CN113903998A - Lithium ion battery and preparation method thereof - Google Patents
Lithium ion battery and preparation method thereof Download PDFInfo
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- CN113903998A CN113903998A CN202111162060.XA CN202111162060A CN113903998A CN 113903998 A CN113903998 A CN 113903998A CN 202111162060 A CN202111162060 A CN 202111162060A CN 113903998 A CN113903998 A CN 113903998A
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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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M10/0569—Liquid materials characterised by the solvents
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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
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- 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
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- 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 relates to the technical field of lithium ion batteries, and particularly provides a preparation method of a lithium ion battery, which comprises the steps of carrying out pre-charging treatment and formation treatment on a semi-finished product battery cell after liquid injection and sealing to prepare the lithium ion battery, wherein the pre-charging treatment is to keep the semi-finished product battery cell still for 1-4h, then charge the semi-finished product battery cell at a current of 0.05-0.1C, the charging time is at least 2.5min, and after the pre-treatment under the conditions, the voltage between a battery cathode and a shell can be increased, and the corrosion potential of the shell is increased, so that the corrosion risk of the battery shell is reduced, the safety is improved, and the service life is prolonged.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery and a preparation method thereof.
Background
In 1991, since the application of a lithium ion battery commercialized by sony of japan, the development of the lithium ion battery is rapid, and the lithium ion battery has been developed from the earliest consumer battery to a power battery for automobiles, and since 2008, with the development of technology, the promotion of national policies, the development of the power battery industry is rapid, and the lithium ion battery has become the most important component of new energy automobile power at present.
For lithium ion power battery, it is the important part of component of electric automobile industry, and the main component of main power battery on the market is soft package, cylinder, square battery three kinds, and for square battery, the shell material adopts the aluminum hull more, and it has good heat dissipation, advantage that mechanical strength is high. The lower plastic is arranged on the cover plate of the shell to connect the battery cell and the shell together.
Because the lower plastic and the battery shell are both made of conductive materials, the battery shell is electrified in a use state, and the normal use and the electrical safety performance of the battery are influenced. Therefore, in the prior art, the material of the lower plastic is changed, and the insulating material is adopted to replace the conductive material, so that the whole shell is uncharged in the use state. However, researches find that when the uncharged battery shell is adopted, the inner side wall of the shell is easy to corrode, the shell is damaged due to serious corrosion, electrolyte leaks, and great hidden danger is generated on the safety of the power lithium ion battery.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the housing is easy to corrode due to the fact that the lower plastic made of an insulating material is not electrified when the housing is used in the prior art, and therefore, the preparation method of the lithium ion battery is provided.
The invention provides a preparation method of a lithium ion battery, which comprises the steps of carrying out pre-charging treatment on a semi-finished product battery cell after liquid injection and sealing to prepare the lithium ion battery, wherein the pre-charging treatment comprises the steps of standing the semi-finished product battery cell after liquid injection and sealing for 1-4h, and then charging at a current of 0.05-0.1C for at least 2.5 min.
Further, in the pre-charging process, the charging time is 2.5-80 min.
Further, the pre-charging process is followed by a formation process and a capacity grading process.
In some preferred embodiments, the formation treatment is to stand the battery after the pre-charging treatment, and then charge the battery to 2.5-3.8V at a current of 0.05-0.2C.
In some preferred embodiments, the capacity grading treatment is to charge the battery after the formation treatment to 4.0-4.5V at a current of 0.3-0.4C, stand for 20-40 min, then discharge the battery to 2.5-3.0V at a current of 0.3-0.4C, and cycle the charging and discharging for 2-3 times.
Further, in the formation treatment, the standing time is 24-36 h.
Further, the preparation method of the semi-finished product battery cell comprises the following steps:
assembling the positive electrode, the negative electrode and the diaphragm into a battery pole group, placing the battery pole group in a packaging shell for assembly, drying, injecting electrolyte, and sealing to obtain the battery.
The positive electrode of the invention can adopt a conventional commercially available positive plate, and can also be obtained by processing conventional materials in the field through a conventional process, for example, the conventional positive active material can be combined on a conventional current collector, and the positive active material can adopt LiMnO2、LiMn2O4、LiNixMnyCozO2、LiCoO2、LiFePO4Wherein x + y + z is 1, in certain preferred embodiments 0.6. ltoreq. x.ltoreq.0.90, 0.05. ltoreq. y.ltoreq.0.2, 0.05. ltoreq. z.ltoreq.0.2. The current collector can be made of aluminum foil, and the thickness of the foil is 10-15 mu m. The combined process may employ existing coating and cold pressing processes. Specifically, a positive electrode active substance, a conductive agent and a binder are uniformly mixed according to a conventional proportion and added into a solvent to prepare positive electrode slurry; and uniformly coating the positive slurry on a positive current collector aluminum foil, drying, cold pressing, and performing die cutting and strip division to prepare the positive plate. The solid content of the positive electrode slurry can be 70-75%, the conductive agent can be a conventional conductive agent such as acetylene black, the binder can be a conventional binder such as styrene butadiene rubber or vinylidene fluoride PVDF, and the solvent can be a conventional organic solvent such as N-methylpyrrolidone NMP.
The negative electrode of the invention can adopt a conventional commercially available negative electrode sheet, and can also be obtained by adding conventional materials in the field through a conventional process, for example, a conventional negative electrode active material can be combined on a conventional current collector, and the negative electrode active material can adopt graphite or silicon negative electrode material. The combined process may employ existing coating and cold pressing processes. Specifically, mixing a negative electrode active material, a conductive agent, a thickening agent and a binder according to a conventional ratio, adding the mixture into solvent water, and uniformly mixing to prepare negative electrode slurry; and uniformly coating the negative electrode slurry on a copper foil of a negative current collector, drying and then carrying out cold pressing to prepare a negative plate. The solid content of the cathode slurry can be 50-55%, the conductive agent can be a conventional conductive agent such as acetylene black, the binder can be a conventional binder such as styrene butadiene rubber or vinylidene fluoride PVDF, and the thickening agent can be a conventional thickening agent such as sodium carboxymethylcellulose.
The electrode solution of the present invention may be a lithium ion electrolyte solution that is conventionally commercially available, or may be self-prepared from existing conventional materials, for example, an electrolyte solution including a solvent, a lithium salt, and an additive, the solvent being at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate. The lithium salt is selected from lithium hexafluorophosphate and/or lithium tetrafluoroborate; the additive is at least one selected from vinylene carbonate, propylene carbonate, vinyl sulfate and lithium difluorophosphate. The molar concentration of the lithium salt is 0.8-1.2mol/L, and a mixed solution of Ethylene Carbonate (EC), dimethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1-1:2:2 can be used as a solvent. The volume percent of the additive may be 0.5-5%.
The separator of the present invention may be used with existing conventional separators such as PE separators, PP/PE composite films, or other commercially available separators.
The invention also provides a lithium ion battery which is prepared according to any one of the preparation methods.
The invention also provides a lithium ion battery which is provided with the positive electrode.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the lithium ion battery provided by the invention, researches show that when the lithium ion battery using plastic under insulation is used, a micro short circuit reaction exists between a cathode and a shell to form slight corrosion, liquid leakage occurs due to long-term use, the lithium ion battery is prepared by pre-charging and formation treatment of a semi-finished product battery cell after liquid injection and sealing, the pre-charging treatment is controlled to be that the semi-finished product battery cell is kept still for 1-4h, then charging is carried out at a current of 0.05-0.1C, the charging time is at least 2.5min, the voltage of the cathode and the shell of the battery can be increased after the pre-treatment under the conditions, and the corrosion potential of the shell is increased, so that the corrosion risk of the battery shell is reduced, the safety is improved, and the service life is prolonged.
2. In the preferred embodiment of the preparation method of the lithium ion battery provided by the invention, the charging time is controlled to be 2.5-80min in the pre-charging treatment process, so that the corrosion resistance of the battery can be further improved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of a lithium ion battery, which includes pre-charging a semi-finished product battery cell, specifically, standing the semi-finished product battery cell for 1 hour at room temperature, and charging for 5min at a current of 0.05C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. And then charging to 4.2V by 0.33C, standing at room temperature for 30min, discharging to 2.8V by 0.33C, and cycling the charging and discharging for 2 times to complete capacity grading, thereby obtaining the lithium ion battery.
The semi-finished product battery cell adopted in the embodiment is prepared by the following method:
(1) preparing a positive plate: taking a positive electrode active material (LiNi)0.6Mn0.2Co0.2O2) The conductive agent acetylene black and the binder polyvinylidene fluoride PVDF are mixed according to the mass ratio of 96.5: 2.5: 1, uniformly mixing to obtain a mixture, adding the mixture into a solvent N-methyl-2-pyrrolidone (NMP) to obtain anode slurry (the solid content is 70%), and mixing the anode slurry according to the ratio of 36mg/cm2Has uniform areal densityCoating the aluminum foil on a positive current collector aluminum foil, wherein the thickness of the aluminum foil is 10 mu m, drying the aluminum foil at 85 ℃, then cold pressing the aluminum foil, and then performing die cutting and slitting to prepare the lithium ion battery positive plate.
(2) Preparing a negative plate: taking negative active material graphite, conductive agent acetylene black, thickening agent sodium carboxymethylcellulose (CMC) and binder Styrene Butadiene Rubber (SBR) according to a mass ratio of 96: 2: 1:1, mixing to obtain a mixture, adding the mixture into solvent water, uniformly mixing and preparing negative electrode slurry (the solid content is 50%); the slurry of the negative electrode is mixed according to the proportion of 20mg/cm2The surface density of the copper foil is uniformly coated on the copper foil of the negative current collector, the thickness of the copper foil is 6 mu m, and the copper foil is dried at 85 ℃ and then is cold-pressed to prepare the negative plate of the lithium ion battery to be manufactured.
(3) Preparing an electrolyte: dissolving lithium hexafluorophosphate in a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a volume ratio of 5:3:2 to obtain a lithium hexafluorophosphate solution with the concentration of 1.15mol/L, and adding 1 vt% of vinylene carbonate, 0.5 vt% of lithium difluorophosphate and 0.5 vt% of vinyl sulfate DTD to obtain the lithium ion battery electrode solution.
(4) Assembling the positive plate, the PE diaphragm (from Enjie corporation, model: SV12) and the negative plate in a laminating manner to obtain a battery pole group, placing the battery pole group in an aluminum packaging shell (from Kedali corporation, model 52148102) with plastic under PE material for assembly, drying in a vacuum drying box, injecting electrolyte, and sealing to obtain a semi-finished product battery core.
Example 2
The embodiment provides a preparation method of a lithium ion battery, which includes pre-charging a semi-finished product battery cell, specifically, standing the semi-finished product battery cell for 1 hour at room temperature, and charging for 10min at a current of 0.05C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. Charging to 4.2V by 0.33C, standing for 30min, discharging to 2.8V according to 0.33C to obtain discharge capacity, circularly charging and discharging for 2 times, completing capacity grading, and obtaining the lithium ion battery.
The semi-finished product battery cell adopted in the embodiment is prepared by the following method:
(1) is justPreparing a pole piece: taking a positive electrode active material (LiNi)0.8Mn0.1Co0.1O2) The conductive agent acetylene black and the binder polyvinylidene fluoride PVDF are mixed according to the mass ratio of 96.5: 2.5: 1, uniformly mixing to obtain a mixture, adding the mixture into a solvent N-methyl-2-pyrrolidone (NMP) to prepare anode slurry (the solid content is 75%), and uniformly mixing the anode slurry according to the ratio of 36mg/cm2The surface density of the aluminum foil is coated on an aluminum foil of a positive current collector, the thickness of the aluminum foil is 10 mu m, the aluminum foil is dried at 85 ℃ and then is cold-pressed, and then die cutting and strip splitting are carried out to prepare the positive plate of the lithium ion battery.
(2) Preparing a negative plate: taking negative active material graphite, a conductive agent acetylene black, a thickening agent sodium carboxymethylcellulose (CMC), and a binder Styrene Butadiene Rubber (SBR) according to a mass ratio of 94: 3: 1.5: 1.5, mixing to obtain a mixture, adding the mixture into solvent water, uniformly mixing and preparing negative electrode slurry (the solid content is 55%); the slurry of the negative electrode is mixed according to the proportion of 20mg/cm2Uniformly coating the copper foil on a negative current collector copper foil with the thickness of 6 mu m, drying at 85 ℃ and then carrying out cold pressing to prepare the lithium ion battery negative plate to be manufactured.
(3) Preparing an electrolyte: dissolving lithium hexafluorophosphate in a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a volume ratio of 5:3:2 to obtain a lithium hexafluorophosphate solution with the concentration of 1.15mol/L, and adding 1 vt% of vinylene carbonate, 0.5 vt% of lithium difluorophosphate and 0.5 vt% of DTDto obtain the lithium ion battery electrode solution.
(4) Assembling the positive plate, the PE diaphragm (from Enjie corporation, model: SV12) and the negative plate in a laminating manner to obtain a battery pole group, placing the battery pole group in an aluminum packaging shell (from Kedali corporation, model 52148102) with plastic under PE material for assembly, drying in a vacuum drying box, injecting electrolyte, and sealing to obtain a semi-finished product battery core.
Example 3
The embodiment provides a preparation method of a lithium ion battery, which includes the steps of pre-charging a semi-finished product battery cell prepared according to the same method as in embodiment 1, specifically, standing the semi-finished product battery cell at room temperature for 1 hour, and charging for 80min at a current of 0.05C. And standing the pretreated battery for 36 hours at room temperature, charging to 2.5V by using a current of 0.2C, finishing formation treatment, filling the battery to 4.2V by using 0.4C, standing for 40min, discharging to 2.5V according to 0.3C to obtain a discharge capacity, circulating for 3 times, finishing capacity grading and obtaining the lithium ion battery.
Example 4
The embodiment provides a preparation method of a lithium ion battery, which includes the steps of pre-charging a semi-finished product battery cell prepared according to the same method as in embodiment 1, specifically, standing the semi-finished product battery cell at room temperature for 1 hour, and charging for 2.5min at a current of 0.1C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. Filling the lithium ion battery with the lithium ion battery to 4.2V at 0.33C, standing for 30min, discharging to 2.8V at 0.33C to obtain discharge capacity, and circulating for 2 times to complete capacity grading to obtain the lithium ion battery.
Example 5
The embodiment provides a preparation method of a lithium ion battery, which includes the steps of pre-charging a semi-finished product battery cell prepared according to the same method as in embodiment 1, specifically, standing the semi-finished product battery cell at room temperature for 1 hour, and charging for 5min at a current of 0.1C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. Filling the lithium ion battery with the lithium ion battery to 4.2V at 0.33C, standing for 30min, discharging to 2.8V at 0.33C to obtain discharge capacity, and circulating for 2 times to complete capacity grading to obtain the lithium ion battery.
Example 6
The embodiment provides a preparation method of a lithium ion battery, which includes the steps of pre-charging a semi-finished product battery cell prepared according to the same method as in embodiment 1, specifically, standing the semi-finished product battery cell at room temperature for 1 hour, and charging for 7.5min with a current of 0.1C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. Filling the lithium ion battery with the lithium ion battery to 4.2V at 0.33C, standing for 30min, discharging to 2.8V at 0.33C to obtain discharge capacity, and circulating for 2 times to complete capacity grading to obtain the lithium ion battery.
Example 7
The embodiment provides a preparation method of a lithium ion battery, which includes the steps of pre-charging a semi-finished product battery cell prepared according to the same method as in embodiment 1, specifically, standing the semi-finished product battery cell at room temperature for 4 hours, and charging for 5min at a current of 0.05C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. Filling the lithium ion battery with the lithium ion battery to 4.2V at 0.33C, standing for 30min, discharging to 2.8V at 0.33C to obtain discharge capacity, and circulating for 2 times to complete capacity grading to obtain the lithium ion battery.
Example 8
The embodiment provides a preparation method of a lithium ion battery, which includes the steps of pre-charging a semi-finished product battery cell prepared according to the same method as in embodiment 1, specifically, standing the semi-finished product battery cell at room temperature for 4 hours, and charging for 10min at a current of 0.05C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. Filling the lithium ion battery with the lithium ion battery to 4.2V at 0.33C, standing for 30min, discharging to 2.8V at 0.33C to obtain discharge capacity, and circulating for 2 times to complete capacity grading to obtain the lithium ion battery.
Example 9
The embodiment provides a preparation method of a lithium ion battery, which includes the steps of pre-charging a semi-finished product battery cell prepared according to the same method as in embodiment 1, specifically, standing the semi-finished product battery cell at room temperature for 4 hours, and charging for 15min at a current of 0.05C. And then standing the pretreated battery for 24 hours at room temperature, and charging the battery to 3.8V at a current of 0.1C to finish the formation treatment. Filling the lithium ion battery with the lithium ion battery to 4.2V at 0.33C, standing for 30min, discharging to 2.8V at 0.33C to obtain discharge capacity, and circulating for 2 times to complete capacity grading to obtain the lithium ion battery.
Comparative example 1
The comparative example provides a preparation method of a lithium ion battery, which is basically the same as that in example 1, except that no pre-charging treatment is performed, specifically, a semi-finished product battery core prepared by the same method in example 1 is subjected to chemical conversion treatment and partial volume treatment, specifically, the semi-finished product battery core is stood at room temperature for 24 hours, charged to 3.8V (chemical conversion treatment) by a current of 0.1C, fully charged to 4.2V by 0.33C, stood for 30min, discharged to 2.8V by 0.33C to obtain a discharge capacity, and the cycle is performed for 2 times to complete partial volume and obtain the lithium ion battery.
Comparative example 2
The present comparative example provides a method for preparing a lithium ion battery, which is substantially the same as example 1 except that the specific conditions of the pre-charge treatment are different, and the pre-charge treatment of the present comparative example is to allow the semi-finished battery cell prepared in the same manner as in example 1 to stand at room temperature for 5 hours and to be charged at a current of 0.1C for 2.5 min.
Comparative example 3
The present comparative example provides a method for preparing a lithium ion battery, which is substantially the same as example 1 except that the specific conditions of the pre-charge treatment are different, and the pre-charge treatment of the present comparative example is to allow the semi-finished battery cell prepared in the same manner as in example 1 to stand at room temperature for 5 hours and to be charged at a current of 0.1C for 5 minutes.
Comparative example 4
The present comparative example provides a method for preparing a lithium ion battery, which is substantially the same as example 1 except that the specific conditions of the pre-charge treatment are different, and the pre-charge treatment of the present comparative example is to allow the semi-finished battery cell prepared in the same manner as in example 1 to stand at room temperature for 5 hours and to be charged at a current of 0.1C for 7.5 minutes.
Comparative example 5
This comparative example provides a method of manufacturing a lithium ion battery, which is substantially the same as example 1 except that the specific conditions of the pre-charge treatment are different, and the pre-charge treatment of this comparative example is to allow the semi-finished battery cell manufactured by the same method as example 1 to stand at room temperature for 30min and to be charged at a current of 0.1C for 7.5 min.
Comparative example 6
The present comparative example provides a method for preparing a lithium ion battery, which is substantially the same as example 1 except that the specific conditions of the pre-charge treatment are different, and the pre-charge treatment of the present comparative example is to allow the semi-finished battery cell prepared in the same manner as in example 1 to stand at room temperature for 1 hour and charge at a current of 0.2C for 7.5 min.
Comparative example 7
This comparative example provides a method of manufacturing a lithium ion battery, which is substantially the same as example 1 except that the specific conditions of the pre-charge treatment are different, and the pre-charge treatment of this comparative example is to allow the semi-finished battery cell manufactured by the same method as example 1 to stand at room temperature for 1 hour and charge at a current of 0.02C for 7.5 min.
Experimental example 1
The lithium ion batteries (two in each group, noted as cell 1 and cell 2) prepared in each example and comparative example were stored at 55 ℃ for 30 days, and then subjected to reliability test and cell safety test (including hot box, short circuit, overcharge and overdischarge test) according to the GB/T-31485 2015 standard, and then the cells were disassembled to confirm the corrosion of the inside of the case.
Among them, the severe corrosion means that the inside of the inner wall of the battery case is blackened seriously. The SEM test shows that the aluminum has serious chap phenomenon, in EDS characterization, P, F elements are arranged in all areas, and F elements in a corrosion area are obviously more and more, which is caused by lithium embedding action in aluminum, so that lithium aluminum alloy is formed, and slight corrosion means that the inner part of the inner wall of a battery shell is locally blackened and blackened in a point shape. The cracking phenomenon of the aluminum material is slight through SEM test, P, F elements are contained in all areas in EDS characterization, and the increase of F element in a corrosion area is less, which is caused by lithium intercalation in aluminum, so that the lithium aluminum alloy is formed. The non-corrosion means that the inner wall of the battery shell is not blackened. The aluminum material has no chap phenomenon through SEM test, P, F elements are arranged in all areas in EDS characterization, and F elements in corrosion areas are not increased.
TABLE 1 test results table
As can be seen from the above table, examples 1 to 9 according to the present invention can significantly improve the corrosion of the battery case and improve the corrosion prevention capability, as compared to comparative examples 1 to 7.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The preparation method of the lithium ion battery is characterized by comprising the steps of carrying out pre-charging treatment on a semi-finished product battery cell after liquid injection and sealing to prepare the lithium ion battery, wherein the pre-charging treatment is to stand the semi-finished product battery cell for 1-4h and then charge the semi-finished product battery cell at a current of 0.05-0.1C for at least 2.5 min.
2. The method according to claim 1, wherein a charging time in the pre-charging process is 2.5 to 80 min.
3. The preparation method of the lithium ion battery according to claim 1 or 2, characterized in that the pre-charging treatment is further followed by a chemical conversion treatment and a capacity grading treatment, preferably, the chemical conversion treatment is to stand the pre-charged battery and then charge the battery to 2.5-3.8V at a current of 0.05-0.2C; preferably, the capacity grading treatment is to charge the battery after the formation treatment to 4.0-4.5V at a current of 0.3-0.4C, stand for 20-40 min, then discharge to 2.5-3.0V at a current of 0.3-0.4C, and circulate the charging and discharging for 2-3 times.
4. The preparation method of the lithium ion battery according to claim 3, wherein the standing time in the formation treatment is 24-36 h.
5. The method for preparing a lithium ion battery according to any one of claims 1 to 4, wherein the method for preparing the semi-finished battery cell comprises the following steps:
assembling the positive electrode, the negative electrode and the diaphragm into a battery pole group;
and (3) placing the battery pole group in a packaging shell for assembly, drying, injecting electrolyte, and sealing to obtain the battery pole group.
6. The method of claim 5, wherein the electrolyte comprises a solvent, a lithium salt, and an additive, and the solvent is at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate; the lithium salt is selected from lithium hexafluorophosphate and/or lithium tetrafluoroborate; the additive is at least one selected from vinylene carbonate, propylene carbonate, vinyl sulfate and lithium difluorophosphate.
7. The method of claim 5, wherein the positive electrode comprises a current collector and a positive active material bonded to the current collector, and the negative electrode comprises a current collector and a negative active material bonded to the current collector.
8. The method of claim 7, wherein the positive active material is selected from the group consisting of LiMnO2、LiMn2O4、LiNixMnyCozO2、LiCoO2、LiFePO4Wherein x + y + z is 1.
9. The method of claim 7, wherein the negative active material is selected from graphite or silicon negative materials.
10. A lithium ion battery, characterized in that it is produced according to the method for producing a lithium ion battery according to any one of claims 1 to 9.
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