CN111766518A - 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
- Publication number
- CN111766518A CN111766518A CN202010560631.4A CN202010560631A CN111766518A CN 111766518 A CN111766518 A CN 111766518A CN 202010560631 A CN202010560631 A CN 202010560631A CN 111766518 A CN111766518 A CN 111766518A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion battery
- lithium ion
- constant
- charging
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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 discloses a quantitative determination method for reversible lithium separation 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 battery0The 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 t0And calculating the reversible lithium analysis amount of the battery in the charging process. The invention can realize the nondestructive detection of lithium analysis of the lithium ion battery, can quantify the content of reversible lithium analysis, and realizes the nondestructive evaluation of the lithium analysis degree of the lithium ion battery.
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 reduction and failure of the battery, and even more serious consequences may occur.
At present, for the detection of lithium separation, nondestructive detection is gradually replacing a disassembly method, and the condition of lithium separation 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 deposition detection method and device", a voltage signal is collected during 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 the second derivative of electric quantity to voltage and voltage, and then, whether lithium deposition occurs in the battery to be detected is detected according to the voltage fluctuation curve. For example, the detection method disclosed in the above patent can obtain the lithium analysis condition of the lithium ion battery by obtaining appropriate electrical parameters and then analyzing the electrical parameters without disassembling the lithium ion battery, and is also known as a detection method for lithium analysis of a lithium ion power battery, for example, a chinese patent with an application number of 201210312700.5, and a battery with an application number of 201710342850.3, as well as 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 deposition to evaluate 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 separation of a lithium ion battery, which comprises the following steps:
s1, taking the 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 S10The 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 curve0；
S4, according to the inflection point time t0And (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 separation Q ═ I0·t0。
Preferably, in step S1, the battery is charged to 70% SOC to 100% SOC by a constant current to constant voltage charging method;
preferably, in step S1, constant current charging is performed to 50% SOC to 70% SOC, and the measured voltage value is V1Then in a size of V1The voltage of the battery is charged to 70% SOC to 100% SOC at a constant voltage.
Preferably, in step S1, the magnitude of the current for constant current charging is 0.2C to 2C.
Preferably, the I 01/50C-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 for constant volume are as follows: constant volume is carried out for 3 weeks under the magnification of 0.5C.
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 battery0Discharging, wherein in the discharging process, before the lithium precipitated on the surface of the negative electrode is exhausted, a 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 in a desorption mode; 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 curve0Namely 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 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 low-current discharge. Therefore, the lithium content Q ═ I can be reversibly analyzed according to the formula0·t0And 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-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 the lithium ion battery to be measured after constant volume, wherein the battery capacity is 1.1Ah, firstly applying a current with the size of 1C to the battery for constant current charging at the temperature of minus 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, carrying out 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 figure 2;
and S4, calculating the reversible lithium separation amount of the battery in the charging process, wherein the reversible lithium separation amount Q is (1.1/20) A multiplied by 0.24h is 13.2 mAh.
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 to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A quantitative determination method for reversibly separating lithium from a lithium ion battery is characterized by comprising the following steps:
s1, taking the 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 S10The 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 curve0；
S4, according to the inflection point time t0And (4) calculating the reversible lithium separation amount of the battery during the charging process.
2. The method for quantitatively determining reversible lithium deposition of a lithium ion battery according to claim 1, wherein the method for calculating the reversible lithium deposition amount comprises: reversible lithium separation Q ═ I0·t0。
3. The method for quantitatively determining lithium ion battery reversible lithium deposition according to claim 1 or 2, wherein in step S1, charging is performed to 70% SOC to 100% SOC by a constant current to constant voltage charging method.
4. The method for quantitatively determining reversibly separated lithium in a lithium ion battery according to any one of claims 1 to 3, wherein in step S1, constant current charging is performed to 50% SOC to 70% SOC, and the measured voltage value is V1Then in a size of V1The voltage of the battery is charged to 70% SOC to 100% SOC at a constant voltage.
5. The method for quantitatively determining reversibly lithium-separated from a lithium ion battery according to any one of claims 1 to 4, wherein the magnitude of the current for constant current charging in step S1 is 0.2C to 2C.
6. The method for quantitatively determining reversibly separated lithium in a lithium ion battery according to any one of claims 1 to 5, wherein I is01/50C-1/5C.
7. The quantitative determination method for lithium ion battery reversible lithium separation according to any one of claims 1 to 6, wherein the charging and discharging temperature of the lithium ion battery to be measured is-30 ℃ to 0 ℃.
8. The method for quantitatively determining lithium ion battery reversible lithium deposition according to any one of claims 1 to 7, wherein in the step S1, specific conditions for constant volume are as follows: constant volume for 3 weeks under 0.5C multiplying power.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010560631.4A CN111766518B (en) | 2020-06-18 | 2020-06-18 | Quantitative determination method for reversible lithium separation of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010560631.4A CN111766518B (en) | 2020-06-18 | 2020-06-18 | Quantitative determination method for reversible lithium separation of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111766518A true CN111766518A (en) | 2020-10-13 |
| CN111766518B CN111766518B (en) | 2022-12-02 |
Family
ID=72721224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010560631.4A Active CN111766518B (en) | 2020-06-18 | 2020-06-18 | Quantitative determination method for reversible lithium separation of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111766518B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112782582A (en) * | 2021-01-29 | 2021-05-11 | 远景动力技术(江苏)有限公司 | Detection method for lithium separation of lithium ion battery cathode |
| CN113805074A (en) * | 2021-09-14 | 2021-12-17 | 远景动力技术(江苏)有限公司 | Testing device and testing method for lithium battery |
| CN114544793A (en) * | 2021-08-24 | 2022-05-27 | 万向一二三股份公司 | Quantitative detection method for lithium analysis amount of lithium ion battery cathode |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016053564A (en) * | 2014-09-01 | 2016-04-14 | 横河電機株式会社 | Secondary battery capacity measurement system and secondary battery capacity measurement method |
| CN105589038A (en) * | 2014-10-21 | 2016-05-18 | 北京有色金属研究总院 | Method for quantitatively detecting reversible lithium loss of lithium-ion batteries |
| CN105703022A (en) * | 2014-11-27 | 2016-06-22 | 中信国安盟固利动力科技有限公司 | Lithium ion power battery charging method capable of controlling battery degradation based on temperatures |
| CN107728078A (en) * | 2017-11-17 | 2018-02-23 | 力信（江苏）能源科技有限责任公司 | Lithium ion battery analyses the detection method of lithium |
| CN108509762A (en) * | 2018-03-29 | 2018-09-07 | 北京普莱德新能源电池科技有限公司 | A kind of the physicochemical change performance parameter analogy method and device of battery |
| CN108732506A (en) * | 2018-04-26 | 2018-11-02 | 合肥国轩高科动力能源有限公司 | A kind of detection method of lithium-ion-power cell analysis lithium |
| CN108761344A (en) * | 2018-06-06 | 2018-11-06 | 江苏塔菲尔新能源科技股份有限公司 | A kind of detection method and system of lithium ion battery analysis lithium |
| US20190058189A1 (en) * | 2015-11-17 | 2019-02-21 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, mixed negative electrode active material, negative electrode for non-aqueous electrolyte secondary battery, lithium ion secondary battery, method for producing negative electrode active material, and method for producing lithium ion secondary battery |
| CN109839598A (en) * | 2019-03-11 | 2019-06-04 | 合肥国轩高科动力能源有限公司 | A kind of non-destructive testing lithium ion cell positive reversible lithium loss method |
| CN109916987A (en) * | 2018-12-29 | 2019-06-21 | 欣旺达惠州动力新能源有限公司 | A kind of electrochemistry analysis lithium analysis method and its modular device |
| CN109932658A (en) * | 2019-03-06 | 2019-06-25 | 肇庆遨优动力电池有限公司 | A kind of detection method of lithium ion battery analysis lithium |
| CN111175662A (en) * | 2018-11-13 | 2020-05-19 | 清华大学 | Lithium ion battery evaluation method and lithium ion battery detection system |
-
2020
- 2020-06-18 CN CN202010560631.4A patent/CN111766518B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016053564A (en) * | 2014-09-01 | 2016-04-14 | 横河電機株式会社 | Secondary battery capacity measurement system and secondary battery capacity measurement method |
| CN105589038A (en) * | 2014-10-21 | 2016-05-18 | 北京有色金属研究总院 | Method for quantitatively detecting reversible lithium loss of lithium-ion batteries |
| CN105703022A (en) * | 2014-11-27 | 2016-06-22 | 中信国安盟固利动力科技有限公司 | Lithium ion power battery charging method capable of controlling battery degradation based on temperatures |
| US20190058189A1 (en) * | 2015-11-17 | 2019-02-21 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, mixed negative electrode active material, negative electrode for non-aqueous electrolyte secondary battery, lithium ion secondary battery, method for producing negative electrode active material, and method for producing lithium ion secondary battery |
| CN107728078A (en) * | 2017-11-17 | 2018-02-23 | 力信（江苏）能源科技有限责任公司 | Lithium ion battery analyses the detection method of lithium |
| CN108509762A (en) * | 2018-03-29 | 2018-09-07 | 北京普莱德新能源电池科技有限公司 | A kind of the physicochemical change performance parameter analogy method and device of battery |
| CN108732506A (en) * | 2018-04-26 | 2018-11-02 | 合肥国轩高科动力能源有限公司 | A kind of detection method of lithium-ion-power cell analysis lithium |
| CN108761344A (en) * | 2018-06-06 | 2018-11-06 | 江苏塔菲尔新能源科技股份有限公司 | A kind of detection method and system of lithium ion battery analysis lithium |
| CN111175662A (en) * | 2018-11-13 | 2020-05-19 | 清华大学 | Lithium ion battery evaluation method and lithium ion battery detection system |
| CN109916987A (en) * | 2018-12-29 | 2019-06-21 | 欣旺达惠州动力新能源有限公司 | A kind of electrochemistry analysis lithium analysis method and its modular device |
| CN109932658A (en) * | 2019-03-06 | 2019-06-25 | 肇庆遨优动力电池有限公司 | A kind of detection method of lithium ion battery analysis lithium |
| CN109839598A (en) * | 2019-03-11 | 2019-06-04 | 合肥国轩高科动力能源有限公司 | A kind of non-destructive testing lithium ion cell positive reversible lithium loss method |
Non-Patent Citations (4)
| Title |
|---|
| BAO ZHANG 等: "Effects of reaction conditions on preparation of FePO4·2H2O and properties of LiFePO4 by solution precipitation route", 《2010 3RD INTERNATIONAL NANOELECTRONICS CONFERENCE (INEC)》 * |
| CHRISTIAN VON LUDERS等: "Lithium plating in lithium-ion batteries investigated by voltage relaxation and in situ neutron diffraction", 《JOURNAL OF POWER SOURCES》 * |
| DONGSHENG REN等: "investigation of Lithium Plating-Stripping Process in Li-Ion Batteries at Low Temperature Using an Electrochemical Model", 《JOURNAL OF ELECTROCHEMICAL SOCIETY》 * |
| 张剑波,等: "基于锂离子电池老化行为的析锂检测", 《电化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112782582A (en) * | 2021-01-29 | 2021-05-11 | 远景动力技术(江苏)有限公司 | Detection method for lithium separation of lithium ion battery cathode |
| 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 |
| CN114544793A (en) * | 2021-08-24 | 2022-05-27 | 万向一二三股份公司 | Quantitative detection method for lithium analysis amount of lithium ion battery cathode |
| CN113805074A (en) * | 2021-09-14 | 2021-12-17 | 远景动力技术(江苏)有限公司 | Testing device and testing method for lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111766518B (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lai et al. | Electrical behavior of overdischarge-induced internal short circuit in lithium-ion cells | |
| CN111766518B (en) | Quantitative determination method for reversible lithium separation of lithium ion battery | |
| CN110501652B (en) | Rapid assessment method and device for available capacity of retired lithium battery | |
| CN110161417B (en) | Lithium ion battery lithium analysis quantitative analysis method based on three-electrode system | |
| CN111175662B (en) | Lithium ion battery evaluation method and lithium ion battery detection system | |
| CN110988086B (en) | Method for detecting structural stability of electrode material in battery cycle process | |
| CN108398649B (en) | Lithium analysis detection method and device | |
| CN111751741B (en) | Nondestructive testing method for lithium ion battery lithium analysis threshold voltage | |
| CN112240986B (en) | Evaluation method for lithium separation and uniformity of large-size soft-package lithium ion battery | |
| CN112098858B (en) | Nondestructive analysis method for capacity attenuation of lithium ion battery | |
| CN111458642A (en) | Nondestructive testing method for lithium separation of lithium ion storage battery | |
| CN112098875B (en) | Method for detecting lithium ion battery lithium precipitation | |
| Wu et al. | Effect of charge rate on capacity degradation of LiFePO4 power battery at low temperature | |
| CN113075566A (en) | Lithium-ion power battery lithium-separation detection method | |
| CN114062932B (en) | Battery lithium precipitation detection method | |
| CN112098866B (en) | Nondestructive analysis method for judging whether lithium separation occurs in battery circulation process | |
| CN112776667B (en) | Vehicle-end power battery lithium separation online monitoring method | |
| WO2020015226A1 (en) | Abuse and over-discharge performance evaluation and capacity recovery method for lead-acid battery | |
| CN113238152A (en) | Lithium battery self-discharge detection method | |
| CN115494400B (en) | Lithium battery lithium separation state online monitoring method based on ensemble learning | |
| JP2005251538A (en) | Inspection method and device of secondary cell | |
| CN114966443A (en) | Method for testing excess ratio of battery cell | |
| CN113341329A (en) | Method and system for determining lithium separation of battery cell through voltage relaxation | |
| Song et al. | Two strain modes and transition point of 18650 lithium-ion battery at different charging rates | |
| CN116298978B (en) | Method for qualitatively analyzing capacity loss of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |