Method for determining a state variable of an electrochemical cell using complex impedance at radioelectric frequencies

• US 9,453,884 B2
• Filed: 12/21/2012
• Issued: 09/27/2016
• Est. Priority Date: 12/23/2011
• Status: Active Grant

• Current Assignee: SAFT SA (Totalenergies Se)
• Original Assignee: SAFT SA (Totalenergies Se)
• Inventors: Patin, Alain, Fleureau, Patrice, Desprez, Philippe, Reboussin, Loc
• Primary Examiner(s): Diao, M'Baye
• Application Number:
  US13/724,783
• Publication Number:
  US 20130162258A1
• Time in Patent Office: 1,376 Days
• Field of Search: 324/427, 324/426, 324/430, 320/132, 702/63, 702/65, 702/75, 702/76, 702/82
• US Class Current: 1/1
• CPC Class Codes: G01R 27/02 Measuring real or complex resistance, reactance, impedance, or other two-pole characteristics derived therefrom, e.g. time constant by measuring phase angle only G01R25/00
• CPC Class Codes: G01R 27/28 Measuring attenuation, gain, phase shift or derived characteristics of electric four pole networks, i.e. two-port networks; Measuring transient response in line transmission systems H04B3/46
• CPC Class Codes: G01R 31/001 Measuring interference from external sources to, or emission from, the device under test, e.g. EMC, EMI, EMP or ESD testing measuring electromagnetic fields G01R29/08; circuits for generating HV pulses in dielectric strength testing G01R31/14
• CPC Class Codes: G01R 31/382 Arrangements for monitoring battery or accumulator variables, e.g. SoC
• CPC Class Codes: G01R 31/389 Measuring internal impedance, internal conductance or related variables
• CPC Class Codes: G01R 31/392 Determining battery ageing or deterioration, e.g. state of health
• CPC Class Codes: H01M 10/42 Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells H01M10/60 takes precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A method is provided for determining a state variable such as aging of an electrochemical cell comprising an electrode plate group, that includes analyzing at least a portion of a response spectrum of the electrochemical cell to application of an electromagnetic wave in a frequency ranging from 10 kHz to 10 GHz, so as to determine an indicator of the value of the state variable.

Claims

1. A processor-implemented method for determining a state variable of an electrochemical cell comprising an electrode plate group, said method comprising:

analyzing, by a processor, at least a portion of a response spectrum of the electrochemical cell to application of an electromagnetic wave in a frequency ranging from 10 kHz to 10 GHz, so as to determine an indicator of the value of said state variable;

determining, by the processor, an indicator of the value of said state variable;

monitoring, by the processor, the state variable of the electrochemical cell based on the determined indicator; and

determining, by the processor, that the electrochemical cell is defective if the response spectrum is outside a predetermined threshold.

2. The method according to claim 1, wherein the frequency ranges from 100 kHz to 10 GHz.

3. The method according to claim 1, wherein the value of the state variable is compared with a reference value and the electrochemical cell is considered to be defective if a difference between the value of the state variable and the reference value exceeds a predetermined threshold.

4. The method according to claim 1, wherein the value of the state variable is obtained by comparing a plot of variation of an indicator value of the state variable with a plot of the change of said indicator obtained from measurement of complex impedance of a reference cell.

5. The method according to claim 4, wherein the state variable is a parameter which varies during use of the electrochemical cell including at least one of its capacity, internal resistance, its state of charge, the state of aging of its electrodes, the state of aging of the electrolyte and the state of aging of the separator.

6. The method according to claim 1, comprising the steps of:

measuring, by the processor, complex impedance of the electrode plate group;

plotting, by the processor a complex impedance spectrum of the electrode plate group, and

determining, by a processor, at least one resonance frequency f₀ of the complex impedance spectrum which is a frequency at which the imaginary part of the complex impedance is zero.

7. The method according to claim 6, wherein the complex impedance spectrum of the electrode plate group is plotted for a range of frequencies between 200 MHz and 1 GHz, and wherein within said range at least one resonance frequency f₀ exists, in order to determine the state variable corresponding to the height of the electrode plate group.

8. The method according to claim 6, wherein the complex impedance spectrum of the electrode plate group is plotted for a range of frequencies between 10 MHz and 200 MHz, and wherein within the said range at least one resonance frequency f₀ exists, in order to determine the state variable corresponding to the length of the unwound electrode plate group.

9. The method according to claim 1, comprising the steps of:

measuring, by the processor, complex impedance of the electrode plate group;

plotting, by the processor, a variation from a frequency ranging from 0.01 MHz to 10 MHz, of at least one indicator selected from the real part of the complex impedance, the imaginary part of the complex impedance or a combination of these so as to determine a state variable.

10. The method according to claim 9, including comparing, by the processor, a plot of variation in at least one of said indicators to a plot of variation in the same indicator or indicators obtained from measurement of complex impedance of a reference electrode plate group.

11. The method according to claim 10, wherein the indicator is the imaginary part of the complex impedance and a variation plot of the indicator as a function of frequency has at least one peak, such that a ratio:

(Immax−

Max (Im1, Im2))/Immax is greater than 0.5

where

Immax denotes the imaginary part of the complex impedance at the peak;

Im1 and Im2 denote the imaginary parts of two points at a base of the peak, and

Max (Im1, Im2) represent a maximum value of Im1 and Im2.

12. The method of claim 11, wherein Immax is greater than 0.75.

13. The method according to claim 9, wherein variation in the real part of the complex impedance as a function of frequency is represented and at least one peak exists such that a ratio:

(Remax−

Max (Re1, Re2))/Remax is greater than 0.5

wherein

the Remax denotes the real part at the peak;

Re1 and Re2 denote the real parts of two points at a base of the peak, and

Max (Re1, Re2) denotes the maximum value of Re1 and Re2.

14. The method according to claim 9, wherein the combination of the real part of the complex impedance and the imaginary part of the complex impedance is an argument of the complex impedance.

15. The method according to claim 1, wherein the electrochemical cell is a lithium cell.

16. The method according to claim 1, wherein the frequency ranges from 1 MHz to 1 GHz.

17. The method according to claim 1, wherein the frequency ranges from 10 MHz to 1 GHz.

18. A processor-implemented method of monitoring the manufacture of electrochemical cells for determining a state variable of an electrochemical cell comprising an electrode plate group, the method comprising:

analyzing, by a processor, at least a portion of a response spectrum of the electrochemical cell to application of an electromagnetic wave in a frequency ranging from 10 kHz to 10 GHz, so as to determine an indicator of the value of said state variable, wherein;

the value of the state variable is measured on each cell manufactured;

a cell is rejected if the difference between the value of the state variable measured and a reference value exceeds a predetermined threshold.

19. The monitoring method according to claim 18, comprising statistical sampling, by the processor, of electrochemical cells on a production line in order to monitor changes in the cells produced.

20. A non-transitory computer readable medium storing instruction, which when executed by a computer causes the computer to implement a method of determining a state variable of an electrochemical cell comprising an electrode plate group, the method comprising:

analyzing, by a processor, at least a portion of a response spectrum of the electrochemical cell to application of an electromagnetic wave in a frequency ranging from 10 kHz to 10 GHz, so as to determine an indicator of the value of said state variable.