CN105633493B - Repair the method that overdischarge is damaged lithium ion battery - Google Patents
Repair the method that overdischarge is damaged lithium ion battery Download PDFInfo
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- CN105633493B CN105633493B CN201410598817.3A CN201410598817A CN105633493B CN 105633493 B CN105633493 B CN 105633493B CN 201410598817 A CN201410598817 A CN 201410598817A CN 105633493 B CN105633493 B CN 105633493B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008439 repair process Effects 0.000 title abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 28
- 238000007600 charging Methods 0.000 claims abstract description 11
- 238000010277 constant-current charging Methods 0.000 claims description 18
- 230000001771 impaired effect Effects 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 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
- 230000008901 benefit Effects 0.000 description 1
- 238000009831 deintercalation 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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 present invention relates to a kind of method that reparation overdischarge is damaged lithium ion battery, include the steps that following sequence executes: step 1: using the constant current of 0.01~0.02C, charging in 2.5~5 hours is carried out to lithium ion battery；Step 2: 20~45 DEG C at a temperature of, standing aging in 12~24 hours is carried out to lithium ion battery；Step 3: using the constant current of 0.05~0.1C, charging in 1.5~3 hours is carried out to lithium ion battery；Step 4: 20~45 DEG C at a temperature of, standing aging in 24~36 hours is carried out to lithium ion battery；Step 5: using the constant current of 0.2~0.5C, lithium ion battery being charged into 4.2V；Step 6: under the constant pressure of 4.2V, it is 0.02C that lithium ion battery, which is charged to electric current,；Step 7: using the constant current of 0.2~0.5C, lithium ion battery being discharged to 3V；Step 8: using the constant current of 0.2~0.5C, lithium ion battery being charged into 3.85~3.9V；Step 9: under the constant pressure of 3.85~3.9V, it is 0.02C that lithium ion battery, which is charged to electric current,.The above method can repair the lithium ion battery that inflatable occurs after overdischarge.
Description
Technical field
The present invention relates to technical field of lithium ion, are damaged lithium ion battery more particularly to a kind of reparation overdischarge
Method.
Background technique
Hold be substantially all on mobile digital product and some other mobile products used that need to charge use lithium from
Sub- battery, leading lithium ion battery to be applied at present can be divided into: lithium ion battery with aluminum shell, cylindrical lithium ion battery and flexible package
Lithium ion battery.
In the use of lithium ion battery and storage process, since battery is there are self discharge, terminal device also has band to carry electricity
Stream, if can make battery over-discharge if charging not in time after battery use and generate gas, battery is caused inflatable occur,
And cause not being available finally.
The overdischarge of so-called battery refers to that battery discharges the electricity of internal reservoir, after voltage drops to certain value, battery after
Continuous electric discharge.For lithium ion battery, over-discharge voltage in general sense is defined as 2.4V.Lithium ion battery overdischarge generates
Gas is mainly in low-voltage section, and since lithium ion deintercalation is completed, continuing electric discharge will lead to the SEI film of cathode graphite surface
(solid electrolyte interface, solid electrolyte interface film) oxygenolysis forms gas, leads to inside battery
Inflatable simultaneously can not be continued to use normally.
Summary of the invention
Based on this, it is necessary to provide a kind of method that reparation overdischarge is damaged lithium ion battery.
A method of it repairing overdischarge and is damaged lithium ion battery, include the steps that following sequence executes:
Step 1: using the constant current of 0.01~0.02C, charging in 2.5~5 hours is carried out to lithium ion battery；
Step 2: 20~45 DEG C at a temperature of, standing aging in 12~24 hours is carried out to lithium ion battery；
Step 3: using the constant current of 0.05~0.1C, charging in 1.5~3 hours is carried out to lithium ion battery；
Step 4: 20~45 DEG C at a temperature of, standing aging in 24~36 hours is carried out to lithium ion battery；
Step 5: using the constant current of 0.2~0.5C, lithium ion battery being charged into 4.2V；
Step 6: under the constant pressure of 4.2V, it is 0.02C that lithium ion battery, which is charged to electric current,；
Step 7: using the constant current of 0.2~0.5C, lithium ion battery being discharged to 3V；
Step 8: using the constant current of 0.2~0.5C, lithium ion battery being charged into 3.85~3.9V；
Step 9: under the constant pressure of 3.85~3.9V, it is 0.02C that lithium ion battery, which is charged to electric current,.
In one of the embodiments,
In step 1, using the constant current charging of 0.01C 5 hours；
In step 2,45 DEG C at a temperature of carry out standing aging in 24 hours；
In step 3, using the constant current charging of 0.05C 3 hours；
In step 4,45 DEG C at a temperature of carry out standing aging in 36 hours；
In steps of 5, battery to be repaired is charged to by 4.2V using the constant current of 0.2C
In step 7,3V is discharged into using the constant current of 0.2C；
In step 8, battery to be repaired is charged to by 3.85V using the constant current of 0.2C；
In step 9, under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
In one of the embodiments,
In step 1, using the constant current charging of 0.02C 2.5 hours；
In step 2,20 DEG C at a temperature of carry out standing aging in 12 hours；
In step 3, using the constant current charging of 0.1C 1.5 hours；
In step 4,20 DEG C at a temperature of carry out standing aging in 24 hours；
In steps of 5, battery to be repaired is charged to by 4.2V using the constant current of 0.2C
In step 7,3V is discharged into using the constant current of 0.2C；
In step 8, battery to be repaired is charged to by 3.85V using the constant current of 0.2C；
In step 9, under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
In one of the embodiments,
In step 1, using the constant current charging of 0.015C 3.75 hours；
In step 2,33 DEG C at a temperature of carry out standing aging in 18 hours；
In step 3, using the constant current charging of 0.075C 2.25 hours；
In step 4,33 DEG C at a temperature of carry out standing aging in 30 hours；
In steps of 5, battery to be repaired is charged to by 4.2V using the constant current of 0.2C
In step 7,3V is discharged into using the constant current of 0.2C；
In step 8, battery to be repaired is charged to by 3.85V using the constant current of 0.2C；
In step 9, under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
The above method passes through the low current charge of 0.01~0.02C first, gas caused by overdischarge is enable to participate in
New SEI film with good uniformity is formed, then reforms SEI film by standing；Then pass through the low current of 0.05~0.1C
Charging keeps SEI film further fine and close and stablizes, then keeps SEI film more stable by standing.It finally can will be impaired
SEI film is repaired, and realizes the reparation to impaired lithium ion battery.
Detailed description of the invention
Fig. 1 is the method flow diagram of an embodiment repaired overdischarge and be damaged lithium ion battery；
Fig. 2 is capacity retention ratio-circulation cycle curve graph by the lithium ion battery and normal lithium ion battery repaired.
Specific embodiment
As shown in Figure 1, for the method flow diagram of an embodiment repaired overdischarge and be damaged lithium ion battery.This method includes
Following steps.
Step S101: using the constant current of 0.01~0.02C, impaired lithium ion battery fill within 2.5~5 hours
Electricity；
This step mainly uses low current to charge, so that gas caused by overdischarge can be in the process
New SEI film is participated in be formed；The charging of low current ensures the uniformity of newly-generated SEI film.Herein using 0.01~
The constant current of 0.02C charges to lithium ion, and representative is to go to charge with the battery marked capacity C of (0.01~0.02) again, electricity
Tankage unit is mAh, saves time h herein, below be also same reason.
Step S102: 20~45 DEG C at a temperature of, the lithium ion battery in step S101 is carried out 12~24 hours
Stand aging；
This step is mainly that newly-generated SEI film is allowed to reform and stablize by way of room temperature or quiescence in high temperature aging.
Step S103: using the constant current of 0.05~0.1C, 1.5~3 are carried out to the lithium ion battery in step S102
The charging of hour；
This step, which mainly passes through lesser electric current, further to be allowed SEI film finer and close and stablizes, while lesser electric current
Lithium not will lead in the precipitation of negative terminal surface.
Step S104: 20~45 DEG C at a temperature of, the lithium ion battery in step S103 is carried out 24~36 hours
Stand aging；
This step mainly allows newly-generated SEI film further to more steady by way of room temperature or the static aging of high temperature
Fixed state can be charged with reaching with normal current.
Step S105: using the constant current of 0.2~0.5C, the lithium ion battery in step S104 is charged into 4.2V；
Step S106: under the constant pressure of 4.2V, it is 0.02C that the lithium ion battery in step S105, which is charged to electric current,；
Step S105~S106 is the normal charging process of battery.
Step S107: using 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: using 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 pressure of 3.85~3.9V, the lithium ion battery in step S108, which is charged to electric current, is
0.02C completes the reparation that over-discharge is damaged lithium ion battery.Step S108~S109 is half electric process of normal benefit of battery.
By the above method, the lithium ion battery that inflatable occurs after overdischarge can be repaired.
The repair process of multiple specific embodiments presented below.
Impaired lithium ion battery for reparation can obtain in the following ways:
Normal battery is discharged by 3V using the constant current of 0.5C；
Again battery is continued to discharge into 1V using the constant current of 0.2C；
Finally battery is continued to discharge into 0V using the constant current of 0.05C, makes normal lithium ion battery that inflatable occur.
In the present embodiment, lithium ion battery used is soft bag lithium ionic cell, and model 484590, nominal capacity is
2300mAh.In other embodiments, lithium ion battery with aluminum shell or cylindrical lithium ion battery are also applied to.
Embodiment 1
Step S201, using constant current charging 5 hours of 0.01C；
Step S202,45 DEG C at a temperature of carry out standing aging in 24 hours；
Step S203, using constant current charging 3 hours of 0.05C；
Step S204,45 DEG C at a temperature of carry out standing aging in 36 hours；
Battery to be repaired is charged to 4.2V using the constant current of 0.2C by step S205；
Step S206: under the constant pressure of 4.2V, it is 0.02C that impaired lithium ion battery, which is charged to electric current,；
Step S207 discharges into 3V using the constant current of 0.2C；
Battery to be repaired is charged to 3.85V using the constant current of 0.2C by step S208；
Step S209: under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
Embodiment 2
Step S301, using constant current charging 2.5 hours of 0.02C；
Step S302,20 DEG C at a temperature of carry out standing aging in 12 hours；
Step S303, using constant current charging 1.5 hours of 0.1C；
Step S304,20 DEG C at a temperature of carry out standing aging in 24 hours；
Battery to be repaired is charged to 4.2V using the constant current of 0.2C by step S305.
Step S306: under the constant pressure of 4.2V, it is 0.02C that impaired lithium ion battery, which is charged to electric current,.
Step S307 discharges into 3V using the constant current of 0.2C；
Battery to be repaired is charged to 3.85V using the constant current of 0.2C by step S308.
Step S309: under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
Embodiment 3
Step S401, using constant current charging 3.75 hours of 0.015C；
Step S402,33 DEG C at a temperature of carry out standing aging in 18 hours；
Step S403, using constant current charging 2.25 hours of 0.075C；
Step S404,33 DEG C at a temperature of carry out standing aging in 30 hours；
Battery to be repaired is charged to 4.2V using the constant current of 0.2C by step S405.
Step S406: under the constant pressure of 4.2V, it is 0.02C that impaired lithium ion battery, which is charged to electric current,.
Step S407 discharges into 3V using the constant current of 0.2C；
Battery to be repaired is charged to 3.85V using the constant current of 0.2C by step S408.
Step S409: under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
Using blue electric cell tester and internal resistance test device, to use the flexible-packaged lithium of Examples 1 to 3 and comparative example from
Sub- battery carries out the test that room temperature capacity, internal resistance, the capacity after over-discharge is repaired and internal resistance carry out cycle performance, capacity and internal resistance
Data are shown in Table 1:
The capacity and internal resistance data of 1. 4 kinds of scheme batteries of table
Remarks: above data is average value；Comparative example is the battery of the same type that overdischarge does not occur normally.
It can see from the data in upper table, the reparation capacity about 4.0% or so after Examples 1 to 3 scheme over-discharge
Loss, internal resistance has the increase of about 2.0m Ω, but does not influence the use of battery whole volume.
The normal temperature circulation life test for carrying out battery using blue electric cell tester under normal temperature environment, to Examples 1 to 3
The battery and comparative example battery of reparation carry out 0.5C charge-discharge test, obtain the lithium ion battery by reparation as shown in Figure 2
With capacity retention ratio-circulation cycle curve graph of normal lithium ion battery.
1. battery and blue electric cell tester are connected；
2. test within circulation 500 weeks using 0.5C charge and discharge, charge and discharge interval quiescent time is 10 minutes；
It can see from 0.5C charge/discharge capacity conservation rate curve under Fig. 1 battery room temperature, repaired using example scheme
Multiple battery all has good cycle performance as comparative example, and capacity retention ratio is 80% or more after 500 weeks.
Using climatic chamber, blue electricity cell tester and vernier caliper, to using Examples 1 to 3 and comparative example
Lithium ion battery carries out the thickness change of 70 DEG C of full electricity storages in 72 hours and the test of capacity restoration rate, performance data are shown in Table 2:
1. battery is carried out 0.5C charge and discharge one week on blue electric cell tester, and electricity is mended to the full electricity of 4.20V；Record electricity
The initial capacity in pond；
2. with the initial full electric thickness of vernier caliper measurement battery and recording；
3. being 70 DEG C by climatic chamber temperature setting, heating rate is 5 degrees/min；
4. battery is put into climatic chamber after being warming up to 70 DEG C, static 72 hours；
5. battery is taken out, the thickness and record of vernier caliper measurement battery are used；
6. battery is carried out 0.5C charge and discharge 2 weeks on blue electric cell tester, the recovery capacity of battery is recorded.
The thickness change and capacity restoration data of 2. 4 kinds of scheme batteries of table, 70 degree of full electricity storages in 72 hours
It can see from the data in upper table, the battery and comparative example battery after being repaired using Examples 1 to 3 scheme are basic
Upper no significant difference all has good high-temperature shelf property.
In summary room temperature 500 weeks long circulating capacity retention ratios, and battery recovery after capacity, internal resistance data come
See, the over-discharge lithium ion battery repaired using the embodiment of the solution of the present invention, performance compared with the battery before over-discharge,
There was no significant difference, and over-discharge can be produced to the lithium ion battery reparation and normal use that gas is not available by the way that we are bright；It reduces
The battery due to caused by battery over-discharge is scrapped.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (4)
1. a kind of method repaired overdischarge and be damaged lithium ion battery includes the steps that following sequence executes:
Step 1: using the constant current of 0.01~0.02C, charging in 2.5~5 hours is carried out to impaired lithium ion battery；
The constant current of the 0.01~0.02C, representative is to go to charge with the battery marked capacity C of (0.01~0.02) again,
Battery capacity unit is mAh, saves time h herein, and the explanation of similar statement is same as above below；
Step 2: 20~45 DEG C at a temperature of, standing aging in 12~24 hours is carried out to lithium ion battery；
Step 3: using the constant current of 0.05~0.1C, charging in 1.5~3 hours is carried out to lithium ion battery；
Step 4: 20~45 DEG C at a temperature of, standing aging in 24~36 hours is carried out to lithium ion battery；
Step 5: using the constant current of 0.2~0.5C, lithium ion battery being charged into 4.2V；
Step 6: under the constant pressure of 4.2V, it is 0.02C that lithium ion battery, which is charged to electric current,；
Step 7: using the constant current of 0.2~0.5C, lithium ion battery being discharged to 3V；
Step 8: using the constant current of 0.2~0.5C, lithium ion battery being charged into 3.85~3.9V；
Step 9: under the constant pressure of 3.85~3.9V, it is 0.02C that lithium ion battery, which is charged to electric current,；
The lithium ion battery is soft bag lithium ionic cell, lithium ion battery with aluminum shell or cylindrical lithium ion battery.
2. the method according to claim 1 repaired overdischarge and be damaged lithium ion battery, which is characterized in that
In step 1, using the constant current charging of 0.01C 5 hours；
In step 2,45 DEG C at a temperature of carry out standing aging in 24 hours；
In step 3, using the constant current charging of 0.05C 3 hours；
In step 4,45 DEG C at a temperature of carry out standing aging in 36 hours；
In steps of 5, battery to be repaired is charged to by 4.2V using the constant current of 0.2C
In step 7,3V is discharged into using the constant current of 0.2C；
In step 8, battery to be repaired is charged to by 3.85V using the constant current of 0.2C；
In step 9, under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
3. the method according to claim 1 repaired overdischarge and be damaged lithium ion battery, which is characterized in that
In step 1, using the constant current charging of 0.02C 2.5 hours；
In step 2,20 DEG C at a temperature of carry out standing aging in 12 hours；
In step 3, using the constant current charging of 0.1C 1.5 hours；
In step 4,20 DEG C at a temperature of carry out standing aging in 24 hours；
In steps of 5, battery to be repaired is charged to by 4.2V using the constant current of 0.2C
In step 7,3V is discharged into using the constant current of 0.2C；
In step 8, battery to be repaired is charged to by 3.85V using the constant current of 0.2C；
In step 9, under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged to electric current,.
4. the method according to claim 1 repaired overdischarge and be damaged lithium ion battery, which is characterized in that in step 1,
Using constant current charging 3.75 hours of 0.015C；
In step 2,33 DEG C at a temperature of carry out standing aging in 18 hours；
In step 3, using the constant current charging of 0.075C 2.25 hours；
In step 4,33 DEG C at a temperature of carry out standing aging in 30 hours；
In steps of 5, battery to be repaired is charged to by 4.2V using the constant current of 0.2C
In step 7,3V is discharged into using the constant current of 0.2C；
In step 8, battery to be repaired is charged to by 3.85V using the constant current of 0.2C；
In step 9, under the constant pressure of 3.85V, it is 0.02C that lithium ion battery, which is charged 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 |
| KR102279000B1 (en) * | 2018-02-23 | 2021-07-20 | 주식회사 엘지에너지솔루션 | Capacity recovering method for secondary battery and capacity recovering device for secondary battery |
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| CN101079509A (en) * | 2006-05-22 | 2007-11-28 | 比亚迪股份有限公司 | A making method for lithium ion secondary cell |
| CN101267055A (en) * | 2008-04-14 | 2008-09-17 | 东莞市迈科新能源有限公司 | A compound method for lithium ion battery |
| CN102185166A (en) * | 2011-04-06 | 2011-09-14 | 恒正科技（苏州）有限公司 | Battery forming and repairing method |
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