CN111430786A - Pre-activation method of lithium ion battery before use - Google Patents
Pre-activation method of lithium ion battery before use Download PDFInfo
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- CN111430786A CN111430786A CN202010411610.6A CN202010411610A CN111430786A CN 111430786 A CN111430786 A CN 111430786A CN 202010411610 A CN202010411610 A CN 202010411610A CN 111430786 A CN111430786 A CN 111430786A
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- China
- Prior art keywords
- battery
- voltage
- temperature
- lithium ion
- before use
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- 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
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007599 discharging Methods 0.000 claims abstract description 21
- 230000004913 activation Effects 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- LFJJGHGXHXXDFT-UHFFFAOYSA-N 3-bromooxolan-2-one Chemical compound BrC1CCOC1=O LFJJGHGXHXXDFT-UHFFFAOYSA-N 0.000 claims abstract description 10
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007600 charging Methods 0.000 claims description 26
- 238000001994 activation Methods 0.000 claims description 18
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000010277 constant-current charging Methods 0.000 abstract description 12
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002904 solvent 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- 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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- 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)
Abstract
The invention provides a preactivation method before using a lithium ion battery, in particular to a preactivation method before using the lithium ion battery after long-term storage, wherein bromobutyrolactone and diethylsulfite in electrolyte of the lithium ion battery are used as additives; the pre-activation method of the lithium ion battery before use comprises the steps of adjusting the temperature of the battery to be more than 75 ℃, conducting small-current constant-current charging and discharging circulation for a plurality of times near a first preset voltage, then adjusting the temperature of the battery to be less than 10 ℃, conducting constant-current charging and discharging for the battery to a second preset voltage, conducting constant-current charging and discharging for a plurality of times between the first preset voltage and the second preset voltage, and conducting constant-current charging and discharging for a plurality of times between a charge cut-off voltage and a discharge cut-off voltage.
Description
Technical Field
The invention relates to a preactivation method of a lithium ion battery before use.
Background
The lithium iron phosphate is taken as a battery material with high safety, low cost and environmental protection, is one of the mainstream materials of the anode material of the lithium ion battery at present, and when the electrolyte of the lithium iron phosphate battery contains 1.2-1.4 volume percent of bromobutyrolactone and 1.8-2.2 volume percent of diethyl sulfite as additives, the safety and the cycle life of the battery can be effectively improved.
Disclosure of Invention
The invention provides a preactivation method before using of a lithium ion battery, in particular to a preactivation method before using of a lithium ion battery after long-term storage, wherein an electrolyte of the lithium ion battery at least contains 1.2-1.4 volume percent of bromobutyrolactone and 1.8-2.2 volume percent of diethyl sulfite as additives; the pre-activation method of the lithium ion battery before use comprises the steps of adjusting the temperature of the battery to be more than 75 ℃, then adjusting the voltage of the battery to be a first preset voltage, wherein the first preset voltage is 2.94-2.96V, carrying out small-current constant-current charging and discharging circulation for a plurality of times near the first preset voltage, then adjusting the temperature of the battery to be below 10 ℃, carrying out constant-current charging on the battery to be a second preset voltage, then carrying out constant-voltage charging on the battery by using the second preset voltage, wherein the second preset voltage is 3.95-4.05V, carrying out constant-current charging and discharging for a plurality of times between the first preset voltage and the second preset voltage, carrying out constant-current charging and discharging for a plurality of times between a charging cut-off voltage and a discharging cut-off voltage, and then adjusting the temperature of the. The pre-activation method provided by the invention has an excellent activation effect on a battery containing bromobutyrolactone and diethylsulfite as additives in an electrolyte before use, but the effective capacity of the battery is kept above 95%.
The specific scheme is as follows:
a pre-activation method before using a lithium ion battery, wherein the electrolyte of the lithium ion battery at least contains 1.2-1.4 volume percent of bromobutyrolactone and 1.8-2.2 volume percent of diethyl sulfite as additives; the pre-activation method of the lithium ion battery before use comprises the following steps:
1) adjusting the temperature of the battery to be over 75 ℃;
2) then adjusting the battery voltage to a first predetermined voltage, wherein the first predetermined voltage is 2.94-2.96V;
3) carrying out small-current constant-current charge-discharge circulation for a plurality of times near a first preset voltage;
4) adjusting the temperature of the battery to be below 10 ℃;
5) charging the battery at a constant current to a second preset voltage, and then charging the battery at a constant voltage of the second preset voltage, wherein the second preset voltage is 3.95-4.05V;
6) charging and discharging at constant current for several times between the first predetermined voltage and the second predetermined voltage
7) Charging and discharging for several times at constant current between the charge cut-off voltage and the discharge cut-off voltage;
8) the battery temperature was adjusted to room temperature.
Further, the step 1 is preceded by storing the battery for more than 30 days.
Further, in the step 1, the temperature is adjusted to 75-80 ℃.
In step 3, the vicinity of the first predetermined voltage is within a range of plus or minus 0.03V of the first voltage, and the small current is 0.02C or less.
Further, in the step 4, the temperature is adjusted to 5-10 ℃.
Further, the positive active material of the lithium ion battery is lithium iron phosphate or modified lithium iron phosphate.
Further, the charge cut-off voltage is 2.7V, and the discharge cut-off voltage is 4.2V.
Further, the electrolytic solution includes a nonaqueous solvent composed of a chain carbonate and a cyclic carbonate.
The invention has the following beneficial effects:
1) the inventors have found that lithium ion batteries using bromobutyrolactone and diethylsulfite as additives in the electrolyte undergo significant capacity fade after long term storage, probably because the heat generation on the battery surface is significant when such batteries are used after long term storage, and probably because of the excessive internal resistance of the battery due to the deposition of electrolyte salts inside the battery during storage, thereby resulting in the capacity fade of the battery.
2) The inventors found that charging and discharging of such a battery at a low current at a high temperature and in the vicinity of a predetermined voltage of 2.94-2.96V could eliminate the internal resistance, presumably due to the fact that cycling at a specific voltage at a high temperature could re-dissolve the salt deposited in the electrolyte inside the battery.
3) And before use, the small-range charge-discharge cycle is carried out at low temperature, so that the effective capacity in the battery can be activated;
4) compared with the battery directly used after storage, the effective capacity of the battery obtained by the activation method is improved by more than 10%.
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples0.95Mn0.05PO4The negative electrode active material is a mixture of natural graphite and artificial graphite in a ratio of 1:1, the electrolyte comprises a mixed organic solvent of EC, DEC and DMC in a volume ratio of 2:1:1, electrolyte salt is 1 mol/L lithium hexafluorophosphate, additives are 1.3 volume percent of bromobutyrolactone and 2.0 volume percent of diethyl sulfite, and the lithium ion battery is stored for 150 days at normal temperature.
Example 1
1) Adjusting the temperature of the battery to 75 ℃;
2) then adjusting the voltage of the battery to 2.94V;
3) performing constant current charge-discharge cycle at 0.02C in the range of 2.91-2.97V for 10 times;
4) adjusting the temperature of the battery to 5 ℃;
5) charging to 3.95V at a constant current of 0.1C, and then charging at a constant voltage until the charging current is lower than 0.01C;
6) charging and discharging 3 times at 0.1C constant current between 2.94V and 3.95V
7) Constant current charging and discharging for 3 times between 4.2V and 2.7V;
8) the battery temperature was adjusted to room temperature.
Example 2
1) Adjusting the temperature of the battery to 80 ℃;
2) then adjusting the voltage of the battery to 2.96V;
3) performing constant current charge and discharge cycle at 0.02C in the range of 2.94-2.98V for 10 times;
4) adjusting the temperature of the battery to 10 ℃;
5) charging to 4.05V at a constant current of 0.1C, and then charging at a constant voltage until the charging current is lower than 0.01C;
6) charging and discharging 3 times at 0.1C constant current between 2.96V and 4.05V
7) Constant current charging and discharging for 3 times between 4.2V and 2.7V;
8) the battery temperature was adjusted to room temperature.
Example 3
1) Adjusting the temperature of the battery to 75 ℃;
2) then adjusting the voltage of the battery to 2.95V;
3) performing constant current charge-discharge cycle at 0.02C in the range of 2.93-2.97V for 10 times;
4) adjusting the temperature of the battery to 8 ℃;
5) charging to 4.00V at a constant current of 0.1C, and then charging at a constant voltage until the charging current is lower than 0.01C;
6) charging and discharging 3 times at 0.1C constant current between 2.95V and 4.00V
7) Constant current charging and discharging for 3 times between 4.2V and 2.7V;
8) the battery temperature was adjusted to room temperature.
Comparative example 1
1) Adjusting the temperature of the battery to 8 ℃;
2) charging to 4.00V at a constant current of 0.1C, and then charging at a constant voltage until the charging current is lower than 0.01C;
3) charging and discharging 3 times at 0.1C constant current between 2.95V and 4.00V
4) Constant current charging and discharging for 3 times between 4.2V and 2.7V;
5) the battery temperature was adjusted to room temperature.
Comparative example 2
1) Adjusting the temperature of the battery to 75 ℃;
2) then adjusting the voltage of the battery to 2.95V;
3) performing constant current charge-discharge cycle at 0.02C in the range of 2.93-2.97V for 10 times;
4) the battery temperature was adjusted to room temperature.
Comparative example 3
No activation process was performed.
Comparative example 4
The additive was 1.3 vol% bromobutyrolactone and no activation was performed.
Comparative example 5
The additive was 2.0 vol% diethyl sulfite and no activation was performed.
Test and results
The batteries of examples 1 to 3 and comparative examples 1 to 5 were tested, and the battery capacity was measured before storage and then again after storage, and the results are shown in table 1. As can be seen from Table 1, when the additive contains both bromobutyrolactone and diethylsulfite, the storage capacity of the battery is obviously reduced, and the capacity of the battery is basically improved by more than 10% after the activation by the method of the invention.
TABLE 1
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (8)
1. A pre-activation method before using a lithium ion battery, wherein the electrolyte of the lithium ion battery at least contains 1.2-1.4 volume percent of bromobutyrolactone and 1.8-2.2 volume percent of diethyl sulfite as additives; the pre-activation method of the lithium ion battery before use comprises the following steps:
1) adjusting the temperature of the battery to be over 75 ℃;
2) then adjusting the battery voltage to a first predetermined voltage, wherein the first predetermined voltage is 2.94-2.96V;
3) carrying out small-current constant-current charge-discharge circulation for a plurality of times near a first preset voltage;
4) adjusting the temperature of the battery to be below 10 ℃;
5) charging the battery at a constant current to a second preset voltage, and then charging the battery at a constant voltage of the second preset voltage, wherein the second preset voltage is 3.95-4.05V;
6) charging and discharging at constant current for several times between the first predetermined voltage and the second predetermined voltage
7) Charging and discharging for several times at constant current between the charge cut-off voltage and the discharge cut-off voltage;
8) the battery temperature was adjusted to room temperature.
2. The method of preactivation before use according to the previous claim, said step 1 further comprising storing the battery for more than 30 days before heating.
3. The pre-activation process before use according to the preceding claim, wherein in step 1 the temperature is adjusted to 75-80 ℃.
4. The pre-activation method before use according to the previous claims, wherein in the step 3, the vicinity of the first predetermined voltage is within a range of plus or minus 0.03V of the first voltage, and the small current is 0.02C or less.
5. The pre-activation method before use as claimed in the preceding claim, wherein in step 4, the temperature is adjusted to 5-10 ℃.
6. The pre-activation method before use according to the above claim, wherein the positive electrode active material of the lithium ion battery is lithium iron phosphate or modified lithium iron phosphate.
7. The preactivation method according to the preceding claim, wherein said charge cut-off voltage is 2.7V and said discharge cut-off voltage is 4.2V.
8. The pre-activation method before use according to the above claim, wherein the electrolyte comprises a non-aqueous solvent, and the non-aqueous solvent is composed of a chain carbonate and a cyclic carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010411610.6A CN111430786A (en) | 2020-05-15 | 2020-05-15 | Pre-activation method of lithium ion battery before use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010411610.6A CN111430786A (en) | 2020-05-15 | 2020-05-15 | Pre-activation method of lithium ion battery before use |
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| Publication Number | Publication Date |
|---|---|
| CN111430786A true CN111430786A (en) | 2020-07-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010411610.6A Withdrawn CN111430786A (en) | 2020-05-15 | 2020-05-15 | Pre-activation method of lithium ion battery before use |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112117506A (en) * | 2020-10-22 | 2020-12-22 | 江苏卫健信息科技有限公司 | Storage method of power lithium ion battery |
| CN114824522A (en) * | 2021-01-28 | 2022-07-29 | 安徽盟维新能源科技有限公司 | Lithium metal battery charging and discharging method |
-
2020
- 2020-05-15 CN CN202010411610.6A patent/CN111430786A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112117506A (en) * | 2020-10-22 | 2020-12-22 | 江苏卫健信息科技有限公司 | Storage method of power lithium ion battery |
| CN114824522A (en) * | 2021-01-28 | 2022-07-29 | 安徽盟维新能源科技有限公司 | Lithium metal battery charging and discharging method |
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Application publication date: 20200717 |