CN112382833A - Liquid injection formation method of lithium ion battery - Google Patents
Liquid injection formation method of lithium ion battery Download PDFInfo
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0569—Liquid materials characterised by the solvents
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Abstract
The invention provides a liquid injection and formation method of a lithium ion battery, which comprises the steps of injecting a first electrolyte, wherein an organic solvent of the first electrolyte is only cyclic carbonate, then injecting a second electrolyte with the volume of the rest total electrolyte, and performing formation to obtain the lithium ion battery. The method comprises the steps of performing pre-formation in electrolyte containing additive methyl vinyl sulfone and 1, 3-propane sultone, improving the affinity of an electrode to tetrafluoroethylene carbonate by utilizing an SEI film formed by methyl vinyl sulfone and 1, 3-propane sultone in advance, and performing formation in the electrolyte containing the tetrafluoroethylene carbonate to improve the film forming effect of the tetrafluoroethylene carbonate, so that the high-temperature stability of the lithium ion battery is improved.
Description
Technical Field
The invention relates to a liquid injection and formation method of a lithium ion battery.
Background
The lithium ion battery has the following characteristics: high voltage, high capacity, low consumption, no memory effect, no public hazard, small volume, small internal resistance, less self-discharge and more cycle times. Although lithium ion batteries have many advantages, the high-temperature safety performance and the high-temperature stability of the lithium ion batteries are still not ideal, and the high-temperature safety performance of the batteries is generally improved by adding high-temperature additives, such as additives containing phosphorus and fluorine, into the electrolyte in the art, but the addition of such additives easily causes the increase of the internal resistance of the batteries, and affects the high-rate performance of the batteries.
Disclosure of Invention
The invention provides an injection formation method of a lithium ion battery, which comprises the steps of injecting a first electrolyte, wherein the organic solvent of the first electrolyte is only cyclic carbonate, the first electrolyte accounts for 55-65% of the volume of the total electrolyte, the first electrolyte contains an additive, and the additive is methyl vinyl sulfone and 1, 3-propane sultone; performing pre-formation, and then injecting a second electrolyte with the volume of the remaining total electrolyte, wherein the organic solvent of the second electrolyte is only chain carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; and carrying out chemical synthesis to obtain the lithium ion battery. The method comprises the steps of performing pre-formation in electrolyte containing additive methyl vinyl sulfone and 1, 3-propane sultone, improving the affinity of an electrode to tetrafluoroethylene carbonate by utilizing an SEI film formed by methyl vinyl sulfone and 1, 3-propane sultone in advance, and performing formation in the electrolyte containing the tetrafluoroethylene carbonate to improve the film forming effect of the tetrafluoroethylene carbonate, so that the high-temperature stability of the lithium ion battery is improved.
The specific scheme is as follows:
an injection formation method of a lithium ion battery comprises the following steps:
1) injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only cyclic carbonate, the first electrolyte accounts for 55-65% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone;
2) adjusting the temperature of the battery to be 2-5 ℃, adopting a current of 0.01-0.02C to perform constant current charging to a first voltage, then performing constant current charging for a plurality of times between the first voltage and a second voltage by using a current of 0.01-0.02C, and performing constant current discharging to a discharge cut-off voltage;
3) adjusting the temperature of the battery to room temperature, and injecting a second electrolyte with the volume of the remaining total electrolyte, wherein the organic solvent of the second electrolyte is only chain carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate;
4) adjusting the temperature of the battery to be 40-55 ℃, charging the battery to a third voltage in a constant current manner, charging the battery in a constant voltage manner by using the third voltage until the charging current is lower than the cut-off current, then charging the battery in the constant current manner to the charging cut-off voltage, and charging the battery in the constant voltage manner by using the charging cut-off current until the charging current is lower than the cut-off current;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for a plurality of times between the charging cut-off voltage and the discharging cut-off voltage to obtain the lithium ion battery.
Further, in the first electrolyte, the volume content of methyl vinyl sulfone is 0.8-1.2 vol%, the volume content of 1, 3-propane sultone is 2.4-3.6 vol%, and the volume ratio of 1, 3-propane sultone: the ratio of methyl vinyl sulfone is more than 2.5: 1.
Further, the volume content of the tetrafluoroethylene carbonate in the second electrolyte solution is 4.6 to 5.2 vol%.
Further, the first voltage is 3.05-3.08V; the second voltage is 3.22-3.25V.
Further, the third voltage is 3.86-3.88V.
Further, the cyclic carbonate is selected from ethylene carbonate, propylene carbonate or a mixture thereof.
Further, the chain carbonate is selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or a mixture thereof.
Further, the positive active material of the lithium ion battery is selected from lithium cobaltate, lithium manganate, ternary material, lithium iron phosphate or mixture thereof; the negative active material is selected from artificial graphite, natural graphite or a mixture thereof.
The invention has the following beneficial effects:
1) the additive tetrafluoroethylene carbonate has good high-temperature resistance, but the additive belongs to an oily solvent and has small polarity, so the bonding force with an electrode is poor, the internal resistance of the battery is greatly increased after an SEI film is formed, the rate performance of the battery is influenced, and the heating phenomenon of a high-rate working battery is serious.
2) The methyl vinyl sulfone and 1, 3-propane sultone combined additive is adopted to form a film on the surface of the electrode in advance, so that the affinity of the tetrafluoroethylene carbonate on the surface of the electrode can be improved, and the excessively high internal resistance after the tetrafluoroethylene carbonate is used can be avoided.
3) And the first electrolyte only adopts cyclic carbonate, so that the reduction of the cycle performance caused by the intercalation of the chain carbonate during the pre-formation of the graphite cathode can be avoided.
4) And in the first electrolyte, the volume ratio of 1, 3-propane sultone: the methyl vinyl sulfone can ensure the stability of SEI film formation at the ratio of more than 2.5:1, when the ratio of 1, 3-propane sultone: when the methyl vinyl sulfone content is less than 2.5:1, the cycle capacity is poor.
5) The pre-formation adopts low-temperature low-current formation, a thin and compact SEI film can be formed, the internal resistance can be reduced, and the high-temperature environment is adopted during the secondary formation, so that the mobility of the tetrafluoroethylene carbonate is improved, and the film formation of the tetrafluoroethylene carbonate on the surface of an electrode is facilitated.
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 active material of the lithium ion battery is lithium cobaltate; the negative active material is natural graphite.
Example 1
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 55% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 1.2 volume percent, and the volume content of 1, 3-propane sultone is 3.6 volume percent;
2) adjusting the temperature of the battery to be 2 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.05V; the second voltage is 3.22V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 4.6 vol%;
4) adjusting the temperature of the battery to 40 ℃, charging the battery to a third voltage in a constant current manner, and charging the battery in a constant voltage manner by using the third voltage until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.86V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Example 2
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 65% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 0.8 volume percent, and the volume content of 1, 3-propane sultone is 2.4 volume percent;
2) adjusting the temperature of the battery to be 5 ℃, adopting a 0.02C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.02C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.08V; the second voltage is 3.25V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.2 vol%;
4) adjusting the temperature of the battery to 55 ℃, charging the battery to a third voltage in a constant current manner, and charging the battery in a constant voltage manner until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.88V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Example 3
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 1.0 volume percent, and the volume content of 1, 3-propane sultone is 3.0 volume percent;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.06V; the second voltage is 3.24V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
4) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 1
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone; the volume content of methyl vinyl sulfone is 1.0 volume%;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.06V; the second voltage is 3.24V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
4) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 2
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is 1, 3-propane sultone; the volume content of the 1, 3-propane sultone is 3.0 volume percent;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.06V; the second voltage is 3.24V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
4) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 3
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 1.0 volume percent, and the volume content of 1, 3-propane sultone is 3.0 volume percent;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.06V; the second voltage is 3.24V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, and the second electrolyte does not contain an additive;
4) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 4
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 1.2 volume percent, and the volume content of 1, 3-propane sultone is 2.4 volume percent;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.06V; the second voltage is 3.24V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
4) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 5
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte does not contain an additive;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.06V; the second voltage is 3.24V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
4) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 6
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 1.0 volume percent, and the volume content of 1, 3-propane sultone is 3.0 volume percent; injecting a second electrolyte with the remaining total electrolyte volume, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, and the second electrolyte contains an additive which is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.06V; the second voltage is 3.24V;
3) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
4) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 7
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 1.0 volume percent, and the volume content of 1, 3-propane sultone is 3.0 volume percent;
2) adjusting the temperature of the battery to 25 ℃ at room temperature, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V at 0.1C; the first voltage is 3.06V; the second voltage is 3.24V;
3) injecting a second electrolyte with the remaining total electrolyte volume, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, and the second electrolyte contains an additive which is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
4) charging the battery at a constant current to a third voltage, and performing constant voltage charging at the third voltage until the charging current is lower than the cut-off current by 0.01C, wherein the third voltage is 3.87V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Comparative example 8
1) Injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only ethylene carbonate, the first electrolyte accounts for 60% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone; the volume content of methyl vinyl sulfone is 1.0 volume percent, and the volume content of 1, 3-propane sultone is 3.0 volume percent;
2) adjusting the temperature of the battery to be 4 ℃, adopting a 0.01C current to perform constant current charging to a first voltage, then performing constant current charging for 3 times between the first voltage and a second voltage by using a 0.01C current, and performing constant current discharging to a discharge cut-off voltage of 2.70V by using a 0.1C current; the first voltage is 3.20V; the second voltage is 3.40V;
3) adjusting the temperature of the battery to 25 ℃, and injecting a second electrolyte with the volume of the rest total electrolyte, wherein the organic solvent of the second electrolyte is only dimethyl carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate; the volume content of tetrafluoroethylene carbonate was 5.0 vol%;
4) adjusting the temperature of the battery to be 50 ℃, charging the battery to a third voltage in a constant current mode, and charging the battery in a constant voltage mode until the charging current is lower than the cutoff current by 0.01C, wherein the third voltage is 3.70V; then charging the battery at a constant current of 0.1C to a charging cut-off voltage of 4.20V, and charging the battery at a constant voltage of the charging cut-off voltage until the charging current is lower than the cut-off current by 0.01C;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for 3 times at 0.2 ℃ between the charge cut-off voltage and the discharge cut-off voltage to obtain the lithium ion battery.
Test and results
The batteries of examples 1 to 3 and comparative examples 1 to 8 were tested, and the cycle capacity retention ratio of the batteries was measured by performing charge and discharge cycles 200 times at 50 ℃ using a current of 2C and a voltage range of 2.7 to 4.2V, and the results are shown in table 1. As can be seen from table 1, the cyclic ratio at high temperature can be increased by forming a film on the surface of the electrode in advance by using the additive combination of methyl vinyl sulfone and 1, 3-propane sultone. When the ratio of 1, 3-propane sultone: when the ratio of methyl vinyl sulfone is less than 2.5:1, the circulation capacity becomes poor; and the influence of the temperature and voltage range of the formation on the capacity retention rate is also very obvious.
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. An injection formation method of a lithium ion battery comprises the following steps:
1) injecting a first electrolyte into a battery shell provided with a battery core, wherein the organic solvent of the first electrolyte is only cyclic carbonate, the first electrolyte accounts for 55-65% of the total volume of the electrolyte, and the first electrolyte contains an additive which is methyl vinyl sulfone and 1, 3-propane sultone;
2) adjusting the temperature of the battery to be 2-5 ℃, adopting a current of 0.01-0.02C to perform constant current charging to a first voltage, then performing constant current charging for a plurality of times between the first voltage and a second voltage by using a current of 0.01-0.02C, and performing constant current discharging to a discharge cut-off voltage;
3) adjusting the temperature of the battery to room temperature, and injecting a second electrolyte with the volume of the remaining total electrolyte, wherein the organic solvent of the second electrolyte is only chain carbonate, the second electrolyte contains an additive, and the additive is tetrafluoroethylene carbonate;
4) adjusting the temperature of the battery to be 40-55 ℃, charging the battery to a third voltage in a constant current manner, charging the battery in a constant voltage manner by using the third voltage until the charging current is lower than the cut-off current, then charging the battery in the constant current manner to the charging cut-off voltage, and charging the battery in the constant voltage manner by using the charging cut-off current until the charging current is lower than the cut-off current;
5) and adjusting the temperature of the battery to be room temperature, and performing constant current circulation for a plurality of times between the charging cut-off voltage and the discharging cut-off voltage to obtain the lithium ion battery.
2. The method of the preceding claim, wherein the first electrolyte solution contains 0.8-1.2 vol% of methyl vinyl sulfone, 2.4-3.6 vol% of 1, 3-propane sultone, and the ratio by volume of 1, 3-propane sultone: the ratio of methyl vinyl sulfone is more than 2.5: 1.
3. The method of any preceding claim, wherein the volume content of tetrafluoroethylene carbonate in the second electrolyte is 4.6-5.2 vol%.
4. The method of the preceding claim, wherein the first voltage is 3.05-3.08V; the second voltage is 3.22-3.25V.
5. The method of the preceding claim, wherein the third voltage is 3.86-3.88V.
6. The process according to the preceding claim, wherein the cyclic carbonate is selected from ethylene carbonate, propylene carbonate or mixtures thereof.
7. The method of the preceding claims, wherein the chain carbonate is selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or mixtures thereof.
8. The method of the preceding claim, wherein the positive active material of the lithium ion battery is selected from lithium cobaltate, lithium manganate, ternary material, lithium iron phosphate or mixtures thereof; the negative active material is selected from artificial graphite, natural graphite or a mixture thereof.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335740A (en) * | 2021-12-29 | 2022-04-12 | 湖北亿纬动力有限公司 | Formation method of lithium ion battery and lithium ion battery |
| CN116454564A (en) * | 2023-06-20 | 2023-07-18 | 江苏正力新能电池技术有限公司 | Secondary liquid injection method, battery and electric equipment |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335740A (en) * | 2021-12-29 | 2022-04-12 | 湖北亿纬动力有限公司 | Formation method of lithium ion battery and lithium ion battery |
| CN116454564A (en) * | 2023-06-20 | 2023-07-18 | 江苏正力新能电池技术有限公司 | Secondary liquid injection method, battery and electric equipment |
| CN116454564B (en) * | 2023-06-20 | 2023-09-08 | 江苏正力新能电池技术有限公司 | Secondary liquid injection method, battery and electric equipment |
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