CN113921893A - Method for constructing equivalent three-electrode system of lithium ion battery - Google Patents

Method for constructing equivalent three-electrode system of lithium ion battery Download PDF

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Publication number
CN113921893A
CN113921893A CN202111131045.9A CN202111131045A CN113921893A CN 113921893 A CN113921893 A CN 113921893A CN 202111131045 A CN202111131045 A CN 202111131045A CN 113921893 A CN113921893 A CN 113921893A
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battery
equivalent
electrode
shell
cathode
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戴海峰
龚辉
乔冬冬
魏学哲
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Tongji University
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Tongji University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a method for constructing an equivalent three-electrode system of a lithium ion battery, which comprises the following steps: s1, respectively obtaining the direct current impedance value R between the positive electrode of the battery and the battery shellPAnd a DC resistance value R between the battery cathode and the battery caseN(ii) a S2, selecting a metal material the same as that of the battery shell as an equivalent reference electrode; s3, selecting the resistance value as RPThe resistance is connected with the anode of the battery and the equivalent reference electrode, and the resistance value is selected to be RNThe resistance of the battery is connected with the negative electrode of the battery and the equivalent reference electrode to complete the construction of an equivalent three-electrode system. Compared with the prior art, the invention has the advantages of no need of modifying the battery, simple and convenient implementation, high measurement precision and the like.

Description

Method for constructing equivalent three-electrode system of lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a method for constructing an equivalent three-electrode system of a lithium ion battery.
Background
The lithium ion battery has the excellent characteristics of high energy density, high output voltage, low self-discharge rate, long service life, no memory effect, environmental friendliness and the like, and is widely applied. In order to better study the positive and negative electrode performances of the battery, a reference electrode is often introduced and used as a standard to test the potential of the positive electrode or the negative electrode with respect to the reference electrode respectively.
The existing three-electrode battery takes metal lithium as a reference electrode, and the reference electrode and the positive and negative electrodes exist in the battery at the same time. The three-electrode battery has complex preparation process, needs to change the structure of the battery, cannot be used for production, and is only limited to performance evaluation of a battery system.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for constructing an equivalent three-electrode system of a lithium ion battery.
The purpose of the invention can be realized by the following technical scheme:
a method for constructing an equivalent three-electrode system of a lithium ion battery comprises the following steps:
s1, respectively obtaining the direct current impedance value R between the positive electrode of the battery and the battery shellPAnd a DC resistance value R between the battery cathode and the battery caseN；
S2, selecting a metal material the same as that of the battery shell as an equivalent reference electrode;
s3, selecting the resistance value as RPThe resistance is connected with the anode of the battery and the equivalent reference electrode, and the resistance value is selected to be RNThe resistance of the battery is connected with the negative electrode of the battery and the equivalent reference electrode to complete the construction of an equivalent three-electrode system.
Preferably, step S1 specifically includes:
s11, respectively measuring to obtain alternating current impedance spectrums between the positive electrode of the battery and the battery shell and between the negative electrode of the battery and the battery shell;
s12, acquiring a direct current impedance value R between the battery anode and the battery shell according to the alternating current impedance spectrum between the battery anode and the battery shellP；
S13, acquiring a direct current impedance value R between the battery cathode and the battery shell according to the alternating current impedance spectrum between the battery cathode and the battery shellN。
Preferably, in step S11: when measuring the alternating current impedance spectrum between the battery anode and the battery shell, connecting the sampling anode of the electrochemical workstation with the battery anode, and connecting the sampling cathode of the electrochemical workstation with the battery shell; when measuring the alternating current impedance spectrum between the battery cathode and the battery shell, the sampling anode of the electrochemical workstation is connected with the battery shell, and the sampling cathode of the electrochemical workstation is connected with the battery cathode.
Preferably, the dc resistance value R between the positive electrode of the battery and the battery case in step S12PIs the real-axis intercept of the ac impedance spectrum between the cell anode and the cell casing.
Preferably, the dc resistance value R between the negative electrode of the battery and the battery case in step S13NIs the real-axis intercept of the ac impedance spectrum between the battery cathode and the battery case.
Preferably, said equivalent reference electrode is arranged outside the cell.
Compared with the prior art, the invention has the following advantages:
according to the invention, the equivalent reference electrode is constructed outside the battery by obtaining the direct current impedance value between the positive electrode of the battery and the battery shell and the direct current impedance value between the negative electrode of the battery and the battery shell, so that the equivalent three-electrode system is finally formed, the battery is not required to be transformed, the implementation is simple and convenient, the precision is high, and the subsequent study on the positive and negative electrode performances of the battery is facilitated.
Drawings
FIG. 1 is a flow chart of a method for constructing an equivalent three-electrode system of a lithium ion battery according to the present invention;
FIG. 2 is a schematic diagram of a method for calculating DC impedance values between a positive electrode and a casing of a battery and between a negative electrode and the casing of the battery according to the present invention;
FIG. 3 is a schematic diagram of the connection mode of the equivalent reference electrode of the lithium ion battery of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. Note that the following description of the embodiments is merely a substantial example, and the present invention is not intended to be limited to the application or the use thereof, and is not limited to the following embodiments.
Examples
As shown in fig. 1, this embodiment provides a method for constructing an equivalent three-electrode system of a lithium ion battery, including the following steps:
s1, respectively obtaining the direct current impedance value R between the positive electrode of the battery and the battery shellPAnd a DC resistance value R between the battery cathode and the battery caseNSpecifically:
step S1 specifically includes:
s11, respectively measuring to obtain alternating current impedance spectrums between the positive electrode of the battery and the battery shell and between the negative electrode of the battery and the battery shell;
s12, acquiring a direct current impedance value R between the battery anode and the battery shell according to the alternating current impedance spectrum between the battery anode and the battery shellP；
S13, acquiring a direct current impedance value R between the battery cathode and the battery shell according to the alternating current impedance spectrum between the battery cathode and the battery shellN。
The theoretical basis of the invention is to construct an equivalent three-electrode system based on the relative potential relationship between the positive electrode and the negative electrode of the battery and the battery shell, so that the surface of the shell of the lithium ion battery cannot be directly communicated with the positive electrode or the negative electrode, otherwise, the shell and the positive electrode or the negative electrode are always in the same potential, and the alternating current impedance spectrum between the positive electrode and the negative electrode and an equivalent reference electrode cannot be measured. Therefore, when the alternating-current impedance spectrum between the battery anode and the battery shell is measured, the sampling anode of the electrochemical workstation is connected with the battery anode, and the sampling cathode of the electrochemical workstation is connected with the battery shell; when measuring the alternating current impedance spectrum between the battery cathode and the battery shell, the sampling anode of the electrochemical workstation is connected with the battery shell, and the sampling cathode of the electrochemical workstation is connected with the battery cathode.
Calculating the DC impedance value R between the positive and negative electrodes and the shell according to the obtained impedance spectrumPAnd RNThe method of (2) is shown in fig. 2. In the alternating current impedance spectrum, the real-axis intercept of the curve represents the direct current impedance value of the lithium ion battery, so that the direct current impedance value R between the positive electrode of the battery and the battery shell can be obtained by calculating the real-axis intercept of the alternating current impedance spectrum curve between the positive electrode of the battery and the battery shellPCorrespondingly, by calculating the intersection between the negative electrode of the battery and the battery caseObtaining the direct current impedance value R between the battery cathode and the battery shell by the real-axis intercept of the flow impedance spectrum curveN。
S2, selecting a metal material the same as that of the battery shell as an equivalent reference electrode;
s3, constructing a three-electrode system, specifically:
s31, selecting the resistance value as RPThe resistance of the battery is connected with the positive electrode of the battery and the equivalent reference electrode;
s32, selecting the resistance value as RNThe resistance of the battery is connected with the negative electrode of the battery and the equivalent reference electrode.
Wherein, the equivalent reference electrode has a resistance value of RPResistance of RNAre all arranged outside the battery. The schematic connection is shown in fig. 3.
According to the invention, the equivalent reference electrode is constructed outside the battery by acquiring the direct current impedance value between the positive electrode of the battery and the battery shell and the direct current impedance value between the negative electrode of the battery and the battery shell, so that an equivalent three-electrode system is finally formed, the battery is not required to be reformed, and the method is simple and convenient to implement and high in precision. Through the equivalent reference electrode, the potential relation between the positive electrode of the battery and the equivalent reference electrode and the potential relation between the negative electrode of the battery and the equivalent reference electrode can be established, so that the positive and negative electrode performances of the battery are researched.
The above embodiments are merely examples and do not limit the scope of the present invention. These embodiments may be implemented in other various manners, and various omissions, substitutions, and changes may be made without departing from the technical spirit of the present invention.

Claims (6)

1. A method for constructing an equivalent three-electrode system of a lithium ion battery is characterized by comprising the following steps:
s1, respectively obtaining the direct current impedance value R between the positive electrode of the battery and the battery shellPAnd a DC resistance value R between the battery cathode and the battery caseN；
S2, selecting a metal material the same as that of the battery shell as an equivalent reference electrode;
s3, selecting the resistance value as RPThe resistance is connected with the anode of the battery and the equivalent reference electrode, and the resistance value is selected to be RNThe resistance of the battery is connected with the negative electrode of the battery and the equivalent reference electrode to complete the construction of an equivalent three-electrode system.
2. The method for constructing an equivalent three-electrode system of a lithium ion battery according to claim 1, wherein step S1 specifically includes:
s11, respectively measuring to obtain alternating current impedance spectrums between the positive electrode of the battery and the battery shell and between the negative electrode of the battery and the battery shell;
s12, acquiring a direct current impedance value R between the battery anode and the battery shell according to the alternating current impedance spectrum between the battery anode and the battery shellP；
S13, acquiring a direct current impedance value R between the battery cathode and the battery shell according to the alternating current impedance spectrum between the battery cathode and the battery shellN。
3. The method for constructing an equivalent three-electrode system of a lithium ion battery according to claim 2, wherein in step S11: when measuring the alternating current impedance spectrum between the battery anode and the battery shell, connecting the sampling anode of the electrochemical workstation with the battery anode, and connecting the sampling cathode of the electrochemical workstation with the battery shell; when measuring the alternating current impedance spectrum between the battery cathode and the battery shell, the sampling anode of the electrochemical workstation is connected with the battery shell, and the sampling cathode of the electrochemical workstation is connected with the battery cathode.
4. The method according to claim 1, wherein the dc resistance R between the positive electrode of the battery and the battery case in step S12 is the same as that of the battery casePIs the real-axis intercept of the ac impedance spectrum between the cell anode and the cell casing.
5. The method for constructing an equivalent three-electrode system of a lithium ion battery according to claim 1, wherein the DC resistance R between the battery cathode and the battery case in step S13NIs a battery cathode and a battery shellThe real-axis intercept of the alternating impedance spectrum in between.
6. The method for constructing an equivalent three-electrode system of a lithium ion battery according to claim 1, wherein the equivalent reference electrode is arranged outside the battery.
CN202111131045.9A 2021-09-26 2021-09-26 Method for constructing equivalent three-electrode system of lithium ion battery Pending CN113921893A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011112690A1 (en) * 2011-09-05 2013-03-07 Audi Ag Method for checking operability of lithium-ion battery cell, involves obtaining measurement value for impedance for frequencies of alternating voltage, and determining whether cell is operated based on measured values of impedance
JP2014059174A (en) * 2012-09-14 2014-04-03 Mitsubishi Electric Corp Impedance detection system, monitoring system, and lithium secondary battery with monitoring function based on such monitoring system
CN203644890U (en) * 2014-01-10 2014-06-11 东莞新能源科技有限公司 Three-electrode lithium ion battery
US20150111077A1 (en) * 2013-10-18 2015-04-23 Ford Global Technologies, Llc Lithium battery with reference electrode
CN108428954A (en) * 2018-03-31 2018-08-21 重庆市紫建电子有限公司 A kind of devices and methods therefor that can quickly study lithium ion battery electrochemical behavior
CN110031772A (en) * 2019-05-23 2019-07-19 中山大学 A kind of real-time estimating method of lithium ion battery equivalent internal resistance

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011112690A1 (en) * 2011-09-05 2013-03-07 Audi Ag Method for checking operability of lithium-ion battery cell, involves obtaining measurement value for impedance for frequencies of alternating voltage, and determining whether cell is operated based on measured values of impedance
JP2014059174A (en) * 2012-09-14 2014-04-03 Mitsubishi Electric Corp Impedance detection system, monitoring system, and lithium secondary battery with monitoring function based on such monitoring system
US20150111077A1 (en) * 2013-10-18 2015-04-23 Ford Global Technologies, Llc Lithium battery with reference electrode
CN203644890U (en) * 2014-01-10 2014-06-11 东莞新能源科技有限公司 Three-electrode lithium ion battery
CN108428954A (en) * 2018-03-31 2018-08-21 重庆市紫建电子有限公司 A kind of devices and methods therefor that can quickly study lithium ion battery electrochemical behavior
CN110031772A (en) * 2019-05-23 2019-07-19 中山大学 A kind of real-time estimating method of lithium ion battery equivalent internal resistance

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