CN113725487A - Storage method of lithium ion battery - Google Patents
Storage method of lithium ion battery Download PDFInfo
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- CN113725487A CN113725487A CN202111018211.4A CN202111018211A CN113725487A CN 113725487 A CN113725487 A CN 113725487A CN 202111018211 A CN202111018211 A CN 202111018211A CN 113725487 A CN113725487 A CN 113725487A
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- voltage
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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
- H01M10/052—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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
-
- 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
Abstract
The invention provides a storage method of a lithium ion battery, wherein a positive active substance of the lithium ion battery is a lithium transition metal oxide, and a negative active substance of the lithium ion battery is a graphite material; the electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the storage method comprises the steps of carrying out constant-current charging and discharging for a plurality of times between a charging cut-off voltage and a discharging cut-off voltage, then carrying out constant-current discharging on a battery until the battery reaches the discharging cut-off voltage, then carrying out constant-current charging until the battery reaches a preset voltage, and then carrying out constant-voltage charging at the preset voltage until the charging current is lower than the charging cut-off current, wherein the preset voltage is the discharging cut-off voltage + a and the volume concentration-b of methylethenesulfonate ester is the volume concentration-b of gamma-valerolactone; wherein a and b are adjustment coefficients; then adjusting the battery to be stored in an environment of 0-15 ℃; the battery obtained by the storage method provided by the invention can obtain higher storage capacity retention rate, has low self-discharge, and has good cycle retention rate after storage.
Description
Technical Field
The invention relates to a storage method of a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, stable working voltage, environmental protection, no memory effect and the like, and the lithium ion battery added with the methyl ethylene sulfonate and the gamma-valerolactone has excellent high-rate charge-discharge performance; however, the inventor finds that the storage life of the battery is poor, the capacity retention rate of the battery is low, which is generally more than half a year of storage, and the battery capacity fading is obvious, and for the phenomenon, the inventor conducts a series of experiments and researches on the storage process of the battery, and finds that the methylethenesulfonate and the gamma-valerolactone can keep a stable state under a specific voltage, and the voltage is related to the concentration of the methylethenesulfonate and the gamma-valerolactone in the electrolyte. Based on the above findings, the inventors propose the following method.
Disclosure of Invention
The invention provides a storage method of a lithium ion battery, wherein a positive active substance of the lithium ion battery is a lithium transition metal oxide, and a negative active substance of the lithium ion battery is a graphite material; the electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the storage method comprises the steps of carrying out constant-current charging and discharging for a plurality of times between a charging cut-off voltage and a discharging cut-off voltage, then carrying out constant-current discharging on a battery until the battery reaches the discharging cut-off voltage, then carrying out constant-current charging until the battery reaches a preset voltage, and then carrying out constant-voltage charging at the preset voltage until the charging current is lower than the charging cut-off current, wherein the preset voltage is the discharging cut-off voltage + a and the volume concentration-b of methylethenesulfonate ester is the volume concentration-b of gamma-valerolactone; wherein a and b are adjustment coefficients; then adjusting the battery to be stored in an environment of 0-15 ℃; the battery obtained by the storage method provided by the invention can obtain higher storage capacity retention rate, has low self-discharge, and has good cycle retention rate after storage.
The specific scheme is as follows:
a storage method of a lithium ion battery is characterized in that a positive active material of the lithium ion battery is a lithium transition metal oxide, and a negative active material of the lithium ion battery is a graphite material; the lithium ion battery electrolyte is characterized by comprising methyl ethylene sulfonate and gamma-valerolactone; the storage method comprises the following steps:
1) charging and discharging for several times at constant current between the charge cut-off voltage and the discharge cut-off voltage;
2) discharging the battery to a discharge cut-off voltage at a constant current;
3) charging at constant current to a predetermined voltage, which is a discharge cut-off voltage + a volume concentration of methylvinylsulfonate-b volume concentration of γ -valerolactone; wherein a and b are adjustment coefficients;
4) charging at a constant voltage with a predetermined voltage until the charging current is lower than the charge cutoff current;
5) and adjusting the battery to be stored in the environment of 0-15 ℃.
Further, the concentration of the methylvinylsulfonate is 3.2 to 3.8 volume percent.
Further, the concentration of the gamma-butyrolactone is 2.5 to 3.0 vol%.
Further wherein the predetermined voltage is a discharge cutoff voltage + a volume concentration of methylvinylsulfonate-b volume concentration of γ -valerolactone; wherein a is 28.5 and b is 12.6.
Further, the lithium transition metal oxide is selected from the group consisting of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, and mixtures thereof.
Further, the charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.7V.
Further, the organic solvent of the electrolyte is a mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate mixed in a volume ratio of 2:1.5: 1.
The invention has the following beneficial effects:
1) the combination of the methyl vinyl sulfonate and the gamma-valerolactone can effectively reduce the internal resistance of the battery and improve the capacity retention performance of the battery in high-rate charge and discharge.
2) The inventors have found that when the storage voltage satisfies the discharge cut-off voltage + a volume concentration of methylvinylsulphonate-b volume concentration of γ -valerolactone, the cell can achieve extremely stable storage performance at that voltage, and the principle is not clear, and it is preliminarily presumed that both additives can maintain a stable state at that voltage, and thus maintain stable chemical properties at the electrode surface.
3) And the inventors have further found that low temperature storage below room temperature is more advantageous for long term storage of the battery.
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 examples. The positive electrode active material is lithium cobaltate. The negative electrode is natural graphite, and the electrolyte salt in the electrolyte is LiPF6The concentration is 1.0mol/L, the organic solvent is ethylene carbonate, and the methyl ethyl carbonate and the dimethyl carbonate are mixed in a volume ratio of 2:1.5: 1.
Example 1
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.2 vol%, and the concentration of the γ -butyrolactone was 2.5 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 2.75+28.5 0.032-12.6 0.025 equal to 3.35V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in the environment of 0 ℃.
Example 2
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.8 vol%, and the concentration of the γ -butyrolactone was 3.0 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 2.75+28.5 0.038-12.6 0.03-3.46V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 15 ℃.
Example 3
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.5 vol%, and the concentration of the γ -butyrolactone was 2.8 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 2.75+28.5 × 0.035-12.6 × 0.028 ═ 3.39V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 5 ℃.
Comparative example 1
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.5 vol%, and the concentration of the γ -butyrolactone was 2.8 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 3.35V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 5 ℃.
Comparative example 2
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.5 vol%, and the concentration of the γ -butyrolactone was 2.8 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 3.45V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 5 ℃.
Comparative example 3
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.8 vol%, and the concentration of the γ -butyrolactone was 3.0 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 3.39V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 15 ℃.
Comparative example 4
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.2 vol%, and the concentration of the γ -butyrolactone was 2.5 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 3.39V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in the environment of 0 ℃.
Comparative example 5
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 3.0 vol%, and the concentration of the γ -butyrolactone was 3.0 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 3.39V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 5 ℃.
Comparative example 6
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 4.0 vol%, and the concentration of the γ -butyrolactone was 2.5 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 3.39V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 5 ℃.
Comparative example 7
The electrolyte of the lithium ion battery comprises methyl ethylene sulfonate and gamma-valerolactone; the concentration of the methylvinylsulfonate was 2.5 vol%, and the concentration of the γ -butyrolactone was 3.0 vol%.
The storage method comprises the following steps:
1) charging and discharging 3 times at constant current of 0.2C between the charge cut-off voltage of 4.25V and the discharge cut-off voltage of 2.75V;
2) discharging the battery at 0.2C with constant current till the discharge cut-off voltage is 2.75V;
3) charging to a predetermined voltage at a constant current of 0.1C; the predetermined voltage is 3.39V;
4) charging at a predetermined voltage at a constant voltage until the charging current is lower than the charge cutoff current by 0.01C;
5) and adjusting the battery to be stored in an environment of 5 ℃.
Test and results
The batteries of examples 1 to 3 and comparative examples 1 to 7 were tested and stored for 180 days, the open circuit voltage of the battery was measured, then the storage capacity retention ratio was calculated using the open circuit voltage/predetermined voltage, and then charge and discharge cycles were performed 200 times at a voltage interval of 2.75 to 4.25V at a current of 1C, and the cycle capacity retention ratio of the battery was measured, and the results are shown in table 1.
TABLE 1
| Storage capacity retention (%) | Retention ratio of circulating Capacity (%) | |
| Example 1 | 96.4 | 98.3 |
| Example 2 | 95.9 | 98.1 |
| Example 3 | 96.2 | 98.5 |
| Comparative example 1 | 89.2 | 94.2 |
| Comparative example 2 | 85.6 | 95.1 |
| Comparative example 3 | 88.7 | 93.8 |
| Comparative example 4 | 84.8 | 94.6 |
| Comparative example 5 | 87.9 | 95.2 |
| Comparative example 6 | 86.8 | 94.5 |
| Comparative example 7 | 86.4 | 94.2 |
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 (7)
1. A storage method of a lithium ion battery is characterized in that a positive active material of the lithium ion battery is a lithium transition metal oxide, and a negative active material of the lithium ion battery is a graphite material; the lithium ion battery electrolyte is characterized by comprising methyl ethylene sulfonate and gamma-valerolactone; the storage method comprises the following steps:
1) charging and discharging for several times at constant current between the charge cut-off voltage and the discharge cut-off voltage;
2) discharging the battery to a discharge cut-off voltage at a constant current;
3) charging at constant current to a predetermined voltage, which is a discharge cut-off voltage + a volume concentration of methylvinylsulfonate-b volume concentration of γ -valerolactone; wherein a and b are adjustment coefficients;
4) charging at a constant voltage with a predetermined voltage until the charging current is lower than the charge cutoff current;
5) and adjusting the battery to be stored in the environment of 0-15 ℃.
2. The process as claimed in the preceding claim, wherein the concentration of methyl vinyl sulfonate is 3.2 to 3.8% by volume.
3. The process according to the preceding claim, wherein the concentration of gamma-butyrolactone is between 2.5 and 3.0% by volume.
4. The method according to the preceding claim, wherein the predetermined voltage + a discharge cut-off voltage + a volume concentration of methylvinylsulfonate-b volume concentration of γ -valerolactone; wherein a is 28.5 and b is 12.6.
5. The method of the preceding claim, wherein the lithium transition metal oxide is selected from the group consisting of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, and mixtures thereof.
6. The method of the preceding claim, wherein the charge cutoff voltage is 4.2V and the discharge cutoff voltage is 2.7V.
7. The method of the preceding claim, wherein the organic solvent of the electrolyte is a mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate mixed in a volume ratio of 2:1.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111018211.4A CN113725487A (en) | 2021-09-01 | 2021-09-01 | Storage method of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111018211.4A CN113725487A (en) | 2021-09-01 | 2021-09-01 | Storage method of lithium ion battery |
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| Publication Number | Publication Date |
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| CN113725487A true CN113725487A (en) | 2021-11-30 |
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| CN202111018211.4A Withdrawn CN113725487A (en) | 2021-09-01 | 2021-09-01 | Storage method of lithium ion battery |
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2021
- 2021-09-01 CN CN202111018211.4A patent/CN113725487A/en not_active Withdrawn
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