This application is a national phase entry under 35 U.S.C. § 371 of International Patent Application PCT/IB2018/059751, filed Dec. 7, 2018, designating the United States of America and published as International Patent Publication WO 2019/111220 A1 on Jun. 13, 2019, which claims the benefit under Article 8 of the Patent Cooperation Treaty to Singapore Patent Application Serial No. 10201710152T, filed Dec. 7, 2017.
The present disclosure relates to a method for assessing a state of charge/discharge (SOC/SOD) for an electrochemical cell. It is also related to a system for assessing a state of charge/discharge (SOC/SOD) for an electrochemical cell.
State of charge of batteries (SOC) is an important factor for the battery user in order to know the remaining unused capacity and to predict the battery end of service under a specific discharge load.
SOC should be determined accurately in both primary (non-rechargeable) and secondary (rechargeable) batteries. Currently, the main SOC determination methods are based on:
These methods are empirical and not universal and they don't apply to all batteries.
Alkaline and dry Zn/MnO2 primary batteries are widely used for many applications including in electronics, games, toys, torch, or remote control. Zn/MnO2 cells are economical, practical and easily found all over the world.
Worldwide sales of alkaline and dry cells are expected to reach USD5B and USD2.6B in 2017, respectively. However, there is no reliable method to determine their state of charge (SOC). SOC is an important factor for the battery user in order to know the remaining unused capacity and to predict the battery end of service under a specific discharge load.
More generally, the aim of the present disclosure is to predict the state of charge of electrochemical cells using thermodynamic data measurements.
This objective is reached for rechargeable batteries with a method for assessing a state of charge/discharge (SOC/SOD) for a secondary electrochemical cell, the cell having a first operational mode during which the cell is charged from a power supply connected to terminals of the cell, a second operational mode during which the cell is discharged into a load and a rest mode, the method comprising steps of:
with parameters α, β and γ depending on chemical data and on the state of health (SOH) of the electrochemical cell.
Entropy and enthalpy are determined by the temperature dependence of open-circuit voltage (OCV) at each SOC, according to:
where n is the number of electrons involved in the elemental electrode redox process. For example, n=1 for H, Li, Na, K . . . , n=2 for Mg, Ca, Zn, Cd, Fe . . . and n=3 for B, Al, Fe . . . .
The above-cited objective is further reached for alkaline and dry cells with a method for assessing a state of discharge (SOD) for a primary electrochemical cell, the cell having an operational mode during which the cell is discharged into a load and a rest mode, the method comprising steps of:
with parameters α′, β′ and γ′ depending on chemical data and on the state of health (SOH) of the electrochemical cell.
The SOC/SOD assessment method according to the present disclosure can be implemented for assessing a state of discharge (SOD) for aqueous or organic lithium cells, and for a rechargeable cell like lithium-ion, NiMH, NiCd, or NaS, sodium-ion, solid state lithium rechargeable cell, redox flow batteries.
The SOC/SOD assessment method according to the present disclosure can be advantageously applied for predicting a state of discharge (SOD) for primary (non-rechargeable) cells such as Li/MnO2 cells, Li/FeS2 cells, Li/CFX cells, alkaline cells, Zinc Carbon dry cells and metal-air cells.
In an advantageous version of the present disclosure, the SOC/SOD assessment method according of the present disclosure is implemented online via an integrated circuit having temperature, current and voltage probes, the integrated circuit being attached to or imbedded in the electrochemical cell. Furthermore, the integrated circuit is a chip provided with computing and/or micro-processing capabilities, and with RF communication capabilities.
Entropy (ΔS) and enthalpy (ΔH) are preferably determined by a temperature dependence of open-circuit voltage (OCV) across the electrochemical cell terminals for each state of charge (SOC) value, according to:
In another embodiment of the present disclosure, there is proposed a method for assessing a state of health (SOH) for a secondary electrochemical cell, the cell having a first operational mode during which the cell is charged from a power supply connected to terminals of the cell, a second operational mode during which the cell is discharged into a load and a rest mode, the method comprising steps of:
In an advantageous version of the present disclosure, the SOH assessment method according to the present disclosure is implemented online via an integrated circuit having temperature, current and voltage probes, the integrated circuit being attached to or imbedded in the electrochemical cell. Furthermore, the integrated circuit is a chip provided with computing and/or micro-processing capabilities, and with RF communication capabilities.
According to another aspect of the present disclosure, a system is proposed for assessing a state of charge/discharge (SOC/SOD) for a secondary or rechargeable electrochemical cell, the cell having a first operational mode during which the cell is charged from a power supply connected to terminals of the cell, a second operational mode during which the cell is discharged into a load and a rest mode, the system comprising:
with parameters α, β and γ depending on chemical data and on the state of health (SOH) of the electrochemical cell.
In another embodiment of the present disclosure, a system is proposed for assessing a state of discharge (SOD) for a primary electrochemical cell, the cell having an operational mode during which the cell is discharged into a load and a rest mode, the system comprising:
with parameters α′, β′ and γ′ depending on chemical data and on the state of health (SOH) of the electrochemical cell.
The SOC/SOD assessment system according to the present disclosure can further comprise an integrated circuit connected to temperature and voltage probes attached to or embedded in the electrochemical cell. This integrated circuit can advantageously implement the calculating means and comprise a telecommunication means.
The integrated circuit can advantageously implement calculating entropy (ΔS) and enthalpy (ΔH) as a temperature dependence of open-circuit voltage (OCV) across the electrochemical cell terminals for each state of charge (SOC) value, according to:
According to another aspect of the present disclosure, a system is proposed for assessing a state of health (SOH) for a secondary electrochemical cell, the cell having a first operational mode during which the cell is charged from a power supply connected to terminals of the cell, a second operational mode during which the cell is discharged into a load and a rest mode, the system comprising:
According to another aspect of the present disclosure, a method and a system are proposed for assessing a state of health (SOH) for a primary (non-rechargeable) electrochemical cell, the cell having an operational mode during which the cell is discharged into a load and a rest mode, the method comprising steps of:
with parameters α′, β′ and γ′ depending on chemical data and on the state of health (SOH) of the electrochemical cell.
According to yet another aspect of the present disclosure, a system is proposed for fast-charging a rechargeable battery, the battery having terminals connected to internal electrochemical cell electrodes with (i) a first operational mode during which the cell is charged from a power supply connected to terminals of the cell, (ii) a second operational mode during which the cell is discharged into a load and (iii) a rest mode, the fast-charging system comprising:
with parameters α, β and γ depending on chemical data and on the state of health (SOH) of the battery.
The SOC assessment unit can advantageously comprise an integrated circuit connected to temperature and voltage probes attached to or embedded in the battery.
The SOC/SOD assessment method according to the present disclosure is based on thermodynamics. Entropy (ΔS) and enthalpy (ΔH) are measured in the course of battery operation (charge and discharge) and during rest (no current). A universal law of SOC as function of entropy and enthalpy is established as:
SOC=α+βΔS+γΔH (Eq.1)
This law applies to primary and secondary batteries. In this equation 1, parameters α, β and γ depend on the battery chemistry and on the battery state of health (SOH).
Thermodynamics data can be used to determine the SOD of both primary (aqueous and organic lithium) and rechargeable (lithium-ion, NiMH, NiCd, NaS, . . . ) cells with very high accuracy (>97%).
SOD assessment can be made online owing to an IC/chip with highly sensitive temperature (<0.1° C.) and voltage (<0.1 mV) probes.
Two different SOCs cannot have simultaneously the same entropy and enthalpy values. It follows that the (ΔS, ΔH, SOC) trinomial is unique.
With reference to
First Experimental Test
In a first experimental test implementing Alkaline Zn/MnO2 cells, with reference to
Entropy and enthalpy measurements have been done using an equipment BA 2000.
An intermittent discharge is applied. At each step a change in SOD of 5% is applied. 20 steps are needed to go from 0% to 100% SOD (i.e., 100% SOC to 0% SOC).
A C/6 discharge rate has been applied. Voltage limits are 0.5 V to 1.9 V and the temperature range is 10° C. to 25° C. The relaxation time is 25 minutes.
Second Experimental Test
In a second experimental test implementing a zinc/carbon dry cell and illustrated by
Thermodynamic measurements have been done using a BA 2000 equipment, with a C/6 rate and a discharge current of 132 mA.
Voltage limits are 0.5 V to 1.9 V, the temperature range is 10° C. to 25° C. with a relaxation time of 25 minutes.
Experimental tests have also been done for Li/MnO2 cells, with reference to
Third Experimental Test
Experimental tests have been done for Li-Ion (secondary) cells with reference to
Summary of Experimental Tests
As showed in
Number | Date | Country | Kind |
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10201710152T | Dec 2017 | SG | national |
Filing Document | Filing Date | Country | Kind |
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PCT/IB2018/059751 | 12/7/2018 | WO |
Publishing Document | Publishing Date | Country | Kind |
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WO2019/111220 | 6/13/2019 | WO | A |
Number | Name | Date | Kind |
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9461496 | Zhang et al. | Oct 2016 | B1 |
20120310565 | Redey | Dec 2012 | A1 |
20160089994 | Keller | Mar 2016 | A1 |
20160146895 | Yazami | May 2016 | A1 |
20160190833 | Roumi | Jun 2016 | A1 |
20160226262 | Fukubayashi | Aug 2016 | A1 |
20170229891 | Lee | Aug 2017 | A1 |
Entry |
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Manane et al.; Accurate state of charge assessment of lithium manganese batteries, vol. 359, Aug. 15, 2017, pp. 422-426. |
International Search Report for International Application No. PCT/IB2018/059751 dated Mar. 11, 2019, 4 pages. |
International Written Opinion for International Application No. PCT/IB2018/059751 dated Mar. 11, 2019, 9 pages. |
Manane et al., Accurate State of Charge Assessment of Lithiummanganese Dioxide Primary Batteries, Journal of Power Sources, vol. 359, (Aug. 15, 2017), pp. 422-426. |
Number | Date | Country | |
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20210057926 A1 | Feb 2021 | US |