CN108614221A - A kind of evaluation method of lithium ion battery formation process - Google Patents
A kind of evaluation method of lithium ion battery formation process Download PDFInfo
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- CN108614221A CN108614221A CN201810508585.6A CN201810508585A CN108614221A CN 108614221 A CN108614221 A CN 108614221A CN 201810508585 A CN201810508585 A CN 201810508585A CN 108614221 A CN108614221 A CN 108614221A
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Abstract
The present invention relates to a kind of evaluation methods of lithium ion battery formation process.This method includes the pressure drop for the first time after detection chemical conversion, ageing process, and the secondary voltage drop after detection partial volume, ageing process compares the difference step of pressure drop for the first time and secondary voltage drop.The evaluation method carries out aging accelerated test respectively to the battery after chemical conversion and partial volume, by the comparison of pressure drop for the first time and secondary voltage drop difference, judges the activation effect of different formation process.The SEI films that good formation process is formed have the characteristics that fine and close, uniform, solubility is small in the electrolytic solution, thermal stability and chemical stability are good, it can prevent electrode material and electrolyte from reacting, it reduces side reaction and reduces self-discharge rate, correspondingly, the pressure drop size that the present invention is generated by aging accelerated test evaluates the formation effect of lithium ion battery, is highly suitable for lithium ion battery manufacturer and fast and accurately screens suitable formation process.
Description
Technical field
The invention belongs to the chemical conversion fields of lithium ion battery, and in particular to a kind of evaluation side of lithium ion battery formation process
Method.
Background technology
Lithium ion battery has energy density height, has extended cycle life, has extended cycle life, multiplying power as high-efficiency energy-storage element
Performance and the advantages that having a safety feature, electronic equipment, communication apparatus, medical instrument and new energy vapour it have been widely used at present
The fields such as vehicle.
Chemical conversion is the important procedure in lithium ion battery production process, forms one layer of passivation layer in negative terminal surface when chemical conversion,
I.e. solid electrolyte interface film (SEI films), the quality of SEI films directly influence the cycle life of battery, stability, self discharge
The chemical properties such as property, safety.Chemical conversion is the first time charge and discharge process of lithium ion battery, as publication No. is
The patent application of CN106684426A discloses a kind of chemical synthesizing method of soft bag lithium ionic cell, first uses 0.01C-0.05C
Electric current to soft bag lithium ionic cell carry out low current precharge, until blanking voltage 3.0V；Use the electric current of 0.1C-1.0C permanent again
Current charge, until blanking voltage 3.6V；Then 0.5C-3.0C electric current constant-current constant-voltage chargings are used, until blanking voltage 4.2V, cut-off electricity
Flow 0.01C-1.0C.
The formation process of lithium ion battery is varied, and the selection of the parameters such as charging current, temperature-pressure mode also increases
The complexity of formation process.The quality for how evaluating different formation process, to make battery manufacturer quickly screening suitableization
Have great importance at process.Currently, mostly use the method for lithium ion battery loop test to evaluate the formation effect of battery,
This method is time-consuming longer, and practicability is poor.
Invention content
The purpose of the present invention is to provide a kind of evaluation methods of lithium ion battery formation process, to solve existing evaluation
Method the problem of time-consuming, poor practicability.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of evaluation method of lithium ion battery formation process, includes the following steps：
1) after battery completes formation process, detection voltage is U1；Then burin-in process is carried out to battery, is examined after burin-in process
Survey voltage is U2, record pressure drop Δ U for the first time1=U1-U2；
2) cyclic test is carried out to the battery after step 1) burin-in process, detection voltage is U3, then to the electricity after partial volume
Pond carries out burin-in process, and detection voltage is U after burin-in process4, record secondary voltage drop Δ U2=U3-U4；
3) the difference DELTA U=Δs U of pressure drop for the first time and secondary voltage drop is calculated1-ΔU2, the Δ U values of more different formation process,
Such as Δ U≤0, illustrate that formation process does not reach activation effect；Such as Δ U ＞ 0, illustrate that formation process reaches activation effect, and Δ U
Value is bigger, illustrates that the formation effect of the formation process is better.
The evaluation method of lithium ion battery formation process provided by the invention carries out the battery after chemical conversion and partial volume respectively
Aging accelerated test judges the activation effect of different formation process by the comparison of pressure drop for the first time and secondary voltage drop difference.Well
The SEI films that are formed of formation process have that fine and close, solubility is small uniformly, in the electrolytic solution, thermal stability and chemical stability are good
The characteristics of, it can prevent electrode material and electrolyte from reacting, reduce side reaction and reduce self-discharge rate, correspondingly, this hair
The bright pressure drop size generated by aging accelerated test evaluates the formation effect of lithium ion battery, is highly suitable for lithium-ion electric
Suitable formation process fast and accurately screens in pond manufacturer.
In step 1), the burin-in process is processing 24-48h at 35-55 DEG C.
In step 2), the cyclic test is that cycle is discharged and charged, and the number of cycle is 2-4 times.Preferably, it follows
During ring, the multiplying power of electric discharge and charging is 1C.In cyclic process, the blanking voltage of formation process is charged to.
In step 2), the burin-in process is processing 24-48h at 35-55 DEG C.
The evaluation method of the lithium ion battery formation process of the present invention, by carrying out aging under above-mentioned optimizing technology parameters
Processing and partial volume processing, can simple, intuitive reaction cell formation effect, evaluation method is simple and shortens the assessment time.
Description of the drawings
Fig. 1 is the process flow chart of the evaluation method of the lithium ion battery formation process of the present invention；
Using the cycle performance comparison of the lithium ion battery of different formation process in Fig. 2 test examples.
Specific implementation mode
Embodiments of the present invention are described further with reference to specific embodiment.
Embodiment 1
The evaluation method of the lithium ion battery formation process of the present embodiment, technological process is as shown in Figure 1, using following step
Suddenly：
1) after lithium ion battery chemical conversion, it is U to detect its voltage1, later by lithium ion battery 45 DEG C of agings for 24 hours,
Detection voltage is U2, record pressure drop Δ U for the first time1=U1-U2；
2) battery after step 1) aging carries out under 1C/1C multiplying powers to cycle electric discharge and charging, cycle-index be twice,
The blanking voltage of formation process is charged to, specific voltage value is detected later, is denoted as U3；Then after cycle being discharged and is charged
Voltage 45 DEG C of agings for 24 hours, detection voltage be U4, record secondary voltage drop Δ U2=U3-U4；
3) the difference DELTA U=Δs U of pressure drop for the first time and secondary voltage drop is calculated1-ΔU2, the Δ U values of more different formation process,
Δ U ＞ 0 and Δ U values are bigger, illustrate that the formation effect of the formation process is better.
Embodiment 2
The evaluation method of the lithium ion battery formation process of the present embodiment, technological process is as shown in Figure 1, using following step
Suddenly：
1) after lithium ion battery chemical conversion, it is U to detect its voltage1, later by lithium ion battery in 35 DEG C of aging 48h,
Detection voltage is U2, record pressure drop Δ U for the first time1=U1-U2；
2) battery after step 1) aging carries out under 1C/1C multiplying powers to cycle electric discharge and charging, cycle-index be twice,
The blanking voltage of formation process is charged to, specific voltage value is detected later, is denoted as U3；Then after cycle being discharged and is charged
For voltage in 35 DEG C of aging 48h, detection voltage is U4, record secondary voltage drop Δ U2=U3-U4；
3) the difference DELTA U=Δs U of pressure drop for the first time and secondary voltage drop is calculated1-ΔU2, the Δ U values of more different formation process,
Δ U ＞ 0 and Δ U values are bigger, illustrate that the formation effect of the formation process is better.
Embodiment 3
The evaluation method of the lithium ion battery formation process of the present embodiment, technological process is as shown in Figure 1, using following step
Suddenly：
1) after lithium ion battery chemical conversion, it is U to detect its voltage1, later by lithium ion battery 55 DEG C of agings for 24 hours,
Detection voltage is U2, record pressure drop Δ U for the first time1=U1-U2；
2) battery after step 1) aging carries out under 1C/1C multiplying powers to cycle electric discharge and charging, cycle-index be twice,
The blanking voltage of formation process is charged to, specific voltage value is detected later, is denoted as U3；Then after cycle being discharged and is charged
Voltage 55 DEG C of agings for 24 hours, detection voltage be U4, record secondary voltage drop Δ U2=U3-U4；
3) the difference DELTA U=Δs U of pressure drop for the first time and secondary voltage drop is calculated1-ΔU2, the Δ U values of more different formation process,
Δ U ＞ 0 and Δ U values are bigger, illustrate that the formation effect of the formation process is better.
Test example
This test example illustrates the method for the present invention in evaluation lithium ion battery formation process by taking the method for embodiment 1 as an example
In practical application.
For the ternary lithium ion battery of model 10Ah Soft Rolls, be respectively adopted formation process 1, formation process 2 to lithium from
Sub- battery carries out chemical conversion treatment, records the pressure drop data of formation process 1 and formation process 2.Wherein formation process 1 is specifically such as table 1
It is shown.
The workflow of 1 formation process 1 of table
Formation process 2 is specific as shown in table 2.
The workflow of 2 formation process 2 of table
The pressure drop data of different formation process is detected, concrete outcome is as shown in Table 3 and Table 4.
The pressure drop data of 3 formation process of table, 1 corresponding lithium ion battery
| Number | U1, V | U2, V | ΔU1, V | U3, V | U4, V | ΔU2, V | (ΔU1-ΔU2), V |
| 1 | 4.1773 | 4.1282 | 0.0491 | 4.1977 | 4.1676 | 0.0301 | 0.0190 |
| 2 | 4.1706 | 4.1257 | 0.0449 | 4.1963 | 4.1697 | 0.0266 | 0.0183 |
| 3 | 4.1787 | 4.1267 | 0.0520 | 4.1959 | 4.1677 | 0.0282 | 0.0238 |
| 4 | 4.1736 | 4.1222 | 0.0514 | 4.1957 | 4.1663 | 0.0294 | 0.0220 |
| 5 | 4.1767 | 4.1247 | 0.0520 | 4.1967 | 4.1676 | 0.0291 | 0.0229 |
| 6 | 4.1748 | 4.1217 | 0.0531 | 4.1956 | 4.1687 | 0.0269 | 0.0262 |
| 7 | 4.1787 | 4.1274 | 0.0513 | 4.193 | 4.1648 | 0.0282 | 0.0231 |
| 8 | 4.1737 | 4.1257 | 0.0480 | 4.1917 | 4.1646 | 0.0271 | 0.0209 |
| 9 | 4.1783 | 4.1288 | 0.0495 | 4.191 | 4.1684 | 0.0226 | 0.0269 |
| 10 | 4.1726 | 4.1262 | 0.0464 | 4.1916 | 4.1688 | 0.0228 | 0.0236 |
| 11 | 4.1737 | 4.1266 | 0.0471 | 4.1919 | 4.1648 | 0.0271 | 0.0200 |
| 12 | 4.1742 | 4.1288 | 0.0454 | 4.1924 | 4.1674 | 0.0250 | 0.0204 |
| 13 | 4.1729 | 4.1304 | 0.0425 | 4.1904 | 4.1698 | 0.0206 | 0.0219 |
| 14 | 4.1727 | 4.1279 | 0.0448 | 4.1902 | 4.1667 | 0.0235 | 0.0213 |
| 15 | 4.1714 | 4.1281 | 0.0433 | 4.1894 | 4.1691 | 0.0203 | 0.0230 |
The pressure drop data of 4 formation process of table, 2 corresponding lithium ion battery
By the above testing result, the pressure drop for the first time of formation process 1 and the difference of secondary voltage drop are larger, it was demonstrated that formation process
1 is the formation process for being more suitable for the type lithium ion battery.
Further loop test mode is used to detect the validity of above-mentioned evaluation result, specially respectively to formation process 1,
Treated the battery of formation process 2 carries out loop test, and loop test flow is：For 1C constant-current constant-voltage chargings to 4.2V, cut-off is electric
0.02C is flowed, then 1C constant-current discharges to 2.75V, recycles 600 cycles；The results are shown in Figure 2 for cyclic test.
As shown in Figure 2, the cycle performance of 1 corresponding lithium ion battery of formation process is substantially better than formation process 2, shows needle
To the lithium ion battery of this kind of model, formation process 1 has better activation effect relative to formation process 2.
Can be obtained by testing above, relative to the method for loop test, method of the invention can simple, intuitive reaction
The quality of lithium ion battery difference formation process shortens the assessment time, to contribute to lithium ion battery manufacturer quick
Filter out suitable chemical synthesis technology.
Claims (6)
1. a kind of evaluation method of lithium ion battery formation process, which is characterized in that include the following steps：
1) after battery completes formation process, detection voltage is U1；Then burin-in process is carried out to battery, electricity is detected after burin-in process
Pressure is U2, record pressure drop Δ U for the first time1=U1-U2；
2) cyclic test is carried out to the battery after step 1) burin-in process, detection voltage is U3, then the battery after partial volume is carried out
Burin-in process, detection voltage is U after burin-in process4, record secondary voltage drop Δ U2=U3-U4；
3) the difference DELTA U=Δs U of pressure drop for the first time and secondary voltage drop is calculated1-ΔU2, the Δ U values of more different formation process, such as Δ U
≤ 0, illustrate that formation process does not reach activation effect；Such as Δ U ＞ 0, illustrate that formation process reaches activation effect, and Δ U values are got over
Greatly, illustrate that the formation effect of the formation process is better.
2. the evaluation method of lithium ion battery formation process as described in claim 1, which is characterized in that described in step 1)
Burin-in process is processing 24-48h at 35-55 DEG C.
3. the evaluation method of lithium ion battery formation process as described in claim 1, which is characterized in that described in step 2)
Cyclic test is that cycle is discharged and charged, and the number of cycle is 2-4 times.
4. the evaluation method of lithium ion battery formation process as claimed in claim 3, which is characterized in that in cyclic process, put
Electricity and the multiplying power of charging are 1C.
5. the evaluation method of lithium ion battery formation process as described in claim 3 or 4, which is characterized in that in cyclic process,
Charge to the blanking voltage of formation process.
6. the evaluation method of lithium ion battery formation process as described in claim 1, which is characterized in that described in step 2)
Burin-in process is processing 24-48h at 35-55 DEG C.
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| CN113589179A (en) * | 2021-07-30 | 2021-11-02 | 江南大学 | Power battery formation process state estimation method based on convex spatial filtering |
| WO2023005064A1 (en) * | 2021-07-30 | 2023-02-02 | 江南大学 | State estimation method for power battery formation process based on convex spatial filtering |
| US11650253B2 (en) | 2021-07-30 | 2023-05-16 | Jiangnan University | State estimation method for power battery formation process based on convex space filtering |
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| WO2023005064A1 (en) * | 2021-07-30 | 2023-02-02 | 江南大学 | State estimation method for power battery formation process based on convex spatial filtering |
| US11650253B2 (en) | 2021-07-30 | 2023-05-16 | Jiangnan University | State estimation method for power battery formation process based on convex space filtering |
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