CN111413631A - Method for testing lithium ion intercalation activation energy in lithium battery by using impedance spectrum - Google Patents
Method for testing lithium ion intercalation activation energy in lithium battery by using impedance spectrum Download PDFInfo
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- CN111413631A CN111413631A CN202010128624.7A CN202010128624A CN111413631A CN 111413631 A CN111413631 A CN 111413631A CN 202010128624 A CN202010128624 A CN 202010128624A CN 111413631 A CN111413631 A CN 111413631A
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- 238000012360 testing method Methods 0.000 title claims abstract description 46
- 230000004913 activation Effects 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- 238000001453 impedance spectrum Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000009830 intercalation Methods 0.000 title claims abstract description 14
- 230000002687 intercalation Effects 0.000 title claims abstract description 14
- 230000010287 polarization Effects 0.000 claims abstract description 23
- 238000012546 transfer Methods 0.000 claims abstract description 11
- 238000001566 impedance spectroscopy Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 5
- 238000010586 diagram Methods 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 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]
- G01R31/385—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]
- G01R31/378—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
- G01R31/387—Determining ampere-hour charge capacity or SoC
-
- 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]
- G01R31/389—Measuring internal impedance, internal conductance or related 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]
- G01R31/396—Acquisition or processing of data for testing or for monitoring individual cells or groups of cells within a battery
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a method for testing lithium ion intercalation activation energy in a lithium battery by using impedance spectroscopy, which comprises the following steps of (1) selecting a test battery cell and determining polarization current I of the test battery cell0Determining the actual capacity C of the test cell on a battery capacity measuring instrument0(ii) a (2) According to the actual capacity C0Discharging or charging the test cell to 40-60% SOC, standing for a certain time, and waiting for measurement; (3) measuring the impedance spectrum of the test cell to be measured in the step (2) at different temperatures, drawing an equivalent circuit diagram according to the impedance spectrum and fitting,obtaining charge transfer resistances Rct at different temperatures; (4) and (4) drawing an lnRct-1/RT curve according to the charge transfer impedance Rct data obtained in the step (3) by an Arrhenius formula, wherein the slope of the curve is the activation energy of the test battery cell. The invention can accurately calculate the activation energy of the battery, thereby quantitatively describing the potential offset balance potential.
Description
Technical Field
The invention belongs to the technical field of battery activation energy measurement, and particularly relates to a method for testing lithium ion intercalation activation energy in a lithium battery by using an impedance spectrum.
Background
The kinetic influencing factors of the lithium ion battery are important for improving the rate capability of the battery, particularly the rate capability under low temperature conditions, L i+The charge transfer process includes L i+Intercalated graphite, solvated L i+L i+L i on SEI diffusion process and electrode+Accepting the reduction of electrons to lithium, whether desolvation or not L i+The diffusion process of the SEI film becomes a speed control step and depends on the characteristics of an electrode and an electrolyte interface, and three factors of voltage curve reduction in the discharge process of the lithium ion battery are ohmic polarization, electrochemical polarization and concentration polarization, wherein the voltage platform of the lithium ion battery is rapidly reduced at the beginning of discharge and rapidly increased after the end of discharge due to L i+Concentration polarization due to slowness of migration inside the electrode; whereas the abrupt decrease and increase are caused by ohmic and electrochemical polarization; at the response time: ohmic polarization < electrochemical polarization < concentration polarization.
Therefore, the polarization phenomenon is an important problem in the charging and discharging of the lithium battery, the reduction of the voltage platform in the discharging process of the lithium battery is mainly influenced by ohmic resistance and polarization resistance, and the polarization resistance is just caused by the polarization phenomenon in the lithium battery. The electrochemical polarization is mainly caused by the activation energy of the electrode during the chemical reaction of the lithium battery, which is shown in the calculation of an Arrhenius equation, and the physical meaning can be understood as that the chemical discharge rate generated on the surface of the electrode active particle is slightly slower than the electron migration rate, so that the actual potential on the surface of the negative electrode particle shifts the equilibrium potential to cause the activation polarization, and the size of the activation energy can be used for quantitatively describing the potential shift equilibrium potential.
Disclosure of Invention
The invention aims to provide a method for testing lithium ion intercalation activation energy in a lithium battery by using impedance spectroscopy, so as to overcome the technical problem.
The technical purpose of the invention is realized by the following technical scheme:
a method for testing lithium ion intercalation activation energy in a lithium battery by using impedance spectroscopy comprises the following steps,
(1) selecting a test cell and determining the polarization current I of the test cell0Determining the actual capacity C of the test cell after circulating for a certain number of cycles on the battery capacity measuring instrument0；
(2) According to the actual capacity C0Discharging or charging the test cell to 40-60% SOC at a certain multiplying power, standing for a certain time, and waiting for measurement;
(3) measuring impedance spectrums of the test battery cell to be measured in the step (2) at different temperatures, drawing an equivalent circuit diagram according to the measured impedance spectrums, and fitting to obtain charge transfer impedances Rct at different temperatures;
(4) and (4) drawing an InRct-1/RT curve according to the charge transfer impedance Rct data obtained in the step (3) by an Arrhenius formula, wherein the slope of the curve is the activation energy of the test battery cell.
Furthermore, in the step (1), the cycle number is 4-8.
Further, in the step (1), the range of the polarization current I0 is 0.2C < I0＜1C。
Further, in the step (2), the discharging or charging at a certain rate is performed at a 0.1C rate.
Further, in the step (3), the different temperatures range from-20 ℃ to 25 ℃.
Further, in the step (3), the frequency of the impedance spectrum is 10-2～105Hz, and the test electric core adopts current disturbance of 1200 mA-1500 mA.
Further, in the step (4), the Alnenius formula is Rct＝A*e-Ea/RTWherein: rct is the charge transfer impedance, a is the pre-factor, Ea is the activation energy, R is the molar gas constant, T refers to the temperature; thus, can obtain
Wherein:c is a formula simplification coefficient which is equal to InA.
Has the advantages that:
the invention can accurately calculate the activation energy of the battery through the test method and the formula, thereby quantitatively describing the phenomena that the voltage platform of the lithium ion battery suddenly drops when the discharge starts and suddenly rises after the discharge is finished, actually shifting the numerical value of the activation polarization in the equilibrium potential by the potential, and obtaining the kinetic parameters of the reaction.
Drawings
FIG. 1 is a plot of lnRct-1/RT curves of embodiment 1 of the present invention;
FIG. 2 is an impedance spectrum of the power lithium ion battery of example 1 of the present invention at different temperatures;
Detailed Description
For better understanding of the present invention, the following examples are given for further illustration of the present invention, but the present invention is not limited to the following examples.
The invention relates to a method for testing lithium ion intercalation activation energy in a lithium battery by using impedance spectroscopy, which comprises the following steps,
(1) selecting a test cell and determining the polarization current I of the test cell0The range of the polarization current I0 is 0.2C < I0Less than 1C, determining the actual capacity C of the test cell after circulating for 4-8 weeks on the battery capacity measuring instrument0；
(2) According to the actual capacity C0Discharging or charging the test cell to 40-60% SOC at 0.1C multiplying power, standing for a certain time, and waiting for measurement;
(3) measuring impedance spectrums of the test battery cell to be measured in the step (2) at different temperatures, wherein the range of the different temperatures is-20-25 ℃, and the frequency of the impedance spectrums is 10-2～105Hz, the test cell adopts current disturbance of 1200 mA-1500 mA; drawing an equivalent circuit diagram according to the measured impedance spectrum and fitting to obtain charge transfer impedances Rct at different temperatures;
(4) drawing an InRct-1/RT curve by an Arrhenius formula according to the charge transfer impedance Rct data obtained in the step (3), wherein the curve is obtained by the methodArrhenius formula is Rct＝A*e-Ea/RTWherein: rct is the charge transfer impedance, a is a pre-factor, which is a constant deduced from experimental data, e is 2.718, Ea is the activation energy, R is the molar gas constant, which is equal to 8.314, and T is the temperature; thus, can obtain
Wherein: c is a formula simplification coefficient which is equal to InA; the slope of the InRct-1/RT curve thus drawn is the activation energy of the test cell.
Example 1
The test method provided by the invention is used for testing the activation energy of the ternary power lithium ion battery.
Selecting test cell and determining polarization current I0Determining the actual capacity of the battery to be 43Ah by circulating for 5 weeks on a battery capacity measuring instrument (New Wigner instruments company), discharging/charging a test battery cell to 50% SOC at a rate of 1C, standing for 1h, and waiting for testing; respectively measuring the impedance spectrum of the test cell at 25 ℃, 10 ℃, 0 ℃, 10 ℃ and 20 ℃ in a 50% SOC state, wherein the frequency range of the impedance spectrum is as follows: 10-2～105Hz, the battery core adopts current disturbance 1200mA, Rct under different temperatures is obtained through equivalent circuit fitting and is respectively 0.00435 omega, 0.00336 omega, 0.00913 omega, 0.02659 omega and 0.06717 omega, finally an InRct-1/RT curve is drawn according to an Arrhenius formula, as shown in figure 1, wherein the slope of the curve is the activation energy of the battery core, and the numerical value is 69.469 KJ/mol.
In order to make the objects, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the above specific embodiments, which are only used for describing the present invention, and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A method for testing lithium ion intercalation activation energy in a lithium battery by using impedance spectroscopy is characterized by comprising the following steps,
(1) selecting a test cell and determining the polarization current I of the test cell0Determining the actual capacity C of the test cell after circulating for a certain number of cycles on the battery capacity measuring instrument0；
(2) According to the actual capacity C0Discharging or charging the test cell to 40-60% SOC at a certain multiplying power, standing for a certain time, and waiting for measurement;
(3) measuring impedance spectrums of the test battery cell to be measured in the step (2) at different temperatures, drawing an equivalent circuit diagram according to the measured impedance spectrums, and fitting to obtain charge transfer impedances Rct at different temperatures;
(4) and (4) drawing an InRct-1/RT curve according to the charge transfer impedance Rct data obtained in the step (3) by an Arrhenius formula, wherein the slope of the curve is the activation energy of the test battery cell.
2. The method for testing lithium ion intercalation activation energy of a lithium battery using impedance spectroscopy as claimed in claim 1, wherein in the step (1), the number of cycles is 4 to 8.
3. The method for testing lithium ion intercalation activation energy in a lithium battery using impedance spectroscopy as claimed in claim 1, wherein in step (1), the polarization current I0In the range of 0.2C < I0＜1C。
4. The method for testing lithium ion intercalation activation energy in a lithium battery using impedance spectroscopy as claimed in claim 1, wherein in the step (2), the discharging or charging at a certain rate is performed at a 0.1C rate.
5. The method for testing lithium ion intercalation activation energy of a lithium battery according to claim 1, wherein in the step (3), the range of the different temperatures is-20 ℃ to 25 ℃.
6. An application as in claim 1The method for testing the lithium ion intercalation activation energy in the lithium battery by impedance spectroscopy is characterized by comprising the step (3). The frequency of the impedance spectrum is 10-2～105Hz, and the test electric core adopts current disturbance of 1200 mA-1500 mA.
7. The method for testing lithium ion intercalation activation energy of lithium battery using impedance spectroscopy as claimed in claim 1, wherein in step (4), said Arrhenius formula is Rct＝A*e-Ea/RTWherein: rct is the charge transfer impedance, a is the pre-factor, Ea is the activation energy, R is the molar gas constant, T refers to the temperature; thus, can obtain
Wherein: c is a formula reduction factor equal to lnA.
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| CN113884913A (en) * | 2021-10-25 | 2022-01-04 | 招商局检测车辆技术研究院有限公司 | Method and device for establishing regression model of electrochemical characteristic impedance of lithium battery |
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| CN109856557A (en) * | 2019-01-21 | 2019-06-07 | 合肥国轩高科动力能源有限公司 | On-line monitoring lithium ion battery electrochemical impedance test method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113884913A (en) * | 2021-10-25 | 2022-01-04 | 招商局检测车辆技术研究院有限公司 | Method and device for establishing regression model of electrochemical characteristic impedance of lithium battery |
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