CN105633493A - Method for repairing lithium ion battery damaged by overdischarge - Google Patents
Method for repairing lithium ion battery damaged by overdischarge Download PDFInfo
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- CN105633493A CN105633493A CN201410598817.3A CN201410598817A CN105633493A CN 105633493 A CN105633493 A CN 105633493A CN 201410598817 A CN201410598817 A CN 201410598817A CN 105633493 A CN105633493 A CN 105633493A
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- lithium ion
- ion battery
- constant current
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- battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 28
- 238000007600 charging Methods 0.000 claims abstract description 16
- 230000001771 impaired effect Effects 0.000 claims description 19
- 238000007599 discharging Methods 0.000 abstract 1
- 230000005611 electricity Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 206010016766 flatulence Diseases 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000008439 repair process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
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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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Abstract
The invention relates to a method for repairing a lithium ion battery damaged by overdischarge. The method comprises the following steps: step 1, charging the lithium ion battery with a constant current of 0.01-0.02C for 2.5-5h; step 2, carrying out standing and aging on the lithium ion battery for 12-24h at a temperature of 20-45 DEG C; step 3, charging the lithium ion battery with a constant current of 0.05-0.1C for 1.5-3h; step 4, carrying out standing and aging on the lithium ion battery for 24-36h at a temperature of 20-45 DEG C; step 5, charging the lithium ion battery with a constant current of 0.2-0.5C to 4.2V; step 6, charging the lithium ion battery under a constant voltage of 4.2V until the current reaches 0.02C; step 7, discharging the lithium ion battery with a constant current of 0.2-0.5C to 3V; step 8, charging the lithium ion battery with a constant current of 0.2-0.5C to 3.85-3.9V; and step 9, charging the lithium ion battery under a constant voltage of 3.85-3.9V until the current reaches 0.02C. With adoption of the method disclosed by the invention, the lithium ion battery with gas expansion caused by overdischarge can be repaired.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of method repairing the impaired lithium ion battery of overdischarge.
Background technology
Being substantially all use lithium ion battery on other mobile products that the digital product of hand-held movement and some needs chargings use, the lithium ion battery currently mainly applied can be divided into: the lithium ion battery of lithium ion battery with aluminum shell, cylindrical lithium ion battery and flexible package.
In the use and storage process of lithium ion battery, owing to battery exists self discharge, terminal unit also has band load electric current, if the words that battery charges after using not in time, battery over-discharge can be made and produce gas, causing that flatulence occurs in battery, and cause finally cannot using.
The overdischarge of so-called battery, refers to that battery discharges the electricity of internal reservoir, and after voltage drops to certain value, battery continues electric discharge. For lithium ion battery, overdischarge pressure in general sense is defined as 2.4V. Lithium ion battery overdischarge produces gas mainly in low-voltage section, owing to lithium ion deintercalation completes, continue electric discharge and can cause the SEI film (solidelectrolyteinterface of negative pole graphite surface, solid electrolyte interface film) oxidation Decomposition, form gas, cause inside battery flatulence and cannot normally be continuing with.
Summary of the invention
Based on this, it is necessary to provide a kind of method repairing the impaired lithium ion battery of overdischarge.
A kind of method repairing the impaired lithium ion battery of overdischarge, including the step that order below performs:
Step 1: adopt the constant current of 0.01��0.02C, lithium ion battery is carried out the charging of 2.5��5 hours;
Step 2: at the temperature of 20��45 DEG C, the standing that lithium ion battery carries out 12��24 hours is aging;
Step 3: adopt the constant current of 0.05��0.1C, lithium ion battery is carried out the charging of 1.5��3 hours;
Step 4: at the temperature of 20��45 DEG C, the standing that lithium ion battery carries out 24��36 hours is aging;
Step 5: adopt the constant current of 0.2��0.5C, lithium ion battery is charged to 4.2V;
Step 6: under the constant voltage of 4.2V, it is 0.02C that lithium ion battery charges to electric current;
Step 7: adopt the constant current of 0.2��0.5C, lithium ion battery is discharged to 3V;
Step 8: adopt the constant current of 0.2��0.5C, lithium ion battery is charged to 3.85��3.9V;
Step 9: under the constant voltage of 3.85��3.9V, it is 0.02C that lithium ion battery charges to electric current.
Wherein in an embodiment,
In step 1, the constant current charge of employing 0.01C 5 hours;
In step 2, the standing carrying out 24 hours at the temperature of 45 DEG C is aging;
In step 3, the constant current charge of employing 0.05C 3 hours;
In step 4, the standing carrying out 36 hours at the temperature of 45 DEG C is aging;
In steps of 5, adopt the constant current of 0.2C that battery to be repaired is charged to 4.2V
In step 7, the constant current of 0.2C is adopted to discharge into 3V;
In step 8, adopt the constant current of 0.2C that battery to be repaired is charged to 3.85V;
In step 9, under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
Wherein in an embodiment,
In step 1, the constant current charge of employing 0.02C 2.5 hours;
In step 2, the standing carrying out 12 hours at the temperature of 20 DEG C is aging;
In step 3, the constant current charge of employing 0.1C 1.5 hours;
In step 4, the standing carrying out 24 hours at the temperature of 20 DEG C is aging;
In steps of 5, adopt the constant current of 0.2C that battery to be repaired is charged to 4.2V
In step 7, the constant current of 0.2C is adopted to discharge into 3V;
In step 8, adopt the constant current of 0.2C that battery to be repaired is charged to 3.85V;
In step 9, under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
Wherein in an embodiment,
In step 1, the constant current charge of employing 0.015C 3.75 hours;
In step 2, the standing carrying out 18 hours at the temperature of 33 DEG C is aging;
In step 3, the constant current charge of employing 0.075C 2.25 hours;
In step 4, the standing carrying out 30 hours at the temperature of 33 DEG C is aging;
In steps of 5, adopt the constant current of 0.2C that battery to be repaired is charged to 4.2V
In step 7, the constant current of 0.2C is adopted to discharge into 3V;
In step 8, adopt the constant current of 0.2C that battery to be repaired is charged to 3.85V;
In step 9, under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
Said method, first passes through the low current charge of 0.01��0.02C, enables gas produced by overdischarge to participate in forming the new good SEI film of uniformity, then makes SEI film reform by standing; Then pass through the low current charge of 0.05��0.1C, make SEI film fine and close and stable further, then make SEI film more stable by standing. Finally just impaired SEI film can be repaired, it is achieved the reparation to impaired lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the method flow diagram repairing the impaired lithium ion battery of overdischarge of an embodiment;
Fig. 2 is the capability retention-circulation cycle curve chart through the lithium ion battery repaired with normal lithium ion battery.
Detailed description of the invention
As it is shown in figure 1, be the method flow diagram repairing the impaired lithium ion battery of overdischarge of an embodiment. The method comprises the steps.
Step S101: adopt the constant current of 0.01��0.02C, impaired lithium ion battery is carried out the charging of 2.5��5 hours;
This step mainly adopts small area analysis to be charged, so that gas produced by overdischarge can participate in new SEI film in the process and be formed; The uniformity of newly-generated SEI film is ensured by the charging of small area analysis to some extent. Adopting the constant current of 0.01��0.02C that lithium ion is charged, representative is to go charging with the battery marked capacity C of (0.01��0.02) times, and battery capacity unit is mAh, saves time h herein herein, below be also same reason.
Step S102: at the temperature of 20��45 DEG C, the standing that the lithium ion battery in step S101 carries out 12��24 hours is aging;
This step allows newly-generated SEI film reform and stable mainly by the mode that room temperature or quiescence in high temperature are aging.
Step S103: adopt the constant current of 0.05��0.1C, the lithium ion battery in step S102 is carried out the charging of 1.5��3 hours;
This step allows SEI film finer and close mainly by less electric current and stable further, and simultaneously less electric current is not result in the lithium precipitation in negative terminal surface.
Step S104: at the temperature of 20��45 DEG C, the standing that the lithium ion battery in step S103 carries out 24��36 hours is aging;
This step allows newly-generated SEI film further to more stable state to reach to charge by normal current mainly by the static aging mode of room temperature or high temperature.
Step S105: adopt the constant current of 0.2��0.5C, the lithium ion battery in step S104 is charged to 4.2V;
Step S106: under the constant voltage of 4.2V, it is 0.02C that the lithium ion battery in step S105 charges to electric current;
Step S105��S106 is the normal charging process of battery.
Step S107: adopt the constant current of 0.2��0.5C, the lithium ion battery in step S106 is discharged to 3V;
This step is the regular picture partial volume process of battery.
Step S108: adopt the constant current of 0.2��0.5C, the lithium ion battery in step S107 is charged to 3.85��3.9V;
Step S109: under the constant voltage of 3.85��3.9V, it is the 0.02C reparation completing to put impaired lithium ion battery that the lithium ion battery in step S108 charges to electric current. Step S108��S109 is that the normal of battery mends half electric process.
Pass through said method, it is possible to repaired by the lithium ion battery that flatulence occurs after overdischarge.
The repair process of multiple specific embodiment presented below.
Impaired lithium ion battery for repairing can obtain in the following ways:
Normal battery is discharged into 3V by the constant current adopting 0.5C;
Battery is continued to discharge into 1V by the constant current adopting 0.2C again;
Battery is continued to discharge into 0V by the constant current finally adopting 0.05C, makes normal lithium ion battery generation flatulence.
In the present embodiment, lithium ion battery used is soft bag lithium ionic cell, and model is 484590, and nominal capacity is 2300mAh. In other embodiments, it is also possible to be applied to lithium ion battery with aluminum shell or cylindrical lithium ion battery.
Embodiment 1
Step S201, the constant current charge of employing 0.01C 5 hours;
Step S202, the standing carrying out 24 hours at the temperature of 45 DEG C is aging;
Step S203, the constant current charge of employing 0.05C 3 hours;
Step S204, the standing carrying out 36 hours at the temperature of 45 DEG C is aging;
Step S205, adopts the constant current of 0.2C that battery to be repaired is charged to 4.2V;
Step S206: under the constant voltage of 4.2V, it is 0.02C that impaired lithium ion battery charges to electric current;
Step S207, adopts the constant current of 0.2C to discharge into 3V;
Step S208, adopts the constant current of 0.2C that battery to be repaired is charged to 3.85V;
Step S209: under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
Embodiment 2
Step S301, the constant current charge of employing 0.02C 2.5 hours;
Step S302, the standing carrying out 12 hours at the temperature of 20 DEG C is aging;
Step S303, the constant current charge of employing 0.1C 1.5 hours;
Step S304, the standing carrying out 24 hours at the temperature of 20 DEG C is aging;
Step S305, adopts the constant current of 0.2C that battery to be repaired is charged to 4.2V.
Step S306: under the constant voltage of 4.2V, it is 0.02C that impaired lithium ion battery charges to electric current.
Step S307, adopts the constant current of 0.2C to discharge into 3V;
Step S308, adopts the constant current of 0.2C that battery to be repaired is charged to 3.85V.
Step S309: under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
Embodiment 3
Step S401, the constant current charge of employing 0.015C 3.75 hours;
Step S402, the standing carrying out 18 hours at the temperature of 33 DEG C is aging;
Step S403, the constant current charge of employing 0.075C 2.25 hours;
Step S404, the standing carrying out 30 hours at the temperature of 33 DEG C is aging;
Step S405, adopts the constant current of 0.2C that battery to be repaired is charged to 4.2V.
Step S406: under the constant voltage of 4.2V, it is 0.02C that impaired lithium ion battery charges to electric current.
Step S407, adopts the constant current of 0.2C to discharge into 3V;
Step S408, adopts the constant current of 0.2C that battery to be repaired is charged to 3.85V.
Step S409: under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
Using blue electricity cell tester and internal resistance test device, the flexible packing lithium ion battery using embodiment 1��3 and comparative example carries out room temperature capacity, internal resistance, capacity after putting reparation and internal resistance and is circulated the test of performance, capacity and internal resistance data are in Table 1:
The capacity of 1. 4 kinds of scheme batteries of table and internal resistance data
Remarks: data above is meansigma methods; Comparative example is that the battery of the same type of overdischarge does not normally occur.
Data from upper table are it will be seen that embodiment 1��3 scheme crosses the loss repairing capacity nearly about 4.0% after putting, and internal resistance has the increase of about 2.0m ��, but does not affect the use of battery whole volume.
Blue electricity cell tester is used to carry out the room temperature cycle life test of battery under normal temperature environment, battery and the comparative example battery repair embodiment 1��3 carry out 0.5C charge-discharge test, obtain the capability retention-circulation cycle curve chart through the lithium ion battery repaired and normal lithium ion battery as shown in Figure 2.
1. battery and indigo plant electricity cell tester are connected;
2. adopting 0.5C discharge and recharge to be circulated test in 500 weeks, discharge and recharge interval quiescent time is 10 minutes;
The battery repaired is the same with comparative example all has good cycle performance it will be seen that adopt embodiment scheme to carry out for 0.5C charge/discharge capacity conservation rate curve from Fig. 1 battery room temperature, and after 500 weeks, capability retention is more than 80%.
Using climatic chamber, blue electricity cell tester and slide gauge, the lithium ion battery using embodiment 1��3 and comparative example carries out thickness change and the test of capacity restoration rate of 70 DEG C of full electricity storages in 72 hours, performance data is in Table 2:
1. battery is carried out 0.5C discharge and recharge one week on blue electricity cell tester, and mend electric to the full electricity of 4.20V; The initial capacity of record battery;
2. with the initial full electricity thickness of vernier caliper measurement battery record;
3. climatic chamber temperature being set to 70 DEG C, heating rate is 5 degrees/min;
4., after being warmed up to 70 DEG C, battery is put into climatic chamber, static 72 hours;
5. battery is taken out, use thickness the record of vernier caliper measurement battery;
6. battery is carried out 0.5C charge and discharge 2 weeks on blue electricity cell tester, the recovery capacity of record battery.
The thickness change of 70 degree of full electricity storages in 72 hours of 2. 4 kinds of scheme batteries of table and capacity restoration data
Data from upper table, it will be seen that battery after adopting embodiment 1��3 scheme to repair and the essentially no notable difference of comparative example battery, all possess good high-temperature shelf property.
The comprehensive above room temperature long circulating capability retention of 500 weeks, and battery recovery after capacity, internal resistance data, the mistake that the embodiment of the solution of the present invention carries out repairing is adopted to put lithium ion battery, its performance is compared with the battery crossed before putting, there was no significant difference, lithium ion battery reparation that aerogenesis cannot use can be put crossing and normally use by we are bright; Reduce and put the battery caused scrap owing to battery is crossed.
Each technical characteristic of embodiment described above can combine arbitrarily, for making description succinct, the all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics is absent from contradiction, all it is considered to be the scope that this specification is recorded.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent. It should be pointed out that, for the person of ordinary skill of the art, without departing from the inventive concept of the premise, it is also possible to making some deformation and improvement, these broadly fall into protection scope of the present invention. Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (4)
1. the method repairing the impaired lithium ion battery of overdischarge, including the step that order below performs:
Step 1: adopt the constant current of 0.01��0.02C, impaired lithium ion battery is carried out the charging of 2.5��5 hours;
Step 2: at the temperature of 20��45 DEG C, the standing that lithium ion battery carries out 12��24 hours is aging;
Step 3: adopt the constant current of 0.05��0.1C, lithium ion battery is carried out the charging of 1.5��3 hours;
Step 4: at the temperature of 20��45 DEG C, the standing that lithium ion battery carries out 24��36 hours is aging;
Step 5: adopt the constant current of 0.2��0.5C, lithium ion battery is charged to 4.2V;
Step 6: under the constant voltage of 4.2V, it is 0.02C that lithium ion battery charges to electric current;
Step 7: adopt the constant current of 0.2��0.5C, lithium ion battery is discharged to 3V;
Step 8: adopt the constant current of 0.2��0.5C, lithium ion battery is charged to 3.85��3.9V;
Step 9: under the constant voltage of 3.85��3.9V, it is 0.02C that lithium ion battery charges to electric current.
2. the method for the impaired lithium ion battery of reparation overdischarge according to claim 1, it is characterised in that
In step 1, the constant current charge of employing 0.01C 5 hours;
In step 2, the standing carrying out 24 hours at the temperature of 45 DEG C is aging;
In step 3, the constant current charge of employing 0.05C 3 hours;
In step 4, the standing carrying out 36 hours at the temperature of 45 DEG C is aging;
In steps of 5, adopt the constant current of 0.2C that battery to be repaired is charged to 4.2V
In step 7, the constant current of 0.2C is adopted to discharge into 3V;
In step 8, adopt the constant current of 0.2C that battery to be repaired is charged to 3.85V;
In step 9, under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
3. the method for the impaired lithium ion battery of reparation overdischarge according to claim 1, it is characterised in that
In step 1, the constant current charge of employing 0.02C 2.5 hours;
In step 2, the standing carrying out 12 hours at the temperature of 20 DEG C is aging;
In step 3, the constant current charge of employing 0.1C 1.5 hours;
In step 4, the standing carrying out 24 hours at the temperature of 20 DEG C is aging;
In steps of 5, adopt the constant current of 0.2C that battery to be repaired is charged to 4.2V
In step 7, the constant current of 0.2C is adopted to discharge into 3V;
In step 8, adopt the constant current of 0.2C that battery to be repaired is charged to 3.85V;
In step 9, under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
4. the method for the impaired lithium ion battery of reparation overdischarge according to claim 1, it is characterised in that
In step 1, the constant current charge of employing 0.015C 3.75 hours;
In step 2, the standing carrying out 18 hours at the temperature of 33 DEG C is aging;
In step 3, the constant current charge of employing 0.075C 2.25 hours;
In step 4, the standing carrying out 30 hours at the temperature of 33 DEG C is aging;
In steps of 5, adopt the constant current of 0.2C that battery to be repaired is charged to 4.2V
In step 7, the constant current of 0.2C is adopted to discharge into 3V;
In step 8, adopt the constant current of 0.2C that battery to be repaired is charged to 3.85V;
In step 9, under the constant voltage of 3.85V, it is 0.02C that lithium ion battery charges to electric current.
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| CN106785144A (en) * | 2016-12-29 | 2017-05-31 | 宁德新能源科技有限公司 | A kind of charging method and device |
| CN110021793A (en) * | 2018-01-09 | 2019-07-16 | 深圳市普兰德储能技术有限公司 | A method of repairing retired performance of lithium ion battery |
| EP3726638A4 (en) * | 2018-02-23 | 2021-02-24 | Lg Chem, Ltd. | Secondary battery capacity recovery method and secondary battery capacity recovery apparatus |
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