CN112510265A - One-step formation hot-pressing method for improving cycle performance of soft package lithium ion battery - Google Patents
One-step formation hot-pressing method for improving cycle performance of soft package lithium ion battery Download PDFInfo
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery, which comprises the following steps: step one, standing the battery cell after liquid injection for a preset time; secondly, continuously placing the static battery cell into a clamp on clamp formation equipment, and then performing formation operation on the battery cell under a preset formation pressure, a preset formation temperature and a preset charging and discharging system; and thirdly, directly increasing the temperature of the formation from the preset formation temperature to the preset hot-pressing temperature on a clamp of the clamp formation equipment under the condition of not changing the position of the battery cell in the constant-current discharge operation stage of the formation operation, and carrying out hot pressing on the battery cell under the preset hot-pressing pressure. According to the invention, after the formation of the battery cell, the hot pressing process is continuously and directly carried out on the battery cell, so that the generation of vacuoles in the battery cell is avoided, the interface contact and the negative film formation in the battery cell are improved, and the cycle life of the battery cell is prolonged.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, environmental friendliness, long cycle life, small self-discharge and the like, and has a very wide application prospect. With the further development of lithium ion batteries, batteries with high energy density are receiving more and more attention. The aluminum-plastic film is used as the shell of the lithium ion battery, the size and the thickness of the aluminum-plastic film can be changed along with the change of design requirements, and compared with an aluminum shell, the aluminum-plastic film has lower surface density and can be greatly improved in energy density.
Formation is an important process in the production process of the lithium ion battery, and during formation, a layer of solid polymer electrolyte membrane is formed on the surface of a negative electrode, and the uniformity and the thickness of the solid polymer electrolyte membrane have great influence on the capacity and the cycle performance of the battery. However, in the conventional formation process, a side reaction occurs when a solid electrolyte membrane is formed on the surface of the negative electrode, and a large amount of gas generated by the side reaction is retained in the battery cell, so that air separation regions exist among the positive plate, the negative plate and the diaphragm, and the next step of the hot pressing process is not favorable for the close adhesion of the positive plate, the negative plate and the diaphragm, and the problem of lithium precipitation is easily caused.
Disclosure of Invention
The invention aims to provide a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery aiming at the technical defects in the prior art.
Therefore, the invention provides a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery, which comprises the following steps:
step one, standing the battery cell after liquid injection for a preset time;
secondly, continuously placing the static battery cell into a clamp on clamp formation equipment, and then performing formation operation on the battery cell under a preset formation pressure, a preset formation temperature and a preset charging and discharging system;
in the second step, the preset charging and discharging system is as follows: firstly, step charging is carried out, and then constant current discharging is carried out;
thirdly, in the constant-current discharge operation stage of the formation operation, directly increasing the temperature of the formation from the preset formation temperature to the preset hot-pressing temperature on a clamp of the clamp formation equipment under the condition of not changing the position of the battery cell, keeping the pressure constant under the preset hot-pressing pressure, and carrying out hot-pressing on the battery cell;
and the hot pressing temperature is preset and is higher than the preset formation temperature.
Preferably, in the first step, the preset time period is 3-4 hours.
Preferably, in the second step, the clamp on the clamp forming equipment is formed, and the preset forming temperature applied to the battery cell is 50-80 ℃;
in the second step, the clamp on the clamp formation equipment, the preset formation pressure applied to the battery cell body is 1-2 MPa/pcs.
Preferably, in the second step, the presetting of the charge-discharge system specifically includes: firstly, carrying out three times of charging operation, and then carrying out one time of constant current discharging operation;
in the first charging operation, the current is 0.1-0.3C, and the battery cell is charged until the battery cell capacity is kept at 0.5-2% SOC;
in the second charging operation, the current is 0.3-0.7C, and the battery cell is charged until the battery cell capacity is kept at 5-10% SOC;
in the third charging operation, the current is 0.8-1.5C, the battery cell is charged to be in a constant voltage charging mode after being fully charged, and the cutoff current is 0.5C;
during constant current discharge operation, the current is 0.8-1.5C, and the battery cell capacity is kept at 50-70% SOC.
Preferably, in the second step, in the constant-current discharge operation process, the fixture on the fixture formation equipment directly performs hot pressing on the battery cell, the preset hot pressing temperature is 70-100 ℃, the preset hot pressing pressure is 1-2 MPa/pcs, and the hot pressing time is 5-10 minutes.
Compared with the prior art, the one-step formation hot-pressing method for improving the cycle performance of the soft-package lithium ion battery has the advantages that after the battery cell is formed, the battery cell is continuously and directly subjected to a hot-pressing procedure, so that the generation of vacuoles in the battery cell is avoided, the internal interface contact of the battery cell and the negative electrode film formation are improved, the volume expansion caused by the insertion and the separation of lithium ions can be better adapted, the cycle life of the battery cell is prolonged, and the method has great practical significance.
Drawings
Fig. 1 is a flowchart of a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery provided by the invention;
fig. 2 is a schematic diagram illustrating comparison of high-temperature cycle performance between a battery cell prepared by formation in example 5 and a battery cell obtained by formation according to a conventional standard formation process, which utilizes a one-step formation hot-pressing method for improving cycle performance of a soft-package lithium ion battery provided by the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the following detailed description of the present invention is provided in conjunction with the accompanying drawings and embodiments.
Referring to fig. 1, the invention provides a one-step formation hot-pressing method for improving cycle performance of a soft package lithium ion battery, which comprises the following steps:
step one, standing the battery cell after liquid injection (namely the battery cell injected with the electrolyte) for a preset time;
secondly, continuously placing the static battery cell into a clamp on clamp formation equipment, and then performing formation operation on the battery cell under a preset formation pressure, a preset formation temperature and a preset charging and discharging system;
in the second step, the preset charging and discharging system is as follows: firstly, step charging is carried out, and then constant current discharging is carried out;
thirdly, in a constant-current discharge operation stage (namely, a discharge process step) of formation operation, directly increasing the formation temperature from a preset formation temperature to a preset hot-pressing temperature on a clamp of the clamp formation equipment under the condition of not changing the position of the battery cell, keeping the pressure constant under the preset hot-pressing pressure, and carrying out hot pressing on the battery cell;
and the hot pressing temperature is preset and is higher than the preset formation temperature.
In the first step, the preset time period may be 3-4 hours in terms of specific implementation.
In the second step, specifically, the clamp on the clamp formation equipment applies a preset formation temperature (i.e., the formation ambient temperature applied and formed) to the battery cell of 50 ℃ to 80 ℃.
In the second step, in the concrete realization, anchor clamps become the anchor clamps on the equipment, and the pressure of predetermineeing formation (the pressure of exerting when formation) that applys to electric core body is 1 ~ 2 MPa/pcs.
In the second step, in particular implementation, the presetting of the charging and discharging system specifically includes: firstly, carrying out three times of charging operation, and then carrying out one time of constant current discharging operation;
in the first charging operation, the current is 0.1-0.3C, and the battery cell is charged until the battery cell capacity is kept at 0.5-2% SOC;
in the second charging operation, the current is 0.3-0.7C, and the battery cell is charged until the battery cell capacity is kept at 5-10% SOC;
in the third charging operation, the current is 0.8-1.5C, the battery cell is charged to be in a constant voltage charging mode after being fully charged, and the cutoff current is 0.5C.
During constant current discharge operation, the current is 0.8-1.5C, and the battery cell capacity is kept at 50-70% SOC.
In the second step, specifically, in the constant-current discharge operation process, the fixture on the fixture formation equipment directly performs hot pressing on the battery cell, the preset hot pressing temperature is 70-100 ℃, the preset hot pressing pressure is 1-2 MPa/pcs, and the hot pressing time is 5-10 minutes.
The method provided by the invention can effectively improve the uniformity, compactness and stability of the solid polymer electrolyte membrane on the surface of the negative electrode, improve the internal interface of the battery cell and improve the cycle performance of the lithium battery.
It should be noted that, for the invention, the invention carries out synchronous hot pressing in the process of forming the clamp, the position of the electric core is not changed after one-step clamping, the gas generated in the electric core is extruded and discharged, the uniform heating is ensured, and the interface contact of each layer in the electric core after hot pressing is more compact. Meanwhile, the invention adopts a three-stage formation process of constant-current charging, constant-voltage charging and constant-current discharging, can effectively improve the uniformity, compactness and stability of the solid polymer electrolyte membrane on the surface of the negative electrode, and improves the electrochemical performance of lithium ion batteries, thereby improving the cycle performance of the lithium ion batteries.
According to the invention, the synchronous hot pressing is carried out in the clamp formation process, the interfaces of all layers in the battery cell are in close contact, the battery cell is uniformly heated, the disturbance in the battery cell carrying process is reduced, and the process flow is shortened. Meanwhile, the invention adopts a 'charging and discharging combined' formation process, can effectively improve the uniformity, compactness and stability of the solid polymer electrolyte membrane on the surface of the negative electrode, and improves the electrochemical performance of the lithium battery.
It should be noted that in the conventional manufacturing process of the soft package battery, the formation of the fixture and the hot pressing are two independent steps, the formation of the fixture activates the positive and negative active materials through charging and discharging under a certain temperature and pressure, and the SEI film is formed on the negative electrode to enhance the electrical performance of the battery cell, and the hot pressing process is to perform high-temperature shaping on the battery cell by using a hot pressing plate of a hot press to ensure the strength of the battery cell and prevent the battery cell from deforming in the subsequent cycle process. In the traditional process, the clamp formation temperature is low, the hot pressing temperature is high, and the temperature required by hot pressing cannot be reached by common clamp formation equipment, so that two steps are required to be carried out separately, and the working procedure time is increased. According to the invention, through optimization of the process, on the premise of ensuring electrical property and cell strength, the formation temperature is increased, the hot pressing temperature is reduced, the two steps of processes are combined into one, and the formation and hot pressing processes can be synchronously realized through clamp formation equipment.
It should be noted that the above-mentioned clamp formation equipment of the present invention is an existing formation equipment, and is a conventional battery formation equipment, and is not described herein again.
In order to more clearly understand the technical solution of the present invention, the technical solution of the present invention is described below by specific examples.
Example 1.
The invention provides a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery, which comprises the following steps: and standing the battery cell after liquid injection, placing the battery cell into a clamp formation device after standing for a period of time, and forming under the conditions of specific pressure, temperature, charge and discharge modes and the like. And when the clamp formation discharge process step is carried out, the clamp formation temperature is increased to a specific temperature, the pressure is kept constant, and the cell hot pressing is completed within a specific time.
In the lithium battery formation operation, the temperature of the clamp is 50 ℃, and the pressure applied to the battery cell body by the clamp on the clamp formation equipment is 1 MPa/pcs. The charging mode is step charging and constant current discharging. In one charging operation, the current is 0.1C, and the charging is carried out until the cell capacity is kept at 0.5% SOC. In the secondary charging operation, the current was 0.3C in magnitude, and the charge was maintained until the cell capacity was 5% SOC. In the three-time charging operation, the current is 0.8C, the charging is changed into constant-voltage charging after the full charge, and the cut-off current is 0.5C. In the constant current discharging step, the current is 0.8C, and the battery cell is discharged until the battery cell capacity is kept at 50% SOC. Meanwhile, the electric core is hot-pressed by a clamp on the clamp formation equipment, the hot-pressing temperature is 70 ℃, the hot-pressing pressure is 1MPa/pcs, and the hot-pressing time is 5 minutes.
Example 2.
The invention provides a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery, which comprises the following steps: and standing the battery cell after liquid injection, placing the battery cell into a clamp formation device after standing for a period of time, and forming under the conditions of specific pressure, temperature, charge and discharge modes and the like. And in the step of forming the fixture into a discharge, the temperature of the fixture is increased to a specific temperature, the pressure is kept constant, and the hot pressing of the battery cell is completed within a specific time.
In the lithium battery formation operation, the temperature of the clamp is 70 ℃, and the pressure applied to the battery cell body by the clamp on the clamp formation equipment is 1.5 MPa/pcs. The charging mode is step charging and constant current discharging. In the first charging operation, the current is 0.2C, and the charging is performed until the cell capacity is maintained at 1% SOC. In the second charging operation, the current was 0.5C in magnitude, and the cell capacity was maintained at 7% SOC. In the third charging operation, the current is 1C, the charging is changed into constant voltage charging after the full charge, and the cut-off current is 0.5C. In the constant current discharging step, the current is 1C, and the battery cell capacity is kept at 60% SOC. Meanwhile, the electric core is hot-pressed by a clamp on the clamp formation equipment, the hot-pressing temperature is 90 ℃, the hot-pressing pressure is 1.5MPa/pcs, and the hot-pressing time is 8 minutes.
Example 3.
The invention provides a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery, which comprises the following steps: and standing the battery cell after liquid injection, placing the battery cell into a clamp formation device after standing for a period of time, and forming under the conditions of specific pressure, temperature, charge and discharge modes and the like. And in the step of forming the fixture into a discharge, the temperature of the fixture is increased to a specific temperature, the pressure is kept constant, and the hot pressing of the battery cell is completed within a specific time.
In the lithium battery formation operation, the temperature of a clamp on the clamp formation equipment is 80 ℃, and the pressure applied by the clamp to the battery cell body is 2 MPa/pcs. The charging mode is step charging and constant current discharging. In the first charging operation, the current is 0.3C, and the charging is performed until the cell capacity is maintained at 2% SOC. In the second charging operation, the current was 0.7C in magnitude, and the cell capacity was maintained at 10% SOC. In the third charging operation, the current is 1.5C, the charging is changed into constant voltage charging after the full charge, and the cut-off current is 0.5C. In the constant current discharging step, the current is 1.5C, and the battery cell capacity is kept at 70% SOC. Meanwhile, the clamp carries out hot pressing on the battery cell, the hot pressing temperature is 100 ℃, the hot pressing pressure is 2MPa/pcs, and the hot pressing time is 10 minutes.
Example 4.
The invention provides a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery, which comprises the following steps: and standing the battery cell after liquid injection, placing the battery cell into a clamp formation device after standing for a period of time, and forming under the conditions of specific pressure, temperature, charge and discharge modes and the like. And in the step of forming the fixture into a discharge, the temperature of the fixture is increased to a specific temperature, the pressure is kept constant, and the hot pressing of the battery cell is completed within a specific time.
In the lithium battery formation operation, the temperature of a clamp on the clamp formation equipment is 70 ℃, and the pressure applied by the clamp to the battery cell body is 1.5 MPa/pcs. The charging mode is step charging and constant current discharging. In the first charging operation, the current is 0.1C, and the charging is performed until the cell capacity is maintained at 1% SOC. In the second charging operation, the current was 0.5C in magnitude, and the cell capacity was maintained at 10% SOC. In the third charging operation, the current is 1.5C, the charging is changed into constant voltage charging after the full charge, and the cut-off current is 0.5C. In the constant current discharging step, the current is 1C, and the battery cell capacity is kept at 60% SOC. Meanwhile, the electric core is hot-pressed by a clamp on the clamp formation equipment, the hot-pressing temperature is 100 ℃, the hot-pressing pressure is 1.5MPa/pcs, and the hot-pressing time is 8 minutes.
Example 5.
The invention provides a one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery, which comprises the following steps: and standing the battery cell after liquid injection, placing the battery cell into a clamp formation device after standing for a period of time, and forming under the conditions of specific pressure, temperature, charge and discharge modes and the like. And in the step of forming the fixture into a discharge, the temperature of the fixture is increased to a specific temperature, the pressure is kept constant, and the hot pressing of the battery cell is completed within a specific time.
In the lithium battery formation operation, the temperature of a clamp on the clamp formation equipment is 50 ℃, and the pressure applied by the clamp to the battery cell body is 1.5 MPa/pcs. The charging mode is step charging and constant current discharging. In one charging operation, the current is 0.2C, and the charging is carried out until the cell capacity is kept at 2% SOC. In the secondary charging operation, the current was 0.7C in magnitude, and the charge was performed until the cell capacity was maintained at 10% SOC. In the three-time charging operation, the current is 1C, the charging is changed into constant-voltage charging after the full charging, and the cut-off current is 0.5C. In the constant current discharging step, the current is 1C, and the battery cell capacity is kept at 60% SOC. Meanwhile, the electric core is hot-pressed by a clamp on the clamp formation equipment, the hot-pressing temperature is 90 ℃, the hot-pressing pressure is 1.5MPa/pcs, and the hot-pressing time is 10 minutes.
Test example 1.
The battery formed according to the formation process of example 5 and the battery formed according to the standard formation process are respectively subjected to a high-temperature cycle test, and the test structure is shown in fig. 2.
As can be seen from fig. 2, the method (i.e., formation process) provided by the present invention can effectively improve the cycle performance of the battery.
In summary, compared with the prior art, the one-step formation hot-pressing method for improving the cycle performance of the soft package lithium ion battery provided by the invention has the advantages that after the formation of the battery cell, the hot-pressing process is continuously and directly performed on the battery cell, the generation of vacuoles in the battery cell is avoided, the interface contact and negative film formation in the battery cell are improved, the volume expansion caused by the insertion and the separation of lithium ions can be better adapted, the cycle life of the battery cell is prolonged, and the method has great practical significance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A one-step formation hot-pressing method for improving the cycle performance of a soft package lithium ion battery is characterized by comprising the following steps:
step one, standing the battery cell after liquid injection for a preset time;
secondly, continuously placing the static battery cell into a clamp on clamp formation equipment, and then performing formation operation on the battery cell under a preset formation pressure, a preset formation temperature and a preset charging and discharging system;
in the second step, the preset charging and discharging system is as follows: firstly, step charging is carried out, and then constant current discharging is carried out;
thirdly, in the constant-current discharge operation stage of the formation operation, directly increasing the temperature of the formation from the preset formation temperature to the preset hot-pressing temperature on a clamp of the clamp formation equipment under the condition of not changing the position of the battery cell, keeping the pressure constant under the preset hot-pressing pressure, and carrying out hot-pressing on the battery cell;
and the hot pressing temperature is preset and is higher than the preset formation temperature.
2. The method of claim 1, wherein the predetermined time period is 3 to 4 hours in the first step.
3. The method of claim 1, wherein in the second step, the clamp is formed into a clamp on a device, and the preset formation temperature applied to the battery cell is 50 ℃ to 80 ℃;
in the second step, the clamp on the clamp formation equipment, the preset formation pressure applied to the battery cell body is 1-2 MPa/pcs.
4. The method of claim 1, wherein in the second step, the presetting of the charge-discharge pattern specifically comprises: firstly, carrying out three times of charging operation, and then carrying out one time of constant current discharging operation;
in the first charging operation, the current is 0.1-0.3C, and the battery cell is charged until the battery cell capacity is kept at 0.5-2% SOC;
in the second charging operation, the current is 0.3-0.7C, and the battery cell is charged until the battery cell capacity is kept at 5-10% SOC;
in the third charging operation, the current is 0.8-1.5C, the battery cell is charged to be in a constant voltage charging mode after being fully charged, and the cutoff current is 0.5C;
during constant current discharge operation, the current is 0.8-1.5C, and the battery cell capacity is kept at 50-70% SOC.
5. The method of claim 4, wherein in the second step, in the constant-current discharge operation process, the cell is directly hot-pressed by a clamp on the clamp formation equipment, the preset hot-pressing temperature is 70-100 ℃, the preset hot-pressing pressure is 1-2 MPa/pcs, and the hot-pressing time is 5-10 minutes.
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CN113851744A (en) * | 2021-09-28 | 2021-12-28 | 惠州锂威新能源科技有限公司 | Battery formation method and application thereof |
CN114335769A (en) * | 2021-12-23 | 2022-04-12 | 湖北亿纬动力有限公司 | Formation aging method of battery cell and lithium ion battery |
CN115172887A (en) * | 2022-07-16 | 2022-10-11 | 深圳市誉辰智能装备股份有限公司 | Battery cell segmentation hot press |
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