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CN111725564A - Formation method of lithium ion battery - Google Patents

Formation method of lithium ion battery Download PDF

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Publication number
CN111725564A
CN111725564A CN202010530186.7A CN202010530186A CN111725564A CN 111725564 A CN111725564 A CN 111725564A CN 202010530186 A CN202010530186 A CN 202010530186A CN 111725564 A CN111725564 A CN 111725564A
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electrolyte
voltage
formation
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temperature
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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
    • H01M10/05—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
    • H01M10/44—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M2300/0088—Composites
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a formation method of a lithium ion battery, wherein a positive electrode active substance of the lithium ion battery is a lithium iron phosphate series substance, and a negative electrode active substance of the lithium ion battery is a lithium titanate series substance, the formation method comprises the steps of heating the battery to 60-70 ℃, then injecting a first electrolyte, adjusting the temperature of the first electrolyte to 40-50 ℃, then adjusting the temperature of the battery to 50-60 ℃, and carrying out pre-formation; and injecting a second electrolyte at the temperature of 30-40 ℃, adjusting the temperature of the battery to 5-10 ℃, performing secondary formation, adjusting the temperature of the battery to 20-25 ℃, and performing formation.

Description

Formation method of lithium ion battery
Technical Field
The invention relates to a formation method of a lithium ion battery.
Background
The development of battery technology has revolutionized the field of energy. From smart phones to electric vehicles, battery technology is ubiquitous, and the aspects of people's life are changed. Whether future batteries can become more powerful or not, lower cost will affect everyone.
At present, the industry is all striving to improve the battery safety in use and simultaneously improve the energy density of the battery. And the improvement of the battery performance also helps to cope with the climate change problem by the utilization of renewable energy.
The lithium ion battery will still dominate the battery industry in the next 10 years, but the development and rise of new technologies will also continuously strengthen the valuation and prospect of the industry. The energy density of lithium batteries in the future may reach around 1.5 to 2 times that of the present, which means that batteries will become smaller. This reduces material and thus cost, but not material costs significantly. The lithium iron phosphate is one of the mainstream materials of the anode materials of the lithium ion battery at present, and when the electrolyte contains vinylene carbonate as an additive, the safety and the cycle life of the battery can be effectively improved.
Disclosure of Invention
The invention provides a formation method of a lithium ion battery, wherein a positive electrode active substance of the lithium ion battery is a lithium iron phosphate series substance, and a negative electrode active substance of the lithium ion battery is a lithium titanate series substance, the formation method comprises the steps of heating the battery to 60-70 ℃, then injecting a first electrolyte, adjusting the temperature of the first electrolyte to 40-50 ℃, then adjusting the temperature of the battery to 50-60 ℃, and carrying out pre-formation; and injecting a second electrolyte at the temperature of 30-40 ℃, adjusting the temperature of the battery to 5-10 ℃, performing secondary formation, adjusting the temperature of the battery to 20-25 ℃, and performing formation.
The specific scheme is as follows:
a formation method of a lithium ion battery comprises the following steps:
1) heating the battery to 60-70 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 40-50 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives;
3) adjusting the temperature of the battery to be 50-60 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging with a charging current of more than 1C to a charging cut-off voltage at a constant current, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than the cut-off current;
5) injecting a second electrolyte, wherein the temperature of the second electrolyte is 30-40 ℃, and the second electrolyte contains vinylene carbonate as an additive;
6) adjusting the temperature of the battery to 5-10 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage with a current of more than 1C, and performing constant-current charge-discharge circulation between the first preset voltage and a second preset voltage with a small current, wherein the first preset voltage is 1.5-1.6V, and the second voltage is 1.8-1.9V;
8) adjusting the temperature of the battery to be 20-25 ℃;
9) formation, the formation is as follows: a constant current charge-discharge cycle is performed between a charge cut-off voltage and a discharge cut-off voltage.
Further, the positive electrode active material of the lithium ion battery is a lithium iron phosphate material, and the negative electrode active material is a lithium titanate material.
Further, the charge cut-off voltage is 2.5V, and the discharge cut-off voltage is 1.2V.
Further, the volume ratio of the first electrolyte to the second electrolyte is 3:1-4: 1.
Further, in the first electrolyte, the mass concentration ratio of the propylene sulfite to the trifluoroethyl phosphonic acid is 2.5-3:1, wherein the propylene sulfite is 4.5-5 mass%.
Further, in the second electrolyte, the mass concentration of the vinylene carbonate is 7-9%.
Further, the positive active material of the lithium ion battery is LiFe0.97Nb0.03PO4F0.03The negative electrode active material is Li3.9Mg0.1Ti4.9Mo0.1O12。
Further, the circulating current in the step 7 is 0.01-0.03C.
The invention has the following beneficial effects:
1) aiming at a battery with a positive electrode made of lithium iron phosphate and a negative electrode made of lithium titanate, the inventor adopts propylene sulfite and trifluoroethyl phosphonic acid with specific content proportion as additives, adopts large current to rapidly adjust the voltage of the battery to a charging voltage, and carries out constant voltage formation under the charging cut-off voltage, under the specific voltage, the propylene sulfite and the trifluoroethyl phosphonic acid form an SEI film on the surface of the electrode together under the charging voltage, and the stability of the battery can be improved. The inventor finds that the voltage can be rapidly adjusted through large current, so that the additive can perform deposition reaction in a specific voltage interval as much as possible, and the stability of the battery can be improved.
2) And quickly adjusting the voltage of the battery to a first preset voltage after the pre-formation, and forming a film in a specific voltage interval by using VC, wherein the VC forms a film on the original SEI film for the second time in the voltage interval, so that the high-temperature stability of the battery is further improved.
3) The inventor finds that the formation temperature has a great influence on the film forming quality of a specific additive aiming at different additives, the film forming quality of the propylene sulfite and the trifluoroethyl phosphonic acid is obviously improved in a temperature range of 50-60 ℃, and compared with the normal temperature formation, the battery has better high-temperature storage performance;
4) in the temperature range of 5-10 ℃, the film forming quality of the vinylene carbonate is obviously improved, and the cycle performance of the battery can be obviously improved;
5) and the temperature of the battery is higher than the temperature of the electrolyte in the liquid injection process, so that the permeation of the electrolyte can be facilitated, and the film forming quality of the electrolyte is improved.
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 active material in the invention is anode active substance LiFe0.97Nb0.03PO4F0.03The negative active material is Li3.9Mg0.1Ti4.9Mo0.1O12(ii) a The organic solvent of the electrolyte is a mixed organic solvent of EC, DEC and DMC in a volume ratio of 2:1:1, and the electrolyte salt is 1mol/L lithium hexafluorophosphate.
Example 1
1) Heating the cell to 60 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 40 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; the mass concentration ratio of the propylene sulfite to the trifluoroethyl phosphonic acid is 2.5:1, wherein the propylene sulfite is 5 mass%, and the trifluoroethyl phosphonic acid is 2 mass%;
3) adjusting the temperature of the battery to 50 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging to a charging cut-off voltage by a constant current of 2C, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than 0.01C, wherein the charging cut-off voltage is 2.5V;
5) injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 3:1, the second electrolyte is 30 ℃, vinylene carbonate is contained in the second electrolyte as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 7%;
6) adjusting the temperature of the battery to 5 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage at 2C, and performing constant-current charge-discharge cycle at 0.01C between the first preset voltage and a second preset voltage, wherein the first preset voltage is 1.5V, and the second voltage is 1.8V;
8) adjusting the temperature of the battery to 20 ℃;
9) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Example 2
1) Heating the cell to 70 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 50 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; the mass concentration ratio of the propylene sulfite to the trifluoroethyl phosphonic acid is 3:1, wherein the propylene sulfite is 4.5%, and the trifluoroethyl phosphonic acid is 1.5%;
3) adjusting the temperature of the battery to 60 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging to a charging cut-off voltage by a constant current of 2C, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than 0.01C, wherein the charging cut-off voltage is 2.5V;
5) injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 4:1, the second electrolyte is 40 ℃, the second electrolyte contains vinylene carbonate as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 9%;
6) adjusting the temperature of the battery to 10 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage at 2C, and performing 0.03C constant-current charge-discharge circulation at a small current between the first preset voltage and a second preset voltage, wherein the first preset voltage is 1.6V, and the second voltage is 1.9V;
8) adjusting the temperature of the battery to 25 ℃;
9) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Example 3
1) Heating the cell to 65 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 45 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; the mass concentration ratio of the propylene sulfite to the trifluoroethyl phosphonic acid is 3:1, wherein the propylene sulfite is 4.8%, and the trifluoroethyl phosphonic acid is 1.6%;
3) adjusting the temperature of the battery to 55 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging to a charging cut-off voltage by a constant current of 2C, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than 0.01C, wherein the charging cut-off voltage is 2.5V;
5) injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 3.5:1, the second electrolyte is 35 ℃, the second electrolyte contains vinylene carbonate as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 8%;
6) adjusting the temperature of the battery to 8 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage at 2C, and performing 0.02C constant-current charge-discharge circulation at a small current between the first preset voltage and a second preset voltage, wherein the first preset voltage is 1.55V, and the second voltage is 1.85V;
8) adjusting the temperature of the battery to 22 ℃;
9) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Comparative example 1
1) Heating the cell to 65 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 45 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; the mass concentration ratio of the propylene sulfite to the trifluoroethyl phosphonic acid is 3:1, wherein the propylene sulfite is 4.8%, and the trifluoroethyl phosphonic acid is 1.6%;
3) adjusting the temperature of the battery to 55 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: performing 0.1C constant current charge-discharge cycle between the charge cut-off voltage and the discharge cut-off voltage for 3 times; the charge cut-off voltage is 2.5V, and the discharge cut-off voltage is 1.2V.
5) Injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 3.5:1, the second electrolyte is 35 ℃, the second electrolyte contains vinylene carbonate as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 8%;
6) adjusting the temperature of the battery to 8 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage at 2C, and performing 0.02C constant-current charge-discharge circulation at a small current between the first preset voltage and a second preset voltage, wherein the first preset voltage is 1.55V, and the second voltage is 1.85V;
8) adjusting the temperature of the battery to 22 ℃;
9) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Comparative example 2
1) Heating the cell to 65 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 45 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; the mass concentration ratio of the propylene sulfite to the trifluoroethyl phosphonic acid is 3:1, wherein the propylene sulfite is 4.8%, and the trifluoroethyl phosphonic acid is 1.6%;
3) adjusting the temperature of the battery to 55 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging to a charging cut-off voltage by a constant current of 2C, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than 0.01C, wherein the charging cut-off voltage is 2.5V;
5) injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 3.5:1, the second electrolyte is 35 ℃, the second electrolyte contains vinylene carbonate as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 8%;
6) adjusting the temperature of the battery to 8 ℃;
7) a secondary formation, the secondary formation being: performing 0.1C constant current charge-discharge cycle between the charge cut-off voltage and the discharge cut-off voltage for 3 times;
8) adjusting the temperature of the battery to 22 ℃;
9) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Comparative example 3
1) Heating the cell to 65 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 45 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; the mass concentration ratio of the propylene sulfite to the trifluoroethyl phosphonic acid is 3:1, wherein the propylene sulfite is 4.8%, and the trifluoroethyl phosphonic acid is 1.6%;
3) adjusting the temperature of the battery to 55 ℃;
4) injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 3.5:1, the second electrolyte is 35 ℃, the second electrolyte contains vinylene carbonate as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 8%;
5) adjusting the temperature of the battery to 22 ℃;
6) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Comparative example 4
1) Heating the cell to 65 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 45 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; wherein the propylene sulfite accounts for 4.8 percent, and the trifluoroethyl phosphonic acid accounts for 3 percent;
3) adjusting the temperature of the battery to 55 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging to a charging cut-off voltage by a constant current of 2C, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than 0.01C, wherein the charging cut-off voltage is 2.5V;
5) injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 3.5:1, the second electrolyte is 35 ℃, the second electrolyte contains vinylene carbonate as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 8%;
6) adjusting the temperature of the battery to 8 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage at 2C, and performing 0.02C constant-current charge-discharge circulation at a small current between the first preset voltage and a second preset voltage, wherein the first preset voltage is 1.55V, and the second voltage is 1.85V;
8) adjusting the temperature of the battery to 22 ℃;
9) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Comparative example 5
1) Heating the cell to 65 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 45 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives; wherein the propylene sulfite is 3 percent, and the trifluoroethyl phosphonic acid is 1.6 percent;
3) adjusting the temperature of the battery to 55 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging to a charging cut-off voltage by a constant current of 2C, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than 0.01C, wherein the charging cut-off voltage is 2.5V;
5) injecting a second electrolyte, wherein the volume ratio of the first electrolyte to the second electrolyte is 3.5:1, the second electrolyte is 35 ℃, the second electrolyte contains vinylene carbonate as an additive, and the mass concentration of the vinylene carbonate in the second electrolyte is 8%;
6) adjusting the temperature of the battery to 8 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage at 2C, and performing 0.02C constant-current charge-discharge circulation at a small current between the first preset voltage and a second preset voltage, wherein the first preset voltage is 1.55V, and the second voltage is 1.85V;
8) adjusting the temperature of the battery to 22 ℃;
9) formation, the formation is as follows: and performing 0.1C constant current charge and discharge cycle 3 times between a charge cut-off voltage and a discharge cut-off voltage, wherein the discharge cut-off voltage is 1.2V.
Test and results
The batteries of examples 1 to 3 and comparative examples 1 to 5 were tested, the battery capacity was measured before storage, and then measured again after 60 days of storage at 50 ℃, and the capacity retention rate was measured after 200 cycles at a current of 0.5C after storage, and the results are shown in table 1. As can be seen from table 1, the batteries obtained by the method of the present invention have greatly improved capacity retention and cycle performance in high temperature storage.
TABLE 1
Figure BDA0002534934580000081
Figure BDA0002534934580000091
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.

Claims (8)

1. A formation method of a lithium ion battery comprises the following steps:
1) heating the battery to 60-70 ℃;
2) injecting a first electrolyte into the battery, wherein the temperature of the first electrolyte is 40-50 ℃, and the first electrolyte contains propylene sulfite and trifluoroethyl phosphonic acid as additives;
3) adjusting the temperature of the battery to be 50-60 ℃;
4) pre-formation, wherein the pre-formation comprises the following steps: charging with a charging current of more than 1C to a charging cut-off voltage at a constant current, and then charging at a constant voltage under the charging cut-off voltage until the charging current is lower than the cut-off current;
5) injecting a second electrolyte, wherein the temperature of the second electrolyte is 30-40 ℃, and the second electrolyte contains vinylene carbonate as an additive;
6) adjusting the temperature of the battery to 5-10 ℃;
7) a secondary formation, the secondary formation being: discharging to a first preset voltage with a current of more than 1C, and performing constant-current charge-discharge circulation between the first preset voltage and a second preset voltage with a small current, wherein the first preset voltage is 1.5-1.6V, and the second voltage is 1.8-1.9V;
8) adjusting the temperature of the battery to be 20-25 ℃;
9) formation, the formation is as follows: a constant current charge-discharge cycle is performed between a charge cut-off voltage and a discharge cut-off voltage.
2. The formation method according to the above claim, wherein the positive electrode active material of the lithium ion battery is a lithium iron phosphate-based material, and the negative electrode active material is a lithium titanate-based material.
3. The formation method according to the preceding claim, wherein the charge cut-off voltage is 2.5V and the discharge cut-off voltage is 1.2V.
4. The chemical synthesis method according to the previous claim, wherein the volume ratio of the first electrolyte to the second electrolyte is 3:1-4: 1.
5. The chemical conversion method according to the preceding claim, wherein the ratio of the concentration by mass of the propylene sulfite to the concentration by mass of the trifluoroethylphosphonic acid in the first electrolyte is 2.5 to 3:1, and the concentration by mass of the propylene sulfite is 4.5 to 5%.
6. The chemical conversion method according to the preceding claim, wherein the vinylene carbonate is present in the second electrolyte at a concentration of 7-9% by mass.
7. The formation method according to the above claim, wherein the positive active material of the lithium ion battery is LiFe0.97Nb0.03PO4F0.03The negative electrode active material is Li3.9Mg0.1Ti4.9Mo0.1O12。
8. The chemical synthesis method according to the previous claim, wherein the circulating current in the step 7 is 0.01-0.03C.
CN202010530186.7A 2020-06-11 2020-06-11 Formation method of lithium ion battery Withdrawn CN111725564A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928349A (en) * 2021-01-21 2021-06-08 中国科学院宁波材料技术与工程研究所 Formation method of lithium-rich battery
CN115611306A (en) * 2022-10-31 2023-01-17 湖南碳鸿新材料有限公司 Lithium ion power battery cathode material and preparation method thereof
WO2023030537A1 (en) * 2021-09-06 2023-03-09 天合光能股份有限公司 Electrolyte injection method for lithium ion battery, and use
WO2023184328A1 (en) * 2022-03-31 2023-10-05 宁德时代新能源科技股份有限公司 Lithium ion battery, battery module, battery pack, and electrical device

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928349A (en) * 2021-01-21 2021-06-08 中国科学院宁波材料技术与工程研究所 Formation method of lithium-rich battery
WO2023030537A1 (en) * 2021-09-06 2023-03-09 天合光能股份有限公司 Electrolyte injection method for lithium ion battery, and use
WO2023184328A1 (en) * 2022-03-31 2023-10-05 宁德时代新能源科技股份有限公司 Lithium ion battery, battery module, battery pack, and electrical device
CN115611306A (en) * 2022-10-31 2023-01-17 湖南碳鸿新材料有限公司 Lithium ion power battery cathode material and preparation method thereof
CN115611306B (en) * 2022-10-31 2023-12-26 上海意定新材料科技有限公司 Negative electrode material of lithium ion power battery and preparation method thereof

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