CN111799520A - Formation method of lithium ion battery - Google Patents

Formation method of lithium ion battery Download PDF

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CN111799520A
CN111799520A CN202010701154.9A CN202010701154A CN111799520A CN 111799520 A CN111799520 A CN 111799520A CN 202010701154 A CN202010701154 A CN 202010701154A CN 111799520 A CN111799520 A CN 111799520A
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electrolyte
battery
voltage
charging
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金妍
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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
    • H01M10/058—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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 lithium ion battery, wherein the anode of the lithium ion battery is lithium iron phosphate (LiFe)1‑ xMxPO4X is 0.03-0.05, M is selected from transition metals; the negative electrode of the lithium ion battery is carbon-coated lithium titanate Li4Ti5O12C, where the carbon content is Li4Ti5O123.5-4 mass%; the formation method comprises the following steps: the negative electrode and the lithium sheet are oppositely arranged, placed in a first electrolyte, and charged at a constant voltage of a first preset voltage until the charging current is lower than a preset current, so that the pre-charging of the negative electrode is completedAnd forming, namely clamping the diaphragm by the anode and the pre-formed cathode to form a battery core, putting the battery core into a shell, injecting a second electrolyte, performing primary formation, injecting a third electrolyte, and performing secondary formation to obtain the lithium ion battery.

Description

Formation method of lithium ion battery
Technical Field
The invention relates to a formation method of a lithium ion battery.
Background
The battery obtained by combining the lithium iron phosphate and the lithium titanate has good safety, can be suitable for being used in a high-temperature environment, and has safer high-temperature service performance, but the cycle performance of the battery is seriously reduced at high temperature due to the decomposition reaction of the electrolyte on the surface of the battery. Before assembling the battery, the lithium titanate battery is pre-formed, and vinylene carbonate is used for preliminarily forming a film on the surface of the lithium titanate cathode while the lithium content of the lithium titanate cathode is adjusted; and after the battery is assembled, injecting a second electrolyte, and performing constant-voltage formation at a high voltage higher than a charge cut-off voltage and at a high temperature higher than room temperature to promote the formation of the cyclohexylbenzene on the surfaces of the positive electrode and the negative electrode. And finally, injecting a third electrolyte, and performing normal temperature formation within a normal charging and discharging voltage range to form the 1, 4-butane sultone into a film. The inventor finds that the formed battery has high-temperature cycle performance through a specific formation step and a film forming sequence of different additives, and the principle is that the positive electrode and the negative electrode form an excellent passive film under the existence of the specific additives. Further, the inventors found that since cyclohexylbenzene has poor film forming properties in the presence of chain carbonates, the second electrolyte solution contains only cyclic carbonates without chain carbonates, thereby improving the film forming properties and the high temperature properties.
Disclosure of Invention
The invention provides a formation method of a lithium ion battery, wherein the anode of the lithium ion battery is lithium iron phosphate (LiFe)1-xMxPO4X is 0.03-0.05, M is selected from transition metals; the negative electrode of the lithium ion battery is carbon-coated lithium titanate Li4Ti5O12C, where the carbon content is Li4Ti5O123.5-4 mass%; the formation method comprises the following steps: the method comprises the steps of oppositely arranging a negative electrode and a lithium sheet, placing the negative electrode and the lithium sheet in a first electrolyte, charging at a constant voltage with a first preset voltage until the charging current is lower than a preset current, completing the pre-formation of the negative electrode, clamping a diaphragm between the positive electrode and the pre-formed negative electrode to form a battery core, placing the battery core into a shell, injecting a second electrolyte, performing the primary formation, injecting a third electrolyte, and performing the secondary formation to obtain the lithium ion battery.
The specific scheme is as follows:
a formation method of a lithium ion battery is provided, wherein the anode of the lithium ion battery is lithium iron phosphate LiFe1-xMxPO4X is 0.03-0.05, M is selected from transition metals; the lithiumThe negative electrode of the ion battery is carbon-coated lithium titanate Li4Ti5O12C, where the carbon content is Li4Ti5O123.5-4 mass%; the formation method comprises the following steps:
1) the method comprises the following steps of (1) oppositely arranging a negative electrode and a lithium sheet, and placing the negative electrode and the lithium sheet in a first electrolyte, wherein the first electrolyte comprises vinylene carbonate as an additive;
2) charging at a first preset voltage and a constant voltage until the charging current is lower than a preset current, wherein the first preset voltage is 1.52-1.54V;
3) forming a battery core by clamping a diaphragm between a positive electrode and a preformed negative electrode, putting the battery core into a shell, and injecting a second electrolyte, wherein the second electrolyte comprises cyclohexylbenzene;
4) adjusting the temperature of the battery to be 50-55 ℃, then charging the battery to a second preset voltage in a constant current mode, and charging the battery in a constant voltage mode under the second preset voltage until the charging current is lower than the preset current, wherein the second preset voltage is 1.95-1.97V;
5) discharging the battery at a constant current to a discharge cut-off voltage, adjusting the temperature of the battery to be 5-10 ℃, then injecting a third electrolyte, wherein the third electrolyte comprises 1, 4-butane sultone, charging the battery at the constant current to a third preset voltage, and charging the battery at a constant voltage under the third preset voltage until the charging current is lower than the preset current, and the third preset voltage is 2.78-2.80V;
6) adjusting the temperature of the battery to be 20-30 ℃, and carrying out charge-discharge circulation for a plurality of times between the charge cut-off voltage and the discharge cut-off voltage.
Further, the discharge cut-off voltage is 1.20-1.25V.
Further, the charge cut-off voltage is 2.70-2.75V.
Further, the first electrolyte comprises 10-12 vol% of vinylene carbonate.
Further, the organic solvent of the second electrolyte is cyclic carbonate, which comprises 4-6 vol% of cyclohexylbenzene.
Further, the organic solvent of the third electrolyte is chain carbonate, wherein the chain carbonate comprises 3-5 vol% of 1, 4-butane sultone.
Further, the volume ratio of the second electrolyte to the third electrolyte is 2-3: 1.
The invention has the following beneficial effects:
1) the method comprises the following steps of pre-forming a lithium titanate battery before assembling the battery, and initially forming a film on the surface of a lithium titanate cathode by using vinylene carbonate while adjusting the lithium content in the lithium titanate cathode;
2) and after the battery is assembled, injecting a second electrolyte, and performing constant-voltage formation at a high voltage higher than a charge cut-off voltage and at a high temperature higher than room temperature to promote the formation of the cyclohexylbenzene on the surfaces of the positive electrode and the negative electrode.
3) And finally, injecting a third electrolyte, and carrying out normal temperature formation within the normal charge-discharge voltage range to form the 1, 4-butane sultone into a film.
4) The inventor finds that the formed battery has high-temperature cycle performance through a specific formation step and a film forming sequence of different additives, and the principle is that the positive electrode and the negative electrode form an excellent passive film under the existence of the specific additives.
5) Further, the inventors found that since cyclohexylbenzene has poor film forming properties in the presence of chain carbonates, the second electrolyte solution contains only cyclic carbonates without chain carbonates, and thus has improved film forming properties and high temperature properties.
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 anode in the invention is lithium iron phosphate LiFe0.96Co0.04PO4(ii) a The negative electrode of the lithium ion battery is carbon-coated lithium titanate Li4Ti5O12C, where the carbon content is Li4Ti5O123.8% by mass of (A).
Example 1
1) The negative electrode and the lithium sheet are oppositely arranged and placed in a first electrolyte, wherein the electrolyte solvent of the first electrolyte is ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the lithium hexafluorophosphate comprises 10 volume percent of vinylene carbonate;
2) charging at a first preset voltage until the charging current is lower than 0.01C, wherein the first preset voltage is 1.52V;
3) clamping a diaphragm by a positive electrode and a preformed negative electrode to form a battery cell, putting the battery cell into a shell, and injecting a second electrolyte, wherein the electrolyte solvent of the second electrolyte is ethylene carbonate, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, and the electrolyte comprises 4 volume percent of cyclohexylbenzene;
4) adjusting the temperature of the battery to be 50 ℃, then charging the battery to a second preset voltage at a constant current of 0.1 ℃, and charging the battery at a constant voltage under the second preset voltage until the charging current is lower than 0.01 ℃, wherein the second preset voltage is 1.95V;
5) discharging the battery at a constant current of 0.1C to a discharge cut-off voltage of 1.20V, adjusting the temperature of the battery to be 5 ℃, then injecting a third electrolyte, wherein the volume ratio of the second electrolyte to the third electrolyte is 2:1, the electrolyte solvent of the third electrolyte is diethyl carbonate, the electrolyte salt is 1mol/L lithium hexafluorophosphate and comprises 3 volume percent of 1, 4-butane sultone, charging the battery at a constant current of 0.1C to a third preset voltage, and charging the battery at a constant voltage under the third preset voltage until the charging current is lower than 0.01C, and the third preset voltage is 2.78V;
6) the temperature of the battery is adjusted to be 20 ℃, and the battery is subjected to charge-discharge cycle for 3 times at 0.1 ℃ between a charge cut-off voltage and a discharge cut-off voltage, wherein the charge cut-off voltage is 2.70V.
Example 2
1) The negative electrode and the lithium sheet are oppositely arranged and placed in a first electrolyte, wherein the electrolyte solvent of the first electrolyte is ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the lithium hexafluorophosphate comprises 12 volume percent of vinylene carbonate;
2) charging at a first preset voltage until the charging current is lower than 0.01C, wherein the first preset voltage is 1.54V;
3) clamping a diaphragm by a positive electrode and a preformed negative electrode to form a battery cell, putting the battery cell into a shell, and injecting a second electrolyte, wherein the electrolyte solvent of the second electrolyte is ethylene carbonate, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, and the electrolyte comprises 6 volume percent of cyclohexylbenzene;
4) adjusting the temperature of the battery to 55 ℃, then carrying out constant current charging to a second preset voltage at 0.1 ℃, and carrying out constant voltage charging at the second preset voltage until the charging current is lower than 0.01 ℃, wherein the second preset voltage is 1.97V;
5) discharging the battery at a constant current of 0.1 ℃ to a discharge cut-off voltage of 1.25V, adjusting the temperature of the battery to 10 ℃, then injecting a third electrolyte, wherein the volume ratio of the second electrolyte to the third electrolyte is 3:1, the electrolyte solvent of the third electrolyte is diethyl carbonate, the electrolyte salt is 1mol/L lithium hexafluorophosphate and comprises 5 volume percent of 1, 4-butane sultone, charging the battery at a constant current of 0.1 ℃ to a third preset voltage, and charging the battery at a constant voltage under the third preset voltage until the charging current is lower than 0.01 ℃ and the third preset voltage is 2.80V;
6) the temperature of the battery is adjusted to be 30 ℃, and the battery is subjected to charge-discharge cycle for 3 times at 0.1 ℃ between a charge cut-off voltage and a discharge cut-off voltage, wherein the charge cut-off voltage is 2.75V.
Example 3
1) The negative electrode and the lithium sheet are oppositely arranged and placed in a first electrolyte, wherein the electrolyte solvent of the first electrolyte is ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the electrolyte salt comprises 11 volume percent of vinylene carbonate;
2) charging at a first preset voltage until the charging current is lower than 0.01C, wherein the first preset voltage is 1.53V;
3) clamping a diaphragm by a positive electrode and a preformed negative electrode to form a battery cell, putting the battery cell into a shell, and injecting a second electrolyte, wherein the electrolyte solvent of the second electrolyte is ethylene carbonate, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, and the electrolyte comprises 5 volume percent of cyclohexylbenzene;
4) adjusting the temperature of the battery to 52 ℃, then performing constant current charging to a second preset voltage at 0.1 ℃, and performing constant voltage charging at the second preset voltage until the charging current is lower than 0.01 ℃, wherein the second preset voltage is 1.96V;
5) discharging the battery at a constant current of 0.1C to a discharge cut-off voltage of 1.22V, adjusting the temperature of the battery to be 8 ℃, then injecting a third electrolyte, wherein the volume ratio of the second electrolyte to the third electrolyte is 2.5:1, the electrolyte solvent of the third electrolyte is diethyl carbonate, the electrolyte salt is 1mol/L lithium hexafluorophosphate, the electrolyte salt comprises 4 vol% of 1, 4-butane sultone, the battery is charged at a constant current of 0.1C to a third preset voltage, and the battery is charged at a constant voltage under the third preset voltage until the charging current is lower than 0.01C, and the third preset voltage is 2.79V;
6) the temperature of the battery is adjusted to be 25 ℃, and the charging and discharging are carried out for 3 times at 0.1 ℃ between the charging cut-off voltage and the discharging cut-off voltage, wherein the charging cut-off voltage is 2.72V.
Comparative example 1
1) Clamping a diaphragm between a positive electrode and a negative electrode to form a battery cell, putting the battery cell into a shell, and injecting a second electrolyte, wherein the electrolyte solvent of the second electrolyte is ethylene carbonate, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, and the electrolyte comprises 5 volume percent of cyclohexylbenzene;
2) adjusting the temperature of the battery to 52 ℃, then performing constant current charging to a second preset voltage at 0.1 ℃, and performing constant voltage charging at the second preset voltage until the charging current is lower than 0.01 ℃, wherein the second preset voltage is 1.96V;
3) discharging the battery at a constant current of 0.1C to a discharge cut-off voltage of 1.22V, adjusting the temperature of the battery to be 8 ℃, then injecting a third electrolyte, wherein the volume ratio of the second electrolyte to the third electrolyte is 2.5:1, the electrolyte solvent of the third electrolyte is diethyl carbonate, the electrolyte salt is 1mol/L lithium hexafluorophosphate, the electrolyte salt comprises 4 vol% of 1, 4-butane sultone, the battery is charged at a constant current of 0.1C to a third preset voltage, and the battery is charged at a constant voltage under the third preset voltage until the charging current is lower than 0.01C, and the third preset voltage is 2.79V;
4) the temperature of the battery is adjusted to be 25 ℃, and the charging and discharging are carried out for 3 times at 0.1 ℃ between the charging cut-off voltage and the discharging cut-off voltage, wherein the charging cut-off voltage is 2.72V.
Comparative example 2
1) The negative electrode and the lithium sheet are oppositely arranged and placed in a first electrolyte, wherein the electrolyte solvent of the first electrolyte is ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the electrolyte salt comprises 11 volume percent of vinylene carbonate;
2) charging at a first preset voltage until the charging current is lower than 0.01C, wherein the first preset voltage is 1.53V;
3) clamping a diaphragm by a positive electrode and a preformed negative electrode to form a battery cell, putting the battery cell into a shell, and injecting a second electrolyte, wherein the electrolyte solvent of the second electrolyte is ethylene carbonate, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, and the electrolyte comprises 5 volume percent of cyclohexylbenzene;
4) adjusting the temperature of the battery to 52 ℃, then performing constant current charging to a second preset voltage at 0.1 ℃, and performing constant voltage charging at the second preset voltage until the charging current is lower than 0.01 ℃, wherein the second preset voltage is 1.96V;
5) the temperature of the battery is adjusted to be 25 ℃, and the battery is subjected to charge-discharge cycle for 3 times at 0.1 ℃ between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.22V, and the charge cut-off voltage is 2.72V.
Comparative example 3
1) The negative electrode and the lithium sheet are oppositely arranged and placed in a first electrolyte, wherein the electrolyte solvent of the first electrolyte is ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the electrolyte salt comprises 11 volume percent of vinylene carbonate;
2) charging at a first preset voltage until the charging current is lower than 0.01C, wherein the first preset voltage is 1.53V;
3) clamping a diaphragm by a positive electrode and a preformed negative electrode to form a battery cell, putting the battery cell into a shell, and continuously injecting a second electrolyte and a third electrolyte, wherein the volume ratio of the second electrolyte to the third electrolyte is 2.5:1, the electrolyte solvent of the second electrolyte is ethylene carbonate, the electrolyte salt is 1mol/L lithium hexafluorophosphate, and the electrolyte salt comprises 5 vol% of cyclohexylbenzene; the electrolyte solvent of the third electrolyte is diethyl carbonate, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the electrolyte salt comprises 4 volume percent of 1, 4-butane sultone;
4) adjusting the temperature of the battery to 52 ℃, then performing constant current charging to a second preset voltage at 0.1 ℃, and performing constant voltage charging at the second preset voltage until the charging current is lower than 0.01 ℃, wherein the second preset voltage is 1.96V;
5) discharging the battery at a constant current of 0.1C to a discharge cut-off voltage of 1.22V, adjusting the temperature of the battery to be 8 ℃, charging the battery at a constant current of 0.1C to a third preset voltage, and charging the battery at a constant voltage of the third preset voltage until the charging current is lower than 0.01C, wherein the third preset voltage is 2.79V;
6) the temperature of the battery is adjusted to be 25 ℃, and the charging and discharging are carried out for 3 times at 0.1 ℃ between the charging cut-off voltage and the discharging cut-off voltage, wherein the charging cut-off voltage is 2.72V.
Comparative example 4
1) The negative electrode and the lithium sheet are oppositely arranged and placed in a first electrolyte, wherein the electrolyte solvent of the first electrolyte is ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the electrolyte salt comprises 11 volume percent of vinylene carbonate;
2) charging at a first preset voltage until the charging current is lower than 0.01C, wherein the first preset voltage is 1.53V;
3) clamping a diaphragm by a positive electrode and a pre-formed negative electrode to form a battery cell, putting the battery cell into a shell, injecting a third electrolyte, wherein the volume ratio of the second electrolyte to the third electrolyte is 2.5:1, the electrolyte solvent of the third electrolyte is diethyl carbonate, the electrolyte salt is 1mol/L lithium hexafluorophosphate, the third electrolyte comprises 4 volume percent of 1, 4-butane sultone, charging is carried out at a constant current of 0.1C until the charging current is lower than 0.01C, and the third predetermined voltage is 2.79V;
4) the temperature of the battery is adjusted to be 25 ℃, and the charging and discharging are carried out for 3 times at 0.1 ℃ between the charging cut-off voltage and the discharging cut-off voltage, wherein the charging cut-off voltage is 2.72V.
Comparative example 5
1) The negative electrode and the lithium sheet are oppositely arranged and placed in a first electrolyte, wherein the electrolyte solvent of the first electrolyte is ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, wherein the electrolyte salt comprises 11 volume percent of vinylene carbonate;
2) charging at a first preset voltage until the charging current is lower than 0.01C, wherein the first preset voltage is 1.53V;
3) clamping a diaphragm by a positive electrode and a preformed negative electrode to form a battery cell, putting the battery cell into a shell, and injecting a second electrolyte, wherein the electrolyte solvent of the second electrolyte is diethyl carbonate, and the electrolyte salt is 1mol/L lithium hexafluorophosphate, and the electrolyte comprises 5 volume percent of cyclohexylbenzene;
4) adjusting the temperature of the battery to 52 ℃, then performing constant current charging to a second preset voltage at 0.1 ℃, and performing constant voltage charging at the second preset voltage until the charging current is lower than 0.01 ℃, wherein the second preset voltage is 1.96V;
5) discharging the battery at a constant current of 0.1C to a discharge cut-off voltage of 1.22V, adjusting the temperature of the battery to be 8 ℃, then injecting a third electrolyte, wherein the volume ratio of the second electrolyte to the third electrolyte is 2.5:1, the electrolyte solvent of the third electrolyte is ethylene carbonate, the electrolyte salt is 1mol/L lithium hexafluorophosphate, the electrolyte salt comprises 4 volume percent of 1, 4-butane sultone, the battery is charged at a constant current of 0.1C to a third preset voltage, and is charged at a constant voltage under the third preset voltage until the charging current is lower than 0.01C, and the third preset voltage is 2.79V;
6) the temperature of the battery is adjusted to be 25 ℃, and the charging and discharging are carried out for 3 times at 0.1 ℃ between the charging cut-off voltage and the discharging cut-off voltage, wherein the charging cut-off voltage is 2.72V.
Test and results
The batteries of examples 1 to 3 and comparative examples 1 to 5 were tested for capacity retention at 55 degrees celsius when the batteries were cycled 100 times and 300 times, and the results are shown in table 1. As can be seen from table 1, the pre-formation process of the negative electrode, the addition sequence of the second and third electrolytes, the compounding of the additives and the selection of the electrolyte solvent in the second electrolyte all have a great influence on the cycle performance of the battery.
TABLE 1
100 times (%) 300 times (%)
Example 1 98.6 95.3
Example 2 98.2 95.1
Example 3 99.1 96.1
Comparative example 1 95.1 92.5
Comparative example 2 94.1 89.5
Comparative example 3 93.2 88.6
Comparative example 4 95.6 93.2
Comparative example 5 95.1 92.7
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 formation method of a lithium ion battery is provided, wherein the anode of the lithium ion battery is lithium iron phosphate LiFe1-xMxPO4X is 0.03-0.05, M is selected from transition metals; the negative electrode of the lithium ion battery is carbon-coated lithium titanate Li4Ti5O12C, where the carbon content is Li4Ti5O123.5-4 mass%; the formation method comprises the following steps:
1) the method comprises the following steps of (1) oppositely arranging a negative electrode and a lithium sheet, and placing the negative electrode and the lithium sheet in a first electrolyte, wherein the first electrolyte comprises vinylene carbonate as an additive;
2) charging at a first preset voltage and a constant voltage until the charging current is lower than a preset current, wherein the first preset voltage is 1.52-1.54V;
3) forming a battery core by clamping a diaphragm between a positive electrode and a preformed negative electrode, putting the battery core into a shell, and injecting a second electrolyte, wherein the second electrolyte comprises cyclohexylbenzene;
4) adjusting the temperature of the battery to be 50-55 ℃, then charging the battery to a second preset voltage in a constant current mode, and charging the battery in a constant voltage mode under the second preset voltage until the charging current is lower than the preset current, wherein the second preset voltage is 1.95-1.97V;
5) discharging the battery at a constant current to a discharge cut-off voltage, adjusting the temperature of the battery to be 5-10 ℃, then injecting a third electrolyte, wherein the third electrolyte comprises 1, 4-butane sultone, charging the battery at the constant current to a third preset voltage, and charging the battery at a constant voltage under the third preset voltage until the charging current is lower than the preset current, and the third preset voltage is 2.78-2.80V;
6) adjusting the temperature of the battery to be 20-30 ℃, and carrying out charge-discharge circulation for a plurality of times between the charge cut-off voltage and the discharge cut-off voltage.
2. The chemical conversion method according to the above claim, wherein the discharge cut-off voltage is 1.20-1.25V.
3. The formation method according to the previous claim, wherein the charge cut-off voltage is 2.70-2.75V.
4. The method according to any of the preceding claims, wherein the first electrolyte solution comprises 10-12 vol% vinylene carbonate.
5. The chemical synthesis process of the preceding claim, wherein the organic solvent of the second electrolyte is a cyclic carbonate comprising 4-6 vol% cyclohexylbenzene.
6. The chemical synthesis method according to the previous claim, wherein the organic solvent of the third electrolyte is a chain carbonate comprising 3-5 vol% of 1, 4-butane sultone.
7. A method according to any preceding claim, wherein the volume ratio of the second electrolyte to the third electrolyte is 2-3: 1.
CN202010701154.9A 2020-07-20 2020-07-20 Formation method of lithium ion battery Withdrawn CN111799520A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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
CN112201871A (en) * 2020-10-22 2021-01-08 苏州极闪控电信息技术有限公司 High-temperature formation method of lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
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
CN112201871A (en) * 2020-10-22 2021-01-08 苏州极闪控电信息技术有限公司 High-temperature formation method of lithium ion battery

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