CN109802183B - High-temperature clamp formation process for lithium battery - Google Patents
High-temperature clamp formation process for lithium battery Download PDFInfo
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- CN109802183B CN109802183B CN201910004582.3A CN201910004582A CN109802183B CN 109802183 B CN109802183 B CN 109802183B CN 201910004582 A CN201910004582 A CN 201910004582A CN 109802183 B CN109802183 B CN 109802183B
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- 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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Abstract
The invention discloses a high-temperature clamp formation process of a lithium battery, which specifically comprises the following steps: clamping the battery cell in a fixture cabinet, heating the battery cell to form a fixture, and setting the battery cell formation process step as shelving; after the placement is finished, constant-current charging is carried out, and gas generated in the battery cell is extruded out through pressurization; increasing the constant-current charging current, the charging voltage and the pressure of the clamp cabinet, and further extruding gas generated in the battery cell; increasing the constant-current charging current, the charging voltage and the pressure of the fixture cabinet again, and shaping the battery cell; compared with the conventional high-temperature pressurization formation, the method reduces the viscosity of the electrolyte, improves the conductivity of the electrolyte and the ion migration speed of the battery material in the formation process so as to shorten the formation time, improve the utilization rate of equipment, improve the discharge rate performance and not influence the service life of the battery.
Description
Technical Field
The invention belongs to a production process of a polymer lithium ion battery, and particularly relates to a high-temperature clamp formation process of a lithium battery.
Background
In recent years, with the popularization of smart mobile terminals and the promotion of reasons such as resources and environmental protection, lithium ion batteries have been widely used in the fields of portable electronic products, electric tools, energy storage, electric vehicles, and the like.
The lithium ion battery needs to be subjected to a pre-charging formation process in the manufacturing process, and the process aims to form an SEI passive film on the surface of a pole piece and prevent the electrolyte from further reacting with the pole piece, so that the adverse conditions of irreversible battery, capacity increase, ballooning and the like are caused.
In the prior art, components with low boiling points, such as ethyl methyl carbonate EMC, ethylene carbonate EC and diethyl carbonate DEC, are selected in the formula of the battery electrolyte, the formation temperature is generally set to be 35-65 ℃, and the defects of high viscosity of the electrolyte, low conductivity and low ion migration speed of battery materials are caused; although some high-temperature pressurization formation processes adopted in the market can form an SEI film more effectively, the cost of equipment for realizing the processes is high, so that the manufacturing cost of the battery is increased, and the formation time needs to be further optimized; some processes can effectively shorten the formation time, but the performance of the produced battery is reduced; therefore, a process for shortening the formation time to improve the utilization rate of the equipment without affecting the performance of the battery is needed.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a high-temperature clamp formation process for lithium ion battery production, which can shorten formation time, improve the utilization rate of equipment and simultaneously does not influence the battery performance.
The purpose of the invention is realized by the following technical scheme:
a high-temperature clamp formation process for a lithium battery specifically comprises the following steps:
(1) high-temperature laying aside: laying aside the battery cell, clamping the battery cell in a clamp cabinet, heating the battery cell into a clamp and pressurizing the battery cell;
(2) constant current charging: after the placement is finished, constant-current charging is carried out, and gas generated in the battery cell is extruded out through pressurization;
(3) secondary constant current charging: increasing the constant-current charging current, the charging voltage and the pressure of the fixture cabinet in the step (2), and further extruding gas generated in the battery cell;
(4) and (3) three-time constant current charging: increasing the constant-current charging current and the charging voltage in the step (3) and the pressure of the fixture cabinet, and shaping the battery cell;
(5) cooling the lower cabinet: and finishing the constant-current charging, releasing the pressure of the clamp cabinet, cooling the lower battery cell cabinet, and finishing the formation process.
Further, in the step (1), the standing time is 1min, the temperature of the formation clamp is set to be 75-85 ℃, the pressure is set to be 1-3Mpa, and the formation temperature is set to be 75-85 ℃, so that the aims of further reducing the viscosity of the electrolyte, improving the conductivity of the electrolyte, improving the ion migration speed of the battery material and shortening the formation time are fulfilled.
Further, in the step (2), the constant current charging current is set to be 0.15-0.25CmA, the voltage is set to be 3-4V, the charging time is set to be 4-6min, the pressure at the moment is 2-4Mpa, the pressure time is set to be 4-6min, gas generation is started in the battery cell at the moment, the gas is extruded out by using smaller pressure, and the bad conditions such as gas expansion are avoided.
Further, in the step (3), the constant current charging current is increased to 0.4-0.6CmA, the charging voltage is set to 3.5-3.9V, the charging time is set to 25-35min, the pressure is increased to 3-5Mpa, the pressure time is set to 25-35min, the gas is continuously generated in the battery cell, the pressure of the clamp is gradually increased, and the gas is further extruded; meanwhile, the contact among the pole piece, the diaphragm and the electrolyte in the battery core is tighter, and the circulation and the oxidation resistance are enhanced at high temperature and high voltage.
Further, in the step (4), the constant current charging current is increased to 0.8-1.2CmA, the time is set to 35-45min, the pressure of the clamp is increased to 6-8Mpa, and the pressure time is set to 35-45min, so that the battery cell is shaped, and the surface deformation of the battery cell caused by uneven internal tension in the charging and discharging process of the battery cell is prevented.
Further, the electrolyte components and the mixture ratio of the electrolyte used for the battery cell of the high-temperature clamp formation process are as follows: propylene carbonate PC 5-8%, ethylene carbonate EC 30-35%, diethyl carbonate DEC 50-60%, 1.05mol/l lithium hexafluorophosphate LiPF6, fluoroethylene carbonate FEC 2-3%, vinylene carbonate VC 1-2%, succinonitrile SN 1-2%, and propane sultone PS 2-2.5%, removing low-boiling point components in the electrolyte, and replacing with high-boiling point components.
Has the advantages that: compared with the conventional high-temperature pressurization formation, the method has the advantages that the viscosity of the electrolyte is reduced, the conductivity of the electrolyte is improved, the ion migration speed of the battery material is increased, the formation time is shortened, the utilization rate of equipment is increased, the discharge rate performance is improved, and the service life of the battery is not influenced.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention;
FIG. 2 is a line graph comparing the test of the formation process at 60 ℃ in the example of the present invention with that of the prior art;
FIG. 3 is a discharge life cycle chart of the formation process at 60 ℃ according to the embodiment of the present invention and the prior art.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
Referring to fig. 1-3, a high-temperature clamp formation process for a lithium battery specifically includes the following steps:
(1) high-temperature laying aside: shelve electric core, with electric core clamping in the anchor clamps cabinet, become anchor clamps temperature and rise to 80 ℃, pressurize electric core after the temperature reaches, pressure sets up to 2Mpa, and the time sets up to 1min, and it sets up to 80 ℃ to become the temperature, and aim at further reduces electrolyte viscosity, improves electrolyte conductivity and improves the ion migration speed of battery material, shortens and becomes the time.
(2) Constant current charging: after the placement is finished, constant current charging is carried out, gas generated in the battery cell is extruded by pressurization, the constant current charging current is set to be 0.2CmA, the voltage is set to be 3.5V, the charging time is set to be 5min, the pressure is 3Mpa at the moment, the pressure time is set to be 5min, gas generation is started in the battery cell at the moment, the gas is extruded by small pressure, and the occurrence of bad conditions such as gas expansion is avoided.
(3) Secondary constant current charging: increasing the constant current charging current to 0.5CmA, setting the charging voltage to 3.7V, setting the charging time to 30min, increasing the pressure to 4Mpa, setting the pressure time to 30min, continuously generating gas in the battery cell, gradually increasing the pressure of the clamp, and further extruding the gas; meanwhile, the contact among the pole piece, the diaphragm and the electrolyte in the battery core is tighter, and the circulation and the oxidation resistance are enhanced at high temperature and high voltage.
(4) And (3) three-time constant current charging: the constant current charging current is increased to 1CmA, the time is set to be 40min, the pressure of the clamp is increased to 7Mpa, the pressure time is set to be 40min, the SEI film in the battery cell is nearly completed, the gas production is basically completed, the battery cell is mainly molded at the moment, and the surface deformation of the battery cell caused by the uneven internal tension in the charging and discharging process of the battery cell is prevented.
(5) Cooling the lower cabinet: and finishing the constant-current charging, releasing the pressure of the clamp cabinet, cooling the lower battery cell cabinet, and finishing the formation process.
In this embodiment, the electrolyte components and the ratio thereof of the battery cell used in the high-temperature clamp formation process are as follows: propylene carbonate PC 6%, ethylene carbonate EC 33%, diethyl carbonate DEC 55%, 1.05mol/l lithium hexafluorophosphate LiPF6, fluoroethylene carbonate FEC 2%, vinylene carbonate VC 1%, succinonitrile SN 1%, and propane sultone PS 2%, wherein low-boiling components in the electrolyte are removed, and high-boiling components are used for substitution.
In this example, the produced batteries with formation temperature set to 60 ℃ and formation temperature set to 80 ℃ were tested and compared, and the discharge rate, cycle life, and formation efficiency were compared.
Taking a 400mAh polymer lithium battery as an example, the 400mAh polymer lithium battery with the formation process temperature of 60 ℃ and the formation temperature of 80 ℃ is respectively taken and tested.
And (3) formation efficiency comparison:
in the prior art, a formation process with a formation temperature of 60 ℃ comprises the following steps: setting the formation temperature to be 60 ℃; the constant current charging is 0.2CmA, and the upper limit voltage is 3.5V; the secondary constant current charging is 0.5CmA, and the upper limit voltage is 3.95V;
the formation process of the embodiment comprises the following steps: setting the formation temperature to 80 ℃; the constant current charging is 0.2CmA, and the upper limit voltage is 3.5V; the secondary constant current charging is 0.5CmA, and the upper limit voltage is 3.7V; the third constant current charging is 1.0CmA, and the upper limit voltage is 3.95V;
the formation process time is shown in tables 1 and 2 below, wherein table 1 is the formation time at 60 ℃ in the prior art, and table 2 is the formation time in the embodiment;
TABLE 1
TABLE 2
As can be seen from the above table, the 80 ℃ pyrolysis time of the present embodiment is 76 minutes, the existing 60 ℃ pyrolysis time is 131 minutes, and the pyrolysis efficiency of the present embodiment is improved by 42%.
And (3) testing discharge rate:
and (3) testing conditions are as follows: after the 400mAh polymer lithium battery obtained by the formation process at the temperature of 60 ℃ and 80 ℃ respectively is fully charged by 1.0C, the lithium battery is discharged at the rate of 0.5C/1.0C/2.0C, and the detected data are compared in the following tables 3 and 4 under the same test conditions:
TABLE 3
TABLE 4
With reference to tables 3 and 4, a line graph (as shown in fig. 2) is prepared with the discharge efficiency as ordinate and the discharge (mA) as abscissa, and it can be seen from fig. 2 that the rate performance of the film formed at 80 ℃ is significantly better than that of the film formed at 60 ℃, indicating that the SEI film forming effect at 80 ℃ is better than that at 60 ℃.
And (3) testing the cycle life:
and (3) testing conditions are as follows: taking a 400mAh polymer lithium battery as an example, the discharge cycle life of charging 400mA to 800mA is tested, and the test steps are as follows:
1. charging to 4.20V with 1C constant current and constant voltage, and cutting off current 0.05C;
2. standing for 5 minutes;
3. discharging to 3.0V at constant current of 2.0C;
4. standing for 5 minutes;
5. the cycle starts from step 1, and the 4 th step is ended, and the cycle number is 300 weeks.
Through tests, a discharge cycle life chart with capacity retention rate as ordinate (%) and cycle number (N) as abscissa shown in FIG. 3 is obtained; referring to the comparative cycle of FIG. 3, it can be seen that there is no significant difference between the cycle life of the formation at 60 ℃ and the cycle life of the formation at 80 ℃.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (5)
1. A high-temperature clamp formation process for a lithium battery is characterized by comprising the following steps:
(1) high-temperature laying aside: laying aside the battery cell, clamping the battery cell in a clamp cabinet, heating the battery cell into a clamp and pressurizing the battery cell;
(2) constant current charging: after the placement is finished, constant-current charging is carried out, and the pressure is increased to extrude gas generated in the battery cell;
(3) secondary constant current charging: increasing the constant-current charging current, the charging voltage and the pressure of the fixture cabinet in the step (2), and further extruding gas generated in the battery cell;
(4) and (3) three-time constant current charging: increasing the constant-current charging current and the charging voltage in the step (3) and the pressure of the fixture cabinet, and shaping the battery cell;
(5) cooling the lower cabinet: finishing constant-current charging, releasing the pressure of the clamp cabinet, cooling the lower battery cell cabinet, and finishing the formation process;
in the step (1), the standing time is 1min, the temperature of the formation clamp is set to be 75-85 ℃, and the pressure is set to be 1-3 Mpa;
in the step (2), the constant current charging current is set to be 0.15-0.25CmA, the voltage is set to be 3-4V, the charging time is set to be 4-6min, the pressure at the moment is 2-4Mpa, and the pressure time is set to be 4-6 min;
in the step (3), the constant current charging current is increased to 0.4-0.6CmA, the charging voltage is set to 3.5-3.9V, the charging time is set to 25-35min, the pressure is increased to 3-5Mpa, and the pressure time is set to 25-35 min.
2. The high-temperature clamp forming process for the lithium battery as claimed in claim 1, wherein the step (3) is specifically as follows: the constant current charging current was increased to 0.5CmA, the charging voltage was set to 3.7V, the charging time was set to 30min, and the pressure was increased to 4Mpa, and the pressure time was set to 30 min.
3. The high-temperature clamp formation process for the lithium battery as claimed in claim 1, wherein in the step (4), the constant current charging current is increased to 0.8-1.2CmA, the time is set to 35-45min, the clamp pressure is increased to 6-8Mpa, and the pressure time is set to 35-45 min.
4. The high-temperature clamp forming process for the lithium battery as claimed in claim 3, wherein the step (4) is specifically as follows: the constant current charging current is increased to 1CmA, the time is set to be 40min, the pressure of the clamp is increased to 7MPa, and the pressure time is set to be 40 min.
5. The high-temperature clamp forming process for the lithium battery as claimed in any one of claims 1 to 4, wherein the electrolyte components and the proportions of the electrolyte components used for the battery core of the high-temperature clamp forming process are as follows: propylene carbonate PC 5% -8%, ethylene carbonate EC 30% -35%, diethyl carbonate DEC 50% -60%, 1.05mol/l lithium hexafluorophosphate LiPF 6%, fluoroethylene carbonate FEC 2% -3%, vinylene carbonate VC 1% -2%, succinonitrile SN 1% -2%, and propane sultone PS 2% -2.5%.
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| CN111430805A (en) * | 2020-03-02 | 2020-07-17 | 东莞锂威能源科技有限公司 | Method for improving self-discharge of lithium ion battery |
| CN111916834A (en) * | 2020-07-06 | 2020-11-10 | 梅州市量能新能源科技有限公司 | Battery flattening formation method |
| CN112670681A (en) * | 2020-12-25 | 2021-04-16 | 珠海冠宇电池股份有限公司 | Rapid aging method for soft-packaged battery cell |
| CN113363607A (en) * | 2021-06-03 | 2021-09-07 | 昆山宝创新能源科技有限公司 | Formation method of lithium ion battery and lithium ion battery |
| CN113948778B (en) * | 2021-10-12 | 2023-06-16 | 远景动力技术(江苏)有限公司 | Lithium ion battery core and formation method and application thereof |
| CN115275091B (en) * | 2022-08-30 | 2024-09-10 | 湖北亿纬动力有限公司 | Thick electrode infiltration method |
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| CN108539305A (en) * | 2018-05-03 | 2018-09-14 | 河南电池研究院有限公司 | A kind of nickelic lithium ion battery chemical synthesis technology of Soft Roll |
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| CN106532131A (en) * | 2016-12-15 | 2017-03-22 | 惠州Tcl金能电池有限公司 | Pressure formation method for lithium ion battery |
| CN108808095A (en) * | 2017-04-30 | 2018-11-13 | 深圳格林德能源有限公司 | A kind of polymer Li-ion battery rapid forming method |
| CN108110350B (en) * | 2017-12-18 | 2021-01-22 | 惠州亿纬创能电池有限公司 | Pressure formation method for lithium ion battery |
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