WO2015080537A1 - Procédé pour mesurer des performances d'accumulateur - Google Patents

Procédé pour mesurer des performances d'accumulateur Download PDF

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Publication number
WO2015080537A1
WO2015080537A1 PCT/KR2014/011642 KR2014011642W WO2015080537A1 WO 2015080537 A1 WO2015080537 A1 WO 2015080537A1 KR 2014011642 W KR2014011642 W KR 2014011642W WO 2015080537 A1 WO2015080537 A1 WO 2015080537A1
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Prior art keywords
cycle
discharge
cell
charge
normal
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PCT/KR2014/011642
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English (en)
Korean (ko)
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김유탁
유어현
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한국전지연구조합
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Publication of WO2015080537A1 publication Critical patent/WO2015080537A1/fr

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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • 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]
    • G01R31/392—Determining battery ageing or deterioration, e.g. state of health
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • 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

Definitions

  • the present invention relates to a method for measuring performance of a cell, and more particularly, to a method for measuring performance of a cell capable of accurately evaluating cycle life for a cell such as a hybrid capacitor in a short time. It is about.
  • a cell such as a battery or a transistor
  • its performance is measured. For example, performance such as electrical characteristics and cycle life are measured.
  • electrochemical devices as energy storage devices such as secondary batteries such as capacitors or lithium ion (Li + ) batteries, have a cycle life standard for developing new products or for quality control of existing products. You need to measure whether you are satisfied.
  • the performance measurement of the cell is also aimed at selecting cells by performance (grade) by evaluating electrical characteristics such as operating voltage, current, and capacity, but most importantly for reliability with consumers. This is because if the cell does not meet the required characteristics or the cycle life is short, the related electrical and electronic products may be damaged. Accordingly, most of the cells before the commercialization, as part of the reliability, the performance, such as electrical characteristics and cycle life is measured.
  • electrochemical devices such as capacitors
  • electrical such as self-discharge (SD), leakage current (LC), equivalent series resistance (ESR), and equivalent capacitance (CAP).
  • SD self-discharge
  • LC leakage current
  • ESR equivalent series resistance
  • CAP equivalent capacitance
  • the cycle life is evaluated (predicted) by decreasing the capacity of the cell by repeating charging and discharging.
  • the criterion of making it become 80% or more of initial stage capacity after repeating several charge and discharge is calculated
  • the cycle life of a cell is measured (predicted) by evaluating remaining capacity after charging and discharging are repeatedly performed in actual use environment conditions (normal conditions) in most cases.
  • actual use environment conditions normal conditions
  • Korean Patent Registration No. 10-0903489, Korean Patent Publication No. 10-2013-0073802 and Japanese Patent Application Publication No. 2009-281916 disclose a related technology.
  • the conventional measuring method including the prior patent documents has a problem that it is not accurate or takes a long time. Specifically, when the charging and discharging are repeatedly repeated under accelerated conditions, deterioration of the cell is severe and has abnormal characteristics.
  • a capacitor having a long lifespan for example, a hybrid capacitor having a cycle life of approximately 500,000 times, or an electric double layer capacitor (EDLC) having a cycle life of approximately 1 million times, takes a long time.
  • EDLC electric double layer capacitor
  • an object of the present invention is to provide a method for measuring the performance of a cell capable of accurately measuring cycle life and the like for a cell such as a hybrid capacitor in a short time.
  • an object of the present invention is to provide a method for measuring the performance of a cell that can also measure the electrical performance, such as leakage current, resistance and / or capacity in the process of measuring the cycle life.
  • It provides a method for measuring the performance of a cell comprising a second step of evaluating the cycle life of the cell in which the first step is performed.
  • the first process includes two or more sections, wherein one or more sections include conditions of a normal charge / discharge sub-cycle and an accelerated charge / discharge sub-cycle; The number of repetitions of the normal charge / discharge sub-cycle and the accelerated charge / discharge sub-cycle; And at least one selected from the ratio of the number of repetition of the normal charge / discharge sub-cycle and the number of repetition of the accelerated charge / discharge sub-cycle.
  • the first process includes P 1 , P 2, and P 3 sections, wherein P 2 sections are more severe in terms of accelerated charge / discharge sub-sub cycles than P 1 and P 3 sections.
  • the number of repetitions of the accelerated charge / discharge sub-sub cycle may proceed in a condition where the number of repetitions of the normal charge / discharge sub-cycle is greater than that of the normal charge / discharge sub-cycle.
  • the normal charge / discharge sub-cycle the normal charge / discharge sub-cycle
  • It may include a normal discharge step of discharging a constant current (CC).
  • CC constant current
  • It may include an accelerated discharge step of discharging a constant current (CC).
  • CC constant current
  • the main-cycle may include: a first stopper that proceeds after a normal charge / discharge sub-cycle; And at least one rest time selected from a second stop that proceeds after the accelerated charge / discharge sub-cycle.
  • the first process which proceeds after repeating the main cycle several times, may further include a normal charge / discharge stable-cycle for charging / discharging under normal conditions. Additionally, the first step may be performed after the normal charge / discharge stable-cycle and may further include a complete discharge cycle for completely discharging the cell.
  • the present invention may further include a step of measuring one or more electrical characteristics selected from leakage current, resistance, self discharge, and capacitance.
  • the cycle life of a cell for example, the cycle life for a cell such as a hybrid capacitor
  • electrical properties such as leakage current, resistance, and / or capacity may also be measured.
  • FIG. 1 is a conceptual diagram for explaining a first step of a measuring method according to an exemplary embodiment of the present invention.
  • FIGS. 2 and 3 illustrate a measuring method according to an exemplary embodiment of the present invention, and are graphs showing voltage characteristics of a cell over time.
  • FIG. 4 shows an overall flowchart of a measuring method according to an exemplary form of the present invention.
  • FIG. 5 is a graph illustrating a result of evaluating voltage over time when discharged under a normal condition (5 mA / F) and each acceleration condition according to an exemplary embodiment of the present invention.
  • FIG. 6 is a graph showing the results of the cycle life evaluation according to an embodiment of the present invention.
  • the performance measurement method of the cell according to the present invention (hereinafter, abbreviated as 'measurement method') is a normal charge / discharge sub-cycle for charging and discharging under normal conditions, and for charging and discharging under accelerated conditions.
  • charging / discharging under normal conditions and charging / discharging under acceleration conditions are performed as one cycle, and this is repeated N times.
  • the second step at least the cycle life is evaluated for the cell in which the first step is performed.
  • Category temperature range The ambient temperature range (minimum operating temperature to maximum operating temperature) designed for continuous operation of the cell.
  • -Rated temperature the maximum value of the ambient temperature to which the rated voltage (V R or U R ) can be applied continuously.
  • V R or U R the peak value of the direct current (DC) voltage or the peak value of the pulse voltage that can be continuously applied to the cell at any temperature between the lowest service temperature and the rated temperature.
  • the "normal condition” and the “acceleration condition” are not particularly limited, and they may vary depending on the type of cell and the like. Normal conditions have the same meaning as usual.
  • the normal condition is the actual use environment condition of the cell. Normal conditions may be selected from, for example, temperature, current and / or voltage, etc., at actual operating environmental conditions of the cell.
  • the normal condition may be an actual use specification of each cell unless specifically defined. For example, in the case of temperature, it may be the use temperature range defined above, and in the case of current and voltage, it may be the rated current I R and the rated voltage V R or U R defined above.
  • acceleration condition is a more severe condition than the normal condition (the actual use environment condition of the cell). Acceleration conditions can also be selected from temperature, current and / or voltage, etc., which are more severe than normal conditions and may be deteriorated to the cell. And in the present invention, “charge / discharge” means “charge and discharge”.
  • the cell to be measured is not particularly limited, and any cell may be charged / discharged.
  • the cell may be selected from electrochemical devices as energy storage devices and the like.
  • the cell is, for example, a general secondary battery such as a lithium ion (Li + ) battery, a lithium polymer battery, a nickel-hydrogen (Ni-H) battery, a lead acid battery, and an electrolytic capacitor; General capacitors such as ceramic capacitors, Al electrolytic capacitors, and Ta capacitors; And Super Capacitors such as Electric Double Layer Capacitors (EDLC), Pseudo Capacitors, and Hybrid Capacitors.
  • the shape, size, etc. of a cell are not restrict
  • the shape of the cell includes, for example, a rectangle, a cylinder, a coin shape, a pouch shape, and the like.
  • the cell to be measured may be selected from specific examples, for example, super capacitors, more specific examples, hybrid capacitors, and the like.
  • the hybrid capacitor includes a positive electrode type and a negative electrode type.
  • the hybrid capacitor includes, for example, an anode hybrid capacitor using a metal oxide material for the anode and activated carbon for the cathode;
  • the cathode includes a cathode hybrid capacitor using a metal oxide and an anode using activated carbon.
  • the metal oxide as an electrode material is, for example, one selected from lithium (Li), titanium (Ti), ruthenium (Ru), manganese (Mn), tantalum (Ta), aluminum (Al), vanadium (V), and the like.
  • the metal element may be included, but is not limited thereto.
  • the performance of the cell measured according to the invention includes at least cycle life characteristics.
  • the performance of a cell measured according to the present invention optionally further includes the electrical characteristics of the cell, and the like. That is, the present invention evaluates (predicts) at least cycle life characteristics of the cell, and optionally further evaluates electrical characteristics of the cell.
  • the electrical characteristics may vary depending on the type of cell, which may be, for example, one or more selected from leakage current, resistance, and capacitance.
  • the resistance may be selected from DC resistance and / or AC resistance, and more specifically, may be selected from DC equivalent series resistance (DC.ESR).
  • the first step is a step of repeating the main cycle M-C several times as described above.
  • the measurement method according to the present invention includes a normal charge / discharge sub-cycle S-C1 and an accelerated charge / discharge sub-cycle S-C2 as one main cycle M-C.
  • the main cycle M-C is repeated several times.
  • the first process is the first step of charging / discharging under normal conditions in accordance with the present invention; After the first step is carried out, including a second step of charging / discharging under an accelerated condition, the first step and the second step as a 'degradation cycle process', and this deterioration cycle process is repeated several times.
  • the number of main-cycles M-C is not limited. Referring to FIG. 1, the number of main-cycles M-C is N times, where N is an integer of 1 or more and the upper limit is not limited. The number N of main-cycles M-C may vary depending on the type of cell and / or the acceleration condition.
  • the main-cycle M-C includes at least one normal charge / discharge sub-cycle S-C1 and at least one accelerated charge / discharge sub-cycle S-C2. That is, the number of times of each sub-cycle S-C1 (S-C2) in one main-cycle M-C is one or two or more times.
  • the normal charge / discharge sub-cycle S-C1 may be n times
  • the accelerated charge / discharge sub-cycle S-C2 may be used. May be m times.
  • n and m are integers of 1 or more, and the upper limit thereof is not limited.
  • the number n of the normal charge / discharge sub-cycles S-C1 and the number m of the accelerated charge / discharge sub-cycles S-C2 are 1.
  • ⁇ 100: may have a ratio of 100 ⁇ 1. That is, n / m may be 0.01 to 100. More specifically, for example, in any one main-cycle MC, the number n of normal charge / discharge sub-cycles S-C1 may be 1 to 100, and the accelerated charge / discharge sub-cycle ( The number m of S-C2) may be 1 to 100.
  • one or more normal charge / discharge cycles and one or more accelerated charge / discharge cycles are repeated continuously.
  • at least one normal charge / discharge sub-cycle S between the accelerated charge / discharge that is, between the accelerated charge / discharge sub-cycle S-C2 and the accelerated charge / discharge sub-cycle S-C2.
  • -C1 proceeds.
  • the first step is S-C1-> S-C2-> S-C1-> S-C2-> S-C1 advances between any one S-C2 and another adjacent S-C2, including the process of S-C1-> S-C2.
  • the cycle life of the cell can be accurately evaluated in a short time by the periodic repetition of the normal charge / discharge sub-cycle (S-C1) and the accelerated charge / discharge sub-cycle (S-C2). . That is, the lifetime evaluation time is shortened by the accelerated charge / discharge sub-cycle S-C2.
  • the normal charge / discharge sub-cycle S-C1 proceeds between the accelerated charge / discharge sub-cycles S-C2, so that the cycle life of the cell can be accurately evaluated.
  • the normal charge / discharge sub-cycle S-C1 proceeds between the accelerated charge / discharge sub-cycles S-C2. If not, the deterioration of the cell becomes severe and has abnormal characteristics. Specifically, deterioration is added to the deterioration, which makes it difficult for the cell to operate normally, which degrades the accuracy of life estimation.
  • the present invention improves this. That is, according to the present invention, by the periodic repetition of the normal charge / discharge sub-cycle (S-C1) and the accelerated charge / discharge sub-cycle (S-C2), accelerated charge / discharge sub-cycle (S-C2) In the case where the normal charge / discharge sub-cycle (S-C1) proceeds between), deterioration due to acceleration is recovered by the normal charge / discharge sub-cycle (S-C1), so that the cell has normal characteristics. . Accordingly, the accuracy of life evaluation is high. And it is possible to shorten the time of life evaluation according to the acceleration conditions of the acceleration charge / discharge sub-cycle (S-C2).
  • the first process may include two or more sections.
  • one or more sections may make the main cycle M-C different from other sections. That is, the condition of the normal charge / discharge sub-cycle S-C1 of the main cycle M-C and the acceleration / charge / discharge sub-cycle S-C2 may be different.
  • the first process includes P 1 ,..., P M sections (M is an integer of 1 or more), wherein at least one or more sections of the main-cycle MC are compared with other sections.
  • the conditions or the number of times of the normal charge / discharge sub-cycle S-C1 and the accelerated charge / discharge sub-cycle S-C2 may be different. That is, the first process has M sections, wherein one or more sections may have different one or more selected from the conditions and the number of times of each sub-cycle (S-C1) (S-C2) compared to other sections. have.
  • the first process is divided into M sections, of which one or more sections are compared with other sections, and the normal charge / discharge sub-cycle (S-C1) and the accelerated charge / discharge sub-cycle (S).
  • the conditions of C2) (temperature, current and / or voltage, etc.);
  • a ratio (value of n / m) of the normal charge / discharge sub-cycle S-C1 and the number of times of the accelerated charge / discharge sub-cycle S-C2 may be different.
  • the first process when M is 3, includes at least P 1 , P 2 and P 3 intervals, wherein P 2 intervals are accelerated charging compared to P 1 and P 3 intervals
  • the conditions of the / discharge sub-sub cycle (S-C2) are more severely processed, or the number of repetitions (m) of the accelerated charge / discharge sub-sub cycle (S-C2) is normal. It can proceed under more conditions (m> n) than the number n of C1).
  • n / m of the P 2 section may be 0.01 ⁇
  • n / m of the P 1 and P 3 section may be 1 ⁇ 100. In this way, the life evaluation time can be shortened more effectively, which can also be very useful for cell life evaluation of super capacitors (hybrid capacitors, etc.).
  • the normal charge / discharge sub-cycle (S-C1) and the accelerated charge / discharge sub-cycle (S-C2) preferably proceed as follows.
  • Preferred embodiments described below may be usefully applied to, for example, super capacitors, more specifically, hybrid capacitors, and the like. This will be described with reference to FIGS. 2 to 4.
  • FIG. 2 and 3 are for explaining the first step of the present invention, which is a graph showing the voltage characteristics over time.
  • the main-cycle (MC) is shown.
  • 3 schematically illustrates N main-cycles (M-C).
  • Figure 4 shows the entire flow chart of the measuring method according to a specific embodiment of the present invention by way of example. In this case, the numerical values shown in FIG. 4 are shown by way of example only for convenience of description.
  • the normal charge / discharge sub-cycle S-C1 charges a cell with a constant current (CC) under normal conditions according to an exemplary embodiment of the present invention, and then uses a constant voltage (CV).
  • the resting step can proceed, for example, for 10 seconds to 5 minutes.
  • the cell can self-discharge and / or charge, for example, to have a voltage of zero (zero) to 0.5V.
  • pause is included herein as long as it does not proceed with charging and discharging. Resting may proceed, for example, through the power off.
  • the constant current (CV) and the constant voltage (CV) means a current and a voltage that is kept constant as defined above, the actual value thereof is not limited.
  • the constant current (CC) charging and the constant voltage (CV) charging proceeds continuously under normal conditions, while in the constant current (CC) charging, the first voltage (V) at a constant current (CC) of the first current (I 1 ). Charge up to 1 ).
  • the first current I 1 and the first voltage V 1 are currents and voltages under normal conditions, respectively, and these depend on the type and standard of the cell.
  • the first current I 1 is the rated current I R of the corresponding cell, which may be determined according to, for example, the rated capacitance C R of the cell.
  • the first current I 1 may be, for example, 0.1 mA / F to 500 A / F, and more specifically, 1 mA / F to 100 A / F or 5 mA / F to 75 mA / F. .
  • the first voltage V 1 is a rated voltage V R of the corresponding cell. As described above, the rated voltage V R may vary depending on the corresponding cell, and the voltage V R may be, for example, 2.1 V, 2.3 V, 2.5 V, 2.7 V, 3.2 V, and the like. After the constant current CC charging, the constant voltage CV is charged at the first voltage V 1 , that is, at the rated voltage V R.
  • the constant current (CC) charging time (in Fig. 2, T 1 -T 2 interval) may be a time to reach the first voltage (V 1 ), that is, a time to reach the rated voltage (V R ). .
  • the constant current CC charging time T 1 -T 2 may be, for example, 1 minute to 20 minutes, and more specifically, 3 minutes to 10 minutes.
  • the constant voltage (CV) charging time (in FIG. 2, the T 2 -T 3 section) may be, for example, 10 minutes to 60 minutes, and more specifically, 20 minutes to 40 minutes.
  • the battery 1 discharges to the second voltage V 2 with the constant current CC of the first current I 1 .
  • the first current I 1 in this normal discharge step is the same as the normal charging step. That is, the first current I 1 may be 0.1 mA / F to 500 A / F as illustrated above, and more specifically, for example, 1 mA / F to 100 A / F or 5 mA / F to 75 mA / F. Can be.
  • the second voltage V 2 may satisfy Equation 1 below.
  • V 1 is a first voltage (V 1), that is the rated voltage (V R) of the cell in the top-charge phase.
  • the second voltage V 2 may be, for example, 0.1V 1 (V R ) to 0.9V 1 (V R ), and more specifically, for example, 0.4V 1 (V R ) to 0.6V 1.
  • the constant current (CC) discharge time (in Fig. 2, T 3 -T 4 section) may be a time to reach the second voltage (V 2 ) satisfying the above Equation (1).
  • the constant current (CC) discharge time (T 3 -T 4 section) may be, for example, 1 minute to 20 minutes, and more specifically, may be 3 minutes to 10 minutes.
  • the normal discharge step may be divided into two steps. Specifically, the normal discharge step is the second voltage with the constant current (CC) of the first current (I 1) 1 primary discharge step of discharging a constant current to drop the voltage to the (CC) of a), and a first current (I 1) ( Secondary discharge step b) for discharging up to V 2 ). And the first discharge step a) may be carried out, for example for 0.5 seconds to 10 seconds, more specifically for example 1 second to 5 seconds, the secondary discharge step b) is 1 minute to 10 minutes, more specific For example, it may proceed for 2 to 8 minutes.
  • the first discharge step a) may be carried out, for example for 0.5 seconds to 10 seconds, more specifically for example 1 second to 5 seconds
  • the secondary discharge step b) is 1 minute to 10 minutes, more specific For example, it may proceed for 2 to 8 minutes.
  • the accelerated charging / discharging sub-cycle may include: an accelerated charging step of charging a cell to a constant current (CC) in an accelerated condition and then charging to a constant voltage (CV) according to an exemplary embodiment of the present invention; And an accelerated discharge step of discharging at a constant current CC.
  • the acceleration condition is included here if it is a more severe charging / discharging condition than the normal condition, as described above, for example, the temperature, current and voltage, such as more severe than the normal condition It may be one or more selected from. More specifically, for example, the temperature may be selected from lower or higher temperature conditions than the actual operating temperature range of the cell. In the case of current and voltage, the current and voltage may be selected from a higher current and voltage than that of the cell. More specifically, for the current, the current is higher than the first current I 1 of the normal charge / discharge sub-cycle S-C1, and in the case of voltage, the voltage higher than the rated voltage V R Can be.
  • the acceleration condition may preferably be selected from currents, and more specifically, from a second current (acceleration current, I 2 ) higher than the first current I 1 , as illustrated below.
  • the constant current (CC) charging and the constant voltage (CV) charging proceeds continuously in an acceleration condition, while in the constant current (CC) charging to the constant current (CC) of the second current (I 2 ) Charge to the first voltage (V 1 ).
  • the second current I 2 is an acceleration current, which is not particularly limited as long as the current is higher than the first current I 1 in the normal charge / discharge sub-cycle S-C1.
  • the second current I 2 may be, for example, 1.2 times or more, for example, 1.2 times to 40 times the first current I 1 , and preferably satisfies Equation 2 below. good.
  • the second current I 2 when the second current I 2 satisfies Equation 2 above, it is useful as an acceleration condition such as, for example, a super capacitor, and more specifically, an acceleration condition such as a hybrid capacitor. Do. That is, it is very advantageous for shortening the life evaluation time of a hybrid capacitor. More specifically, the second current I 2 may be two to fifteen times the first current I 1 . If the first of the second current (I 2), as a example, 10 times the first current (I 1) of an example, the first current (I 1) 25mA / F, which may be an acceleration current of 250mA / F .
  • the constant current (CC) charging time (in Fig. 2, T 6 -T 7 section) is the time to reach the first voltage (V 1 ) by charging the second current (I 2 ), namely If the time to reach the rated voltage (V R) is good.
  • the constant current (CC) charging time (T 6 -T 7 ) may be, for example, 0.5 seconds to 20 seconds, more specifically, for example, may be 2 seconds to 10 seconds.
  • the constant voltage (CV) charging time in FIG. 2, T 7 -T 8 section) may be, for example, 30 seconds to 10 minutes at the first voltage V 1 , and more specifically, for example, 1 minute to 5 minutes. Can be minutes.
  • the battery device discharges to the second voltage V 2 with the constant current CC of the second current I 2 .
  • the second current I 2 and the second voltage V 2 in the accelerated discharge step are as described above. That is, the second current I 2 is the current of the accelerated charging step, which preferably satisfies Equation 2 above.
  • the second voltage V 2 in the accelerated discharge step is a voltage in the normal discharge step, which preferably satisfies Equation 1 above.
  • the constant current (CC) discharge time (in Fig. 2, T 8 -T 9 section) is the time to reach the second voltage (V 2 ) by the discharge of the second current (I 2 ), namely What is necessary is just time to reach the voltage which satisfy
  • the constant current (CC) discharge time (T 8 -T 9 ) may be, for example, 0.5 seconds to 20 seconds, more specifically, for example, may be 2 seconds to 10 seconds.
  • the main-cycle (MC) includes the normal charge / discharge sub-cycle (S-C1) and the accelerated charge / discharge sub-cycle (S-C2) as described above, optionally further resting time It may include.
  • the resting period is the first stop (R1) proceeds after the normal charge / discharge sub-cycle (S-C1);
  • a second stopper R2 that proceeds after the accelerated charge / discharge sub-cycle S-C2.
  • the main-cycle MC may include a first stop R1 performed after the one or more normal charge / discharge sub-cycles S-C1 and / or one or more accelerated charge / discharge subs. It may further include a second stop (R2) is carried out after the cycle (S-C2). The pause may proceed, for example, through the power off.
  • the first stop R1 is performed after the normal discharge step of the normal charge / discharge sub-cycle S-C1, which may be performed for 1 minute to 10 minutes, for example.
  • the first pauser R1 may include a first idle stage R11 and a second idle stage R12.
  • the first idle stage R11 may be performed for a period of 10 seconds to 2 minutes (T 4 -T 5 section in FIG. 2)
  • the second idle stage R12 may be performed for a period of 2 minutes to 8 minutes ( In FIG. 2, the step T 5 -T 6 may be performed.
  • the first rest stage R11 may be performed for 1 minute
  • the second rest stage R12 may be performed for 4 minutes.
  • the second stop R2 proceeds after the accelerated discharge step of the accelerated charge / discharge sub-cycle S-C2, which may be performed, for example, for 1 minute to 10 minutes.
  • the second pause (R2) may also include a first pause stage (R21) and a second pause stage (R22).
  • the first rest stage R21 may be performed for a period of 10 seconds to 2 minutes (T 9 -T 10 section in FIG. 2), and the second rest stage R22 may be performed for a period of 2 minutes to 8 minutes ( In FIG. 2, the T 10 -T 11 section may be performed.
  • the first rest stage R21 may be performed for one minute
  • the second rest stage R22 may be performed for four minutes.
  • the first process may further include a normal charge / discharge stable cycle (C3) that proceeds after repeating the above-described main-cycle (M-C) several times. That is, the apparatus may further include a normal charge / discharge stable-cycle C3 which proceeds after the accelerated charge / discharge sub-cycle S-C2. Specifically, after the normal charge / discharge stable-cycle C3 proceeds with the accelerated charge / discharge sub-cycle S-C2 of N times the main cycle MC, more specifically, N times the main cycle MC. It may proceed after the second stop (R2) of the).
  • the normal charge / discharge stable-cycle (C3) is for stabilizing cells degraded by the accelerated charge / discharge sub-cycle (S-C2), which proceeds under normal conditions.
  • the charge / discharge (charge / discharge) is one cycle under normal conditions, and the charge / discharge cycle is performed one or more times. For example, proceed 1 to 3 times.
  • the charging / discharging conditions of the normal charging / discharging stable cycle C3 are the same as those of the normal charging / discharging sub-cycle S-C1 (normal conditions).
  • the normal charge / discharge stable-cycle (C3) the normal charging step of charging the cell to a constant current (CC) after charging the cell under a constant condition (CV) under normal conditions; And a normal discharge step of discharging at a constant current CC.
  • this normal charge / discharge stable-cycle (C3) specific embodiments of each of the normal charging and discharging steps are the same as those described in the normal charging / discharging sub-cycle (S-C1), and thus a detailed description thereof. Is omitted.
  • the normal charge / discharge stable-cycle C3 is a period of time T 11 -T 12 .
  • the first process is performed subsequent to the normal charge / discharge stable-cycle (C3), and includes a complete discharge cycle for completely discharging to the minimum voltage of the cell ( C4) may be further included. That is, the cell is discharged to the discharge voltage through the complete discharge cycle C4.
  • the complete discharge cycle C4 is a period of time T 12 -T 15 .
  • the complete discharge cycle C4 is discharged to the third voltage V 3 with the constant current CC of the first current I 1 after the normal charge / discharge stable cycle C3 is performed, for example.
  • the first current I 1 is as described above.
  • the third voltage V 3 is a full discharge voltage [minimum voltage] of the corresponding cell, which may vary depending on the type of cell.
  • the third voltage V 3 may be, for example, 0 (zero) to 1.15V.
  • the third voltage V 3 may be a unique OCV (open circuit voltage) of a cell, and may vary from cell to cell, but may be, for example, 0 to 1V.
  • the third voltage V 3 may be, for example, 0.1V.
  • the constant current (CC) discharge time (in Fig. 3, the period of time T 12 -T 13 ) is not particularly limited as long as it is a time until reaching the third voltage (V 3 ). Which may for example be from 1 minute to 10 minutes.
  • constant voltage (CV) is the holding time (in Fig. 3, the time period of T 13 -T 15) is, for example, it is from 5 minutes to 60 minutes. At this time, in some cases, a slight increase in voltage may occur in the cell in the constant voltage (CV) holding step. For example, in FIG. 3, a voltage may slightly increase at a time T 14 during the period of time T 13 -T 15 .
  • the second step evaluates at least the cycle life of the cell.
  • the life of the cell may be evaluated through at least one selected from a capacity change rate and a resistance change rate after the first process.
  • the second process is a first step of measuring the initial capacity of the cell, according to the first embodiment; A second step of measuring a holding capacity after repeating the first step; And a third step of determining a cycle life of the cell by comparing the initial capacity and the maintenance capacity.
  • the initial capacity before the normal charge / discharge sub-cycle (S-C1) is measured.
  • the initial capacity may be, for example, the rated capacitance C R of the corresponding cell.
  • the holding capacity held by the cell is measured each time. That is, the holding capacity of the second step is the cell capacity in N times.
  • the cycle capacity of the cell is evaluated by comparing the initial capacity with the maintenance capacity in N times.
  • the cell is based on the following Equation 3 below. It is possible to determine (prediction) the cycle life of.
  • C O is an initial capacity and C N is a maintenance capacity after N first processes.
  • C s is a reference capacity, which is 0.5 to 0.8 although it may vary depending on the type of cell.
  • the first process is performed N times until the holding capacity (C N ) becomes 80% of the initial capacity (C O ).
  • the specific multiple for N times can be estimated (predicted) by the actual cycle life of the cell.
  • the specific drainage may vary depending on the acceleration conditions, for example, may be 1.2 times to 100 times.
  • the holding capacity C N may use, for example, a discharge capacity value of the normal charge / discharge sub-cycle S-C1 constituting the main cycle MC. More specifically, the holding capacity C N may use the capacity measured after the constant current CC discharge is performed in the Nth normal charge / discharge sub-cycle S-C1. At this time, the measurement of the holding capacity (C N ) is not particularly limited, which may be calculated according to, for example, Equation 4 below.
  • Equation 4 V N is a voltage at the time of measurement, and V R is the first voltage V 1 as described above.
  • ⁇ T is the constant current (CC) discharge time (in FIG. 2, the interval of time T 3 -T 4 , the unit is sec), I 1 is the first current as described above, and C R is the rated capacitance of the cell. to be.
  • the holding capacity (C N ) used for evaluating the life of the cell may be a discharge capacity after repeating the main cycle ( N ) several times (N times), which is the Nth normal charge / discharge as described above. It may be the discharge capacity in the sub-cycle S-C1 or the discharge capacity measured after the normal charge / discharge stable-cycle C3.
  • the present invention may further include a step of measuring the electrical characteristics of the cell, in addition to the first step and the second step.
  • a step of measuring the electrical characteristics of the cell for example, the third process of measuring the leakage current (LC); A fourth step of measuring resistance; And at least one process selected from a fifth process of measuring self discharge.
  • the third process may be performed, for example, in the charging step of the normal charge / discharge sub-cycle (S-C1).
  • the third process is to find the leakage current LC at the time of charging the constant voltage CV under the normal condition, which may be performed 30 seconds before the end of the charging of the constant voltage CV, for example.
  • the measurement of the leakage current LC may be used as a measure for evaluating initial basic characteristics of the cell, which may also be used as a cycle life assessment of the cell.
  • the fourth process may be performed in the process of discharging and / or after discharging.
  • the resistance measured by the fourth process is at least one selected from DC resistance and AC resistance.
  • the fourth process includes a first resistance measuring step performed in a process of discharging a constant current (CC) of a normal charge / discharge sub-cycle (S-C1); And a second resistance measurement step performed after the constant current CC discharge of the normal charge / discharge sub-cycle S-C1 is performed.
  • CC constant current
  • S-C1 normal charge / discharge sub-cycle
  • the resistance measurement method in the fourth step is not particularly limited.
  • the first resistance measuring step may be based on Equation 5 and Graph 1 below.
  • Equation 5 and graph 1 R d is a DC internal resistance (DC.IR), and ⁇ V is a drop voltage ( ⁇ V 3 ) generated during constant current (CC) discharge.
  • I is a discharge current, which is the first current I 1 as described above. At this time, the discharge current may be in accordance with a) to c) below.
  • the dropping voltage does not indicate a voltage ⁇ V 4 that falls momentarily at the start of discharge, but may indicate a dropped voltage ⁇ V 3 obtained at the intersection of an auxiliary line extending a straight line portion and a time starting point at the start of discharge. have.
  • a) ⁇ V 3 can reduce the current to 1/2, 1/5, or 1/10 when the charge voltage exceeds 20% (0.20 x V R ).
  • the discharge current value of 10 A or less may be one significant digit, and the second digit of the calculated value may be cut off.
  • the resistance measured in the fourth step may be used as a measure for evaluating the initial basic characteristics of the cell, or may be used to evaluate the cycle life of the cell. That is, the cycle horizontality of the cell can be evaluated (predicted) based on the measured change rate of the resistance.
  • the second process is to evaluate the life of the cell through the resistance according to the second embodiment, the step of measuring the initial resistance of the cell; B) measuring a holding resistance after repeating the first step; And c) evaluating a cycle life of the cell by comparing the initial resistance and the sustain resistance.
  • step c) may evaluate (predict) the cycle life of the cell based on, for example, Equation 6 below.
  • R O is an initial resistance
  • R N is a sustain resistance after N first processes.
  • R s is a reference resistance, which is 2 to 5 although it may vary depending on the type of cell.
  • the first process is repeated until the holding resistance R N is twice the initial resistance. And 5 times to 1000 times for the N times can be evaluated (predicted) by the actual cycle life of the cell, but this may be different from the acceleration conditions.
  • the self-discharge of the fifth process may be measured according to [Graph 2] and conditions a) to d) below.
  • the charging time is set to 8h including the maximum charging rise time 30 min in which the applied voltage reaches 95%.
  • the cycle life of the cell for example, the cycle life of the cell such as a hybrid capacitor can be accurately measured in a short time.
  • the electrical characteristics such as leakage current, resistance, self-discharge, and / or capacity may also be measured in the process of measuring the cycle life of the cell.
  • a positive electrode hybrid capacitor having a lithium oxide electrode applied to the positive electrode and an activated carbon electrode applied to the negative electrode having a rated voltage (V R ) of 2.3 V and a rated capacitance (C R ) of 120F was used.
  • V R rated voltage
  • C R rated capacitance
  • the cells were repeatedly charged / discharged under constant conditions and accelerated / discharged under constant current constant voltage (CC_CV).
  • the amount of current (current) was varied as the acceleration condition for each specimen. That is, the acceleration conditions were increased by 2 times, 10 times, 11 times, 15 times, and 20 times with respect to the current amount (5 mA / F) under normal conditions according to each specimen. Acceleration conditions (current) for each specimen are shown in Table 1 below. In Table 1 below, 'standard' is a normal condition.
  • the voltage over time during discharge under the normal conditions (5mA / F) and each acceleration condition the voltage was evaluated, and the results are shown graphically in Figure 5 attached.
  • Figure 6 is a graph showing the cycle life evaluation results.
  • 'Ref' is the result of the specimen that proceeded charging / discharging only under normal conditions (5mA / F, 0.6A).
  • the 'example' is the result of the specimen repeated a number of times, with one charge / discharge in a normal condition and nine charge / discharge in an accelerated condition according to an exemplary embodiment of the present invention, repeated several times .
  • the acceleration condition proceeded to the acceleration condition (75mA / F, 9A) of 15 times than the normal condition (5mA / F, 0.6A).
  • the 'Comparative Example' performs charging / discharging once under normal conditions (5mA / F, 0.6A), and then continues charging / discharging several times only after the acceleration conditions (75mA / F, 9A). The result is a test piece.
  • the x-axis is the capacity change rate (initial 100%) and y is the number of cycles.
  • the acceleration can shorten the life evaluation time.
  • the number of cycles to have the same capacity (eg, 90%) as 'Ref' becomes shorter, which means shorter life evaluation time.
  • the rate of change in capacity according to the number is uniform. In other words, the capacity drops sharply initially, but from some point the slope of the curve is almost constant. This means high accuracy.
  • the rate of change of capacity continues to drop rapidly.
  • This may be advantageous for shortening the life assessment time, but it is not considered accurate. That is, when charging / discharging continuously only under the acceleration condition, deterioration is added to deterioration and it has a sudden capacity change. It is not accurate because it is used as a measure of the life evaluation of a cell even in an abnormal capacity.
  • the cycle life of a cell for example, the cycle life for a cell such as a hybrid capacitor, can be measured accurately in a short time.

Abstract

La présente invention porte sur un procédé pour mesurer des performances d'accumulateur. Il est procuré un procédé pour mesurer des performances d'accumulateur, lequel procédé met en œuvre : un premier processus de répétition de cycle principal comprenant un sous-cycle de charge/décharge normal pour la charge et la décharge dans une condition normale, et un sous-cycle de charge/décharge accéléré pour la charge et la décharge dans une condition accélérée ; et un second processus d'évaluation de la durée de vie de cycle de l'accumulateur pour lequel le premier processus a été effectué.
PCT/KR2014/011642 2013-11-29 2014-12-01 Procédé pour mesurer des performances d'accumulateur WO2015080537A1 (fr)

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CN112731182A (zh) * 2020-12-21 2021-04-30 天津力神电池股份有限公司 一种快速评价锂离子电池循环寿命的方法
CN114252795A (zh) * 2021-11-30 2022-03-29 上海电气国轩新能源科技有限公司 一种预测锂离子电池循环寿命的方法
CN114397351A (zh) * 2022-01-19 2022-04-26 湖南裕能新能源电池材料股份有限公司 快速评估磷酸铁锂正极材料循环性能的方法

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CN106443483B (zh) * 2016-11-07 2019-07-16 成都雅骏新能源汽车科技股份有限公司 一种电动汽车用镍氢电池的脉冲循环寿命测试方法
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KR102043645B1 (ko) 2018-04-03 2019-12-02 주식회사 엘지화학 이차전지의 불량 검출을 위한 저전압 발현 수준 연산 시스템 및 검출 방법
CN110703100B (zh) * 2019-10-17 2021-11-16 河南电池研究院有限公司 一种动力锂电池全生命周期远程监控系统
US11762031B2 (en) * 2020-08-31 2023-09-19 Medtronic, Inc. Electrochemical cell state of health detection
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