CN114597499A - Formation method and preparation method of lithium ion battery and lithium ion battery - Google Patents
Formation method and preparation method of lithium ion battery and lithium ion battery Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 35
- 238000010277 constant-current charging Methods 0.000 claims abstract description 18
- 238000007600 charging Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000005653 Brownian motion process Effects 0.000 abstract description 5
- 238000005537 brownian motion Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 5
- 150000002222 fluorine compounds Chemical group 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a formation method and a preparation method of a lithium ion battery and the lithium ion battery, wherein the formation method comprises the following steps: injecting electrolyte into the naked electric core, heating and standing; applying a first pressure to the first processing battery, and carrying out constant current charging at a first current; charging the second processing battery with a second current at a constant current; charging the third processing battery with a third current at a constant current; and applying a second pressure to the fourth processing battery, and carrying out constant current charging with a third current to obtain the lithium ion battery. According to the formation method of the lithium ion battery, the short-time film formation is carried out by adopting low-current charging, then the compact film formation is carried out by adopting high-current charging, the side reaction and the Brownian motion are accelerated at high temperature, and the deposition of fluoride is improved, so that the thermal stability of an anode sheet is improved; meanwhile, the last constant-current charging uses lower pressure, so that the pressure change is realized, the pressure is reduced, the stress of the pole piece is released, and the deformation rate of the battery cell is reduced.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a formation method and a preparation method of a lithium ion battery and the lithium ion battery.
Background
In the first charge and discharge process of the liquid lithium ion battery, the electrode material and the electrolyte react on a solid-liquid phase interface to form a passivation layer covering the surface of the electrode material. The passivation layer is an interfacial layer, characterized by a solid electrolyte, which is an electronic insulator but Li+Of good electrical conductivity, Li+Can be freely inserted and extracted through the passivation layer, so the passivation film is called a solid electrolyte interface film (solid electrolyte interface film), namely an SEI film.
In the lithium ion secondary battery, the charging and discharging of the battery are completed through the process of lithium ion intercalation and deintercalation at the negative electrode, and the intercalation process of the lithium ions is bound to pass through the SEI film covering the carbon negative electrode, so the characteristics of the SEI film determine the kinetics of lithium intercalation and deintercalation and the interface stability of the electrolyte at the negative electrode, and also determine the performance of the whole battery, such as cycle life, self-discharge, rated rate, low-temperature performance of the battery, and the like. The performance of the SEI film can be improved by continuous modification of battery materials and development of new solvents and additives. SEI films for positive electrode materials are now being studied little by little, but attention is constantly increasing; new techniques and new methods for studying SEI films are yet to be expanded. With the increasing demand of people on the energy density of batteries, the safety requirement of the batteries is high. In order to obtain good performance of a traditional liquid flexible-package polymer lithium ion battery, a high-rate graphite material is adopted for an anode, and a high-voltage lithium cobaltate material is adopted for a cathode, so that poor thermal stability of the anode is easy to occur under the condition, and a technical scheme for solving the problems is urgently needed.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, a formation method of a lithium ion battery is provided to solve the problem of poor thermal stability of a negative pole piece.
In order to achieve the purpose, the invention adopts the following technical scheme:
a formation method of a lithium ion battery comprises the following steps:
step S1, injecting electrolyte into the bare cell, heating and standing to obtain a first processing battery;
step S2, applying a first pressure to the first processing battery, setting a first temperature, standing, and performing constant current charging with a first current to obtain a second processing battery;
step S3, charging the second processing battery at the first pressure and the first temperature with a second current at a constant current to obtain a third processing battery;
step S4, charging the third processing battery at the first pressure and the first temperature with a third current at a constant current to obtain a fourth processing battery;
step S5, applying a second pressure to the fourth processing battery at the first temperature, and performing constant current charging with a third current to obtain a lithium ion battery;
the first pressure is greater than the second pressure, the first current is less than the second current, and the second current is less than the third current.
According to the formation method of the lithium ion battery, the low-current charging is adopted for slowly forming the film, the firmness of the SEI film is increased by slowly forming the film, then the high-current charging is carried out for densely forming the film, the side reaction and the Brownian motion are accelerated at high temperature, and the deposition of fluoride is improved, so that the thermal stability of the anode sheet is improved; meanwhile, the last constant-current charging uses lower pressure, so that variable pressure is realized, the stress of the pole piece is released along with the reduction of the pressure, and the deformation rate of the battery cell is reduced.
Preferably, the temperature after heating in the step S1 is 40-60 ℃, and the standing time is 8-20 h. The temperature is 40 deg.C, 43 deg.C, 46 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 54 deg.C, 57 deg.C, 60 deg.C. The standing time is 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 19.8h and 20 h.
Preferably, the first pressure is 0.8 to 1.2MPa, and the second pressure is 0.2 to 0.5 MPa. The first pressure is 0.8MPa, 0.9MPa, 1.0MPa, 1.05MPa, 1.15MPa, 1.19MPa, 1.2 MPa. The second pressure is 0.2MPa, 0.25MPa, 0.28MPa, 0.29MPa, 0.3MPa, 0.35MPa, 0.39MPa, 0.40MPa, 0.42MPa, 0.5 MPa.
Preferably, the first current is 0.3-0.5C multiplying current, the second current is 1-1.2C multiplying current, and the third current is 1.5-1.8C multiplying current. The first current is 0.3C multiplying power current, 0.35C multiplying power current, 0.38C multiplying power current, 0.39C multiplying power current, 0.41C multiplying power current, 0.43C multiplying power current, 0.46C multiplying power current, 0.49C multiplying power current and 0.5C multiplying power current; the second current is 1C multiplying power current, 1.1C multiplying power current, 1.13C multiplying power current, 1.18C multiplying power current and 1.2C multiplying power current; the third current is 1.5C multiplying current, 1.56C multiplying current, 1.59C multiplying current, 1.64C multiplying current, 1.65C multiplying current, 1.68C multiplying current, 1.72C multiplying current, 1.76C multiplying current and 1.8C multiplying current. The use becomes pressure and can make release electric core pressure, avoids electric core to warp, uses the alternating current, can make electric core film-forming under the undercurrent, becomes under the heavy current and charges, and the two combines, makes the electric core that the formation reachs have better performance.
Preferably, the first temperature is 80-90 ℃. The first temperature is 80 deg.C, 82 deg.C, 84 deg.C, 86 deg.C, 88 deg.C, 90 deg.C.
Preferably, in step S5, the fourth processing battery is subjected to a second pressure at the first temperature, and is subjected to constant current charging with a third current, and is left to stand to obtain the lithium ion battery.
Preferably, a standing treatment is provided among the constant current charging of step S2, step S3, step S4 and step S5. And the battery cell is subjected to temporary standing after constant current charging, so that the battery cell is more stable in SEI film obtained by battery cell formation, and the performance is better.
Preferably, the SOC of the second processing battery is 2-3%, the SOC of the third processing battery is 10-13%, the SOC of the fourth processing battery is 80-93%, and the SOC of the lithium ion battery in the step S5 is 93-98%. The second treatment battery is obtained by using low current formation, the SOC is slowly improved in the formation process, the SEI film obtained by formation is more stable and firmer, and the phenomenon of lithium precipitation and black spots is not easy to occur. The third processing battery is formed by using slightly larger current, the fourth processing battery is formed by using larger current, the charge content of the battery is greatly increased, the formation time is shortened, and the lithium ion battery is formed continuously by using larger current in the step S5, so that the formation degree is further increased.
The second purpose of the invention is: aiming at the defects of the prior art, the preparation method of the lithium ion battery is provided, and the preparation method is simple and has good controllability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of the lithium ion battery comprises the steps of the formation method of the lithium ion battery. The preparation method of the lithium ion battery comprises the steps of filling a naked battery cell into a shell, injecting electrolyte, packaging, carrying out the formation steps, and grading to obtain the lithium ion battery.
The third purpose of the invention is that: aiming at the defects of the prior art, the lithium ion battery is provided, and has good pole piece thermal stability and strong thermal shock resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery is prepared by the preparation method of the lithium ion battery.
Preferably, the lithium ion battery comprises a positive pole piece, a negative pole piece, an isolating membrane, electrolyte and a shell, wherein the positive pole piece and the negative pole piece are separated by the isolating membrane, the positive pole piece, the negative pole piece, the isolating membrane and the electrolyte are arranged on the shell, and the melting peak temperature of the negative pole piece is 150-160 ℃. Compared with the prior art, the lithium ion battery has higher melting peak temperature, can resist stronger thermal impulse, and has good performance and safety. The formation process adopts a small current to form a film in a short time, then utilizes a large current to charge, enables an SEI film to be compact, accelerates side reaction and Brownian motion at a high temperature, improves the deposition of fluoride, and further improves the thermal stability of the negative pole piece.
Compared with the prior art, the invention has the beneficial effects that: according to the formation method of the lithium ion battery, the low-current charging is adopted for slow film formation, the firmness of the SEI film is increased, then the high-current charging is adopted for compact film formation, the side reaction and the Brownian motion are accelerated at high temperature, and the deposition of fluoride is improved, so that the thermal stability of a negative pole piece is improved; meanwhile, the last constant-current charging uses lower pressure, so that variable pressure is realized, the stress of the pole piece is released along with the reduction of the pressure, and the deformation rate of the battery cell is reduced.
Drawings
Fig. 1 is a graph of time-voltage formation in example 1 of the present invention.
FIG. 2 is a melting peak temperature test chart of two tests conducted on example 1 of the present invention and comparative example 1, respectively.
Fig. 3 is a distribution diagram of the liquid retention capacity of the lithium ion batteries prepared in example 1 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the present invention is not limited thereto.
Example 1
A formation method of a lithium ion battery comprises the following steps:
step S1, injecting electrolyte into the bare cell, and standing for 12 hours at 45 ℃ to obtain a first processing battery;
step S2, applying a first pressure of 1.0MPa to the first processing battery, setting a first temperature of 85 ℃, standing for 1min, and performing constant current charging for 8.5min by using a first current with a rate of 0.2C to obtain a second processing battery;
step S3, carrying out constant current charging on the second processing battery for 5min at 85 ℃ under the first pressure of 1.0MPa and the first temperature and with the current multiplying the second current by 1.0C to obtain a third processing battery;
step S4, carrying out constant current charging on the third processing battery for 31.55min at 85 ℃ under the first pressure of 1.0MPa and the first temperature and with the current of the third current multiplying power of 1.5C to obtain a fourth processing battery;
and step S5, applying a second pressure of 0.3MPa to the fourth processing battery at the first temperature of 85 ℃, and carrying out constant current charging for 2.6min by using a current with the rate of 1.5C of a third current to obtain the lithium ion battery.
Example 2
The difference from example 1 is that: the first current is 0.3C multiplying power, the second current is 1C multiplying power, and the third current is 1.5C multiplying power.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is that: the first current is 0.5C multiplying power, the second current is 1C multiplying power, and the third current is 1.5C multiplying power.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is that: the first pressure is 0.8MPa, and the second pressure is 0.2 MP.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is that: the first pressure is 0.9MPa, and the second pressure is 0.3 MP.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is that: the first pressure is 1.2MPa, and the second pressure is 0.5 MP.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that: the temperature after heating in the step S1 is 50 ℃, and the standing time is 16 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that: the temperature after heating in the step S1 is 55 ℃, and the standing time is 18 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that: the temperature after heating in the step S1 is 60 ℃, and the standing time is 8 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is that: the temperature after heating in the step S1 is 40 ℃, and the standing time is 20 h.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from example 1 is that: the first current, the second current and the third current are all 1.2C multiplying power.
And (3) performance testing: the lithium ion batteries prepared in the above examples 1 to 10 were subjected to performance tests, the melting peak temperature and the liquid retention coefficient of the pole piece were tested, and the test results are recorded in table 1.
TABLE 1
As can be seen from table 1, the lithium ion battery prepared by the formation method of the lithium ion battery of the present invention has better thermal stability and liquid retention coefficient than comparative example 1. As can be seen from fig. 1, the voltage of the lithium ion battery prepared by the formation in this example 1 reaches 4500mV, which has a higher battery voltage. From comparison of examples 1 to 3, when the first current is set to be 0.2C rate current, the second current is set to be 1C rate current, and the third current is set to be 1.5C rate current, the thermal stability of the prepared lithium ion battery is better. The formation is carried out by using the current with the small multiplying power, and the formation is carried out by using the current with the large multiplying power, so that the SEI film is more compact, the side reaction and the Brownian motion are accelerated at high temperature, the deposition of fluoride is improved, the thermal stability of the anode sheet is improved, the prepared lithium ion battery has good thermal shock resistance, and the lithium ion battery can pass the test and has good safety. Compared with the embodiments 1 and 4-6, when the first pressure is set to be 1.0MPa and the second pressure is set to be 0.3MP, the performance of the prepared lithium ion battery is better, because the first pressure is higher, the formed interface is good (the diaphragm is in good contact with the pole piece and the bonding is reliable), and therefore lithium cannot be separated out from the inside of the battery cell when the battery cell is charged and discharged for recycling, and the safety risk is further reduced; and the second pressure uses smaller pressure, and under the condition of variable pressure, the stress of the pole piece is released, and the deformation rate of the battery cell is reduced. As shown by comparison of examples 1 and 7-10, when the temperature after heating in step S1 is set to be 45 ℃ and the standing time is set to be 12 hours, the performance of the prepared lithium ion battery is better.
Table 2 table for testing liquid retention performance of the lithium ion batteries prepared in example 1 and comparative example 1.
As can be seen from FIG. 3, the liquid retention of the present invention is relatively concentrated, and the liquid retention level is at 7.27, and is located at a position with a medium upper position, which shows that the lithium ion battery of the present invention has good overall performance, good consistency and good quality stability. Specifically, it can be seen from table 2 that example 1 of the present invention has better liquid retention, improved liquid retention performance by 0.08, reduced liquid retention sigma by 0.048, smaller fluctuation, and better consistency than comparative example 1.
Table 3 melting peak temperature test tables of the lithium ion batteries prepared in example 1 and comparative example 1.
As can be seen from fig. 2 and table 3, example 1 and comparative example 1 have better melting peak temperature values, the melting peak temperature values of the two tests are as high as 154.43 ℃ and 156.95 ℃, after the two tests, the minimum values of example 1 and comparative example 1 are 154.43 ℃ and 136.57 ℃, respectively, and the melting peak temperature value of example 1 is 17.86 ℃ higher than that of comparative example 1, so that the thermal shock of the lithium ion battery is remarkably improved.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (11)
1. A formation method of a lithium ion battery is characterized by comprising the following steps:
step S1, injecting electrolyte into the bare cell, heating and standing to obtain a first processing battery;
step S2, applying a first pressure to the first processing battery, setting a first temperature, standing, and performing constant current charging with a first current to obtain a second processing battery;
step S3, charging the second processing battery at the first pressure and the first temperature with a second current at a constant current to obtain a third processing battery;
step S4, charging the third processing battery at the first pressure and the first temperature with a third current at a constant current to obtain a fourth processing battery;
step S5, applying a second pressure to the fourth processing battery at the first temperature, and performing constant current charging with a third current to obtain a lithium ion battery;
the first pressure is greater than the second pressure, the first current is less than the second current, and the second current is less than the third current.
2. The formation method of the lithium ion battery according to claim 1, wherein the temperature after heating in the step S1 is 40-60 ℃, and the standing time is 8-20 h.
3. The method of claim 1, wherein the first pressure is 0.8 to 1.2MPa and the second pressure is 0.2 to 0.5 MPa.
4. The method of claim 3, wherein the first current is 0.3-0.5C-rate current, the second current is 1-1.2C-rate current, and the third current is 1.5-1.8C-rate current.
5. The method for forming a lithium ion battery according to claim 1, wherein the first temperature is 80 to 90 ℃.
6. The method according to claim 1, wherein the step S5 is to apply a second pressure to the fourth processing battery at the first temperature, perform constant current charging at a third current, and obtain the lithium ion battery by standing.
7. The method of claim 1, wherein a standing process is provided among the steps S2, S3, S4 and S5 during the constant current charging.
8. The method of claim 7, wherein the SOC of the second process battery is 2-3%, the SOC of the third process battery is 10-13%, the SOC of the fourth process battery is 80-93%, and the SOC of the lithium ion battery in step S5 is 93-98%.
9. A method for producing a lithium ion battery, comprising the step of the method for forming a lithium ion battery according to any one of claims 1 to 8.
10. A lithium ion battery, characterized by being produced by the method for producing a lithium ion battery according to claim 9.
11. The lithium ion battery of claim 10, comprising a positive electrode plate, a negative electrode plate, a separator, an electrolyte and a casing, wherein the separator separates the positive electrode plate from the negative electrode plate, the casing is provided with the positive electrode plate, the negative electrode plate, the separator and the electrolyte, and the melting peak temperature of the negative electrode plate is 150-160 ℃.
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| CN116190827A (en) * | 2022-12-06 | 2023-05-30 | 安徽格兰科新材料技术有限公司 | Method for shortening formation time of lithium ion battery |
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