CN111682272A - Lithium ion battery formation method and lithium ion battery - Google Patents
Lithium ion battery formation method and lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 241
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 241
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000007600 charging Methods 0.000 claims abstract description 291
- 239000011265 semifinished product Substances 0.000 claims abstract description 119
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 239000013067 intermediate product Substances 0.000 claims abstract description 27
- 238000004806 packaging method and process Methods 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 abstract description 4
- 238000005755 formation reaction Methods 0.000 description 49
- 238000010277 constant-current charging Methods 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 230000008901 benefit Effects 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a lithium ion battery formation method and a lithium ion battery, which comprise the following steps: providing a lithium ion battery semi-finished product into which electrolyte is injected, and carrying out primary standing operation on the lithium ion battery semi-finished product; pressurizing the semi-finished product of the lithium ion battery after the semi-finished product is stood for the first time, then performing multiple charging operations, and charging to cut-off voltage to obtain an intermediate product of the lithium ion battery, wherein the charging current of the multiple charging operations is gradually increased, the charging current is 0.1-1.5C, the charging frequency is more than or equal to 3, and the current difference value of the two charging operations is 0.05-1.0C; and carrying out secondary standing operation on the lithium ion battery intermediate product, and then carrying out exhaust packaging operation to complete formation operation. And multiple charging is adopted for formation operation, so that the uniformity and speed of the SEI film formation are flexible and controllable, the uniform and stable SEI film is favorably formed, and the performance and quality of the lithium ion battery finished product are improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery formation method and a lithium ion battery.
Background
The lithium ion battery has the characteristics of high energy density, high working voltage, long service life, no memory effect and the like, is widely applied to the fields of aerospace, medical treatment, energy storage and the like, and along with the promotion of large-scale application of the lithium ion battery in recent years, the power lithium ion battery develops rapidly, and the manufacturing process technology of the power lithium ion battery also makes great progress, wherein the formation is an important process in the production process of the lithium battery, a passivation layer, namely a solid electrolyte interface film (SEI) for short is formed on the surface of a negative electrode during the formation, and a part of lithium ions of the positive electrode are consumed during the formation process of the SEI film and simultaneously react with an electrolyte to generate gas.
At present, the traditional process generally comprises the following steps: after the battery is injected with liquid, the battery is stood for a period of time at room temperature, then is heated and stood, then is formed, then is stood at room temperature after being formed, is exhausted, sealed and formed, and finally is subjected to capacity grading.
Meanwhile, under a high-capacity high-voltage physical system of the lithium ion battery, the electrolyte is difficult to infiltrate, the film formation is not uniform and unstable in the formation process, the formation of an SEI film in the formation process is hindered, meanwhile, the film formation is difficult due to the uneven infiltration of the electrolyte, the quality of the SEI film directly influences the electrochemical properties of the battery, such as the cycle life, the stability, the self-discharge property, the safety and the like, the battery is greatly influenced, gas is generated in the formation process of the lithium ion battery, the battery swells, the reaction interface is poor, and the performance of the battery can be influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a lithium ion battery formation method which can be operated more flexibly and can form a uniform and stable SEI film, and a lithium ion battery, so that the multiplying power discharge performance of the battery is improved, the discharge capacity is increased, and the cycle performance is improved.
The purpose of the invention is realized by the following technical scheme:
a lithium ion battery formation method comprises the following steps:
providing a lithium ion battery semi-finished product into which electrolyte is injected, and carrying out primary standing operation on the lithium ion battery semi-finished product;
pressurizing the semi-finished product of the lithium ion battery after the semi-finished product is stood for the first time, then performing multiple charging operations, and charging to cut-off voltage to obtain an intermediate product of the lithium ion battery, wherein the charging current of the multiple charging operations is gradually increased, the charging current is 0.1-1.5C, the charging frequency is more than or equal to 3, and the current difference value of the two charging operations is 0.05-1.0C;
and carrying out secondary standing operation on the lithium ion battery intermediate product, and then carrying out exhaust packaging operation to complete formation operation.
In one embodiment, in the first standing operation of the semi-finished product of the lithium ion battery, the standing time is 10-14 h, and the temperature of the first standing is controlled to be 43-47 ℃.
In one embodiment, the pressurizing pressure is controlled to be 1.15MPa to 1.25MPa in the pressurizing operation of the lithium ion battery semi-finished product after the lithium ion battery semi-finished product is firstly stood.
In one embodiment, the charging temperature is controlled to be 55 ℃ to 65 ℃ during the plurality of charging operations.
In one embodiment, the charge state of charge is 70% or less and the cut-off voltage is 3.9V to 4.0V in multiple charging operations.
In one embodiment, the plurality of charging operations includes a first charging operation, a second charging operation, a third charging operation, and a fourth charging operation.
In one embodiment, the charging current of the first charging operation is 0.1C to 0.4C, the charging state of charge is not more than 5% SOC, the charging current of the second charging operation is 0.45C to 0.65C, the charging state of charge is not more than 10% SOC, the charging current of the third charging operation is 0.7C to 0.9C, the charging state of charge is not more than 20% SOC, the charging current of the fourth charging operation is 1.0C to 1.5C, and the charging state of charge is not more than 70% SOC.
In one embodiment, in the secondary standing operation of the lithium ion battery intermediate product, the standing time is 2-4 h, and the temperature of the secondary standing is controlled to be 22-28 ℃.
In one embodiment, before the first standing operation is performed on the lithium ion battery semi-finished product, a pre-sealing operation is further performed on the lithium ion battery semi-finished product.
A lithium ion battery is prepared by the lithium ion battery formation method.
Compared with the prior art, the invention has at least the following advantages:
the invention adopts a multi-charging method to form the lithium ion battery semi-finished product, the charging current is 0.1-1.5C, and the charging current is increased gradually, namely, the lithium ion battery semi-finished product is formed by increasing current gradually, so that the uniformity and the speed of the SEI film are more flexible and controllable, and a more uniform and stable SEI film is formed, thereby being beneficial to improving the multiplying power discharge performance and the cycle performance of the lithium ion battery and increasing the discharge capacity of the lithium ion battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow chart illustrating steps of a method for forming a lithium ion battery according to an embodiment of the present invention;
FIG. 2 is a comparative graph of discharge capacity ratios of batteries of example 1, example 2, example 3, example 4, example 5 and comparative example 1 according to the present invention;
FIG. 3 is a graph showing the discharge cycle performance test of 1C/3C batteries after high-temperature storage at 60 ℃ for the batteries of example 3, example 4, example 5 and comparative example 1 according to the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, referring to fig. 1, a method for forming a lithium ion battery includes the following steps:
and S110, providing the lithium ion battery semi-finished product after the electrolyte is injected, and carrying out a first standing operation on the lithium ion battery semi-finished product.
It should be noted that, in the preparation process of the lithium ion battery, generally, the positive electrode slurry and the negative electrode slurry are respectively coated and processed to obtain the positive electrode plate and the negative electrode plate, and then the obtained positive electrode plate, the negative electrode plate and the diaphragm are assembled and molded to form the electrode core, the electrode core is placed in the aluminum plastic film, and the electrolyte is injected to obtain the semi-finished product of the lithium ion battery.
In one embodiment, in the first standing operation of the semi-finished product of the lithium ion battery, the standing time is 10-14 h, and the temperature of the first standing is controlled to be 43-47 ℃. It should be noted that the electrolyte is an ion conductor playing a role in conducting between the positive plate and the negative plate of the lithium ion battery, during the charging and discharging process of the lithium ion battery, lithium ions are transmitted between the positive plate and the negative plate back and forth, the infiltration effect of the electrolyte can affect the film forming effect of the SEI film, thereby affecting the finished performance of the lithium ion battery, wherein, along with the extension of the standing time, the electrolyte can be ensured to fully infiltrate the positive plate and the negative plate, thereby achieving good infiltration effect, but the longer standing time can reduce the production efficiency, thereby resulting in low equipment utilization rate, meanwhile, the longer standing time is required for the semi-finished product of the lithium ion battery at room temperature, the electrolyte can be ensured to fully infiltrate the positive plate and the negative plate, thereby being not beneficial to the improvement of the production benefit, along with the rise of the standing temperature, the movement of substance, the electrolyte can more quickly and better infiltrate the positive plate and the negative plate, when the temperature is too high, the property of the electrolyte is easily influenced, and the positive plate, the negative plate and the diaphragm can be damaged, so that the performance of a finished lithium ion battery product is influenced, more energy needs to be input, the energy consumption is higher, the energy saving is not facilitated, under the comprehensive consideration, the standing time is controlled to be 10-14 h, and the temperature for standing for the first time is preferably 43-47 ℃, so that the good infiltration effect can be achieved, the time for standing for the first time can be effectively shortened, the production time is saved, and the production benefit is improved. More preferably, in the first standing operation of the semi-finished product of the lithium ion battery, the standing time is 12 hours, and the temperature of the first standing is controlled to be 45 ℃. Therefore, the wetting effect can be further ensured, and the subsequent better formation of an SEI film is facilitated.
In one embodiment, before the first standing operation is performed on the lithium ion battery semi-finished product, a pre-sealing operation is also performed on the lithium ion battery semi-finished product. It should be noted that, in the production process of the lithium ion battery, an air bag is generally reserved, because there is gas generated in the subsequent process of forming the SEI film, the generated gas can be stored in the air bag, through the operation of pre-sealing the lithium ion battery semi-finished product, that is, the opening of the air bag is sealed, the pole core and the electrolyte formed by assembling the positive plate, the negative plate and the diaphragm can be sealed, the contact with the external environment is avoided, the influence of the external environment on the subsequent SEI film forming process is avoided, thereby being beneficial to reducing the requirement on the environment in the production operation and being beneficial to reducing the production difficulty, meanwhile, the reserved air bag region can be used for storing the gas, and the normal operation of the subsequent charging operation is ensured.
And S120, pressurizing the lithium ion battery semi-finished product after the lithium ion battery semi-finished product is firstly placed, then performing multiple charging operations, and charging to cut-off voltage to obtain a lithium ion battery intermediate product, wherein the charging current of the multiple charging operations is gradually increased, the charging current is 0.1-1.5C, the charging frequency is more than or equal to 3, and the current difference value of the two charging operations is 0.05-1.0C.
It should be noted that, the lithium ion battery semi-finished product can be placed in the clamping plate, the lithium ion battery semi-finished product is pressurized by the pressure device, so that the lithium ion battery semi-finished product is subjected to a certain pressure, and since gas is generated in the subsequent process of charging the lithium ion battery to form the SEI film, gas such as ethylene, hydrogen, carbon monoxide and the like can be generated, by pressurizing the lithium ion battery semi-finished product, on one hand, the electrolyte can be ensured to be better contacted with the positive plate and the negative plate, the formation of the SEI film is promoted, in the SEI film forming process, on the other hand, the gas is promoted to escape from the electrolyte, the gas is stored in a reserved air bag after escaping, the normal operation of the charging operation is avoided being influenced, the bubble amount in the electrolyte is favorably reduced, so that the lithium ion battery finished product has a larger battery capacity, and then the lithium ion battery, charging to a cut-off voltage to form an SEI film, wherein after a plurality of charging operations are finished, the charging state of charge is not more than 70%, the cut-off voltage is 3.9V-4.0V, and it is worth mentioning that in the pressurizing operation of the lithium ion battery semi-finished product, the reserved air bag area is prevented from being pressurized, so that gas can be stored in the air bag after escaping, and the normal operation of the subsequent charging operation is ensured.
Wherein, in the multiple charging operation, the charging frequency is more than or equal to 3, that is, 3 times and more than 3 times of multiple charging operation are adopted to carry out formation of the lithium ion battery semi-finished product to form the SEI film, for example, the charging frequency of the multiple charging operation is 3 times, 4 times, 5 times, 6 times or more than 6 times, the charging current is 0.1C-1.5C, the charging current is prevented from being too high or too low, the charging current is controlled, the current difference value of the two charging operations before and after is 0.05C-1.0C, thus, the charging operation of the lithium ion battery semi-finished product by increasing the current gradually can be ensured, meanwhile, the current difference between the charging operations is prevented from being too large, the uniform and stable SEI film structure is favorably formed, the SEI film forming effect is good, compared with the traditional one-step charging operation, the charging current and the charging time of the multiple charging operation are more flexible, thereby, the uniformity and the speed of the SEI film are more flexible and controllable, and the SEI film which is more stable and uniform is favorably obtained, so that the rate discharge performance and the cycle performance of the lithium ion battery are favorably improved, the discharge capacity of the lithium ion battery is favorably increased, the temperature resistance of the lithium ion battery is better due to the stable and uniform formed SEI film, the low-temperature discharge capacity and the high-temperature rate discharge performance of the lithium ion battery are improved, and meanwhile, the formation time is favorably saved, and the production benefit is improved.
In one embodiment, in the multiple charging operations, the shelf life of the lithium ion battery semi-finished product is less than or equal to 3min in the two charging operations. It should be noted that, because the lithium ion battery semi-finished product is subjected to multiple charging operations, and the charging current is gradually increased, after each charging operation is completed, the charging is stopped, the charging current is increased again, and the lithium ion battery semi-finished product is charged next time, in the process of current replacement, the lithium ion battery semi-finished product is shelved for a certain time, the shelved time is less than or equal to 3min, and when the shelved time is greater than 3min, the shelved time is too long, on one hand, the normal running of an SEI film formation reaction is affected, so that the stability of the obtained SEI film structure is affected, on the other hand, the overlong shelved time greatly increases the time cost, and is not beneficial to improving the production efficiency, and under comprehensive consideration, in the two charging operations, the shelved time of the.
In one embodiment, the pressurizing pressure is controlled to be 1.15 MPa-1.25 MPa in the pressurizing operation of the lithium ion battery semi-finished product after the lithium ion battery semi-finished product is firstly stood. It should be noted that, in the operation of pressurizing the lithium ion battery semi-finished product, since the positive plate and the negative plate are easily damaged, proper pressurizing pressure needs to be controlled, so as to avoid damage to the lithium ion battery semi-finished product, when the pressurizing pressure is greater than 1.25Mpa, the pressure applied to the lithium ion semi-finished product is too large, so that damage is easily caused, and the excessive pressurizing pressure may cause the positive plate and the negative plate to be broken and fragmented, so as to affect the performance and quality of the obtained lithium ion battery semi-finished product, when the pressurizing pressure is less than 1.15Mpa, the pressure is small, the effect is not obvious, so that gas in the electrolyte is not discharged, the formation of an SEI film is affected, and under comprehensive consideration, the pressurizing pressure is controlled to be 1.15 Mpa-1.25 Mpa. Preferably, in the pressurizing operation of the lithium ion battery semi-finished product after the first standing, the pressurizing pressure is controlled to be 1.2 Mpa. Therefore, the pressurizing pressure is moderate, so that gas in the electrolyte can be better discharged, and meanwhile, the lithium ion semi-finished product is prevented from being damaged.
In one embodiment, the charging temperature is controlled to be 55 ℃ to 65 ℃ during the plurality of charging operations. It should be noted that, in multiple charging operations, the charging temperature of each charging operation is controlled to 55-65 ℃, which is beneficial to accelerating the charging operation and improving the production efficiency, but when the temperature is too high, the properties of the electrolyte are easily affected, which affects the normal operation of the SEI film formation reaction, so that the obtained SEI film has a non-uniform and unstable structure and affects the film formation effect, and the too high temperature may damage the positive plate, the negative plate and the diaphragm, thereby affecting the performance of the finished lithium ion battery, the input energy is also large, the energy consumption is high, which is not beneficial to energy saving, and under comprehensive consideration, in multiple charging operations, the charging temperature is controlled to 55-65 ℃, and more preferably, in multiple charging operations, the charging temperature is controlled to 60 ℃.
In one embodiment, the plurality of charging operations includes a first charging operation, a second charging operation, a third charging operation, and a fourth charging operation. It should be noted that, the lithium ion battery semi-finished product is charged through the first charging operation, the second charging operation, the third charging operation and the fourth charging operation, that is, the lithium ion battery semi-finished product is charged four times to realize the formation operation of the lithium ion battery semi-finished product, the number of the multiple charging operations is set to four times, the charging number is moderate, the labor cost investment of the current replacement operation is saved, meanwhile, the charging current and the charging time are ensured to be more flexible and controllable, a more stable and uniform SEI film is obtained, thereby the rate discharge performance and the cycle performance of the lithium ion battery are improved, the discharge capacity of the lithium ion battery is also increased, the formed SEI film is stable and uniform, the temperature resistance of the lithium ion battery is better, and the low-temperature discharge capacity and the high-temperature rate discharge performance of the lithium ion battery are, meanwhile, the method is also beneficial to saving formation time and improving production benefit.
Specifically, in order to ensure the formation of a stable and uniform SEI film and improve formation efficiency, in one embodiment, the charging current of the first charging operation is 0.1C to 0.4C, the charging state of charge is not more than 5% SOC, the charging current of the second charging operation is 0.45C to 0.65C, the charging state of charge is not more than 10% SOC, the charging current of the third charging operation is 0.7C to 0.9C, the charging state of charge is not more than 20% SOC, the charging current of the fourth charging operation is 1.0C to 1.5C, and the charging state of charge is not more than 70% SOC. It should be noted that, in the first charging operation, the current of 0.1C to 0.4C is used for charging, that is, in the first charging operation, the small current is used for charging the lithium ion battery semi-finished product, which is beneficial to slowly forming a compact SEI film structure and obtaining a SEI film with a more stable structure, preferably, the charging time of the first charging operation is controlled to be 4.5min to 5.5min, the charging state is less than or equal to 5% SOC, more preferably, the charging current of the first charging operation is controlled to be 0.3C, the charging time of the first charging operation is 5min, in the secondary charging operation, the current of 0.45-0.65C is adopted for charging, the charging current is increased, the speed of the charging operation is favorably increased, the formation of an SEI film is promoted, so that the SEI film is formed more rapidly, preferably, the charging time of the secondary charging operation is controlled to be 4min to 5min, and the charging state of charge is 10% SOC or less. More preferably, the charging current of the secondary charging operation is controlled to be 0.5C, the charging time of the secondary charging operation is 4.5min, in the third charging operation, the charging is performed by using the current of 0.7C-0.9C, the charging current is further increased, the speed of the charging operation is further increased, the formation of an SEI film is further promoted, the production efficiency is improved, the production benefit is improved, preferably, the charging time of the third charging operation is controlled to be 4.5 min-5.5 min, the charging state is less than or equal to 20% SOC, more preferably, the charging current of the third charging operation is controlled to be 0.8C, the charging time of the third charging operation is 5min, in the fourth charging operation, the charging is performed by using the current of 1.0C-1.5C, the charging current is further increased, the speed of the charging operation is greatly increased, the formation time is saved, the production efficiency is improved, preferably, the charging time of the fourth charging operation is controlled to be 23 min-25 min, the charging state of charge is less than or equal to 70 percent SOC, the cut-off voltage is 3.9V-4.0V, and more preferably, the charging current of four times of charging is controlled to be 1.3C, and the charging time of four times of charging operation is 24 min.
It can be understood that, the formation operation is performed on the lithium ion battery semi-finished product by four charging methods, in the first charging operation, the charging is performed by using a small current of 0.1 to 0.4C, which is beneficial to forming a compact SEI film structure, because the formation operation is performed on the lithium ion battery semi-finished product by using a small current, a long formation time is required, and the production efficiency is affected, therefore, in the second charging operation, the third charging operation, and the four charging operations, the lithium ion battery semi-finished product is charged by using currents of 0.45 to 0.65C, 0.7 to 0.9C, and 1.0 to 1.5C, respectively, by increasing the charging current gradually, on one hand, the charging speed can be increased gradually, the formation efficiency is improved, on the other hand, the charging current is increased gradually, so that the current difference between the charging operations is small, which is beneficial to forming a uniform and stable SEI film structure, and the SEI film forming effect is good, therefore, the formation efficiency is improved, the film forming effect of the SEI film is ensured, the performance and the quality of finished lithium ion batteries are improved, the multiplying power discharge performance, the cycle performance and the temperature resistance of the lithium ion batteries are improved, and the discharge capacity is also increased.
And S130, carrying out secondary standing operation on the lithium ion battery intermediate product, and then carrying out exhaust packaging operation to complete formation operation.
It should be noted that after the lithium ion battery semi-finished product is charged, an intermediate product of the lithium ion battery is obtained, because in the charging process, a polarization phenomenon exists, and both mass transfer and charge transfer have polarization, which results in a higher voltage, the polarization can be eliminated by performing a secondary standing operation on the intermediate product of the lithium ion battery, and meanwhile, the electrolyte is also facilitated to further infiltrate the positive plate and the negative plate, which is beneficial to further improving the capacity of the lithium ion battery.
In one embodiment, in the secondary standing operation of the lithium ion battery intermediate product, the standing time is 2-4 h, and the temperature of the secondary standing is controlled to be 22-28 ℃. It should be noted that, along with the extension of the standing time, the complete elimination of polarization is favorably ensured, and the electrolyte is favorably used for better infiltrating the positive plate and the negative plate, but the standing time is too long, the investment of production time cost is increased, the production efficiency is reduced, and the effect of increasing the capacity of the lithium ion battery is not obvious by continuously increasing the standing time, and under comprehensive consideration, the standing time of the secondary standing operation is controlled to be 2-4 h, and the standing temperature is 22-28 ℃. More preferably, in the secondary standing operation of the lithium ion battery intermediate product, the standing time is 3 hours, and the temperature of the secondary standing is controlled to be 25 ℃. Thus, elimination of the polarization phenomenon can be ensured.
A lithium ion battery is prepared by the lithium ion battery formation method.
The invention also provides a lithium ion battery which is prepared by the lithium ion battery formation method. As another example, the lithium ion battery is a soft package lithium ion battery. The lithium ion battery is prepared by any one of the above lithium ion battery formation methods, and the formed SEI film is stable and uniform, so that the rate discharge performance, the temperature resistance and the cycle performance of the lithium ion battery can be improved, the discharge capacity of the lithium ion battery is increased, and the finished product quality of the lithium ion battery is high. It should be noted that, please refer to the prior art for the preparation process of the lithium ion battery before formation and after formation, and the present invention is not repeated herein.
Compared with the prior art, the invention has at least the following advantages:
the invention adopts a multi-charging method to form the lithium ion battery semi-finished product, the charging current is 0.1-1.5C, and the charging current is increased gradually, namely, the lithium ion battery semi-finished product is formed by increasing current gradually, so that the uniformity and the speed of the SEI film are more flexible and controllable, and a more uniform and stable SEI film is formed, thereby being beneficial to improving the multiplying power discharge performance and the cycle performance of the lithium ion battery and increasing the discharge capacity of the lithium ion battery.
The following is a detailed description of the embodiments.
Example 1
S111, providing a lithium ion battery semi-finished product in which electrolyte is injected, performing pre-sealing operation on the lithium ion battery semi-finished product, sealing an air bag opening of the lithium ion battery semi-finished product, performing primary standing operation on the lithium ion battery semi-finished product, standing for 10 hours, and controlling the temperature of the primary standing to be 43 ℃.
S121, placing the lithium ion battery semi-finished product after the first standing in a clamping plate, pressurizing the lithium ion battery semi-finished product after the first standing, controlling the pressurizing pressure to be 1.15Mpa, then performing the first charging operation, performing 0.4C constant current charging for 5min, controlling the charging state to be 3.5% SOC, controlling the temperature of the first charging operation to be 55 ℃, performing secondary charging operation on the lithium ion battery semi-finished product after the first charging, performing 0.45C constant current charging for 8min, controlling the charging state to be 6% SOC, controlling the temperature of the secondary charging operation to be 55 ℃, performing three times of charging operation on the lithium ion battery semi-finished product after the secondary charging, performing 0.5C constant current charging for 10min, controlling the charging state to be 12% SOC, controlling the temperature of the three times of charging operation to be 55 ℃, performing four times of constant current charging operation on the lithium ion battery semi-finished product after the three times of charging, performing 0.55C constant current charging for 50min, the charging state of charge is 60% SOC, the temperature of four charging operations is controlled to be 55 ℃, and the lithium ion battery intermediate product is obtained after charging to the cut-off voltage of 3.9V.
S131, performing secondary standing operation on the lithium ion battery intermediate product, standing for 2 hours, controlling the temperature of the secondary standing to be 25 ℃, performing exhaust packaging operation under a vacuum condition, pricking the air bag, vacuumizing, extracting gas in the air bag, sealing, cutting and removing the air bag, and finishing formation operation.
Example 2
S112, providing a lithium ion battery semi-finished product in which electrolyte is injected, performing pre-sealing operation on the lithium ion battery semi-finished product, sealing an air bag opening of the lithium ion battery semi-finished product, performing primary standing operation on the lithium ion battery semi-finished product, standing for 12 hours, and controlling the temperature of the primary standing to be 45 ℃.
S122, placing the lithium ion battery semi-finished product after the first standing in a clamping plate, performing pressurization operation on the lithium ion battery semi-finished product after the first standing, controlling the pressurization pressure to be 1.2Mpa, then performing first charging operation, performing 0.4C constant current charging for 5min, controlling the charging state to be 3.5% SOC, controlling the temperature of the first charging operation to be 60 ℃, performing secondary charging operation on the lithium ion battery semi-finished product after the first charging, performing 0.6C constant current charging for 4.5min, controlling the charging state to be 8.5% SOC, controlling the temperature of the secondary charging operation to be 60 ℃, performing three times of charging operation on the lithium ion battery semi-finished product after the secondary charging, performing 0.8C constant current charging for 5min, controlling the charging state to be 16% SOC, controlling the temperature of the three times of charging operation to be 60 ℃, performing four times of charging operation on the lithium ion battery semi-finished product after the third charging, performing 1.0C constant current charging for 24min, the charging state of charge is 65% SOC, the temperature of four charging operations is controlled to be 60 ℃, and the lithium ion battery intermediate product is obtained after charging to the cut-off voltage of 3.95V.
S132, performing secondary standing operation on the lithium ion battery intermediate product, standing for 3 hours, controlling the temperature of the secondary standing to be 25 ℃, performing exhaust packaging operation under a vacuum condition, pricking the air bag, vacuumizing, extracting gas in the air bag, sealing, cutting and removing the air bag, and finishing formation operation.
Example 3
S113, providing a lithium ion battery semi-finished product in which electrolyte is injected, performing pre-sealing operation on the lithium ion battery semi-finished product, sealing an air bag opening of the lithium ion battery semi-finished product, performing primary standing operation on the lithium ion battery semi-finished product, standing for 14 hours, and controlling the temperature of the primary standing to be 47 ℃.
S123, placing the lithium ion battery semi-finished product after the first standing in a clamping plate, pressurizing the lithium ion battery semi-finished product after the first standing, controlling the pressurizing pressure to be 1.25Mpa, then performing the first charging operation, performing 0.4C constant current charging for 5min, controlling the charging state to be 3.5% SOC, controlling the temperature of the first charging operation to be 65 ℃, performing secondary charging operation on the lithium ion battery semi-finished product after the first charging, performing 0.45C constant current charging for 8min, controlling the charging state to be 6% SOC, controlling the temperature of the secondary charging operation to be 65 ℃, performing three times of charging operation on the lithium ion battery semi-finished product after the secondary charging, performing 0.5C constant current charging for 10min, controlling the charging state to be 12% SOC, controlling the temperature of the three times of charging operation to be 65 ℃, performing four times of charging operation on the lithium ion battery semi-finished product after the three times of charging, performing 1.5C constant current charging for 24min, the charging state of charge is 70% SOC, the temperature of four charging operations is controlled to be 65 ℃, and the lithium ion battery intermediate product is obtained after charging to the cut-off voltage of 4.0V.
S133, performing secondary standing operation on the lithium ion battery intermediate product, standing for 4 hours, controlling the temperature of the secondary standing to be 25 ℃, performing exhaust packaging operation under a vacuum condition, pricking the air bag, vacuumizing, extracting gas in the air bag, sealing, cutting and removing the air bag, and finishing formation operation.
Example 4
S114, providing a lithium ion battery semi-finished product in which electrolyte is injected, performing pre-sealing operation on the lithium ion battery semi-finished product, sealing an air bag opening of the lithium ion battery semi-finished product, performing primary standing operation on the lithium ion battery semi-finished product, standing for 12 hours, and controlling the temperature of the primary standing to be 45 ℃.
S124, placing the lithium ion battery semi-finished product after the first standing in a clamping plate, pressurizing the lithium ion battery semi-finished product after the first standing, controlling the pressurizing pressure to be 1.2Mpa, then performing the first charging operation, performing 0.4C constant current charging for 5min, controlling the charging state to be 3.5% SOC, controlling the temperature of the first charging operation to be 60 ℃, performing secondary charging operation on the lithium ion battery semi-finished product after the first charging, performing 0.6C constant current charging for 4.5min, controlling the charging state to be 8.5% SOC, controlling the temperature of the secondary charging operation to be 60 ℃, performing three-time charging operation on the lithium ion battery semi-finished product after the secondary charging, performing 0.8C constant current charging for 40min, controlling the charging state to be 65% SOC, controlling the temperature of the three-time charging operation to be 60 ℃, and charging to be 3.95V of a cut-off voltage to obtain the lithium ion battery intermediate product.
And S134, carrying out secondary standing operation on the lithium ion battery intermediate product, standing for 3h, controlling the temperature of the secondary standing to be 25 ℃, carrying out exhaust packaging operation under the vacuum condition, pricking the air bag, vacuumizing, extracting gas in the air bag, sealing, cutting and removing the air bag, and finishing formation operation.
Example 5
S115, providing a lithium ion battery semi-finished product in which electrolyte is injected, performing pre-sealing operation on the lithium ion battery semi-finished product, sealing an air bag opening of the lithium ion battery semi-finished product, performing primary standing operation on the lithium ion battery semi-finished product, standing for 12 hours, and controlling the temperature of the primary standing to be 45 ℃.
S125, placing the lithium ion battery semi-finished product after the first standing in a clamping plate, performing pressurization operation on the lithium ion battery semi-finished product after the first standing, controlling the pressurization pressure to be 1.2Mpa, then performing first charging operation, performing 0.4C constant current charging for 5min, controlling the charging state to be 3.5% SOC, controlling the temperature of the first charging operation to be 60 ℃, performing secondary charging operation on the lithium ion battery semi-finished product after the first charging, performing 0.6C constant current charging for 4.5min, controlling the charging state to be 8.5% SOC, controlling the temperature of the secondary charging operation to be 60 ℃, performing three times of charging operation on the lithium ion battery semi-finished product after the secondary charging, performing 0.8C constant current charging for 5min, controlling the charging state to be 16% SOC, controlling the temperature of the three times of charging operation to be 60 ℃, performing four times of charging operation on the lithium ion battery semi-finished product after the third charging, performing 1.0C constant current charging for 10min, and the charging state of charge is 45% SOC, the temperature of the four charging operations is controlled to be 60 ℃, the lithium ion battery semi-finished product after the four charging operations is subjected to five charging operations, the lithium ion battery semi-finished product is subjected to 1.2C constant current charging for 10min, the charging state of charge is 65% SOC, the temperature of the five charging operations is controlled to be 60 ℃, and the lithium ion battery intermediate product is obtained after the lithium ion battery semi-finished product is charged to the cut-off voltage of 3.95V.
And S135, carrying out secondary standing operation on the lithium ion battery intermediate product, standing for 3h, controlling the temperature of the secondary standing to be 25 ℃, carrying out exhaust packaging operation under the vacuum condition, pricking the air bag, vacuumizing, extracting gas in the air bag, sealing, cutting and removing the air bag, and finishing formation operation.
Comparative example 1
Providing a lithium ion battery semi-finished product which is injected with electrolyte, carrying out pre-sealing operation on the lithium ion battery semi-finished product, sealing an air bag opening of the lithium ion battery semi-finished product, carrying out primary standing operation on the lithium ion battery semi-finished product, standing for 12 hours, and controlling the temperature of the primary standing to be 45 ℃.
Placing the lithium ion battery semi-finished product after the first standing in a clamping plate, carrying out pressurization operation on the lithium ion battery semi-finished product after the first standing, controlling the pressurization pressure to be 1.2Mpa, then carrying out first charging operation, carrying out 0.4C constant current charging for 5min, controlling the charging state to be 3.5% SOC, controlling the temperature of the first charging operation to be 60 ℃, carrying out secondary charging operation on the lithium ion battery semi-finished product after the first charging, carrying out 0.4C constant current charging for 10min, controlling the charging state to be 8.5% SOC, controlling the temperature of the secondary charging operation to be 60 ℃, carrying out three times of charging operation on the lithium ion battery semi-finished product after the secondary charging, carrying out 0.4C constant current charging for 10min, controlling the charging state to be 16% SOC, controlling the temperature of the three times of charging operation to be 60 ℃, carrying out four times of charging operation on the lithium ion battery semi-finished product after the three times of charging, carrying out 0.4C, the charging state of charge is 65% SOC, the temperature of four charging operations is controlled to be 60 ℃, and the lithium ion battery intermediate product is obtained after charging to the cut-off voltage of 3.95V.
And (3) carrying out secondary standing operation on the lithium ion battery intermediate product, standing for 3h, controlling the temperature of the secondary standing to be 25 ℃, carrying out exhaust packaging operation under the vacuum condition, pricking the air bag, vacuumizing, extracting gas in the air bag, sealing, cutting and removing the air bag, and finishing formation operation.
Experiment: the lithium ion battery intermediate products formed by the lithium ion battery intermediates of the embodiments 1 to 5 and the comparative example 1 are subjected to capacity grading and packaging to obtain the lithium ion battery, and the test: (1) the battery has the advantages of (1) rate capability of the battery, (2) rate capability after high-temperature storage at 60 ℃, (3) battery discharge capacity at low temperature of-10 ℃, and (4) battery discharge cycle performance after high-temperature storage at 60 ℃. Test results show that, compared with comparative example 1, the lithium ion batteries of the embodiments of the present invention have excellent battery rate performance under different rates, in particular, the lithium ion batteries of the embodiments of the present invention can maintain good battery rate performance under different rates after being stored at 60 ℃, and the discharge cycle performance is better, which proves that the rate performance and the discharge cycle performance of the lithium ion batteries of the embodiments of the present invention are better under high temperature conditions, while the discharge capacity ratio of the lithium ion batteries of the embodiments of the present invention is better than that of the lithium ion batteries of the embodiment of the present invention under-10 ℃, which proves that the discharge capacity of the lithium ion batteries of the embodiments of the present invention is better under low temperature conditions, and detailed table 1 and fig. 2 to fig. 3 are provided. In order to avoid the situation that the data in the graph is too dense and difficult to distinguish, only the data of example 3, example 4 and example 5 are selected in fig. 3 and are plotted with the data of comparative example 1, and the result is shown in fig. 3. The effects of the other embodiments are similar to those of embodiment 3, and are not described again.
TABLE 1 multiplying power test and comparison table
As can be seen from table 1, compared to comparative example 1, while the formation efficiency is improved, the lithium ion batteries of embodiments 1 to 5 of the present invention respectively perform different rate tests at 25 ℃, and perform different rate tests after being stored at 60 ℃, the lithium ion batteries of embodiments 1 to 5 of the present invention have higher capacity retention rates and better battery rate performance, wherein the battery rate performance of embodiment 3 is the best.
FIG. 2 is a graph showing the discharge capacity ratio of 1C/3A pulse batteries at a low temperature of-10 ℃ in examples 1 to 5 of the present invention and comparative example 1. Wherein DB represents the lithium ion battery of comparative example 1; SY-1 represents the lithium ion battery of example 1; SY-2 represents the lithium ion battery of example 2; SY-3 represents the lithium ion battery of example 3; SY-4 represents the lithium ion battery of example 4; SY-5 represents the lithium ion battery of example 5. As can be seen from fig. 2, the lithium ion batteries of examples 1 to 5 have better discharge capacities under low temperature conditions than comparative example 1.
Fig. 3 is a graph showing the discharge cycle performance of the batteries according to examples 3 to 5 of the present invention and comparative example 1 after storage at a high temperature of 60 ℃. Wherein DB represents the lithium ion battery of comparative example 1; SY-3 represents the lithium ion battery of example 3; SY-4 represents the lithium ion battery of example 4; SY-5 represents the lithium ion battery of example 5. As can be seen from fig. 3, the capacity retention rate of the lithium ion batteries of examples 3 to 5 is higher than that of comparative example 1 after the lithium ion batteries are stored at a high temperature of 60 ℃, which proves that the lithium ion batteries prepared by the method of the present invention have better cycle performance under the condition of a high temperature (60 ℃), the formation process time is shortened, and the production benefit is improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A lithium ion battery formation method is characterized by comprising the following steps:
providing a lithium ion battery semi-finished product into which electrolyte is injected, and carrying out primary standing operation on the lithium ion battery semi-finished product;
pressurizing the semi-finished product of the lithium ion battery after the semi-finished product is stood for the first time, then performing multiple charging operations, and charging to cut-off voltage to obtain an intermediate product of the lithium ion battery, wherein the charging current of the multiple charging operations is gradually increased, the charging current is 0.1-1.5C, the charging frequency is more than or equal to 3, and the current difference value of the two charging operations is 0.05-1.0C;
and carrying out secondary standing operation on the lithium ion battery intermediate product, and then carrying out exhaust packaging operation to complete formation operation.
2. The lithium ion battery formation method according to claim 1, wherein in the first standing operation of the lithium ion battery semi-finished product, the standing time is 10-14 h, and the temperature of the first standing is controlled to be 43-47 ℃.
3. The lithium ion battery formation method according to claim 1, wherein in the pressurizing operation of the lithium ion battery semi-finished product after the first standing, the pressurizing pressure is controlled to be 1.15Mpa to 1.25 Mpa.
4. The lithium ion battery formation method according to claim 1, wherein in performing the plurality of charging operations, the charging temperature is controlled to be 55 ℃ to 65 ℃.
5. The lithium ion battery formation method of claim 1, wherein in multiple charging operations, the charging state of charge is 70% or less, and the cut-off voltage is 3.9V to 4.0V.
6. The lithium ion battery formation method of claim 1, wherein the multiple charging operations include a first charging operation, a second charging operation, a third charging operation, and a fourth charging operation.
7. The lithium ion battery formation method of claim 6, wherein the charging current of the first charging operation is 0.1C-0.4C, the charging state of charge is 5% SOC or less, the charging current of the second charging operation is 0.45C-0.65C, the charging state of charge is 10% SOC or less, the charging current of the third charging operation is 0.7C-0.9C, the charging state of charge is 20% SOC or less, the charging current of the fourth charging operation is 1.0C-1.5C, and the charging state of charge is 70% SOC or less.
8. The lithium ion battery formation method according to claim 1, wherein in the secondary standing operation of the lithium ion battery intermediate product, the standing time is 2 to 4 hours, and the temperature of the secondary standing is controlled to be 22 to 28 ℃.
9. The lithium ion battery formation method according to claim 1, wherein a pre-sealing operation is further performed on the lithium ion battery semi-finished product before the lithium ion battery semi-finished product is subjected to the first standing operation.
10. A lithium ion battery, characterized in that it is produced by the method of any one of claims 1 to 9.
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