CN111162337A - Formation method of power lithium ion battery for high-temperature environment - Google Patents

Formation method of power lithium ion battery for high-temperature environment Download PDF

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Publication number
CN111162337A
CN111162337A CN202010112773.4A CN202010112773A CN111162337A CN 111162337 A CN111162337 A CN 111162337A CN 202010112773 A CN202010112773 A CN 202010112773A CN 111162337 A CN111162337 A CN 111162337A
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voltage
charging
carbonate
ion battery
lithium ion
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朱虎
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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
    • H01M10/42—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
    • 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
    • H01M10/05—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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a formation method of a power lithium ion battery used in a high-temperature environment, wherein a positive active substance of the lithium ion battery is manganese-based transition metal lithium oxide, an electrolyte comprises an organic solvent and an additive, and the solvent consists of ethylene carbonate and propylene carbonate; the additive comprises 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate, wherein the volume ratio of the 1, 3-propylene sultone to the vinylene carbonate to the vinyl sulfate is 1-1.5:0.6-0.8: 1.8-2.0. The formation method includes performing pre-charging in a voltage range not higher than a first predetermined voltage, and performing pulse charging in a voltage range not lower than a second predetermined voltage. The cycle life of the lithium ion battery obtained by the method under the high-temperature environment is greatly prolonged.

Description

Formation method of power lithium ion battery for high-temperature environment
Technical Field
The invention relates to a formation method of a power lithium ion battery used in a high-temperature environment.
Background
Because of high output, the operational environment of heavy current, battery temperature is generally higher at the during operation of power lithium ion battery, and high temperature environment can seriously influence power lithium ion battery's cycle life, generally set up cooling system to power lithium ion battery group among the prior art, thereby reduce the operating temperature of group battery, but cooling system has increased the manufacturing cost of group battery, the maintenance cost, and the weight and the volume of group battery, and cooling system is difficult to the inside temperature of cooling battery core, consequently, the effect help to the operational life of battery is not big.
Disclosure of Invention
The invention provides a formation method of a power lithium ion battery used in a high-temperature environment, wherein a positive active substance of the lithium ion battery is manganese-based transition metal lithium oxide, an electrolyte comprises an organic solvent and an additive, and the solvent consists of ethylene carbonate and propylene carbonate; the additive comprises 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate, wherein the volume ratio of the 1, 3-propylene sultone to the vinylene carbonate to the vinyl sulfate is 1-1.5:0.6-0.8: 1.8-2.0. The formation method includes performing pre-charging in a voltage range not higher than a first predetermined voltage, and performing pulse charging in a voltage range not lower than a second predetermined voltage. The cycle life of the lithium ion battery obtained by the method under the high-temperature environment is greatly prolonged.
The specific scheme is as follows:
a chemical synthesis method of a power lithium ion battery used in a high-temperature environment is provided, wherein a positive active material of the lithium ion battery is manganese-based transition metal lithium oxide, the electrolyte comprises an organic solvent and an additive, and the solvent consists of ethylene carbonate and propylene carbonate; the additive comprises 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate, wherein the volume ratio of the 1, 3-propylene sultone to the vinylene carbonate to the vinyl sulfate is 1-1.5:0.6-0.8: 1.8-2.0. The formation method includes performing pre-charging in a voltage range not higher than a first predetermined voltage, and performing pulse charging in a voltage range not lower than a second predetermined voltage.
Further, the formation method comprises the following steps:
1) charging to a first preset voltage at a constant current of 0.02-0.05C, wherein the first preset voltage is 3.35-3.40V;
2) performing constant-current charge-discharge cycle between a first preset voltage and a discharge cut-off voltage for a plurality of times;
3) charging at a first preset voltage and constant voltage until the charging current is lower than 0.01C;
4) charging to a second predetermined voltage with a constant current of 0.02-0.05C, wherein the second predetermined voltage is 4.05-4.10V
5) Charging at a second predetermined voltage until the charging current is lower than 0.01C;
6) charging at constant current to a charge cut-off voltage;
7) discharging at constant current to a second preset voltage, and standing;
8) performing constant-current charge-discharge cycle between the charge cut-off voltage and the discharge cut-off voltage for several times;
9) vacuumizing and sealing.
Further, wherein the lithium manganese-based transition metal oxide is LiMnxM1-xO2Wherein x is more than or equal to 0.7 and less than or equal to 0.9, and M is selected from Co, Ni, Mg and Al.
Further, wherein LiMnxM1-xO2Is LiMn0.8Co0.1Ni0.1O2。
Furthermore, the volume ratio of the ethylene carbonate to the propylene carbonate in the solvent is 2:1-1: 2.
Further, the volume ratio of the 1, 3-propylene sultone to the vinylene carbonate to the vinyl sulfate is 1.2:0.7: 1.9.
Further, the discharge cutoff voltage is 2.75V, and the charge cutoff voltage is 4.25V.
The invention has the following beneficial effects:
1) the manganese-based material selected as the positive active material has good temperature resistance and high safety performance.
2) The inventor finds that the three specific additives are combined in a specific proportion to improve the cycle performance of the manganese-based material through long-term research, the specific mechanism is not clear, and the primary speculation is probably that the three additives can form a stable dielectric layer on the surface of the manganese-based material to improve the high-temperature stability of the electrode material.
3) The inventors have found through studies that the solubility of the three additives in the cyclic carbonate solvent is higher than that of other organic solvents, the life of the battery can be improved, and the high-temperature stability of the cyclic carbonate is higher.
4) And a specific formation mode is set for the electrode material and the electrolyte composition, and the pre-formation under the first preset voltage and the pulse formation under the second preset voltage are beneficial to further improving the high-temperature cycle life 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 active material of the positive electrode is LiMn0.8Co0.1Ni0.1O2. The active material of the negative electrode is a natural graphite and artificial graphite negative electrode with the mass ratio of 1: 1.
Example 1
The electrolyte is 1M lithium hexafluorophosphate, and the solvent consists of ethylene carbonate and propylene carbonate in a volume ratio of 2: 1; the volume percentage of 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate in the additive are respectively 1%, 0.6% and 1.8%.
1) Charging to a first preset voltage by a constant current of 0.02C, wherein the first preset voltage is 3.35V;
2) performing constant-current charge and discharge circulation for 4 times at 0.05 ℃ between a first preset voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 2.75V;
3) charging at a first preset voltage and constant voltage until the charging current is lower than 0.01C;
4) charging to a second predetermined voltage with a constant current of 0.02C, wherein the second predetermined voltage is 4.05V
5) Charging at a second predetermined voltage until the charging current is lower than 0.01C;
6) charging at a constant current of 0.1C to a charge cut-off voltage, wherein the charge cut-off voltage is 4.25V;
7) discharging at constant current of 0.1 ℃ to a second preset voltage, and standing for 2 h;
8) performing constant current charge and discharge circulation at 0.1 deg.C between the charge cut-off voltage and the discharge cut-off voltage for 4 times;
9) vacuumizing and sealing.
Example 2
The electrolyte is 1M lithium hexafluorophosphate, and the solvent consists of ethylene carbonate and propylene carbonate in the volume ratio of 1: 2; the volume percentage of 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate in the additive are respectively 1.5%, 0.8% and 2.0%.
1) Charging to a first preset voltage by a constant current of 0.05C, wherein the first preset voltage is 3.40V;
2) performing constant-current charge and discharge circulation for 4 times at 0.05 ℃ between a first preset voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 2.75V;
3) charging at a first preset voltage and constant voltage until the charging current is lower than 0.01C;
4) charging to a second predetermined voltage with a constant current of 0.05C, wherein the second predetermined voltage is 4.10V
5) Charging at a second predetermined voltage until the charging current is lower than 0.01C;
6) charging the battery at a constant current of 0.1 ℃ to a charge cut-off voltage, wherein the charge cut-off voltage is 4.25V;
7) discharging at constant current of 0.1 ℃ to a second preset voltage, and standing for 2 h;
8) performing constant current charge and discharge circulation at 0.1 deg.C between the charge cut-off voltage and the discharge cut-off voltage for 4 times;
9) vacuumizing and sealing.
Example 3
The electrolyte is 1M lithium hexafluorophosphate, and the solvent consists of ethylene carbonate and propylene carbonate in the volume ratio of 1: 1; the volume percentage of 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate in the additive are respectively 1.2%, 0.7% and 1.9%.
1) Charging to a first preset voltage by a constant current of 0.03C, wherein the first preset voltage is 3.40V;
2) performing constant-current charge and discharge circulation for 4 times at 0.05 ℃ between a first preset voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 2.75V;
3) charging at a first preset voltage and constant voltage until the charging current is lower than 0.01C;
4) charging to a second predetermined voltage with a constant current of 0.03C, wherein the second predetermined voltage is 4.10V
5) Charging at a second predetermined voltage until the charging current is lower than 0.01C;
6) charging the battery at a constant current of 0.1 ℃ to a charge cut-off voltage, wherein the charge cut-off voltage is 4.25V;
7) discharging at constant current of 0.1 ℃ to a second preset voltage, and standing for 2 h;
8) performing constant current charge and discharge circulation at 0.1 deg.C between the charge cut-off voltage and the discharge cut-off voltage for 4 times;
9) vacuumizing and sealing.
Comparative example 1
The electrolyte is 1M lithium hexafluorophosphate, and the solvent consists of ethylene carbonate and propylene carbonate in the volume ratio of 1: 1; the volume percentage of 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate in the additive are respectively 1.2%, 0.7% and 1.9%.
1) Performing constant-current charge and discharge circulation for 4 times at 0.1 ℃ between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 2.75V, and the charge cut-off voltage is 4.25V;
2) vacuumizing and sealing.
Comparative example 2
The additive contained only 1, 3-propylene sultone, and other parameters were the same as in example 3.
Comparative example 3
The additive contained vinylene carbonate only, and other parameters were the same as in example 3.
Comparative example 4
The additive contained only vinyl sulfate, and the other parameters were the same as in example 3.
Comparative example 5
The additive only contains vinylene carbonate and vinyl sulfate, and other parameters are the same as those of the example 3.
Comparative example 6
1, 3-propylene sultone and vinyl sulfate in the additive, and other parameters are the same as those in example 3.
Comparative example 7
The additive only contains vinylene carbonate and vinyl sulfate, and other parameters are the same as those of the example 3.
Experiment and data
The batteries obtained by the chemical synthesis methods of examples 1 to 3 and comparative examples 1 to 7 were subjected to charge-discharge cycles 200 times at a rate of 1C at 50 degrees celsius, respectively, and the capacity retention rates of the batteries of the respective groups were measured, and the results are shown in the following table. The formation step has a good promotion effect on the cycle life, in the combination of the additives, the combination effect of the three additives is higher than that of a single additive and higher than that of the two additives, and when the two additives are mixed, the effect is even lower than that of certain single additives.
TABLE 1
Figure BDA0002390591380000051
Figure BDA0002390591380000061
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 chemical synthesis method of a power lithium ion battery used in a high-temperature environment is provided, wherein a positive active material of the lithium ion battery is manganese-based transition metal lithium oxide, the electrolyte comprises an organic solvent and an additive, and the solvent consists of ethylene carbonate and propylene carbonate; the additive comprises 1, 3-propylene sultone, vinylene carbonate and vinyl sulfate, wherein the volume ratio of the 1, 3-propylene sultone, the vinylene carbonate and the vinyl sulfate is 1-1.5:0.6-0.8:1.8-2.0, and the formation method comprises the steps of pre-charging in a voltage range not higher than a first preset voltage and pulse charging in a voltage range not lower than a second preset voltage.
2. The chemical synthesis method according to claim 1, comprising:
1) charging to a first preset voltage at a constant current of 0.02-0.05C, wherein the first preset voltage is 3.35-3.40V;
2) performing constant-current charge-discharge cycle between a first preset voltage and a discharge cut-off voltage for a plurality of times;
3) charging at a first preset voltage and constant voltage until the charging current is lower than 0.01C;
4) charging to a second predetermined voltage with a constant current of 0.02-0.05C, wherein the second predetermined voltage is 4.05-4.10V
5) Charging at a second predetermined voltage until the charging current is lower than 0.01C;
6) charging at constant current to a charge cut-off voltage;
7) discharging at constant current to a second preset voltage, and standing;
8) performing constant-current charge-discharge cycle between the charge cut-off voltage and the discharge cut-off voltage for several times;
9) vacuumizing and sealing.
3. The formation method according to claims 1-2, wherein the lithium manganese-based transition metal oxide is LiMnxM1-xO2Wherein x is more than or equal to 0.7 and less than or equal to 0.9, and M is selected from Co, Ni, Mg and Al.
4. The chemical conversion method according to claim 3, wherein LiMnxM1-xO2Is LiMn0.8Co0.1Ni0.1O2。
5. The process of claims 2-4, wherein the volume ratio of ethylene carbonate to propylene carbonate in the solvent is from 2:1 to 1: 2.
6. The process of the preceding claim, wherein the volume ratio of 1, 3-propene sultone, vinylene carbonate and vinyl sulfate is 1.2:0.7: 1.9.
7. The method of the preceding claim, wherein the discharge cutoff voltage is 2.75V and the charge cutoff voltage is 4.25V.
CN202010112773.4A 2020-02-24 2020-02-24 Formation method of power lithium ion battery for high-temperature environment Withdrawn CN111162337A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112151871A (en) * 2020-09-28 2020-12-29 苏州酷卡环保科技有限公司 Formation method of high-temperature lithium ion battery
CN112164786A (en) * 2020-09-14 2021-01-01 苏州极闪控电信息技术有限公司 Preparation method of lithium vanadium phosphate lithium ion battery
CN112201854A (en) * 2020-11-11 2021-01-08 江苏卫健信息科技有限公司 Formation method of power lithium ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112164786A (en) * 2020-09-14 2021-01-01 苏州极闪控电信息技术有限公司 Preparation method of lithium vanadium phosphate lithium ion battery
CN112151871A (en) * 2020-09-28 2020-12-29 苏州酷卡环保科技有限公司 Formation method of high-temperature lithium ion battery
CN112201854A (en) * 2020-11-11 2021-01-08 江苏卫健信息科技有限公司 Formation method of power lithium ion battery

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