CN116930785A - Method and system for nondestructive detection of cyclic lithium separation - Google Patents
Method and system for nondestructive detection of cyclic lithium separation Download PDFInfo
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- CN116930785A CN116930785A CN202310922060.8A CN202310922060A CN116930785A CN 116930785 A CN116930785 A CN 116930785A CN 202310922060 A CN202310922060 A CN 202310922060A CN 116930785 A CN116930785 A CN 116930785A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000001514 detection method Methods 0.000 title claims abstract description 34
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 20
- 238000000926 separation method Methods 0.000 title abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 75
- 238000006073 displacement reaction Methods 0.000 claims abstract description 41
- 238000007599 discharging Methods 0.000 claims abstract description 40
- 230000008859 change Effects 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims abstract description 18
- 238000012544 monitoring process Methods 0.000 claims abstract description 15
- 238000009659 non-destructive testing Methods 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 21
- 238000011897 real-time detection Methods 0.000 abstract description 7
- 230000022131 cell cycle Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 230000033366 cell cycle process Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000035772 mutation Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a method and a system for nondestructive testing of cyclic lithium separation, wherein the method comprises the following steps: charging and discharging the battery through preset current; and in the circulation process, the charge-discharge voltage, the charge-discharge capacity and the charge-discharge energy are monitored in real time. Detecting a voltage and capacity change curve of the battery; integrating the voltage and the capacity in the cyclic process to obtain an average charging voltage and an average discharging voltage; summing the average charging voltage and the average discharging voltage in the cyclic process to obtain charging voltage increase and discharging voltage increase caused by lithium loss at the same time; processing the charge-discharge voltage variation in the cyclic process to obtain a displacement voltage LVC caused by lithium loss; and monitoring a displacement voltage curve and a capacity attenuation curve in the circulation process, and judging the occurrence of a lithium precipitation phenomenon and the critical service life of the occurrence of the lithium precipitation according to the change of the displacement voltage curve. The invention solves the technical problems that the lithium precipitation detection cost is high due to the difficulty of nondestructive detection, and the real-time detection is difficult due to the actual cell cycle lithium precipitation phenomenon.
Description
Technical Field
The invention relates to the technical field of lithium ion power batteries, in particular to a method and a system for nondestructive detection of cyclic lithium separation.
Background
At present, the lithium ion battery lithium precipitation detection method mainly comprises the steps of detecting the potential of a negative electrode through a three-electrode test to judge whether lithium precipitation risk exists or not and observing whether lithium precipitation exists or not through an interface dismantling interface. However, the three electrodes cannot detect lithium precipitation during actual cell cycling, and interface disassembly is not only required to damage the cell but also cannot lock the occurrence time of lithium precipitation. The prior patent application publication No. CN111082173A, namely a lithium ion battery rapid charging method based on lithium precipitation prevention, is based on commercial software of an electrochemical model, judges the negative electrode potential of the battery under different temperatures, different charging currents, different states of charge and different health states, and calibrates the model by comparing the actually measured negative electrode potential of the three-electrode battery with the negative electrode potential simulated by the electrochemical model, and parameterizes and scans the calibrated model to obtain a maximum current spectrogram without lithium precipitation. However, the data adopted by the prior art construction model still needs to be checked by using a three-electrode test method, only the lithium precipitation time can be predicted, and the lithium precipitation phenomenon in the actual cell cycle process can not be detected in real time.
The prior patent application publication No. CN113805074A discloses a testing device and a testing method for a lithium battery, wherein the testing device comprises: the charging and discharging module is used for performing charging and discharging tests on the battery; the acquisition module is used for acquiring the voltage value of the battery in the charging and discharging process; the analysis module is used for calculating the state of charge of the battery and the value of dV/dSOC, wherein V represents the voltage value, and SOC represents the state of charge; and the output module is used for outputting the test result curve and data associated with the lithium precipitation point. Although the prior art avoids adopting a three-electrode test method, nondestructive testing can not be carried out on lithium precipitation of the battery.
In summary, the technical problems of high lithium precipitation detection cost and difficult real-time detection of lithium precipitation phenomenon in the actual cell cycle process caused by the difficulty of nondestructive detection in the prior art exist.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: how to solve the technical problems that in the prior art, the lithium precipitation detection cost is high due to the difficulty of nondestructive detection, and the lithium precipitation phenomenon in the actual cell cycle process is difficult to detect in real time.
The invention adopts the following technical scheme to solve the technical problems: the method for circularly separating lithium to realize nondestructive detection comprises the following steps:
s1, carrying out charge-discharge cyclic operation on a battery through preset current;
s2, monitoring charge and discharge data in charge and discharge cycle operation in real time, and detecting a voltage change curve and a capacity change curve of the battery;
s3, integrating the processing voltage change curve and the capacity change curve in the charge-discharge cycle operation to obtain an average charge voltage and an average discharge voltage;
s4, in the charge-discharge cycle operation, summing the average charge voltage and the average discharge voltage to obtain a charge voltage increment value and a discharge voltage increment value;
s5, processing the charging voltage increase value and the discharging voltage increase value to obtain a displacement voltage LVC caused by lithium loss;
s6, acquiring and monitoring a displacement voltage curve and a capacity attenuation curve according to the displacement voltage LVC, judging that the lithium precipitation phenomenon occurs according to the change states of the displacement voltage curve and the capacity attenuation curve, and acquiring the critical service life of the battery when the lithium precipitation occurs and the lithium precipitation moment.
The invention creatively carries out charge and discharge circulation on the battery through preset current, and detects the voltage and the capacity of the battery in the circulation process; and then carrying out integral processing on the voltage and the capacity to obtain an average charging voltage and an average discharging voltage, further processing to obtain a displacement voltage, and determining when the lithium precipitation phenomenon occurs when the battery circulates under a preset current according to whether the processed displacement voltage change curve has mutation. Therefore, the invention can realize nondestructive detection of lithium precipitation and has low detection cost.
In a more specific technical scheme, in step S1, a preset current is obtained through processing according to the charging rate of the battery.
In a more specific technical scheme, the range of values of the charging rate includes: [1/6C,2C ].
In a more specific aspect, in step S2, the charge and discharge data includes: charge-discharge voltage, charge-discharge capacity, and charge-discharge energy.
The invention utilizes the preset current and the preset battery charging north to charge and discharge the battery, and detects the voltage and the capacity of the battery in real time in the circulation process, thereby being convenient for detecting the lithium precipitation phenomenon of the battery in real time.
In a more specific technical solution, step S5 includes:
s51, calculating an average charging voltage as Vav, c and an average discharging voltage as Vav and d by using preset logic;
s52, taking 1/2 of the sum of the average charging voltage and the average discharging voltage as LV value;
s53, calculating the average charging voltage Vav, c, the average discharging voltage Vav, d and LV, and taking the variation of LV as the displacement voltage LVC.
In a more specific embodiment, in step S52, the average charging voltage Vav, c and the average discharging voltage Vac, d are obtained by the following logic:
Vav,c＝Ec/Qc
Vac,d＝Ed/Qd
where Vc is a charge voltage, vd is a discharge voltage, qc is a charge capacity, qd is a discharge capacity, ec is a charge energy, ed is a discharge energy, c is a charge, and d is a discharge.
In a more specific embodiment, in step S52, the displacement voltage LVC is obtained by the following logic process:
LV＝1/2(Vav,c+Vav,d)
LVC＝LVn-LV 20
wherein n is the number of cycles.
According to the invention, through in-situ detection of the rapid increase of LVC caused by lithium reserve loss, whether lithium precipitation occurs in the battery cycle process and the moment of occurrence of the lithium precipitation are detected in a nondestructive manner, so that the real-time detection of the lithium precipitation phenomenon in the battery cycle is realized.
In a more specific technical scheme, in step S6, when the lithium precipitation phenomenon occurs in the battery, the number of weeks corresponding to the abrupt point of the displacement voltage curve is obtained as the occurrence time of the lithium precipitation.
In a more specific technical scheme, in step S6, according to the lithium precipitation detection method, the lithium precipitation condition of the battery at any number of weeks is determined, and the lithium precipitation life is calculated accordingly.
In a more specific technical scheme, the cyclic lithium-precipitation nondestructive testing system comprises:
the charging and discharging module is used for carrying out charging and discharging cyclic operation on the battery through preset current;
the voltage capacity curve monitoring module is used for monitoring charge and discharge data in charge and discharge cycle operation in real time, detecting a voltage change curve and a capacity change curve of the battery, and is connected with the charge and discharge module;
the average charging and discharging voltage acquisition module is used for integrating the processing voltage change curve and the capacity change curve in the charging and discharging cycle operation so as to obtain average charging voltage and average discharging voltage, and the average charging and discharging voltage acquisition module is connected with the voltage capacity curve monitoring module;
the charge-discharge voltage increment acquisition module is used for summing the average charge voltage and the average discharge voltage in charge-discharge cyclic operation so as to obtain a charge voltage increment value and a discharge voltage increment value, and is connected with the average charge-discharge voltage acquisition module;
the displacement voltage obtaining module is used for processing the charging voltage increasing value and the discharging voltage increasing value to obtain a displacement voltage LVC caused by lithium loss, and is connected with the charging and discharging voltage increment obtaining module;
the lithium-precipitation nondestructive detection result acquisition module is used for acquiring and monitoring a displacement voltage curve and a capacity attenuation curve according to the displacement voltage LVC, judging that the lithium-precipitation phenomenon occurs according to the change states of the displacement voltage curve and the capacity attenuation curve, and acquiring the critical service life of the battery when lithium precipitation occurs and the lithium precipitation moment, wherein the lithium-precipitation nondestructive detection result acquisition module is connected with the displacement voltage acquisition module.
Compared with the prior art, the invention has the following advantages:
the invention creatively carries out charge and discharge circulation on the battery through preset current, and detects the voltage and the capacity of the battery in the circulation process; and then carrying out integral processing on the voltage and the capacity to obtain an average charging voltage and an average discharging voltage, further processing to obtain a displacement voltage, and determining when the lithium precipitation phenomenon occurs when the battery circulates under a preset current according to whether the processed displacement voltage change curve has mutation. Therefore, the invention can realize nondestructive detection of lithium precipitation and has low detection cost.
The invention utilizes the preset current and the preset battery charging north to charge and discharge the battery, and detects the voltage and the capacity of the battery in real time in the circulation process, thereby being convenient for detecting the lithium precipitation phenomenon of the battery in real time.
According to the invention, through in-situ detection of the rapid increase of LVC caused by lithium reserve loss, whether lithium precipitation occurs in the battery cycle process and the moment of occurrence of the lithium precipitation are detected in a nondestructive manner, so that the real-time detection of the lithium precipitation phenomenon in the battery cycle is realized.
The invention solves the technical problems of high lithium precipitation detection cost caused by the difficulty of nondestructive detection in the prior art and difficult real-time detection of the lithium precipitation phenomenon in the actual cell cycle process.
Drawings
FIG. 1 is a schematic diagram showing basic steps of a method for nondestructive testing of cyclic lithium separation in example 1 of the present invention;
fig. 2 is a graph showing average charging voltage of the battery of example 1 of the present invention at a preset current;
FIG. 3 is a graph showing average discharge voltage at a predetermined current for the battery of example 1 of the present invention;
fig. 4 is a graph showing the average charge voltage and half of the average discharge voltage of the battery of example 1 at a preset current;
fig. 5 is a graph showing the displacement voltage caused by lithium loss at a preset current for the battery of example 1 of the present invention;
fig. 6 is a graph showing a cycle of a lithium battery at a preset current for the battery of example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in FIG. 1, the cyclic lithium-precipitation nondestructive testing method provided by the invention comprises the following basic steps:
step S1, carrying out charge and discharge circulation on a battery through preset current;
the preset current is determined by the charging multiplying power of the battery, wherein the charging multiplying power can be any value in the range of 1/6C-2C.
For example, the battery may be subjected to charge-discharge cycles by a current having a charge rate of 1C.
And step S2, monitoring the charge-discharge voltage, the charge-discharge capacity and the charge-discharge energy in real time in the circulation process. Detecting a voltage and capacity change curve of the battery;
s3, integrating the voltage and the capacity in the cyclic process to obtain an average charging voltage and an average discharging voltage;
step S4, summing the average charging voltage and the average discharging voltage in the cyclic process to obtain charging voltage increase and discharging voltage increase caused by lithium loss at the same time;
as shown in fig. 2 to 4, in the present embodiment, the battery is charged and discharged, and the charge voltage Vc, the discharge voltage Vd, the charge capacity Qc, the discharge capacity Qd, the charge energy Ec, and the discharge energy Ed for each turn during the cycle are recorded.
S5, processing the charge-discharge voltage variation in the cyclic process to obtain a displacement voltage LVC caused by lithium loss;
as shown in fig. 5, in the present embodiment, the average charge voltage is Vav, c, the average discharge voltage is Vav, d, and 1/2 of the sum of the average charge voltage and the average discharge voltage is LV (LVn in the n-th week), and the variation of LV is the displacement voltage LVC due to lithium loss. Then there are: vav, c=ec/Qc, vac, d=ed/Qd, lv=1/2 (Vav, c+vav, d), lvc=lvn-LV 20 . Lithium precipitation will cause lithium reserve loss, which will increase the average charging voltage and average discharging power at the same timePressing. By in-situ detection of the sharp increase in LVC caused by loss of lithium reserves, it is possible to detect, without loss, whether and when lithium evolution occurs during battery cycling.
In this embodiment, the preset current is determined by the charge-discharge rate of the battery. Wherein, the charge-discharge multiplying power can be any value in the range of 1/6C-2C.
And S6, monitoring a displacement voltage curve and a capacity attenuation curve in the circulation process, and judging the occurrence of the lithium precipitation phenomenon and the critical service life of the lithium precipitation occurrence according to the change of the displacement voltage curve.
As shown in fig. 6, in the case that it is determined that lithium precipitation occurs in the battery under the preset current in this embodiment, the time of occurrence of the lithium precipitation is obtained, and the number of weeks corresponding to the abrupt change point of the displacement voltage is the time of occurrence of the lithium precipitation. And determining whether the lithium is separated from the battery in any number of weeks according to the lithium separation detection method, and determining the cycle life of the lithium separation critical point.
In this embodiment, in the above steps S1 to S6, it may be determined whether the lithium is extracted and the time of the lithium extraction in the battery during the cycle according to the lithium extraction detection method. The above embodiment can give a relatively critical "lithium" cycle life, and it can be determined from fig. 2 to 6 that the lithium is extracted from the battery in the embodiment, and the lithium is extracted for about 400 weeks.
In summary, the present patent creatively determines the time of lithium precipitation of the battery under the preset current according to the lithium precipitation detection method, and detects the lithium precipitation phenomenon in a nondestructive manner, with low detection cost.
In summary, the invention creatively carries out charge and discharge circulation on the battery through preset current, and detects the voltage and the capacity of the battery in the circulation process; and then carrying out integral processing on the voltage and the capacity to obtain an average charging voltage and an average discharging voltage, further processing to obtain a displacement voltage, and determining when the lithium precipitation phenomenon occurs when the battery circulates under a preset current according to whether the processed displacement voltage change curve has mutation. Therefore, the invention can realize nondestructive detection of lithium precipitation and has low detection cost.
The invention utilizes the preset current and the preset battery charging north to charge and discharge the battery, and detects the voltage and the capacity of the battery in real time in the circulation process, thereby being convenient for detecting the lithium precipitation phenomenon of the battery in real time.
According to the invention, through in-situ detection of the rapid increase of LVC caused by lithium reserve loss, whether lithium precipitation occurs in the battery cycle process and the moment of occurrence of the lithium precipitation are detected in a nondestructive manner, so that the real-time detection of the lithium precipitation phenomenon in the battery cycle is realized.
The invention solves the technical problems of high lithium precipitation detection cost caused by the difficulty of nondestructive detection in the prior art and difficult real-time detection of the lithium precipitation phenomenon in the actual cell cycle process.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The method for circularly separating lithium for nondestructive testing is characterized by comprising the following steps:
s1, carrying out charge-discharge cyclic operation on a battery through preset current;
s2, monitoring charge and discharge data in the charge and discharge cycle operation in real time, and detecting a voltage change curve and a capacity change curve of the battery;
s3, in the charge-discharge cycle operation, integrating the voltage change curve and the capacity change curve to obtain an average charge voltage and an average discharge voltage;
s4, in the charge-discharge cycle operation, summing the average charge voltage and the average discharge voltage to obtain a charge voltage increase value and a discharge voltage increase value;
s5, processing the charging voltage increasing value and the discharging voltage increasing value to obtain a displacement voltage LVC caused by lithium loss;
and S6, acquiring and monitoring a displacement voltage curve and a capacity attenuation curve according to the displacement voltage LVC, judging that the lithium precipitation phenomenon occurs according to the change states of the displacement voltage curve and the capacity attenuation curve, and acquiring the critical service life of the battery when the lithium precipitation occurs and the lithium precipitation moment.
2. The method according to claim 1, wherein in the step S1, the preset current is obtained by processing according to a charging rate of the battery.
3. The cyclic lithium-ion non-destructive testing method according to claim 2, wherein the range of values of the charging rate includes: [1/6C,2C ].
4. The method according to claim 1, wherein in the step S2, the charge and discharge data includes: charge-discharge voltage, charge-discharge capacity, and charge-discharge energy.
5. The method according to claim 1, wherein the step S5 comprises:
s51, obtaining the average charging voltage as Vav, c and the average discharging voltage as Vav and d by using preset logic;
s52, taking 1/2 of the sum of the average charging voltage and the average discharging voltage as LV;
s53, calculating the average charging voltage Vav, c, the average discharging voltage Vav, d and the LV to take the variation of the LV value as the displacement voltage LVC.
6. The method according to claim 1, wherein in the step S52, the average charging voltage Vav, c and the average discharging voltage Vac, d are obtained by using the following logic:
Vav,c＝Ec/Qc
Vac,d＝Ed/Qd
where Vc is a charge voltage, vd is a discharge voltage, qc is a charge capacity, qd is a discharge capacity, ec is a charge energy, ed is a discharge energy, c is a charge, and d is a discharge.
7. The method according to claim 1, wherein in the step S52, the displacement voltage LVC is obtained by the following logic processing:
LV＝1/2(Vav,c+Vav,d)
LVC＝LVn-LV 20
wherein n is the number of cycles.
8. The method according to claim 1, wherein in step S6, when the lithium precipitation phenomenon occurs in the battery, the number of weeks corresponding to the abrupt point of the displacement voltage curve is obtained as the occurrence time of the lithium precipitation.
9. The method according to claim 1, wherein in step S6, according to the method, the lithium deposition condition of the battery at any number of weeks is determined, and the lithium deposition lifetime is obtained.
10. A cyclic lithium-ion non-destructive testing system, the system comprising:
the charging and discharging module is used for carrying out charging and discharging cyclic operation on the battery through preset current;
the voltage capacity curve monitoring module is used for monitoring charge and discharge data in the charge and discharge cycle operation in real time, detecting a voltage change curve and a capacity change curve of the battery, and is connected with the charge and discharge module;
the average charging and discharging voltage acquisition module is used for integrating and processing the voltage change curve and the capacity change curve in the charging and discharging cycle operation so as to obtain average charging voltage and average discharging voltage, and the average charging and discharging voltage acquisition module is connected with the voltage capacity curve monitoring module;
the charge-discharge voltage increment acquisition module is used for summing the average charge voltage and the average discharge voltage in the charge-discharge cycle operation to obtain a charge voltage increment value and a discharge voltage increment value, and is connected with the average charge-discharge voltage acquisition module;
the displacement voltage obtaining module is used for processing the charging voltage increasing value and the discharging voltage increasing value to obtain a displacement voltage LVC caused by lithium loss, and is connected with the charging and discharging voltage increment obtaining module;
and the lithium-precipitation nondestructive detection result acquisition module is used for acquiring and monitoring a displacement voltage curve and a capacity attenuation curve according to the displacement voltage LVC, judging that the lithium-precipitation phenomenon occurs according to the displacement voltage curve and the change state of the capacity attenuation curve, acquiring the critical service life of the battery when the lithium precipitation occurs and the lithium precipitation moment, and connecting the lithium-precipitation nondestructive detection result acquisition module with the displacement voltage calculation module.
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