CN110611124A - Micro-electricity pre-charging activation method of lithium ion battery - Google Patents
Micro-electricity pre-charging activation method of lithium ion battery Download PDFInfo
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- CN110611124A CN110611124A CN201810614483.2A CN201810614483A CN110611124A CN 110611124 A CN110611124 A CN 110611124A CN 201810614483 A CN201810614483 A CN 201810614483A CN 110611124 A CN110611124 A CN 110611124A
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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
Abstract
The invention discloses a micro-electricity pre-charging activation method of a lithium ion battery. The method specifically comprises the following steps: step one, the cleaned lithium ion battery is charged for 6-10min by adopting 0.02-0.06C micro-current. Step two: and (4) aging the lithium ion battery charged in the step one at a high temperature of 42-48 ℃ for 22-25 h. Step three: and (4) aging the lithium ion battery aged at the high temperature in the step two at the temperature of 22-28 ℃ for 20-26h at normal temperature, thus completing the micro-precharge activation of the lithium ion battery. In the micro-electricity pre-charge activation method, a stable SEI film is formed on the surface of the negative electrode of the battery through small-current charging, high-temperature aging and normal-temperature aging, the cycle life of the battery is prolonged, and meanwhile, the micro-electricity pre-charge activation method can reduce the self-discharge rate of the lithium ion battery and improve the yield of the battery. After the lithium ion battery is subjected to pre-charging activation by adopting the micro-electricity pre-charging activation method, the self-discharge rate of the lithium ion battery is reduced by 35-60%.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery formation, and particularly relates to a micro-precharge activation method of a lithium ion battery.
Background
The lithium ion battery is a secondary battery, has the advantages of high discharge voltage, high energy density, light weight, small volume, small environmental pollution and the like, and is widely applied to the fields of power supply energy storage devices, electric automobiles and the like. With the increasing market demand of lithium ion batteries, manufacturers of lithium ion batteries need to improve the production efficiency of the batteries and expand the production capacity on one hand, and need to ensure the product quality on the other hand, so that the production process of the batteries needs to be optimized. At present, the degree of mechanization and automation of battery production is higher, and the pre-charging becomes a key factor for restricting the production efficiency and the product quality of the battery in the production process of quality and quantity guarantee.
In the first charging process of the battery, a layer of solid electrolyte interface film (SEI film) is formed on the surface of a negative electrode, and the SEI film is a passivation film, can effectively prevent the co-intercalation of solvent molecules, avoids the damage to electrode materials caused by the co-intercalation of the solvent molecules, greatly improves the cycle performance and the service life of the electrode, and is of great importance to the performance of the battery due to the formation of the stable SEI film. The problems of unstable SEI film and high self-discharge rate of the lithium ion battery caused by pre-charging easily directly affect the electrochemical stability of the battery and the yield of the battery, so the pre-charging process needs to be optimized.
While ensuring product performance, battery manufacturers need to improve production efficiency, wherein improving the yield of batteries is an important direction. In the formation process, the self-discharge rate of the battery is an important factor influencing the qualified rate of the battery, and how to reduce the self-discharge rate of the battery is a problem which needs to be solved urgently. If the pretreatment process for charging the battery can be optimized, the problem of high self-discharge rate of the battery can be well solved, and the yield of the battery is further improved.
To date, researchers have conducted a great deal of research into pre-charge activation of lithium ion batteries. The Chinese patent with the application number of 201410704571.3 entitled "a pre-charging formation method of a lithium ion battery" provides a pre-charging formation method of a lithium battery, which completes the pre-charging process through two times of pre-charging and two times of air extraction pretreatment, can timely extract waste gas generated by chemical reaction in the battery during the formation process, reduces the swelling rate of the battery, and prolongs the service life of the battery. The invention discloses a formation treatment method of a lithium manganate battery, which is a Chinese invention patent with the application number of 201310311924.9 named as 'a lithium manganate battery formation treatment method', and mainly comprises the steps of battery pre-charging, vacuumizing, high-temperature standing at 40-45 ℃, battery sealing, high-temperature aging, packaging and the like. The patent of Chinese invention with the application number of 201610912572.6 entitled "formation method of square lithium battery" discloses a formation method of a square lithium battery, which mainly comprises the steps of standing a semi-finished product of the square lithium battery at normal temperature and high temperature in sequence, then pre-vacuumizing, pre-charging with low current and high current in sequence under the vacuum condition, and then filling inert gas in a system until the air pressure in a battery formation frame is recovered to the standard atmospheric pressure. The method is beneficial to improving the formation effect, increasing the yield of the battery and improving the electrochemical stability of the battery. The batteries prepared by the method have excellent electrochemical stability and low battery swelling rate, but the improvement effect on the self-discharge rate of the batteries in the formation process is poor, and the preparation process needs to be vacuumized for many times and is complicated.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a micro-precharge activation method of a lithium ion battery. The method specifically comprises the following steps: step one, the cleaned lithium ion battery is charged by a micro-current constant current with the charging rate of 0.02-0.06C for 6-10 min. Step two: and (3) aging the lithium ion battery subjected to the micro-current constant-current charging in the step one at a high temperature of 42-48 ℃ for 22-25 h. Step three: and (4) aging the lithium ion battery aged at the high temperature in the step two at the normal temperature of 22-28 ℃ for 20-26h to complete the micro-precharge activation of the lithium ion battery. In the micro-electricity pre-charging activation method, a stable SEI film is formed on the surface of the negative electrode of the battery through small-current charging, high-temperature aging and normal-temperature aging, the cycle life of the battery is prolonged, and the problem that the performance of the battery is influenced due to the fact that the SEI film is unstable due to pre-charging of the lithium ion battery is solved. Meanwhile, the micro-electricity pre-charging activation method increases the cathode deposition surface after metal corrosion, reduces the probability of metal dendrite formation by metal impurities, can reduce the self-discharge rate of the battery, and improves the yield of the battery. After the lithium ion battery is subjected to pre-charging activation by adopting the micro-electricity pre-charging activation method, the self-discharge rate of the lithium ion battery is reduced by 35-60%.
The technical effect to be achieved by the invention is realized by the following scheme:
the invention discloses a micro-electricity pre-charging activation method of a lithium ion battery, which comprises the following steps:
the method comprises the following steps: taking the cleaned lithium ion battery, and charging with a micro-current constant current with a charging rate of 0.02-0.06C for 6-10 min;
step two: performing high-temperature aging on the lithium ion battery subjected to the micro-current constant-current charging in the step one;
step three: and (5) aging the lithium ion battery aged at the high temperature in the step two at normal temperature to complete micro-electricity pre-charging activation of the lithium ion battery.
According to the micro-electricity pre-charging activation method of the lithium ion battery, a stable SEI film can be formed on the surface of the negative electrode of the battery through one-time low-current charging and then high-temperature aging and normal-temperature aging in sequence, so that the cycle life of the battery is prolonged. Meanwhile, the micro-electricity pre-charging activation method increases the cathode deposition surface after metal corrosion, reduces the probability of metal dendrite formation by metal impurities, can reduce the self-discharge rate of the battery, and improves the yield of the battery.
Further, the lithium ion battery after the cleaning in the step one is not required to be aged, and is directly subjected to micro-current constant-current charging. The pre-charging activation process is simplified, and the time required by the pre-charging activation process is shortened.
Further, in the step one, the charging multiplying power is 0.03-0.05C; the charging time is 6-8 min. Preferably, the charging rate is 0.05C; the charging time is 8 min. The current required by micro-electricity pre-charging is small, the charging time is short, and the pre-charging efficiency can be effectively improved.
Further, the charging voltage of the micro-current constant-current charging in the step one is 2.4V.
Further, the temperature of the high-temperature aging in the step two is 42-48 ℃; the high-temperature aging time is 22-25 h.
Further, the temperature of the normal-temperature aging in the third step is 22-28 ℃; the time for aging at normal temperature is 20-26 h.
Further, after the lithium ion battery is subjected to pre-charging activation by adopting the micro-electricity pre-charging activation method, the self-discharge rate of the lithium ion battery is reduced by 35% -60%. And (3) carrying out micro-precharge activation on the lithium ion batteries in the examples, not carrying out micro-precharge activation on the lithium ion batteries in the comparative examples, carrying out self-discharge settlement on the lithium ion batteries in the examples and the comparative examples, and counting the self-discharge rate. Meanwhile, the degree of densification of the SEI films of the lithium ion batteries in the examples and the comparative examples is compared through an EIS curve.
The invention has the following advantages:
1. in the micro-electric pre-charging activation method, the pre-charging current is small, and the pre-charging time is short.
2. After the micro-charging activation method is adopted, a stable SEI film is formed on the surface of the negative electrode of the lithium ion battery.
3. The micro-electricity pre-charging activation method increases the cathode deposition surface after metal corrosion, reduces the probability of metal dendrite formation by metal impurities, reduces the self-discharge rate of the battery, and improves the yield of the battery.
Drawings
Fig. 1 is a curve of the charging voltage versus time for the micro-precharge of a lithium ion battery according to the present invention.
Fig. 2 is an EIS test result comparison of the lithium ion battery subjected to micro-precharge activation and the lithium ion battery not subjected to micro-precharge activation in the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1
In this example, 18650 lithium ion batteries were used as experimental batteries, selected from the AWA17K07XA batches, amounting to 57548 pcs. The battery parameters are as follows: the capacity is 2400mAh, and the surface density of the positive electrode of the battery is 440 +/-8.8 g/m2The density of the negative electrode surface is 219.6 +/-3.9 g/m2The thickness of the separator was 18 μm, and the amount of the injected liquid was 5.25. + -. 0.2 g.
23571pcs are selected to carry out micro-electricity pre-charging activation, and the specific steps are as follows: charging the cleaned lithium ion battery by a micro-current constant current with the charging rate of 0.05C, wherein the charging voltage is 2.4V, and the charging time is 8 min; then aging at 45 ℃ for 24h, and then continuing aging at 25 ℃ for 24h to finish the micro-charging activation process. And then, charging the battery to full charge, aging, performing self-discharge settlement, and counting the self-discharge rate.
Comparative example 1
And (3) directly charging the rest 33977pcs lithium ion batteries in the AWA17K07XA batch to full charge and aging without pre-charging activation, then performing self-discharge settlement, and counting the self-discharge rate.
Example 2
In this example, 18650 lithium ion batteries were used as experimental batteries, selected from the AWA17K07XB batches, amounting to 58200 pcs. The battery parameters are as follows: the capacity is 2400mAh, and the surface density of the positive electrode of the battery is 440 +/-8.8 g/m2The density of the negative electrode surface is 219.6 +/-3.9 g/m2The thickness of the separator was 18 μm, and the amount of the injected liquid was 5.25. + -. 0.2 g.
23491pcs are selected to carry out micro-electricity pre-charging activation, and the specific steps are as follows: charging the cleaned lithium ion battery by a micro-current constant current with the charging rate of 0.05C, wherein the charging voltage is 2.4V, and the charging time is 8 min; then aging at 45 ℃ for 24h, and then continuing aging at 25 ℃ for 24h to finish the micro-charging activation process. And then, charging the battery to full charge, aging, performing self-discharge settlement, and counting the self-discharge rate.
Comparative example 2
And (3) directly charging the residual 34709pcs lithium ion batteries in the AWA17K07XB batch to full charge and aging without pre-charging activation, then carrying out self-discharge settlement, and counting the self-discharge rate.
Example 3
In this example, 18650 lithium ion batteries were used as experimental batteries, selected from the AWA17K18XA batches, amounting to 60225 pcs. The battery parameters are that the capacity is 2400mAh, and the positive electrode surface density of the battery is 440 +/-8.8 g/m2The density of the negative electrode surface is 220.8 +/-4.3 g/m2The thickness of the diaphragm was 20 μm, and the amount of injected liquid was 5.25. + -. 0.2 g.
22640pcs are selected to carry out micro-electricity pre-charging activation, and the specific steps are as follows: charging the cleaned lithium ion battery by a micro-current constant current with the charging rate of 0.05C, wherein the charging voltage is 2.4V, and the charging time is 8 min; then aging at 45 ℃ for 24h, and then continuing aging at 25 ℃ for 24h to finish the micro-charging activation process. And then, charging the battery to full charge, aging, performing self-discharge settlement, and counting the self-discharge rate.
Comparative example 3
And (3) directly charging the 37585pcs lithium ion batteries left in the AWA17K18XA batch to full charge and aging without pre-charging activation, then carrying out self-discharge settlement, and counting the self-discharge rate.
Example 4
In this example, 18650 lithium ion batteries were used as experimental batteries, and the batteries were selected from AWA17K17XN batches, 60704pcs total. The battery parameters are that the capacity is 2400mAh, and the positive electrode surface density of the battery is 440 +/-8.8 g/m2The density of the negative electrode surface is 220.8 +/-4.3 g/m2The thickness of the diaphragm was 20 μm, and the amount of injected liquid was 5.25. + -. 0.2 g.
Selecting 31960pcs from the raw materials to perform micro-electro pre-charging activation, and specifically comprising the following steps: charging the cleaned lithium ion battery by a micro-current constant current with the charging rate of 0.05C, wherein the charging voltage is 2.4V, and the charging time is 8 min; then aging at 45 ℃ for 24h, and then continuing aging at 25 ℃ for 24h to finish the micro-charging activation process. And then, charging the battery to full charge, aging, performing self-discharge settlement, and counting the self-discharge rate.
Comparative example 4
And (3) directly charging the rest 28744pcs lithium ion batteries in the AWA17K17XN batch to full charge and aging without pre-charging activation, then carrying out self-discharge settlement, and counting the self-discharge rate.
Fig. 1 is a plot of the charging voltage versus time for the micro-precharge of the li-ion batteries of examples 1-4. As can be seen from the figure, the voltage is stabilized at 2.4V when the charging is carried out for 6-8min at the current of 0.05C.
FIG. 2 is an EIS test result comparing the lithium ion battery subjected to micro-precharge activation in examples 1-2 with the lithium ion battery not subjected to micro-precharge activation in comparative examples 1-2 at a temperature of 5 ℃. As can be seen from the figure, the internal resistance of the lithium ion battery in example 1-2 in the first half circle (i.e., the internal resistance through the SEI film) is greater than that of the lithium ion battery in comparative example 1-2, which shows that the lithium ion battery subjected to micro-precharge activation forms a denser SEI film, and the SEI film is more stable, and the cycle life of the battery can be prolonged, compared with the lithium ion battery without micro-precharge activation.
The self-discharge settlement results in examples 1 to 4 and comparative examples 1 to 4 described above are as follows:
as can be seen from the data in the table, in examples 1 to 4, compared with comparative examples 1 to 4, the self-discharge rate of the lithium ion battery after the micro-precharge activation is respectively reduced by 1.56%, 1.31%, 0.72% and 1.2% compared with the lithium ion battery without the micro-precharge activation, and the self-discharge rate of the battery after the pre-charge activation is 40% to 65% of that of the battery without the pre-charge activation, which indicates that the micro-precharge activation can significantly reduce the self-discharge rate of the battery and improve the yield of the battery.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention and not for limiting the same, and although the embodiments of the present invention are described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the embodiments of the present invention, and these modifications or equivalent substitutions cannot make the modified technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A micro-electricity pre-charging activation method of a lithium ion battery is characterized by comprising the following steps:
the method comprises the following steps: taking the cleaned lithium ion battery, and charging with a micro-current constant current with a charging rate of 0.02-0.06C for 6-10 min;
step two: performing high-temperature aging on the lithium ion battery subjected to the micro-current constant-current charging in the step one;
step three: and (5) aging the lithium ion battery aged at the high temperature in the step two at normal temperature to complete micro-electricity pre-charging activation of the lithium ion battery.
2. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: and (4) directly carrying out micro-current constant-current charging on the lithium ion battery after the cleaning in the step one without aging.
3. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: in the first step, the charging multiplying power is 0.03-0.05C; the charging time is 6-8 min.
4. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: in the first step, the charging multiplying power is 0.05C; the charging time is 8 min.
5. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: in the first step, the charging voltage of the micro-current constant-current charging is 2.4V.
6. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: the temperature of the high-temperature aging in the second step is 42-48 ℃.
7. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: and the high-temperature aging time in the second step is 22-25 h.
8. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: the temperature for normal-temperature aging in the third step is 22-28 ℃.
9. The micro-precharge activation method of the lithium ion battery according to claim 1, wherein: the time for aging at normal temperature in the third step is 20-26 h.
10. A method of micro-precharge activation of a lithium ion battery as claimed in any one of claims 1 to 9, wherein: after the lithium ion battery is subjected to pre-charging activation by adopting the micro-electricity pre-charging activation method, the self-discharge rate of the lithium ion battery is reduced by 35-60%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113903998A (en) * | 2021-09-30 | 2022-01-07 | 蜂巢能源科技有限公司 | Lithium ion battery and preparation method thereof |
| CN114188596A (en) * | 2021-11-23 | 2022-03-15 | 郑州比克电子有限责任公司 | Pre-activation method of lithium ion battery |
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| CN101621137A (en) * | 2008-06-30 | 2010-01-06 | 深圳市比克电池有限公司 | Lithium ion battery precharge process system |
| CN102035026A (en) * | 2009-09-25 | 2011-04-27 | 三星Sdi株式会社 | Method for manufacturing lithium ion secondary battery |
| CN105870508A (en) * | 2016-04-06 | 2016-08-17 | 中航锂电（洛阳）有限公司 | Formation method for lithium ion battery |
| WO2017212815A1 (en) * | 2016-06-06 | 2017-12-14 | 日立化成株式会社 | Trickle charging power supply system |
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2018
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| CN101621137A (en) * | 2008-06-30 | 2010-01-06 | 深圳市比克电池有限公司 | Lithium ion battery precharge process system |
| CN102035026A (en) * | 2009-09-25 | 2011-04-27 | 三星Sdi株式会社 | Method for manufacturing lithium ion secondary battery |
| CN105870508A (en) * | 2016-04-06 | 2016-08-17 | 中航锂电（洛阳）有限公司 | Formation method for lithium ion battery |
| WO2017212815A1 (en) * | 2016-06-06 | 2017-12-14 | 日立化成株式会社 | Trickle charging power supply system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113903998A (en) * | 2021-09-30 | 2022-01-07 | 蜂巢能源科技有限公司 | Lithium ion battery and preparation method thereof |
| CN114188596A (en) * | 2021-11-23 | 2022-03-15 | 郑州比克电子有限责任公司 | Pre-activation method of lithium ion battery |
| CN114188596B (en) * | 2021-11-23 | 2023-09-01 | 郑州比克电子有限责任公司 | Pre-activation method of lithium ion battery |
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Application publication date: 20191224 |