CN111766518B - Quantitative determination method for reversible lithium separation of lithium ion battery - Google Patents
Quantitative determination method for reversible lithium separation of lithium ion battery Download PDFInfo
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- CN111766518B CN111766518B CN202010560631.4A CN202010560631A CN111766518B CN 111766518 B CN111766518 B CN 111766518B CN 202010560631 A CN202010560631 A CN 202010560631A CN 111766518 B CN111766518 B CN 111766518B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 230000002441 reversible effect Effects 0.000 title claims abstract description 21
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 8
- 238000000926 separation method Methods 0.000 title claims description 4
- 238000004458 analytical method Methods 0.000 claims abstract description 16
- 238000007600 charging Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010280 constant potential charging Methods 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 238000010277 constant-current charging Methods 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 11
- 238000011156 evaluation Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
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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]
- G01R31/378—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] specially adapted for the type of battery or accumulator
-
- 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
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- 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
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Abstract
The invention discloses a quantitative determination method for reversible lithium analysis of a lithium ion battery, which comprises the following steps: taking a lithium ion battery to be tested with constant volume, firstly charging by adopting a constant-current to constant-voltage charging mode, and then applying a voltage I to the battery 0 The small current is subjected to constant current discharge, the change of voltage along with time during the discharge period is recorded, the obtained V-t curve is subjected to second-order differential processing to obtain a dV/dt-t curve, and then the time t of the inflection point of the curve is used for obtaining the time t 0 And calculating the reversible lithium analysis amount of the battery in the charging process. The invention can realize nondestructive detection of lithium ion battery lithium analysis, can quantify the content of reversible lithium analysis, and can realize nondestructive evaluation of lithium ion battery lithium analysis degree.
Description
Technical Field
The invention relates to the technical field of lithium ion battery detection, in particular to a quantitative determination method for reversible lithium analysis of a lithium ion battery.
Background
The continuous progress of the power battery technology enables the new energy industry to be rapidly developed. With the progress of technology and the continuous change of the work and life demands of people, higher requirements are put on the performance of the power battery. Among them, rapid charging is one of expectations for the performance of lithium ion batteries. However, lithium ion batteries are prone to lithium precipitation under the conditions of high-rate charging, low-temperature charging, increased polarization after cycling and the like, and the lithium precipitation accelerates the capacity attenuation of the batteries, so that the internal resistance of the batteries is increased, and lithium dendrites may puncture a diaphragm to cause internal short circuit, thereby causing safety problems. The above conditions can accelerate the aging of the lithium ion battery, resulting in the performance degradation and failure of the battery, and even more serious consequences may occur.
At present, for the detection of lithium analysis, nondestructive detection is gradually replacing a disassembly method, and the condition of lithium analysis of the battery can be obtained without irreversible disassembly of the battery in the nondestructive detection. For example, in a patent with application number 201810194583.4 entitled "lithium precipitation detection method and device", a voltage signal is collected in the discharging process of a battery to be detected, then, a discharging curve of the battery to be detected is obtained according to the voltage signal, the discharging curve represents the relation between voltage and discharging duration, so that a voltage fluctuation curve of the battery to be detected is obtained according to the discharging curve, the voltage fluctuation curve represents the relation between a second derivative of electric quantity to voltage and voltage, and then, whether lithium precipitation occurs in the battery to be detected is detected according to the voltage fluctuation curve. For example, the detection method disclosed by the patent is characterized in that a lithium ion battery is obtained by acquiring appropriate electrical parameters and analyzing the electrical parameters under the condition that the lithium ion battery is not disassembled by the detection method disclosed by the patent application No. 201210312700.5 entitled "a detection method for lithium ion of a lithium ion power battery", and a battery management system and a battery system.
The above-described detection methods can reflect the lithium deposition inside the lithium ion battery under nondestructive conditions, but all of them are qualitative analysis, but cannot detect the amount of lithium deposition and cannot evaluate the severity of lithium deposition. Therefore, it is important to develop a method for quantitatively or semi-quantitatively analyzing the amount of lithium deposited, especially for evaluating the degree of lithium deposition.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a quantitative determination method for reversible lithium analysis of a lithium ion battery.
The invention provides a quantitative determination method for reversible lithium analysis of a lithium ion battery, which comprises the following steps:
s1, taking a lithium ion battery to be tested after constant volume, and charging by adopting a constant-current-to-constant-voltage charging mode;
s2, applying I to the battery charged in the step S1 0 The small current is subjected to constant current discharge, and the change of voltage along with time during the discharge period is recorded to obtain a V-t curve;
s3, carrying out second-order differential processing on the V-t curve to obtain a dV/dt-t curve, and recording inflection point time t of the curve 0 ；
S4, according to the inflection point time t 0 And (4) calculating the reversible lithium separation amount of the battery during the charging process.
Preferably, the calculation method of the reversible lithium evolution quantity is as follows: reversible lithium evolution Q = I 0 ·t 0 。
Preferably, in the step S1, the charging is performed by a constant current to constant voltage charging method to 70% to 100% soc;
preferably, in the step S1, the constant current charging is performed to 50% SOC-70% SOC, and the measured voltage value is V 1 Then in a size of V 1 The voltage of (3) is charged to 70-100% SOC.
Preferably, in the step S1, the magnitude of the constant current charging current is 0.2C to 2C.
Preferably, the I 0 Is 1/50C to 1/5C.
Preferably, the charging and discharging temperature of the lithium ion battery to be tested is-30 ℃ to 0 ℃.
Preferably, in step S1, the specific conditions of constant volume are as follows: constant volume for 3 weeks at 0.5C rate.
The invention has the following beneficial effects:
the invention firstly charges the lithium ion battery to be tested, and then applies a small current I to the battery 0 Performing discharge during the discharge processBefore the lithium precipitated on the surface of the negative electrode is exhausted, the V-t curve is a mixed potential superposition characteristic curve of the lithium intercalated into the graphite and the lithium precipitated on the surface of the negative electrode; when the lithium precipitated on the surface of the negative electrode is exhausted, the V-t curve at this time is a characteristic curve of lithium intercalation and deintercalation into and from graphite. Therefore, the second order differential processing is carried out on the V-t curve obtained in the discharging process, and the inflection point time t in the obtained dV/dt-t curve 0 Namely the time for reversible lithium-evolution oxidation depletion of the surface of the negative electrode. Since the potential of the negative electrode is low (about 0 to 0.2V) and lithium deposited on the surface of the negative electrode is preferentially oxidized during the low-current discharge, the magnitude of the discharge current is approximately equal to the magnitude of the extraction current of lithium deposited on the surface of the negative electrode before the lithium deposited on the surface of the negative electrode is exhausted during the low-current discharge. Therefore, the lithium quantity Q = I can be reversibly analyzed according to the formula 0 ·t 0 And then the reversible lithium analysis amount of the lithium ion battery to be detected can be calculated. The method of the invention not only can realize the nondestructive detection of lithium analysis of the lithium ion battery, but also can quantify the content of reversible lithium analysis, and realize the nondestructive evaluation of the lithium analysis degree of the lithium ion battery.
Drawings
FIG. 1 is a V-t curve of example 1.
FIG. 2 is the dV/dt vs. t curve of example 1.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
S1, taking a lithium ion battery to be tested with constant volume, wherein the battery capacity is 1.1Ah, applying a current with the size of 1C to the battery for constant current charging at the temperature of-20 ℃, charging to 50% SOC, measuring the voltage value to be 3.78V, and then applying a voltage with the size of 3.78V to the battery for constant voltage charging to 70% SOC;
s2, applying a small current with the size of 1/20C to the charged battery to perform constant current discharge, and recording the change of voltage along with time during discharge to obtain a V-t curve, as shown in figure 1;
s3, performing second-order differential processing on the V-t curve to obtain a dV/dt-t curve, and recording the inflection point time of the curve as 0.24h as shown in FIG. 2;
and S4, calculating the reversible lithium deposition amount of the battery in the charging process, wherein the reversible lithium deposition amount Q = (1.1/20) A × 0.24h =13.2mAh.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (6)
1. A quantitative determination method for reversibly separating lithium from a lithium ion battery is characterized by comprising the following steps:
s1, taking a lithium ion battery to be tested after constant volume, and charging by adopting a constant-current-to-constant-voltage charging mode;
s2, applying I to the battery charged in the step S1 0 The small current is subjected to constant current discharge, the change of voltage along with time during the discharge period is recorded to obtain a V-t curve, and the I 0 1/50C-1/5C;
s3, carrying out second-order differential processing on the V-t curve to obtain a dV/dt-t curve, and recording inflection point time t of the curve 0 ；
S4, according to the inflection point time t 0 Calculating the reversible lithium analysis amount of the battery in the charging process; the calculation method of the reversible lithium analysis amount comprises the following steps: reversible lithium evolution Q = I 0 ·t 0 。
2. The method of claim 1, wherein the step S1 comprises charging the lithium ion battery by a charging method of constant current to constant voltage to 70% SOC-100%.
3. The method of claim 1, wherein in step S1, the lithium ion battery is first constant-current charged to 50% SOC-70% 1 Then in a size of V 1 Is charged to 70%100%SOC。
4. The method for quantitatively determining lithium reversibly separated from a lithium ion battery according to claim 1, wherein in the step S1, the magnitude of the current for constant current charging is 0.2 to 2C.
5. The quantitative determination method for lithium ion battery reversible lithium separation according to claim 1, wherein the charging and discharging temperature of the lithium ion battery to be measured is-30 ℃ to 0 ℃.
6. The method for quantitatively determining lithium ion battery reversible lithium deposition according to claim 1, wherein in the step S1, specific conditions for constant volume are as follows: constant volume for 3 weeks under 0.5C multiplying power.
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| CN112782582B (en) * | 2021-01-29 | 2023-09-15 | 远景动力技术(江苏)有限公司 | Method for detecting lithium ion battery negative electrode lithium precipitation |
| CN114544793B (en) * | 2021-08-24 | 2024-06-07 | 万向一二三股份公司 | Quantitative detection method for lithium ion battery negative electrode lithium precipitation amount |
| CN113805074B (en) * | 2021-09-14 | 2024-07-02 | 远景动力技术(江苏)有限公司 | Testing device and testing method for lithium battery |
| CN115327421A (en) * | 2022-08-25 | 2022-11-11 | 同济大学 | Irreversible lithium analysis amount in-situ quantitative detection method based on differential voltage |
| CN116008827A (en) * | 2022-12-23 | 2023-04-25 | 湖北亿纬动力有限公司 | Determination method and device for lithium ion battery lithium precipitation potential and electronic equipment |
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