6-3.85V, and the battery is vacuumized in the formation process.
Preferably, the battery is charged to 4.2V by using a preset current in stages, and the steps are as follows: the battery is firstly placed at a first preset current A1Charging the battery at constant current with the voltage limited to 2.8-3.2V; then laying aside, and using second preset current A2Charging the battery at constant current with a voltage limited of 3.4-3.6V; then laying aside, using a third preset current A3To batteryCarrying out constant-current charging, and limiting the voltage to 4.2V; a is described1≤A2≤A3。
Preferably, the battery is first set aside at a first preset current A1Charging the battery at constant current with a voltage limited of 2.8-3.2V for 30-100 min; then laying aside, and using second preset current A2Charging the battery at constant current with voltage limited to 3.4-3.6V for 30-100 min; then laying aside, using a third preset current A3Charging the battery at constant current with the voltage limited by 4.2V, then charging at constant voltage until the current is limited by 0.05CmA, wherein the charging time is 100-; a is described1≤A2≤A3。
Preferably, the 0.01CmA ≦ A1≤A2≤A3≤0.5CmA。
Preferably, the battery is left at a fourth preset current A4Constant current discharging is carried out on the battery to 3.6-3.85V, then constant voltage discharging is carried out until the current limiting is 0.05CmA, and the discharging time is 100-360 min.
Preferably, 0.01CmA ≦ A4≤0.5CmA。
Preferably, after formation, before the probe is separated from the battery, the formation equipment samples the voltage of the battery, automatically rejects and collects the battery with the voltage less than 3.6V after aging, and performs secondary formation.
Has the advantages that: in the invention, the battery is charged to full charge of 4.2V, then the battery is discharged to a state of 3.6-3.85V, and the side reaction in the SEI film forming process is completely reacted by using high-voltage formation, so that the formed SEI film is more compact and stable; and the battery is charged to 4.2V by adopting preset current in stages, and the preset current in the later stage is more than or equal to the preset current in the last stage, so that the stability of the SEI film is improved. Experimental results show that the lithium ion battery obtained by the formation method has smaller internal resistance, thinner battery thickness and excellent high-temperature cycle performance.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a formation method of a lithium ion battery, which is characterized in that the battery is charged to 4.2V by adopting preset current and then discharged to 3.6-3.85V, and the battery is vacuumized in the formation process.
Example 2
The invention provides a formation method of a lithium ion battery, which comprises the following steps:
(1) standing for 5min, and performing constant-current charging on the battery at a current of 0.01CmA, limiting the voltage to 2.8V, and limiting the time to 30 min;
(2) standing for 3min, and performing constant-current charging on the battery at a current of 0.1CmA, limiting the voltage to 3.4V and limiting the time to 30 min;
(3) standing for 3min, performing constant current charging on the battery at a current of 0.5CmA, limiting the voltage to 4.2V, performing constant voltage charging to limit the current to 0.05CmA, and limiting the time to 100 min;
(4) standing for 3min, performing constant current discharge on the battery at a current of 0.01CmA, limiting the voltage to 3.6V, performing constant voltage discharge to limit the current to 0.05CmA, and limiting the time to 100 min;
(5) and (5) placing.
The battery is vacuumized in the whole formation process, after formation is finished, before the probe is separated from the battery, formation equipment samples the voltage of the battery, the battery with the voltage less than 3.6V is automatically removed and collected after aging, and secondary formation is carried out.
Example 3
The invention provides a formation method of a lithium ion battery, which comprises the following steps:
(1) standing for 5min, and performing constant current charging on the battery at a current of 0.2CmA, limiting the voltage to 3.2V and limiting the time to 100 min;
(2) standing for 3min, and performing constant-current charging on the battery at a current of 0.2CmA, limiting the voltage to 3.6V and limiting the time to 100 min;
(3) standing for 3min, performing constant current charging on the battery at a current of 0.2CmA, limiting the voltage to 4.2V, performing constant voltage charging to limit the current to 0.05CmA, and limiting the time to 540 min;
(4) standing for 3min, performing constant current discharge on the battery at a current of 0.5CmA, limiting the voltage to 3.7V, performing constant voltage discharge until the current is limited to 0.05CmA, and limiting the time for 360 min;
(5) and (5) placing.
The battery is vacuumized in the whole formation process, after formation is finished, before the probe is separated from the battery, formation equipment samples the voltage of the battery, the battery with the voltage less than 3.6V is automatically removed and collected after aging, and secondary formation is carried out.
Example 4
The invention provides a formation method of a lithium ion battery, which comprises the following steps:
(1) standing for 5min, and performing constant current charging on the battery at a current of 0.03CmA, limiting the voltage to 3.0V and the time to 80 min;
(2) standing for 3min, and performing constant-current charging on the battery at a current of 0.1CmA, with a voltage limit of 3.5V and a time limit of 80 min;
(3) standing for 3min, performing constant current charging on the battery at a current of 0.3CmA, limiting the voltage to 4.2V, performing constant voltage charging to limit the current to 0.05CmA, and limiting the time to 300 min;
(4) standing for 3min, performing constant current discharge on the battery at a current of 0.4CmA, limiting the voltage to 3.75V, performing constant voltage discharge until the current is limited to 0.05CmA, and limiting the time for 200 min;
(5) and (5) placing.
The battery is vacuumized in the whole formation process, after formation is finished, before the probe is separated from the battery, formation equipment samples the voltage of the battery, the battery with the voltage less than 3.6V is automatically removed and collected after aging, and secondary formation is carried out.
Example 5
The invention provides a formation method of a lithium ion battery, which comprises the following steps:
(1) standing for 5min, and performing constant-current charging on the battery at a current of 0.01CmA, with a voltage limit of 2.9V and a time limit of 50 min;
(2) standing for 3min, and performing constant-current charging on the battery at a current of 0.05CmA, with a voltage limit of 3.6V and a time limit of 50 min;
(3) standing for 3min, performing constant current charging on the battery at a current of 0.2CmA, limiting the voltage to 4.2V, performing constant voltage charging to limit the current to 0.05CmA, and limiting the time to 250 min;
(4) standing for 3min, performing constant current discharge on the battery at a current of 0.2CmA, limiting the voltage to 3.8V, performing constant voltage discharge to limit the current to 0.05CmA, and limiting the time to 260 min;
(5) and (5) placing.
The battery is vacuumized in the whole formation process, after formation is finished, before the probe is separated from the battery, formation equipment samples the voltage of the battery, the battery with the voltage less than 3.6V is automatically removed and collected after aging, and secondary formation is carried out.
Example 6
The experiment provides a square aluminum-shell battery with the model number of 2714891, the capacity of 50Ah, and the formation steps are as follows:
(1) standing for 5min, and performing constant current charging on the battery at a current of 0.05CmA, limiting the voltage to 3.0V and the time to 60 min;
(2) standing for 3min, and performing constant-current charging on the battery at a current of 0.1CmA, limiting the voltage to 3.4V and limiting the time to 50 min;
(3) standing for 3min, performing constant-current charging on the battery at a current of 0.25CmA, limiting the voltage to 4.2V, performing constant-voltage charging to limit the current to 0.05CmA, and limiting the time to 360 min;
(4) standing for 3min, performing constant current discharge on the battery at a current of 0.25CmA, limiting the voltage to 3.85V, performing constant voltage discharge to limit the current to 0.05CmA, and limiting the time to 150 min;
(5) and (5) placing.
The lithium ion battery of the present embodiment was subjected to an electrical property test, and the thickness internal resistance, the high-temperature cycle number and the capacity retention rate of the lithium ion battery were tested, and the test results are detailed in table 1.
Comparative example
For square aluminum-shell batteries of the same model 2714891, the capacity is 50Ah, the battery formation process is the same as that in example 6 except that the battery formation process comprises the following formation steps:
(1) standing for 5min, and performing constant current charging on the battery at a current of 0.05CmA, limiting the voltage to 3.0V and the time to 60 min;
(2) standing for 3min, and performing constant-current charging on the battery at a current of 0.1CmA, limiting the voltage to 3.4V and limiting the time to 50 min;
(3) standing for 3min, performing constant current charging on the battery at a current of 0.25CmA, limiting the voltage to 3.85V, performing constant voltage charging to limit the current to 0.05CmA, and limiting the time to 240 min;
(4) and (5) placing.
And (3) performing an electrical property test on the lithium ion battery in the comparative ratio, and testing the resistance, the thickness, the high-temperature cycle number and the capacity retention rate of the lithium ion battery, wherein the test results are detailed in table 1.
Table 1 electrical performance test data for lithium ion batteries
| Average thickness/mm | Average internal resistance/m omega | Cycle number of high temperature cycle | Capacity retention ratio/%) | |
| Example 6 | 26.52 | 0.653 | 336 | 95.7 |
| Comparative example | 27.18 | 0.686 | 336 | 80.1 |
From the above table, it can be seen that the thickness and internal resistance in example 6 are smaller than those in the comparative example, and the capacity retention rate in example 6 is significantly higher than that in the comparative example under the same cycle number, and thus it can be seen that a battery having a low thickness, low internal resistance, and excellent high-temperature cycle performance can be obtained by the formation method of the present invention.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A formation method of a lithium ion battery is characterized in that the battery is charged to 4.2V by adopting preset current, then discharged to 3.6-3.85V, and the battery is vacuumized in the formation process;
the method comprises the following steps of charging the battery to 4.2V by adopting preset current in stages: the battery is firstly placed at a first preset current A1Charging the battery at constant current with the voltage limited to 2.8-3.2V; then laying aside, and using second preset current A2Charging the battery at constant current with a voltage limited of 3.4-3.6V; then laying aside, using a third preset current A3Charging the battery at constant current, and limiting the voltage to 4.2V; a is described1≤A2≤A3；
The battery is firstly placed at a first preset current A1Charging the battery at constant current with a voltage limited of 2.8-3.2V for 30-100 min; then laying aside, and using second preset current A2Charging the battery at constant current with voltage limited to 3.4-3.6V for 30-100 min; then laying aside, using a third preset current A3Charging the battery at constant current with the voltage limited by 4.2V, then charging at constant voltage until the current is limited by 0.05CmA, wherein the charging time is 100-; a is described1≤A2≤A3(ii) a Laying the battery at a fourth preset current A4Constant current discharging is carried out on the battery to 3.6-3.85V, then constant voltage discharging is carried out until the current limiting is 0.05CmA, and the discharging time is 100-360 min.
2. The method of claim 1, wherein 0.01CmA ≦ A1≤A2≤A3≤0.5CmA。
3. The method of claim 1, wherein 0.01CmA ≦ A4≤0.5CmA。
4. The formation method of the lithium ion battery according to claim 1, further comprising the steps of sampling the battery voltage by formation equipment after the formation is finished and before the probe is separated from the battery, automatically removing and collecting the battery with the voltage less than 3.6V after aging, and performing secondary formation.
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| CN201711338702.0A CN108321435B (en) | 2017-12-14 | 2017-12-14 | Formation method of lithium ion battery |
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| CN109616711A (en) * | 2018-12-18 | 2019-04-12 | 国联汽车动力电池研究院有限责任公司 | A kind of pulse formation method for lithium ion battery |
| CN110854458B (en) * | 2019-11-07 | 2021-10-22 | 河南电池研究院有限公司 | Formation method of high-voltage soft package lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012227035A (en) * | 2011-04-21 | 2012-11-15 | Toyota Motor Corp | Method of manufacturing nonaqueous electrolyte secondary battery |
| CN106654427A (en) * | 2017-01-22 | 2017-05-10 | 珠海格力电器股份有限公司 | Formation method of lithium ion battery |
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| CN102709601A (en) * | 2012-02-23 | 2012-10-03 | 深圳市慧通天下科技股份有限公司 | Parallel formation method of lithium ion secondary battery |
| CN103326069B (en) * | 2012-03-20 | 2016-05-04 | 北汽福田汽车股份有限公司 | A kind of chemical synthesizing method of LiMn2O4 electrokinetic cell |
| CN102760908B (en) * | 2012-07-16 | 2014-11-05 | 宁波世捷新能源科技有限公司 | Quick formation method for lithium ion battery adapting to various cathode material systems |
| CN103151565B (en) * | 2013-03-20 | 2015-06-24 | 东莞市力嘉电池有限公司 | First-time charging forming method for lithium-ion secondary battery |
| CN106229572B (en) * | 2016-08-25 | 2019-07-12 | 合肥国轩高科动力能源有限公司 | Formation method for inhibiting high-temperature cycle gas production of high-nickel ternary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012227035A (en) * | 2011-04-21 | 2012-11-15 | Toyota Motor Corp | Method of manufacturing nonaqueous electrolyte secondary battery |
| CN106654427A (en) * | 2017-01-22 | 2017-05-10 | 珠海格力电器股份有限公司 | Formation method of lithium ion battery |
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