US20010028238A1 - Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries - Google Patents
Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries Download PDFInfo
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- US20010028238A1 US20010028238A1 US09/779,466 US77946601A US2001028238A1 US 20010028238 A1 US20010028238 A1 US 20010028238A1 US 77946601 A US77946601 A US 77946601A US 2001028238 A1 US2001028238 A1 US 2001028238A1
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Images
Classifications
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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
-
- 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
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
-
- 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 judging the condition of a secondary battery such as a nickel-hydrogen battery and lithium secondary battery and, more particularly, to a method for judging the initial activity and degradation thereof.
- the present invention further relates to a method for regenerating a secondary battery and, more particularly, to a method for regenerating a nickel-hydrogen battery.
- Secondary batteries are essential parts of moving motors such as portable electron equipments and electric motor vehicles as power sources thereof. These secondary batteries generate electrochemical reactions to obtain an electric energy. So, the properties of facilitating the generation of electrochemical reaction, that is activity, greatly affects various battery performance such as the discharge capacity, output characteristic, cycle charging and discharging characteristic, and safety. Accordingly, the activity of the battery can be used as the index of various battery performance. If the initial activity, for example, of the secondary battery can be detected, it can be known whether the secondary battery exhibits desired battery performance or not, and it can be judged whether the battery is inferior or not.
- the secondary batteries such as nickel-hydrogen batteries, may not exhibit a high initial activity, because electrodes thereof do not sufficiently react with electrolytes just after production thereof, so that the potential battery performance thereof may not be obtained.
- these secondary batteries have been charged or discharged prior to using thereof, and consequently the activity thereof has been increased until a required battery performance can be effected.
- the secondary batteries such as nickel-hydrogen batteries
- they have been initially subjected to a predetermined number of charging and discharging cycles from a fully charged condition to the discharged condition with a predetermined final discharge voltage until the initial capacity activity (potential discharge capacity/theoretical discharge capacity) increases to a predetermined standard or more, before shipping or practically using thereof.
- the initial activity can be known, it can be judged before using whether the secondary battery is inferior or not, and consequently it becomes unnecessary to charge and discharge the inferior secondary batteries. This results in the overall production costs of the secondary batteries being decreased by the production costs which have been conventionally needed to charge and discharge the inferior secondary batteries.
- the secondary battery cannot supply identical power constantly.
- the supplying power varies with the number of using times. More specifically, as the charging and discharging cycle of the secondary battery is repeated, the electrodes, electrolyte or the like are degraded to gradually decrease the discharging capacity of the battery. Thus, battery degradation occurs and the battery performance decreases. As described above, the battery performance of the secondary battery is lowered due to a large number of using thereof. Consequently, it has become impossible to generate necessary charging and discharging even by applying prescribed charging operation to the secondary battery. Thus, the supplying power decreases. At last, the battery life has ended to require changing thereof.
- the secondary battery which has been degraded with the repetition of charging and discharging cycle may be changed to a new one after required battery performance has not been effected thereby, but in accordance with their use like the preceding moving motor, the secondary battery may have to be changed to a new one before required battery performance has not been effected thereby. In this case, the degraded condition of the secondary battery must be determined before the required battery performance is not effected.
- the method for determining the degraded condition of the secondary battery it can be considered to forecast the degradation time of electrodes, electrolytes or the like before using the secondary battery.
- the degradation manner of the electrodes and electrolytes or the like, and the process to the degradation thereof depend on the using conditions of the secondary batteries. Accordingly, the degradation time is extremely difficult to forecast beforehand.
- the internal resistance has been mainly used as the index of the degradation and initial activity of the batteries.
- the battery condition cannot be sufficiently understood. If a high internal resistance is measured, for example, the reason therefor has been not understood.
- the discharge output of the battery being not obtained sufficiently, conventionally, there has been a problem that the reason therefor is not clear, and it is difficult to increase the discharge output.
- the battery output is small, because the internal resistance is great though the open voltage of the battery is sufficiently great, it has been difficult to judge whether the increase of the internal resistance results from inferior welding of members such as electrode of the battery, for example, which is impossible to recover, or the initial activity which is able to be overcome by repeated charge and discharge cycles.
- the judgement of the degradation of the battery is possible, but the manner of degradation (degradation mode) cannot be judged.
- nickel-hydrogen batteries include a positive electrode which uses nickel oxide or the like as a positive electrode active material, a negative electrode which uses a hydrogen-occluding alloy as a negative electrode active material, and an electrolyte interposed between the positive electrode and negative electrode.
- the electrolyte may be dried up during using thereof to deteriorate the battery performance. And as the charging and discharging cycle is repeated may times, the surface of the negative electrode (negative electrode alloy) may be oxidized to degrade the negative electrode, thereby lowering the battery performance.
- the manner of degradation (degradation mode) of the secondary battery generally depends on the using conditions thereof.
- the nickel-hydrogen battery for example, is used in electric cars or hybrid cars at about a normal temperature, the negative electrode thereof is gradually oxidized to be degraded.
- the nickel-hydrogen battery is used in an environment of which the temperature varies greatly to an extremely high temperature, the battery is dried up to be degraded.
- the battery performance is lowered due to drying of the electrolyte, it can be recovered readily by supplementing the electrolyte.
- the battery performance is lowered due to the oxidization of the surface of the negative electrode, it can be recovered by changing the degraded negative electrode for a new one.
- the hydrogen-occluding alloy for use as the negative electrode active material is relatively expensive, so that changing costs of batteries may increase. Consequently, there has been demanded to provide a method for recovering the battery performance without changing the degraded negative electrode for a new one when the negative electrode is degraded and the battery performance is lowered.
- the present invention has been made in consideration of the above circumstances, and a first object of the present invention is to provide a method and device for judging the condition of secondary batteries, which are capable of judging the same more quickly and in more detail, as compared to the conventional method and device.
- a second object of the present invention is to provide a method and device for judging the condition of secondary batteries, which are capable of judging the level of the degradation and initial activity thereof in detail and quickly.
- a third object of the present invention is to provide a method for regenerating secondary batteries such as nickel-hydrogen batteries, which is capable of regenerating degraded secondary batteries properly in accordance with the degraded condition thereof.
- a first aspect of the present invention which is the method for judging the condition of secondary batteries, is characterized in that the method includes the steps of varying the charging current or discharging current of the secondary batteries, calculating the quantity of electricity which is related to the follow-up variation characteristic of a terminal voltage of the secondary batteries, relative to the variation of the charging current or discharging current, and judging the condition related to the charging and discharging performance of the secondary batteries based on the quantity of electricity.
- a second aspect of the present invention which is a preferred embodiment of the first aspect of the present invention, is characterized in that the charging current or discharging current is varied stepwise between predetermined two electric currents, and calculating the quantity of electricity based on the variation wave form of the terminal voltage after the variation of the charging current or discharging current starts stepwise.
- a third aspect of the present invention which is a preferred embodiment of the second aspect of the present invention, is characterized in that the quantity of electricity includes that related to the variation of the terminal voltage at the time the terminal voltage rapidly varies just after the variation of the charging current or discharging current starts stepwise, and that related to the variation of the terminal voltage while the terminal voltage gently varies after varying rapidly.
- a fourth aspect of the present invention which is a preferred embodiment of the third aspect of the present invention, is characterized in that the quantity of electricity is calculated based on a first quantity of electricity composed of the variation of the terminal voltage at the time the terminal voltage rapidly varies just after the variation of the charging current or discharging current starts stepwise and/or a second quantity of electricity composed of the variation of the terminal voltage during a predetermined period of time while the terminal voltage gently varies after varying rapidly.
- a fifth aspect of the present invention which is a preferred embodiment of the fourth aspect of the present invention, is characterized in that the battery performance is judged low when the first quantity of electricity or second quantity of electricity exceeds a predetermined threshold.
- a sixth aspect of the present invention which is a preferred embodiment of the second aspect of the present invention, is characterized in that the charging current or discharging current is varied stepwise between electric current 0 and a predetermined electric current.
- a seventh aspect of the present invention which is a preferred embodiment of the first aspect of the present invention, is characterized in that the quantity of electricity is calculated based on the relation between an AC current component composed of the charging current or discharging current, which periodically varies with a predetermined frequency, and an AC voltage component having the predetermined frequency, which is included in the terminal voltage.
- An eighth aspect of the present invention which is a preferred embodiment of the first aspect of the present invention, is characterized in that where the internal impedance of the secondary battery is defined as a parallel impedance which is composed of predetermined parallel resistance and parallel electrostatic capacity, which are connected in parallel, and a series resistance which is connected in series with the parallel impedance, the quantity of electricity is composed of the quantity of electricity, which varies with impedance value of the parallel impedance or resistance of the parallel resistance, and the quantity of electricity, which varies with the resistance of the series resistance.
- a ninth aspect of the present invention which is a preferred embodiment of the eighth aspect of the present invention, is characterized in that the level of the degradation of the ion conduction performance of the electrolyte is estimated based on the resistance of the serial resistance.
- a tenth aspect of the present invention which is a preferred embodiment of the eighth aspect of the present invention, is characterized in that the increase of the film thickness on the surfaces of the electrodes is estimated based on the impedance of the parallel impedance or the resistance of the parallel resistance.
- An eleventh aspect of the present invention which is the method for judging the condition of secondary battery is characterized in that after charging or discharging with a predetermined current is performed in the secondary battery for a predetermined period of time, charging or discharging is interrupted, the voltage difference between the terminal voltage measured between the positive electrode terminal and negative electrode terminal when charging or discharging is interrupted, and that measured after charging or discharging is interrupted, is obtained, the internal resistance related value which is related to the internal resistance of the secondary battery is obtained based on the difference and the predetermined current, and the internal resistance related value is compared with a previously obtained relation between the internal resistance related value and battery condition, thereby judging the battery condition of the secondary battery.
- a twelfth aspect of the present invention which is a preferred embodiment of the eleventh aspect of the present invention, is characterized in that the internal resistance related value is obtained based on the voltage difference obtained in a predetermined period of time when the variation rate of the terminal voltage is a predetermined rate or more after charging or discharging is stopped, and the predetermined electric current.
- a thirteenth aspect of the present invention which is a preferred embodiment of the eleventh aspect of the present invention, is characterized in that the internal resistance related value is obtained based on the voltage difference obtained in a predetermined period of time when the variation rate of the terminal voltage is less than a predetermined rate after charging or discharging is interrupted, and the predetermined electric current.
- a fourteenth aspect of the present invention which is a preferred embodiment of the twelveth or thirteenth aspect of the present invention, is characterized in that the predetermined rate is the variation rate of the terminal voltage at the time the approximately linear variation of the terminal voltage is finished just after the charging or discharging is interrupted.
- a fifteenth aspect of the present invention which is a preferred embodiment of one of the twelveth through fourteenth aspects of the present invention, is characterized in that the internal resistance related value is the resistance calculated using the formula of (voltage difference/predetermined electric current).
- a sixteenth aspect of the present invention which is another method for judging the condition of the secondary battery in accordance with the present invention, is characterized in that the quantity of electricity related to the impedance of the secondary battery or the quantity of electricity related to the maximum power density is detected by applying an AC voltage to the secondary battery, and the performance of the secondary battery is judged based on the detected quantity of electricity.
- a seventeenth aspect of the present invention which is a preferred embodiment of the sixteenth aspect of the present invention, is characterized in that the maximum power density as the discharging performance of the secondary battery is obtained based on the quantity of electricity which is related to the impedance.
- An eighteenth aspect of the present invention which is a preferred embodiment of the sixteenth aspect of the present invention, is characterized in that the quantity of electricity is obtained after or while charging and discharging is performed for initial activation of the secondary battery, and the initial power activity of the secondary battery is judged based on the obtained quantity of electricity.
- a nineteenth aspect of the present invention which is a preferred embodiment of the eighteenth aspect of the present invention, is characterized in that where the quantity of electricity is within a predetermined range, the initial power activity of the secondary battery is judged to exceed a predetermined level to finish charging and discharging for initial activation of the secondary battery.
- a twentieth aspect of the present invention which is a preferred embodiment of the eighteenth aspect of the present invention, is characterized in that when the quantity of electricity is not within a predetermined range, the initial power activity of the secondary battery is judged less than a predetermined level to start charging and discharging for initial activation of the secondary battery, again.
- a twenty-first aspect of the present invention which is a preferred embodiment of the sixteenth aspect of the present invention, is characterized in that the power degradation of the secondary battery is judged based on the obtained quantity of electricity.
- a twenty-second aspect of the present invention which is a preferred embodiment of the eighteenth aspect of the present invention, is characterized in that where the quantity of electricity is outside a predetermined range, the life of the secondary battery is judged to end.
- a twenty-third aspect of the present invention which is a preferred embodiment of one of the sixteenth through twenty-second aspects of the present invention, is characterized in that the quantity of electricity is composed of an AC impedance related quantity of electricity, which is related to the AC impedance component including a component varying with the frequency of the AC voltage, out of the impedance of the secondary battery.
- a twenty-fourth aspect of the present invention which is a preferred embodiment of the sixteenth aspect of the present invention, is characterized in that the quantity of electricity related to the component of the impedance of the secondary battery, which does not vary with the frequency component of the AC voltage, is obtained as a DC impedance related quantity of electricity, the quantity of electricity related to component of the impedance of the secondary battery, which varies with the frequency component of the AC voltage, is obtained as a AC impedance related quantity of electricity, and the secondary battery is judged good when both the DC impedance related quantity of electricity and AC impedance related quantity of electricity are a predetermined value or less while the secondary battery is judged inferior when both the DC impedance related quantity of electricity and AC impedance related quantity of electricity are more than a predetermined value.
- a twenty-fifth aspect of the present invention which is a preferred embodiment of the sixteenth aspect of the present invention, is characterized in that by applying an AC voltage of a large number of frequency values within a predetermined frequency band to the secondary battery, the real axis component and imaginary axis component of the impedance of the secondary battery are obtained against each frequency value, and the quantity of electricity which is related to the impedance is calculated from the obtained real axis component and imaginary axis component.
- a twenty-sixth aspect of the present invention which is a preferred embodiment of the twenty-fifth aspect of the present invention, is characterized in that the AC impedance component is calculated based on the diameter of a circular arc-shaped locus of the impedance in a two-dimensional plane of which axes are the real axis component and the imaginary axis component.
- a twenty-seventh aspect of the present invention which is a device for judging the condition of the secondary battery, is characterized in that the device includes an AC voltage applying element for applying AC voltages having a large number of different frequencies to the secondary battery simultaneously or successively, a terminal voltage detecting element for detecting a terminal voltage of the secondary battery against each frequency, a current detecting element for detecting the electric current of the secondary battery against each frequency, an AC impedance component detecting element for detecting the AC impedance component of the secondary battery, which varies with the frequency of the applied AC voltage, based on the detected terminal voltage and electric current, and a discharging performance judging element for judging at least the discharging performance of the secondary battery based on the AC impedance component.
- a twenty-eighth aspect of the present invention which is another device for judging the condition of the secondary battery, is characterized in that the device includes an AC voltage applying element for applying AC voltages having a large number of different frequencies to the secondary battery simultaneously or successively, a terminal voltage detecting element for detecting a terminal voltage of the secondary battery against each frequency, a current detecting element for detecting the electric current of the secondary battery against each frequency, a DC impedance component detecting element for detecting the DC impedance of the secondary battery, which does not vary with the frequency of the applied AC voltage, based on the detected terminal voltage and electric current, and a discharging performance judging element for determining whether the detected DC impedance related quantity of electricity is a predetermined value or less and judging at least the discharging performance of the secondary battery based on the AC impedance component.
- a twenty-ninth aspect of the present invention which is a preferred embodiment of the twenty-eighth aspect, is characterized in that the device further includes an AC impedance component detecting element for detecting the AC impedance component of the secondary battery, which varies with the frequency of the applied AC voltage, based on the detected terminal voltage and electric current, and the discharging performance judging element determines whether the detected DC impedance related quantity of electricity and detected AC impedance related quantity of electricity are respectively predetermined values or less and judges at least the discharging performance of the secondary battery.
- a thirtieth aspect of the present invention which is a preferred embodiment of the twenty-seventh through twenty-ninth aspects, is characterized the device further includes a bias voltage applying element for applying a bias voltage adapted to hold the secondary battery in a slightly discharging condition at the time the terminal voltage and electric current are detected.
- a thirty-first aspect of the present invention which is another method for judging the condition of the secondary battery in accordance with the present invention, is characterized in that a first resistance component mainly composed of an ion conduction resistance of an electrolyte is obtained by a predetermined method as an internal resistance related value which is related to the internal resistance of the secondary battery, and the obtained first resistance component is compared with a previously obtained relation between the first resistance component and battery condition to judge the condition of the secondary battery.
- a thirty-second aspect of the present invention which is still another method for judging the condition of the secondary battery in accordance with the present invention, is characterized in that a second resistance component mainly composed of a reaction resistance of electrodes is obtained by a predetermined method as an internal resistance related value which is related to the internal resistance of the secondary battery, and the obtained second resistance component is compared with a previously obtained relation between the second resistance component and battery condition to judge the condition of the secondary battery.
- a thirty-third aspect of the present invention which is a further method for judging the condition of the secondary battery in accordance with the present invention, is characterized in that a first resistance component mainly composed of a ion conduction resistance of an electrolyte, and a second resistance component mainly composed of a reaction resistance of electrodes are respectively obtained by a predetermined method as the internal resistance related values which are related to the internal resistance of the secondary battery, and both the first and second resistance components are compared with a previously obtained relation between the first and second resistance components and the battery condition to judge the condition of the secondary battery.
- a thirty-fourth aspect of the present invention which is a still further method for judging the condition of the secondary battery in accordance with the present invention, is characterized in that a first resistance component mainly composed of a ion conduction resistance of an electrolyte, and a second resistance component mainly composed of a reaction resistance of electrodes are respectively obtained by a predetermined method as the internal resistance related values which are related to the internal resistance of the secondary battery, and a resistance component ratio showing the ratio of the first resistance component and second resistance component is obtained, and is compared with a previously obtained relation between the resistance component ratio and the battery condition to judge the condition of the secondary battery.
- a thirty-fifth aspect of the present invention which is a preferred embodiment of the thirty-fourth aspect, is characterized in that the resistance component ratio is calculated by the formula of arctan (second resistance component/first resistance component).
- a thirty-sixth aspect of the present invention which is a preferred embodiment of the thirty-third aspect, is characterized in that a degradation judgement standard of the sum of the first resistance component and second resistance component, which is a border value between a normal condition and degraded condition is previously obtained in a reference battery equivalent to the secondary battery, and the sum of the first and second resistance components which are obtained in the secondary battery is compared with the obtained degradation judgement standard to judge whether the secondary battery is in a normal condition or degraded condition.
- a thirty-seventh aspect of the present invention which is a preferred embodiment of the thirty-fourth or thirty-fifth aspect, is characterized in that when the secondary battery is judged to be in a degraded condition, the degraded condition is divided into a first degraded condition which is mainly caused by an increase of an ion conduction resistance, a second degraded condition which is mainly caused by an increase of both the ion conduction resistance and an increase of a reaction resistance, and a third degraded condition which is mainly caused by an excessive increase of the reaction resistance, a first border value as a border value between the first degraded condition and second degraded condition relative to the previously obtained resistance component ratio, and a second border value as a border value between the second degraded condition and third degraded condition relative to the previously obtained resistance component ratio are respectively obtained, the resistance component ratio obtained in the secondary battery is compared with the first border value and second border value to judge whether the secondary battery is in the first degraded condition, second degraded condition or
- a thirty-eighth aspect of the present invention which is a still further method for judging the condition of the secondary battery in accordance with the present invention, is characterized in that a first resistance component mainly composed of an ion conduction resistance of an electrolyte, and a second resistance component mainly composed of a reaction resistance of electrodes are respectively obtained by a predetermined method as the internal resistance related value which is related to the internal resistance of the secondary battery, an internal resistance co-ordinate showing a co-ordinate of the internal resistance of the secondary battery is plotted in a plane co-ordinate of which one axis component is the first resistance component and the other axis component is the second resistance component, and the internal resistance co-ordinate is compared with a previously obtained relation between the internal resistance co-ordinate and battery condition, which has been previously plotted on the plane co-ordinate, to judge the condition of the secondary battery.
- a thirty-ninth aspect of the present invention which is a preferred embodiment of the thirty-eighth aspect, is characterized in that a normal region as a set region of the internal resistance co-ordinate where a reference battery equivalent to the secondary battery is in a normal condition, and a degradation region as a set region of the internal resistance co-ordinate where the reference battery is in a degraded condition, are previously investigated and plotted in the plane co-ordinate, the position of the internal resistance co-ordinate of the secondary battery relative to the normal region and degradation region is investigated to judge whether the secondary battery is in a normal condition or degraded condition.
- a fortieth aspect of the present invention which is a preferred embodiment of the thirty-eighth or thirty-ninth aspect, is characterized in that when the secondary battery is judged to be in a degraded condition, the degraded condition is divided into a first degraded condition which is mainly caused by an increase of an ion conduction resistance, a second degraded condition which is mainly caused by an increase of the ion conduction resistance and a reaction resistance, and a third degraded condition which is mainly caused by an excessive increase of the reaction resistance, a first degradation region as a set region of the internal resistance co-ordinate where a reference battery equivalent to the secondary battery is in the first degraded condition, a second degradation region as a set region of the internal resistance co-ordinate where the reference battery is in a second degraded condition and a third degradation region as a set region of the internal resistance co-ordinate where the reference battery is in a third degraded condition are previously investigated respectively, and plotted in the plane co-ordinate, the
- a forty-first aspect of the present invention which is a preferred embodiment of the thirty-first aspect, is characterized in that after charging or discharging of the secondary battery with a predetermined current is performed for a predetermined period of time, charging or discharging is interrupted, the voltage difference between the terminal voltage measured between the positive electrode terminal and negative electrode terminal at the time charging or discharging is interrupted, and the terminal voltage measured after charging or discharging is interrupted, is obtained, and the first resistance component is obtained based on the obtained voltage difference and predetermined current.
- a forty-second aspect of the present invention which is a preferred embodiment of the forty-first aspect of the present invention, is characterized in that the first resistance component is obtained based on the voltage difference which is obtained in a predetermined period of time when the variation rate of the terminal voltage is a predetermined value or more after charging or discharging is interrupted, along with the predetermined electric current.
- a forty-third aspect of the present invention which is a preferred embodiment of the thirty-second aspect, is characterized in that after charging or discharging with a predetermined current is performed by the secondary battery for a predetermined period of time, charging or discharging is interrupted, the voltage difference between the terminal voltage measured between the positive electrode terminal and negative electrode terminal at the time charging or discharging is interrupted, and the terminal voltage measured after charging or discharging is interrupted, is obtained, and the second resistance component is obtained based on the obtained voltage difference and predetermined electric current.
- a forty-fourth aspect of the present invention which is a preferred embodiment of the forty-third aspect of the present invention, is characterized in that the internal resistance related value is obtained based on the voltage difference which is obtained in a predetermined period of time when the variation rate of the terminal voltage is less than a predetermined rate after charging or discharging is interrupted, along with the predetermined electric current.
- a forty-fifth aspect of the present invention which is a preferred embodiment of the thirty-first aspect of the present invention, is characterized in that by applying AC voltages having a large number of frequency values within a predetermined frequency band to the secondary battery, the real axis component value and imaginary axis component value of the impedance are measured against each frequency value, a circular arc-shaped locus of the impedance is obtained in a plane co-ordinate wherein a real axis and imaginary axis perpendicularly intersect each other with the real axis component value being as the real axis component, and the imaginary axis component value being as the imaginary axis component, and the distance between the intersection of the circular arc-shaped locus and the imaginary axis, and the origin of the plane co-ordinate is obtained, thereby obtaining the first resistance component.
- a forty-sixth aspect of the present invention which is a preferred embodiment of the thirty-second aspect of the present invention, is characterized in that by applying AC voltages having a large number of frequency values within a predetermined frequency band to the secondary battery, the real axis component value and imaginary axis component value of the impedance are measured against each frequency value, a circular arc-shaped locus of the impedance is obtained in a plane co-ordinate wherein a real axis and imaginary axis perpendicularly intersect each other with the real axis component value being as the real axis component, and the imaginary axis component value being as the imaginary axis component, and the diameter of a circular component of the circular arc-shaped locus is obtained, thereby obtaining the second resistance component.
- a forty-seventh aspect of the present invention which is a preferred embodiment of the forty-sixth aspect of the present invention, is characterized in that condition of the secondary battery is judged by comparing the second resistance component of the secondary battery with a previously obtained relation between the second resistance component and the maximum power density.
- a forty-eighth aspect of the present invention which is a still further method for judging the condition of the secondary battery in accordance with the present invention, is characterized in that when the average thickness of an oxidized layer formed on a surface of an active material of a negative electrode of the secondary battery is less than a predetermined standard, the level of the degradation of the negative electrode is judged low, and when the average thickness of the oxidized layer is the predetermined standard or more, the level of the degradation of the negative electrode is judged high.
- a forty-ninth aspect of the present invention which is a preferred embodiment of the forty-eighth aspect of the present invention, is characterized in that the predetermined standard is the average thickness of the oxidized layer, which is measured at the time the discharge capacity of a reference battery equivalent to the secondary battery rapidly decreases or the internal resistance of the reference battery rapidly increases.
- a fiftieth aspect of the present invention which is a preferred embodiment of the forty-ninth aspect of the present invention, is characterized in that the average thickness of the oxidized layer as the standard is 1000 nm.
- a fifty-first aspect of the present invention which is a method for regenerating the secondary battery in accordance with the present invention, is characterized in that when the level of the degradation of the negative electrode is low, electrolyte is only supplied, and when the level of the degradation of the negative electrode is high, a reducing agent is added to the electrolyte.
- a fifty-second aspect of the present invention which is a preferred embodiment of the fifty-first aspect of the present invention, is characterized in that the average thickness of the oxidized layer which is formed on the surface of the active material of the negative electrode is less than a predetermined standard, the level of the degradation of the negative electrode is judged low, and electrolyte is only supplied, and when the average thickness of the oxidized layer is the predetermined standard or more, the level of the degradation of the negative electrode is judged high, and the reducing agent is added to the electrolyte.
- a fifty-third aspect of the present invention which is a preferred embodiment of the fifty-second aspect of the present invention, is characterized in that the predetermined standard is the average thickness of the oxidized layer, which is measured at the time the discharge capacity of a reference battery equivalent to the secondary battery rapidly decreases or the internal resistance of the reference battery rapidly increases.
- a fifty-fourth aspect of the present invention which is a preferred embodiment of the fifty-third aspect of the present invention, is characterized in that the average thickness of the oxidized layer as the standard is 1000 nm.
- a fifty-fifth aspect of the present invention which is another method for regenerating the secondary battery in accordance with the present invention, is characterized in that when the level of the degradation of the negative electrode is low, electrolyte is only supplied, and when the level of the degradation of the negative electrode is high, the negative electrode is taken from a battery container and is subjected to a reducing treatment.
- a fifty-sixth aspect of the present invention which is a preferred embodiment of the fifty-fifth aspect of the present invention, is characterized in that a negative electrode active material is mechanically separated from the negative electrode in a nonoxidized liquid, and is subjected to the reducing treatment.
- a fifty-seventh aspect of the present invention which is a preferred embodiment of one of the fifty-first through fifty-sixth aspect, is characterized in that the secondary battery is a nickel-hydrogen battery including a negative electrode of which a negative electrode active material is a hydrogen-occluding alloy, and an electrolyte interposed between a positive electrode and the negative electrode.
- the secondary battery is a nickel-hydrogen battery including a negative electrode of which a negative electrode active material is a hydrogen-occluding alloy, and an electrolyte interposed between a positive electrode and the negative electrode.
- a fifty-eighth aspect of the present invention which is a preferred embodiment of one of the thirty-first through fiftieth aspect, is characterized in that the condition of the secondary battery is judged with the method of one of the thirty-first through fiftieth aspect, and when the level of the degradation of the negative electrode is judged low, an electrolyte is only supplied, and when the level of the degradation of the negative electrode is judged high, a reducing agent is added to the electrolyte.
- a fifty-ninth aspect of the present invention which is a preferred embodiment of the thirty-seventh or fortieth aspect, is characterized in that the condition of the secondary battery is judged with the method of the thirty-seventh or fortieth aspect, and when the secondary battery is judged to be in the first degraded condition, an electrolyte is only supplied, and when the secondary battery is judged to be in the second degraded condition, a reducing agent is added to the electrolyte.
- a sixtieth aspect of the present invention which is a preferred embodiment of the thirty-seventh or fortieth aspect, is characterized in that the condition of the secondary battery is judged with the method of the thirty-seventh or fortieth aspect, and when the secondary battery is judged to be in the first degraded condition, an electrolyte is only supplied, and when the secondary battery is judged to be in the second degraded condition, the negative electrode is taken from the battery container and is subjected to a reducing treatment.
- a sixty-first aspect of the present invention which is a preferred embodiment of the sixtieth aspect, is characterized in that a negative electrode active material is mechanically separated from the negative electrode in a non oxidized liquid and the negative electrode active material is subjected to the reducing treatment.
- FIG. 1 is a map showing a previously measure relation between an internal resistance co-ordinate of a reference battery of the same kind as a secondary battery, and battery condition thereof;
- FIG. 2 is a curve graph showing the variation of the internal resistance co-ordinate in a plane co-ordinate of FIG. 1 with the increase of the number of using times of the secondary battery;
- FIG. 3 is a graph showing the variation of an electric current of a charging current charged in the secondary battery with time in accordance with the present invention
- FIG. 4 is a graph showing the variation of a voltage of a charging current charged in the secondary battery with time
- FIG. 5 is a graph showing the proportional relation between a first resistance and internal resistance which are respectively obtained when the reference battery of the same kind as the secondary battery 1 is degraded in Embodiment 1;
- FIG. 6 is a graph showing the proportional relation between a second resistance and internal resistance which are respectively obtained when the reference battery of the same kind as the secondary battery 1 is in the initially activated condition in Embodiment 2;
- FIG. 7 is a graph showing the variation of a voltage of a discharging current discharged from the secondary battery with time
- FIG. 8 is a block circuit diagram illustrating a circuit of a judging device and connection of a secondary battery to the judging device in the judging methods 1-1 and 1-2.
- FIG. 9 is a graph showing the variation of an electric current of a pulse-containing current to be supplied from a pulse current source to the secondary battery with time in the judging method 1-1;
- FIG. 10 is a graph showing the variation of a voltage of a pulse current measured by terminal voltage measuring means with time in the judging method 1-1;
- FIG. 11 is a graph showing the variation of a voltage of a pulse current measured by terminal voltage measuring means with time in the judging method 1-2;
- FIG. 12 is a block diagram of a circuit for performance-judgement in accordance with the present invention.
- FIG. 13 is a diagram showing an equivalent circuit of a battery illustrated in FIG. 12;
- FIG. 14 is a vector diagram showing the relation between an AC voltage to be applied to a battery, and an AC current flowing therethrough;
- FIG. 15 is a characteristic line graph showing the variation of the relation between a real axis component and imaginary axis component of an impedance of a battery with frequency;
- FIG. 16 is a characteristic line graph showing the relation between an AC impedance component Zac of a battery and the maximum output density thereof;
- FIG. 17 is a flow chart showing the initial activity judging action in the judging method 2-1;
- FIG. 18 is a block circuit diagram of a battery degradation judging device for mounting on an electromobile, which uses the circuit of FIG. 12;
- FIG. 19 is a schematic plan view of a portable battery degradation judging device which uses the circuit of FIG. 12.
- FIG. 20 is a graph showing recovering of the battery performance due to a reducing treatment of the regenerating method 2, in the battery of which only a negative electrode has been subjected to the reducing treatment, the battery of which both a positive electrode and negative electrode (electrode body) have been subjected to the reducing treatment, and the battery of which only an electrolyte has been supplemented;
- FIG. 21 is a graph showing the effect of the degradation of the negative electrode on the discharging capacity and internal resistance
- FIG. 22 is a graph showing the effect of the amount of a reducing agent on recovering of the battery performance in the reducing treatment of the regeneration method 2;
- FIG. 23 is a graph showing the effect of the treating temperature on recovering of the battery performance in the reducing treatment of the regeneration method 2;
- FIG. 24 is a graph showing the effect of the treating time on recovering of the battery performance in the reducing treatment of the regeneration method 2;
- FIG. 25 is a graph showing the difference in recovering of the battery performance between the case where a negative electrode has been subjected to a reducing treatment and the case where a negative electrode has not been subjected to a reducing treatment when the level of the degradation of the negative electrode is low;
- FIG. 26 is a graph showing the difference in recovering of the battery performance between the case where a negative electrode active material is mechanically separated from a negative electrode in a reducing liquid and the case where a negative electrode active material is mechanically separated from a negative electrode in water;
- FIG. 27 is a schematic diagram illustrating the method for supplementing an electrolyte in a battery, and the means therefor in the regenerating method 1;
- FIG. 28 is a view illustrating a safety valve as one part of the means for supplementing an electrolyte in a battery in the regenerating method 1, and more particularly,
- FIG. 28( a ) is an exploded view thereof
- FIG. 28( b ) is a longitudinal sectional view thereof
- FIG. 29 is a view illustrating a modification of one part of the means for supplementing an electrolyte in a battery in the regenerating method 1, and more particularly,
- FIG. 29( a ) is a view illustrating the state where the battery is used in a normal condition
- FIG. 29( b ) is a view illustrating the state where an electrolyte or that containing a reducing agent is supplemented;
- FIG. 30 is a graph showing the difference in recovering of the battery performance between the case where a negative electrode has been subjected to a reducing treatment and the case where a negative electrode has not been subjected to a reduction treatment when the negative electrode is oxidized to be degraded;
- FIG. 31 is a graph showing the difference in lowering of the battery performance between the case where a positive electrode has been subjected to a reducing treatment and the case where a positive electrode has not been subjected to a reducing treatment;
- FIG. 32 is a view obtained by plotting a first resistance component and second resistance component which are measured by a current interrupter method in embodiments on the map of FIG. 1;
- FIG. 33 is a view obtained by plotting a first resistance component and second resistance component which are measured by an AC impedance method in embodiments on the map of FIG. 1;
- FIG. 34 is an equivalent circuit diagram illustrating the theory of the present invention.
- the first through tenth aspects of the present invention which is the methods for judging the condition of the secondary battery, is characterized in that the method includes the steps of varying the charging current or discharging current of the secondary battery, calculating the quantity of electricity, which is related to the follow-up variation characteristic of the terminal voltage of the secondary battery, relative to the current variation, and judging the condition related to the charging and discharging performance of the secondary battery based on the quantity of electricity.
- the present inventors have conducted various experiments and analysis thereof, and found based thereon that the variation of the charging and discharging performance (especially, the capacity thereof) and, more particularly, the capacity degradation, capacity shortage and high-rate discharging properties can be estimated from the quantity of electricity, which is related to the follow-up variation characteristic of the terminal voltage of the secondary battery, relative to the charging current or discharging current.
- This method enables a real-time judgement, as is fundamentally different from the conventional method of estimating the capacity by charging and discharging the battery actually, and measuring the variation of the terminal voltage, or the like, so as to be used practically.
- the variation of the terminal voltage lags behind that of the charging and discharging current.
- the transit phenomenon circuit theory or AC circuit theory such “lag of the variation of the terminal voltage behind that of the charging and discharging current” reversely means the lead of current over voltage.
- Such quantity of electricity is made equivalent to the circuit including the electrostatic capacity C in the above-described circuit theory, and can be expressed as an impedance element in a step current (current varying stepwise) or AC current circuit.
- Reference character Va denotes a secondary battery having an open voltage of Vo which is a terminal voltage in the case of an internal impedance of a secondary battery to be measured being assumed O
- reference character Z denotes an actual internal impedance of the secondary battery to be measured.
- this internal impedance Z can be roughly expressed by an equivalent circuit including a parallel impedance section composed of a predetermined resistance (also referred to as parallel resistance) Rp and electrostatic capacity (also referred to as parallel electrostatic capacity) C which are connected in parallel, and a series impedance section composed of a series resistance Rs which is connected to the parallel impedance section in series.
- a parallel impedance section composed of a predetermined resistance (also referred to as parallel resistance) Rp and electrostatic capacity (also referred to as parallel electrostatic capacity) C which are connected in parallel
- a series impedance section composed of a series resistance Rs which is connected to the parallel impedance section in series.
- a small parallel electrostatic capacity may be added to the series resistance Rs, and a floating electrostatic capacity may occur against earth, but they are comparatively small so as to be negligible.
- the present inventors' experiments and analyses have revealed that the electrostatic capacity C and parallel resistance Rp are generated in the electrically conductive film and polarization double layer which are formed on the battery electrodes. As the battery degradation proceeds, the thickness of the electrically conductive film increases, and consequently, the parallel resistance Rp increases whereas the electrostatic capacity C decreases.
- the series resistance Rs is generated with the electric resistances of the electrodes and current collectors, and the ion conduction resistance of the electrolyte, or the like, and the parallel resistance which is connected to this series resistance Rs in parallel is small.
- the electric resistances of the electrodes and current collectors are hardly related to the battery degradation while the ion condition resistance of the electrolyte increases as the electrolyte becomes short or dirty.
- the battery degradation caused by the growth of the electrically conductive film can be estimated by the parallel resistance Rp, and the battery degradation caused by the lowering of the ion conduction performance of the electrolyte can be estimated by the series resistance Rs, and these resistances can be separated based on the difference in the equivalent circuit, that one of them is connected to the electrostatic capacity C in parallel whereas the other one is not connected thereto.
- the measurement of the series resistance Rs and parallel resistance Rp in the internal impedance Z of FIG. 34 can be analyzed based on the so-called transit phenomenon theory by applying a step current, obtaining the succeeding variation of the terminal voltage V, and detecting the variation of the difference between the obtained terminal voltage V and the open voltage Vo.
- step current applying method (which is also referred to as current interrupter method) will be explained with reference to FIG. 34.
- reference numeral 100 denotes a constant current source with a built-in switch, and a constant current source variable resistance 105 which is equivalent to a series power source 103 along with an internal impedance 104 of the battery charges the battery with a predetermined constant current by turning on the switch 101 .
- Reference numeral 102 denotes a bias voltage adapted to cancel the open voltage Vo, and has a voltage equal to the open voltage Vo.
- the parallel resistance Rp, electrostatic capacity C and series resistance Rs can be calculated from an AC current I of a predetermined frequency to be added to the internal impedance Z and an AC voltage thereacross.
- the condition of the secondary battery can be judged from the quantity of electricity, which is related to the variation of the terminal voltage at the time the terminal voltage rapidly varies just after the start of the stepwise variation, and the quantity of electricity, which is related to the variation of the terminal voltage at the time the terminal voltage gently varies after varying rapidly.
- condition of the secondary battery can be judged from a first quantity of electricity composed of the variation of the terminal voltage at the time the terminal voltage rapidly varies just after the start of the stepwise variation, and/or a second quantity of electricity composed of the variation of the terminal voltage in a predetermined period of time the terminal voltage gently varies after varying rapidly.
- the electric charge of the electrostatic capacity C mainly flows into the parallel resistance Rp so as to enable an easy and accurate measurement.
- condition of the secondary battery can be judged based on the relation between the AC current component composed of the charging or discharging current which periodically varies with a predetermined frequency, and the AC voltage component having the above frequency, which is included in the terminal voltage.
- the internal impedance of the secondary battery is expressed by a parallel impedance composed of a predetermined parallel resistance and parallel electrostatic capacity, which are respectively connected in parallel, and a series resistance which is connected to this parallel impedance in series
- the condition of the secondary battery can be judged from the quantity of electricity, which is related to the impedance of the parallel impedance or the resistance of the parallel resistance, and the quantity of electricity, which is related to the resistance of the series resistance.
- the level of the degradation of the ion conduction performance of the electrolyte can be estimated by the resistance of the series resistance.
- the increase of the thickness of the film on the surface of the electrode can be estimated by the impedance of the parallel impedance or the resistance of the parallel resistance.
- the present inventors have examined the variation of the terminal voltage to be measured between a positive electrode terminal and negative electrode terminal of a secondary battery at the time the secondary battery is charged and discharged, and at the time after charging and discharging is temporarily interrupted and passing a pulse current in a stable condition with a predetermined charging depth (SOC), and is interrupted (or at the time the current drops and after current drops).
- SOC charging depth
- the terminal voltage rapidly drops (namely, approximately lineally drops) just after charging is interrupted, as illustrated in FIG. 4, and then gently drops with time.
- the quantity of dropped terminal voltage can be divided into a component corresponding to the rapid drop just after the interruption of charging ( ⁇ V 1 ), and a component corresponding to the succeeding gentle drop ( ⁇ V 2 ).
- R 1 ⁇ V 1 /I o 1
- R 2 ⁇ V 2 /I o 2
- the present inventors have prepared two nickel-hydrogen batteries with a predetermined identical standard as secondary batteries such that one of them has a sufficient battery performance such as a high power density while the other one has a decreased battery performance such as a decreased power density due to a large number of repetition of charging and discharging.
- the variation of the terminal voltage of these batteries have been respectively examined by passing charging current to these batteries and interrupting it under identical conditions illustrated in FIG. 3.
- ⁇ V 1 of the battery having a decreased performance has become great, as compared with that of the battery having a sufficient performance.
- This result is considered to be related to the surface of the electrode active material, particularly the surface of the negative electrode active material, being oxidized to increase the ion conduction resistance of the electrolyte in the interface between the electrolyte and electrode active material, or the like.
- the present inventors have prepared another two nickel-hydrogen batteries with a predetermined identical standard as secondary batteries such that one of them remains new while the other one is subjected to charging and discharging under proper conditions to be activated.
- the variation of the terminal voltage of these batteries have been respectively examined by passing a charging current to these batteries and interrupting it under identical conditions illustrated in FIG. 3.
- ⁇ V 2 of the activated battery has become small, as compared with that of the new battery. This result is considered to be related to the decrease of the reaction resistance of the electrodes, which is caused by the activation of the secondary battery.
- R 2 expressed by the equation 2 decreases.
- the present inventors Upon investigating the relation between the internal resistance and R 2 of the activated battery, the present inventors have also found that they are proportional to each other, as illustrated in FIG. 6.
- the voltage rapidly elevates just after discharging is interrupted, and then gently elevates with time. Namely, just after discharging is interrupted, the voltage elevates approximately lineally.
- the quantity of elevated voltage can be divided into a component corresponding to the rapid elevation just after the interruption of discharging ( ⁇ V 3 ), and a component corresponding to the succeeding gentle elevation ( ⁇ V 4 ).
- R 4 ⁇ V 4 /I 1 4
- R 1 through R 4 are respectively obtained based on the terminal voltage difference which are obtained by charging and discharging a secondary battery of which the condition is to be judged with a predetermined electric current for a predetermined period of time, interrupting charging and discharging, and measuring terminal voltages between a positive electrode terminal and negative electrode terminal upon interruption of charging or discharging and after interruption thereof, and the predetermined electric current, and are respectively related to the internal resistance of the secondary battery.
- the present inventors have found that the condition of the secondary battery can be judged by comparing the thus obtained internal resistance related value with a previously obtained relation between the internal resistance related value and battery condition.
- a point where the voltage which has rapidly (approximately lineally) varied, starts to vary gently such as a point where the voltage drop varies from ⁇ V 1 to ⁇ V 2 , and a point where the voltage elevation varies from ⁇ V 3 to ⁇ V 4 , will be referred to as a transition point.
- the variation rate of the voltage difference between the terminal voltage measured between a positive electrode and negative electrode at the time charging or discharging is interrupted, and that after charging or discharging is interrupted varies greatly.
- the degradation of the secondary battery means the condition where a desired battery performance such as a high power density has not been achieved, that is the condition where a battery performance enough for the uses of the secondary battery has not been achieved.
- a desired battery performance such as a high power density
- a battery performance enough for the uses of the secondary battery has not been achieved.
- normal condition when a battery performance enough for the uses of the secondary battery is achieved, such condition of the secondary battery will be referred to as “normal condition”.
- the initial activity includes not only the activity just after the production of the battery but also the activity at the time the battery is activated by charging and discharging. Furthermore, the initial activity also includes the activity of the battery which has been actually used but degradation is sufficiently low.
- the internal resistance related value which is related to the internal resistance of the secondary battery to be judged is obtained.
- the internal resistance related value is a value related to the internal resistance which has a close relation with the battery condition so as to depend on the battery condition.
- the battery performance such as power density decreases with the increase of the internal resistance, and consequently, the internal resistance can be used as an index of the battery condition.
- the internal resistance related value is compared with a previously obtained relation between the internal resistance related value and battery condition, which enables a detailed judgement of the battery condition, as compared with the method of merely obtaining the internal resistance.
- the level of the normal condition depends on the number of using times, that is charging-discharging cycles.
- the initial activity of the secondary battery, and the battery life until the degradated condition after judging the battery condition, that is the level of the normal condition can be judged. Consequently, where a motor device, for example, is driven by a secondary battery as a power source, if the secondary battery is expected to become in a degraded condition during driving after judgement, the secondary battery can be prevented from becoming in a degraded condition while driving the motor device by performing a regeneration treatment, or the like beforehand.
- the terminal voltage quickly varies after charging or discharging is interrupted, to reach an electric potential required to measure the above-described voltage difference in an extremely short period of time. Consequently, the measurement of the electric potential can be performed in a short period of time.
- the measurement of the voltage variation after interruption of charging or discharging can be performed in a much shorter period of time and at lower costs, as compared with the measurement of the variations of both voltage and current.
- the internal resistance related value which is related to the internal resistance of the secondary battery can be obtained quickly based on the voltage difference and the predetermined current by means of a predetermined calculating device. And the internal resistance related value can be obtained at any time regardless of the using condition of the secondary battery. Furthermore, if the internal resistance related value is a value which can be calculated with a simple equation, it can be obtained with ease using a calculating device with a simple construction.
- the internal resistance related value which is related to the internal resistance of the secondary battery can be obtained based on the voltage difference and predetermined current in a short period of time and at low costs.
- the battery condition of the secondary battery can be judged in detail and quickly. And the judgement can be performed at any time with ease.
- the terminal voltage to be measured between the positive electrode terminal and negative electrode terminal at the time the charging or discharging is interrupted may be an open voltage or the above-described standard voltage which corresponds to the open voltage.
- the internal resistance related value is not limited specifically, but the resistance calculated with the formula of (voltage difference/predetermined current) is preferably used.
- This resistance is the ratio of the above-described voltage difference to the above-described predetermined current, which shows the relation thereof dimensionally, and can be obtained with ease by a division calculation.
- the electric current at the time charging or discharging is interrupted is not limited specifically.
- the interrupting timing may be during charging or discharging, or may be at the time charging or discharging is completed.
- the interrupting method is not limited specifically.
- the electric current may be broken in a power source of the battery, or may be interrupted with a switch or the like which is provided between the power source and the secondary battery.
- a constant current which does not vary with time is used as a current for charging. Otherwise, a current which varies with time may be used. For example, by passing a charging current which varies with time, and then interrupting it, a voltage drop curve similar to that shown in FIG. 4 is obtained.
- a pulse current can be used as a current for charging.
- the time the pulse current drops corresponds to the time the current is interrupted.
- the amplitude of the pulse current can be used as the current just prior to current drop.
- the previously obtained relation between the internal resistance related value and the battery condition may be obtained with a reference battery equivalent to the secondary battery.
- the reference battery may be the same kind as the secondary battery, for example.
- the secondary battery to which the device and method of the present invention can be applied is not limited to a special kind. Any well-known secondary battery will do.
- the present invention can be applied to nickel-hydrogen batteries and lithium secondary batteries.
- the variation of the terminal voltage in a period of time the terminal voltage rapidly varies just after interrupting of charging or discharging that is the voltage difference between the terminal voltage at the time charging or discharging is interrupted and that at the transition point can be expressed by the voltage difference obtained in a predetermined period of time the variation rate of the terminal voltage is greater than a predetermined rate after interrupting of charging or discharging.
- this voltage difference increases with the degradation of the secondary battery. Namely, the internal resistance related value which is obtained based on this voltage difference and the current at the time charging or discharging is interrupted has a close relation with the degradation of the secondary battery.
- the degraded condition thereof can be judged in detail. Namely, the level of the degradation of the secondary battery in a degraded condition can be judged in detail.
- the measurement of the variation of the terminal voltage after interrupting of charging or discharging can be performed in a much shorter period of time and at lower costs, as compared with the measurement of the variations of both voltage and current. So, with the present invention, the level of degradation of the secondary battery can be judged in a much shorter period of time and at much lower costs, as compared with the conventional judging method.
- the predetermined value may be the variation rate at the time the approximately lineally variation of the terminal voltage is finished just after interrupting of charging or discharging.
- the formula for calculating the internal resistance related value is not limited specifically, but it is preferable to calculate it using the formula of (voltage difference/predetermined current), as disclosed in the fifth aspect.
- the resistance calculated with this formula will be referred to as a first resistance.
- the voltage difference increases, as described above, and consequently, the first resistance increases. This enables the first resistance to be measured with ease and accuracy. And, as illustrated in FIG. 5, in the degraded battery, the internal resistance thereof and the first resistance are proportional to each other.
- the present invention by comparing the first resistance obtained from the variation of the voltage which varies rapidly just after interrupting of charging or discharging of the secondary battery, and the electric current at the time charging or discharging is interrupted, using the above resistance-calculating formula, with the previously obtained proportional relation between the internal resistance and first resistance, the internal resistance of the secondary battery is estimated, and the level of the degradation of the secondary battery can be judged based on the previously obtained relation between the internal resistance and degraded condition.
- the first resistance can be obtained from the dropped voltage of the terminal voltage of the secondary battery, which drops rapidly, and the amplitude of the pulse current.
- a battery of the same type as the above-described secondary battery, for example, can be used as the reference battery.
- the method for measuring the internal resistance of the degraded reference battery of the same type as the secondary battery is not limited specifically.
- a well-known measuring method will do.
- the internal resistance of the degraded reference battery can be obtained from the inclination of the line I-V.
- it is preferable to measure the internal resistance using batteries of the identical standard.
- the internal resistance of the batteries of another standard may be used as an index.
- the proportional relation between the internal resistance and first resistance may be obtained by previously measuring the internal resistances relative to the first resistances as required, plotting the measured internal resistances on a co-ordinate, and making a line graph, as shown in FIG. 5, or may be obtained as a numerical formula with an approximate calculation such as the minimum second power method, or the like.
- the former method has the advantage that the proportional relation can be obtained with ease whereas the latter method has the advantage that the proportional relation can be obtained in detail.
- the variation of the terminal voltage in a period of time the terminal voltage gently varies just after a rapid variation of the voltage due to the interruption of charging or discharging that is the voltage difference between the terminal voltage at the transition point and that at the time the variation of the terminal voltage becomes negligibly small
- the voltage difference obtained in a predetermined period of time the variation rate of the terminal voltage is less than a predetermined rate after interrupting of charging or discharging As described above, this voltage difference decreases with the activation of a new secondary battery. Namely, the internal resistance related value which is obtained based on this voltage difference and the current at the time charging or discharging is interrupted has a close relation with the initial activity of the secondary battery.
- the initial activity thereof can be judged in detail. Namely, the initial activity of the secondary battery having an initial activity can be judged in detail.
- the measurement of the variation of the terminal voltage after interrupting of charging or discharging can be performed in a much shorter period of time and at lower costs, as compared with the measurement of the variations of both voltage and current. So, with the present invention, the initial activity of the secondary battery can be judged in a much shorter period of time and at much lower costs, as compared with the conventional judging method.
- the predetermined value may be the variation rate at the end of the approximately lineally variation of the terminal voltage just after interrupting of charging or discharging.
- the formula for obtaining the internal resistance related value is not limited specifically, but it is preferable to calculate it using the formula of (voltage difference/predetermined current), as disclosed in the fifteenth aspect.
- the resistance calculated with this formula will be referred to as a second resistance.
- the first resistance is small. This enables the second resistance to be measured with ease and accuracy. And, as illustrated in FIG. 6, in the degraded battery, the internal resistance thereof and the second resistance are proportional to each other.
- the present invention by comparing the second resistance obtained from the variation of the voltage which varies gently just after rapid increase of voltage due to the interruption of charging or discharging and the electric current at the time charging or discharging is interrupted, using the above resistance-calculating formula, with the previously obtained proportional relation between the internal resistance and second resistance, the internal resistance of the secondary battery is estimated, and the initial activity of the secondary battery can be judged based on the previously obtained relation between the internal resistance and initial activity.
- the second resistance can be obtained from the dropping amount of the terminal voltage of the secondary battery, which drops gently, and the amplitude of the pulse current thereof.
- the method for previously measuring the internal resistance and second resistance of the degraded reference battery of the same type as the secondary battery is not limited specifically.
- a well-known measuring method will do. For example, they can be obtained from the inclination of the line I-V. In this case, it is preferable to measure them using batteries of the identical standard.
- the internal resistance of the secondary battery of which the initial activity is to be judged can be estimated accurately with batteries of another standard, the internal resistance of the batteries of another standard may be used as an index.
- the proportional relation between the internal resistance and first resistance may be obtained by previously measuring the internal resistances relative to the second resistances as required, plotting the measured internal resistances on a co-ordinate, and making a line graph, as shown in FIG. 6, or may be obtained as a numerical formula with an approximate calculation such as the minimum second power method or the like.
- the former method has the advantage that the proportional relation can be obtained with ease whereas the latter method has the advantage that it can be obtained in detail.
- the present invention it is preferable to obtain the first resistance, similarly to the twelveth aspect, and the second resistance, similarly to the thirteenth aspect, and compare both the first and second resistances with the previously obtained relations between the first and second resistances and battery conditions, thereby judging the condition of the secondary battery.
- the judgement can be performed from two kinds of resistances, and consequently, the battery condition of the secondary battery can be judged in more detail.
- the ratio of the first resistance to second resistance indicates the mutual relation thereof so that the battery condition of the secondary battery can be judged in more detail.
- the following device can be used as the device for judging the degradation of the secondary battery or the initial activity thereof.
- the device includes a pulse current source for supplying a pulse current to a secondary battery to charge said secondary battery, terminal voltage measuring means for measuring the variation of the terminal voltage of the secondary battery, voltage control means which is connected to the terminal voltage measuring means in series for controlling the voltage to be applied to the terminal voltage measuring means when the voltage equal to the output voltage of the secondary battery is applied, and at least one calculating means out of first calculating means for calculating an internal resistance of the secondary battery by comparing a first resistance which is obtained from the dropping amount of a rapidly dropping voltage of the pulse current, and a current at the time just before the pulse current drops, with a previously obtained proportional relation between the internal resistance and first resistance, and second calculating means for calculating an estimated value of an internal resistance of the secondary battery by comparing a second resistance which is obtained from the dropping amount of a gently dropping voltage of the pulse current just after a rapid drop of the voltage of the pulse current, and a current just before the pulse current drops, with a previously obtained proportional relation between the internal resistance and second resistance.
- this judging device With this judging device, the level of the degradation or initial activity of the secondary battery can be judged by the judging method of the present invention in a shorter period of time and at lower costs, as compared with the conventional judging method. In addition, this judging device can achieve the following advantage.
- an electric current having a voltage greater than the output voltage of the secondary battery must be supplied from a pulse current source. More specifically, the pulse current source must supply a current which has a voltage obtained by combining an output voltage of the secondary battery and the variation (dropping amount) of the terminal voltage, which is adapted to judge the level of degradation or initial activity of the secondary battery.
- the voltage of the pulse current is applied to the circuit including the terminal voltage measuring means and voltage control means, but an output voltage of the secondary battery is applied to the voltage control means so that the terminal voltage measuring means measures the dropping amount of the terminal voltage of the secondary battery. Consequently, the dropping amount of the terminal voltage of the secondary battery can be measured with the terminal voltage measuring means with eases and accuracy.
- the pulse current source supplies a pulse current having a voltage of 12.01 V which is obtained by combining these voltages.
- the voltage of the pulse current may be measured with the terminal voltage measuring means without using the voltage control means. In such case, the voltage must be measured with the measurement range of 10 V order. However, it is difficult to measure the dropping amount of 0.01 V accurately with the measurement range of 10 V.
- the calculating means can estimate the internal resistance of the secondary battery with accuracy. Consequently, at least one of the level of degradation or initial activity of the secondary battery can be judged with accuracy based on the internal resistance accurately estimated.
- the construction (circuit) of the pulse current source is not limited specifically.
- the pulse current source with a well-known construction can be also used.
- the kind of elements of the voltage control means is not limited specifically as far as the same voltage as the output voltage of the secondary battery can be applied thereto.
- a bias DC power source having a DC bias voltage and a resistance element can be used.
- the bias DC power source has an advantage that a great amount of electric current is prevented from flowing in the terminal voltage measuring means.
- the resistance element especially the resistance element having a variable resistance, has an advantage that a fine adjustment of the voltage to be applied to the voltage control means can be performed with ease.
- the construction (circuit) thereof is not limited specifically, as far as the means has a measurement range capable of measuring the dropping amount of the terminal voltage of the secondary battery with accuracy.
- a well-known voltage measuring means can be used.
- a used nickel•hydrogen battery (layer type of 95Ah) is prepared as a secondary battery, and the level of the degradation of the secondary battery is judged using the condition judging device illustrated in FIG. 8.
- the condition judging device illustrated in FIG. 8 includes a pulse current source 12 for supplying a pulse current to a secondary battery 10 to charge the same, terminal voltage measuring means 13 for measuring the dropping amount of the terminal voltage of the secondary battery, voltage control means 14 which is connected to the terminal voltage measuring means 13 in series and to which the voltage equal to the output voltage of the secondary battery 10 is applied, and calculating means 15 for obtaining an estimated value of the internal resistance of the secondary battery 10 .
- the pulse current to be supplied to the secondary battery 10 from the pulse current source 12 has a voltage obtained by combining an output voltage of the secondary battery 10 and the dropping amount of the terminal voltage of the secondary battery 10 , and, as shown in FIG. 9, the current thereof varies into a rectangular shape.
- the voltage control means 14 is provided so as to be connected to the terminal voltage measuring means 13 in series, and is composed of a bias DC power source 14 a adapted to apply a DC bias voltage of which the level is equal to the output voltage of the secondary battery, and a variable resistance element 14 b for finely adjusting the voltage to be applied to the voltage control means 14 into the voltage equal to the output voltage of the secondary battery 10 .
- the strength of the pulse current supplied from the pulse current source 12 is measured just before dropping thereof with an ammeter 16 as the amplitude thereof.
- the calculating means 15 obtains a first resistance from the measurement data of the amplitude of the pulse current and the dropping amount of the terminal voltage of the secondary battery 10 measured with the terminal voltage measuring means 13 , which are totalled in the memory section 17 , and estimates the internal resistance of the secondary battery 10 by comparing the first resistance with the proportional relation of the internal resistance and first resistance, which has been previously examined in a reference battery, and inputted.
- the voltage to be applied to the voltage control means 14 is equalized to the output voltage of the secondary battery 10 , and then a pulse current is supplied to the secondary battery 10 from the pulse current source 12 .
- the measurement data of the amplitude of the pulse current is fed to the memory section 17 at all time and totalled therein.
- the terminal voltage measuring means 13 starts to measure the dropping amount of the terminal voltage of the secondary battery 10 .
- a voltage dropping curve shown in FIG. 10 can be obtained.
- the transition point of the dropping voltage of the terminal voltage can be measured with accuracy.
- short time intervals of 50 ⁇ sec. or less can be adopted.
- the measurement data concerning the dropping amount of the terminal voltage of the secondary battery, which is measured with the terminal voltage measuring means 13 is also fed to the memory section 17 at all time and totalled therein.
- the dropping amount of the voltage which rapidly drops at the time the terminal voltage drops ( ⁇ 1 ) and the amplitude of the pulse current (I o ) are calculated from these measurement data, and the first resistance is calculated from ⁇ 1 and I o .
- the first resistance is compared with the proportional relation of the internal resistance and first resistance, which is shown in FIG. 5, and an estimated value of the internal resistance of the secondary battery 10 is obtained. The level of the degradation of the secondary battery 10 can be judged based on thus obtained estimated value of the internal resistance.
- a new nickel•hydrogen battery (layer type of 95Ah) is prepared as a secondary battery, and the initial activity of the secondary battery is judged, using the condition judging device illustrated in FIG. 8.
- the calculating means capable of obtaining an estimated value of the internal resistance of the secondary battery by calculating the dropping amount of the terminal voltage which gently drops just after a rapid drop of the terminal voltage and the amplitude of the pulse current at that time from the measurement data concerning the amplitude of the pulse current totalled in the memory 17 and the dropping amount of the terminal voltage of the secondary battery 10 , which has been measured by the terminal voltage measuring means 13 , obtaining a second resistance from the calculated dropping amount and pulse current, and comparing the second resistance with the proportional relation of the internal resistance and second resistance, which has been previously examined in a reference battery, and inputted.
- the proportional relation between the internal resistance and second resistance which have been respectively examined when a reference battery (new) of the same type (standard) as that of the secondary battery 10 is initially activated is previously obtained.
- the proportional relation as shown in FIG. 6 can be obtained.
- the voltage to be applied to the voltage control means 14 is equalized to the output voltage of the secondary battery 10 , and then a pulse current is supplied to the secondary battery 10 from the pulse current source 12 .
- the pulse current to be supplied to the secondary battery 10 from the pulse current source 12 has a composite voltage of the output voltage of the secondary battery and the voltage for judgement, which is dropped for judging the initial activity of the secondary battery, and the current varies, similarly to the pulse current shown in FIG. 9.
- the measurement data of the amplitude of the pulse current measured with the ammeter 16 is fed to the memory section 17 at all time and totalled therein.
- the terminal voltage measuring means 13 starts to measure the dropping amount of the terminal voltage of the secondary battery 10 .
- a voltage dropping curve shown in FIG. 11 can be obtained.
- the measurement data concerning the dropping amount of the terminal voltage of the secondary battery, which is measured with the terminal voltage measuring means 13 is also fed to the memory section 17 at all time and totalled therein.
- the dropping amount of the voltage which gently drops at the time the terminal voltage of the secondary battery 10 drops ( ⁇ 2 ) and the amplitude of the pulse current (I o ) are calculated from these measurement data, and the second resistance is calculated from ⁇ 2 and I 0 .
- the second resistance is compared with the proportional relation of the internal resistance and second resistance, which is shown in FIG. 6, and an estimated value of the internal resistance of the secondary battery 10 is obtained. The initial activity of the secondary battery 10 can be judged based on thus obtained estimated value of the internal resistance.
- the method of charging or discharging the secondary battery of which the battery condition is to be judged with a predetermined current in a predetermined period of time, interrupting charging or discharging of the secondary battery, obtaining a voltage difference between the terminal voltage measured between a positive electrode terminal and negative electrode terminal at the time charging or discharging is interrupted, and the terminal voltage measured after interrupting of charging or discharging, and obtaining an internal resistance related value which is related to the internal resistance of the secondary battery based on the obtained voltage difference and the predetermined current, will be referred to as a current interrupter method.
- the performance of the battery is judged based on the quantity of electricity which is related to the impedance or maximum power density (W/kg) obtained by applying an AC voltage to the secondary battery, and consequently, troublesome measuring operations requiring a great-sized equipment, such as charging of the battery in a long period of time and then discharging it, can be omitted, and degradation of the battery due to charging and discharging can be prevented.
- W/kg maximum power density
- this method has an advantage of enabling a quick judgement of the battery condition at a required time.
- the present method is also applicable to the measurement of the battery condition of a primary battery.
- the maximum power density (W/kg) as the discharging performance of the battery is obtained based on the quantity of electricity, which is related to the impedance of the battery, and the performance of the battery is judged based on the maximum power density (W/kg).
- the judgement of the battery performance is performed based on the initial power activity (maximum power density/standard power density) and power degradation (1-(maximum power density/standard power density)) being respectively within a predetermined permissible range or not.
- the maximum power density is a preferable parameter for judging at least the discharging performance of the battery, such as the initial activity and degradation thereof.
- the initial activity and degradation of the battery are judged based on the maximum power density.
- the maximum power density is obtained based on the AC impedance component of the battery. So, the circuit construction and operation become extremely simple, and degradation of the battery caused by the measurement of the maximum power density can be restrained.
- the present inventors have conducted examinations and found that the maximum power density of the battery and the AC impedance thereof (the impedance component of the impedance of the battery, which varies with frequency) have a strong linear mutual relation.
- the present inventors have further found from the above findings that the discharge performance of the battery, such as the initial output activity and output degradation thereof, can be readily judged with the measurement of the AC impedance component of the battery.
- this film can be made equivalent to a dielectric having a leakage resistance, and this dielectric can be made equivalent to a parallel RC circuit in an AC circuit, which includes a reaction resistance composed of a resistance component R varying with the reaction activity, and a capacitor having an electrostatic capacity C determined with the equivalent thickness of the film and dielectric constant thereof.
- the sum of the resistance component (also referred to as AC resistance component) R out of the AC impedance component Zac, and the DC impedance component (also referred to as DC resistance component as the component out of the impedance of the battery, which does not depend on the frequency variation) r can be obtained as the DC internal resistance of the battery from the inclination of the characteristic line which is obtained by plotting the variation of the terminal voltage per unit quantity of discharging due to discharging of the battery on a two-dimensional plane.
- the initial activity of the battery is judged based on the obtained quantity of electricity so that the initial activity can be judged readily.
- the degradation of the battery is judged based on the obtained quantity of electricity so that the level of lowering of the battery performance with time can be known with ease.
- the quantity of electricity includes an AC impedance component which is composed of the component varying with the frequency of an AC voltage, out of the impedance of the battery.
- the AC impedance component of the battery and the maximum power density thereof have a good linear relation with each other so that the performance of the battery, particularly the discharging performance and charging loss can be judged preferably.
- the DC impedance component of the battery corresponds to the resistance of the part which do not depend on the degradation of the battery and the electrochemical charging and discharging reaction resistance, such as the electric resistance of the electrode or the like. So, if this DC impedance component is abnormally great due to inferior welding, or the like, it can be judged that the improvement is impossible even with cycles of initial charging and discharging.
- the level of the initial activity and that of the degradation of the battery can be estimated from the AC impedance component thereof. With this method, the judgement whether the maximum output density is good or not can be performed.
- an AC voltage of a large number of frequencies within a predetermined frequency band is applied to the battery to obtain a real axis component and imaginary axis component of the impedance of the battery against each frequency, and an AC impedance component or DC impedance component as the quantity of electricity is calculated from the real axis component and imaginary axis component.
- the above-described AC impedance component and DC impedance component of the battery can be preferably obtained.
- the power density may be judged based on the real axis component of the AC impedance component of the battery, or the imaginary axis component thereof.
- the AC impedance component is calculated based on the diameter of an arc locus of the impedance on a two-dimensional plane including the real axis component and imaginary axis component as axes thereof.
- the above-described AC impedance component of the battery can be preferably obtained.
- the device for judging the battery performance includes an AC voltage applying element for applying an AC voltage having a large number of different frequencies to a secondary battery sequentially or simultaneously, a terminal voltage detecting element for detecting the terminal voltage of the secondary battery against each frequency, a current detecting element for detecting the quantity of electricity of the secondary battery against each frequency, an AC impedance component detecting element for detecting the AC impedance component composed of the component which varies with the applied AC voltage, out of the impedance of the battery from the detected terminal voltage and electric current, and a performance judging element for judging at least the discharging performance of the battery based on the AC impedance component.
- This arrangement has excellent operational advantage that the judgement of the battery performance can be judged when necessary, and a great discharging of the battery is not required.
- the present judging device is applied to the judgement of the primary battery, the condition thereof can be also judged.
- the device for examining the battery includes an AC voltage applying element for applying an AC voltage having a large number of different frequencies to a secondary battery sequentially or simultaneously, a terminal voltage detecting element for detecting the terminal voltage of the secondary battery against each frequency, a current detecting element for detecting the quantity of electricity of the secondary battery against each frequency, a DC impedance component detecting element for detecting the DC impedance component r composed of the component which varies with the applied AC voltage, out of the impedance of the battery from the detected terminal voltage and electric current, and a performance judging element for judging at least the discharging performance of the battery based on the DC impedance component.
- This arrangement has excellent operational advantages that the performance of the battery, such as the welding resistance of the electrode, can be readily judged, and a great amount of discharging of the battery is not required.
- the present judging device is applied to the judgement of the primary battery, the condition thereof can be also judged.
- the device as disclosed in the twenty-eighth aspect further includes the arrangement disclosed in the twenty-seventh aspect, and consequently, the performance can be judged based on both the impedance components with a single measurement.
- a bias power source is added to the measurement circuit in the direction in which the discharge current of the battery reduces so that the measurement in a small amount of discharging can be performed, thereby reducing the measurement error.
- FIG. 12 is a block circuit diagram of the device for judging the initial activity of a nickel•hydrogen alloy battery in accordance with the present invention.
- Reference numeral 21 denotes a battery
- 22 denotes an ammeter
- 23 denotes an AC power source of which frequency is variable
- 24 denotes a bias DC power source
- 25 denotes a resistance for limiting current
- 26 denotes a controller.
- one single battery is used as the battery 21 .
- a battery module composed of a plurality of single batteries which are connected in series may be used. It is preferable to charge the battery 21 until 20 to 80% of full charge capacity before judgement thereof.
- a bias DC power source is used for reducing the DC current. Alternatively, this bias DC power source may be omitted. It is preferable to measure in a discharging mode of the battery 1 , wherein the open voltage of the battery is greater than the sum of the bias voltage and the maximum voltage of the AC power source.
- the battery in a slightly discharged condition is used.
- the open voltage of the battery 1 is 1.2V
- the amplitude of the applied AC voltage is 0.2 V
- the bias voltage is set to about 1V. This results in error and noise in the measured value which is caused by an excess charging and discharging current being able to be avoided.
- FIG. 13 is a diagram showing a circuit equivalent to the battery 21 in a charged condition to which an AC voltage is applied.
- the AC impedance component Zac is equivalent to a parallel circuit composed of a resistance R and capacitor C.
- the initial activation treatment wherein the battery prior to used is subjected to the repetition of charging and discharging cycles, can be regarded as the process of breaking down one kind of dielectric (insulator) film having a small leakage resistance R. too, and the initial activity can be estimated from this AC impedance component Zac.
- Zreal shows a real axis component of the impedance Z of the battery 21 and jZim shows the imaginary axis component of the impedance Z.
- Zac ( R /(1+ ⁇ 2 C 2 R 2 ))+ j ( ⁇ CR 2 /(1+ ⁇ 2 R 2 R 2 ))
- the maximum power density may be estimated using not the AC impedance component Zac but the AC resistance component R.
- Zreal shows a real axis component of the impedance Z of the battery 21 and jZim shows the imaginary axis component of the impedance Z.
- the diameter of an approximately arc-shaped part Mc of this complex impedance line M is obtained by an approximation method as the AC impedance component Zac of this battery 21 (S 16 ).
- the obtained AC impedance component Zac is examined whether it is less than a predetermined threshold Zacth or not (S 18 ), and if less than the predetermined threshold Zacth, the judgement that the initial activity is sufficient is made, and a signal indicating this judgement is outputted (S 20 ), or if greater than the predetermined threshold Zacth, the judgement that the initial activity is insufficient is made, and a signal indicating this judgement is outputted (S 22 ).
- the accurate initial activity can be judged with a compact device in a short period of time so as to have a great practical advantage. And the continuation or finishing of the charging and discharging cycles for the initial activation treatment can be also judged based on the judgment results, and consequently, power can be saved, and the productivity can be improved.
- the above-described judging method was applied to the judgement of the initial activity of the battery.
- This method can be also applied to the judgement of the battery life by merely changing the threshed Zacth of the AC impedance component Zac, and furthermore, the present level of degradation of the battery can be detected at all time by previously memorizing the relation between the battery degradation and AC impedance component Zav on a map, and substituting the calculated AC impedance component Zac into this map.
- the above-described judging method was applied to the judgement of the charging and discharging performance of the battery 21 based on the AC impedance component Zac of the battery. It is clear that the charging and discharging performance of the battery 21 may be judged using the real axis component Zacreal of the AC impedance component Zac or the imaginary axis component Zacim thereof, preferably the real axis component Zacreal.
- the judgement of the charging and discharging performance of the battery 21 may be made from the quantity of electricity related to the maximum power density (W/kg) of the battery 21 , which is obtained by another method.
- This device is assembled in an electric vehicle, and, by request, the calculation results thereof are displayed on a display panel provided near a driver s seat and monitored by a car control device.
- Reference numeral 20 denotes a combination battery. This combination battery is composed of a large number of battery modules (only 20 ( i ), 20 ( i+ 1), 20 ( i+ 2) are illustrated) which are connected in series. Each battery module is composed of ten single batteries, for example, which are connected in series, and both ends of the combination battery 20 and connecting points of the battery modules are connected to a controller (not shown) for use in the combination battery via monitor cables L 1 through Ln for monitoring the voltage of the battery module.
- Reference numeral 27 denotes an analogue switch network which connects adjacent two out of the monitor cables L 1 through Ln to the charging and discharging performance judging circuit ( 21 through 26 in FIG. 12).
- This device 30 is used for judgement of the degradation of the combination battery in a service station or the like.
- a circuit illustrated in FIG. 12 is provided within a casing 31 , and a liquid crystal panel 32 for displaying the level of the degradation, and a switch 33 for changing over the bias voltage are provided on a surface of the casing 31 . It is also possible to detect the input voltage, and automatically change over the bias voltage in accordance with the detected input voltage such that the current becomes less than a predetermined current.
- Reference numeral 34 denotes a pair of input cables.
- a detection terminal rod 35 is provided at an end of each input cable 34 .
- the quality of an electric circuit within a battery can be judged based on the DC impedance component r of the battery using the method explained in the method 2-1.
- the battery check can be performed electrically with ease and accuracy.
- the flow chart shown in FIG. 17 in the method 2-1 can be performed in each charging and discharging cycle for initial activation. If the judgement in S 18 is not yes even with a predetermined threshold number of charging and discharging cycles for initial activation, a signal indicating that the AC impedance component is excessively bad may be outputted to finish this routine.
- the battery check can be performed electrically with ease and high accuracy.
- the initial activity and degradation of the secondary battery are judged and the check thereof are performed. These methods can be also applied to the primary battery. In this case, the operational advantage that the degradation of the primary battery due to the discharge loss and discharging thereof can be restrained.
- the AC voltage applying element in order to effect the arrangement of “measuring the terminal voltage across a battery by passing an AC current to the battery”, as disclosed above, “the AC voltage applying element” is used.
- the AC voltage applying element is “the AC power source of which the frequency is variable”.
- the above-described “AC voltage applying element of which the frequency is variable” includes “the load of which the internal impedance periodically varies with a predetermined frequency”.
- a three-terminal switch of which the resistance varies according to the sinusoidal function to change the control voltage, such as a transistor can be used as “a load of which the internal impedance periodically varies with a predetermined frequency”.
- the method of applying an AC voltage to a secondary battery, and detecting the quantity of electricity, which is related to the impedance of the secondary battery or related to the maximum power density will be referred to as an AC impedance method.
- the internal resistance of the secondary battery is generated due to various factors. Especially great factors are the ion conduction resistance of the electrolyte, and the reaction resistance of the electrodes.
- the present inventors have found that the degradation of the secondary battery includes three kinds of degradation modes (first, second and third degraded condition) which differs from each other in the manner of increasing of the resistance, as follows.
- the first resistance component is mainly composed of the ion conduction resistance of electrolyte so as to be as an ion conduction parameter.
- This increase of the first resistance component is mainly caused by drying of electrolyte. Accordingly, by supplementing the electrolyte to a battery, the battery performance can be recovered.
- both the first resistance component and second resistance component increase to degrade the battery.
- the second resistance component is mainly composed of an reaction resistance of electrodes, and consequently, serves as an electrochemically reactive parameter of the electrodes.
- an electrolyte is dried up in the initial degraded condition.
- the surface of the negative electrode (negative electrode active material) is oxidized to increase the reaction resistance of the electrodes. In this case, it is insufficient to supplement the electrolyte to the battery. It is necessary to activate the negative electrode again by removing an oxide on the surface thereof, thereby reducing the reaction resistance thereof.
- the present inventors have performed charging and discharging of a secondary battery of which the battery condition is to be judged with a predetermined current in a predetermined period of time, and interrupted charging and discharging thereof.
- a voltage difference between the terminal voltage measured between a positive electrode terminal and negative electrode terminal at the time charging or discharging is interrupted, and the terminal voltage measured after interruption of charging or discharging, is obtained, and a first resistance and second resistance are respectively obtained based on the obtained voltage difference and the predetermined current as the internal resistance related values, which are related to the internal resistance of the secondary battery.
- the first resistance corresponds to a first resistance component mainly composed of the ion conduction resistance of the electrolyte
- the second resistance corresponds to a second resistance component mainly composed of the reaction resistance of the electrodes.
- the present inventors have found that the first and second resistance components can be obtained with a predetermined method such as a current interrupter method and AC impedance method as the internal resistance related values which are respectively related to the internal resistance of the secondary battery of which the battery condition is to be judged.
- a predetermined method such as a current interrupter method and AC impedance method
- the first resistance component and second resistance component respectively have a predetermined relation with the battery condition.
- the resistance component ratio which is calculated by the formula of arctan (second resistance component/first resistance component), of which the value calculated by this formula being an angle of a right triangle between one adjacent side composed of the first resistance component r 1 and the hypotenuse composed of the second resistance component r 2 has a predetermined relation with the battery condition.
- the present inventors have found that by obtaining the first resistance component, second resistance component and the resistance component rate which are the internal resistance related values respectively related to the internal resistance of the secondary battery of which the battery condition is to be judged with a predetermined method, the battery condition of the secondary battery can be judged based on the comparison of at least one of these values with the previously obtained relation with the battery condition.
- the first resistance component is mainly composed of the ion conduction resistance of electrolyte so as to have a close relationship with the condition of the electrolyte.
- the second resistance component is mainly composed of the reaction resistance of the electrodes so as to have a close relation with the condition of the electrodes.
- condition judging method of the secondary battery which is disclosed in one of the twenty-first through twenty-fifty aspects, the condition of the electrodes, electrolyte or the like can be judged in detail based on the magnitude of each of the first resistance component and second resistance component, and the ratio thereof. This results in the detailed judgement whether the secondary battery is in a normal condition or degraded condition becoming possible. Especially, when the secondary battery is in a degraded condition, the level and reason of the degradation can be judged in detail.
- the battery condition of the secondary battery can be judged as follows, for example.
- the degradation judging standard value as the border value of the sum of the first resistance component and second resistance component of the reference battery which is equivalent to the secondary battery 21 between a normal condition and a degraded condition is previously obtained. If the sum of the first resistance component and second resistance component of the secondary battery is less than the degradation judging standard value, the secondary battery is judged to be in a normal condition. And if the sum is greater than the degradation judging standard value, the secondary battery is judged to be in a degraded condition. Therefore, by merely calculating the sum of the first resistance component and second resistance component, it can be judged whether the secondary battery is in a normal condition or degraded condition.
- the degradation judging standard value also depends on the usage and using condition of the battery as well as the kind of the battery.
- the secondary battery is judged to be in a normal condition upon calculating the sum of the first resistance component and second resistance component, at least one of measured values of r 1 , r 2 and ⁇ of the secondary battery is compared with the above-described normal relation. This method facilitates the judgement of the normal condition in detail.
- the secondary battery is judged to be in a degraded condition based on the sum of the first resistance component and second resistance component, at least one of measured values of r 1 , r 2 and ⁇ of the secondary battery is compared with the degraded relation. This method facilitates the judgement of the degraded condition in detail.
- the battery condition is previously judged from the internal resistance, and the first resistance component or second resistance component are measured after estimating an important measured value of the first or second resistance component based on the judged battery condition.
- This method facilitates a more accurate judgment of the battery condition. This results in the battery condition of the secondary battery being able to be judged more accurately and more quickly.
- the battery condition can be judged with the degraded condition further divided into these degradation modes.
- this condition judging method facilitates the detailed judgement of the degraded condition of the secondary battery. Especially, by using this condition judging method after judging whether the secondary battery is in a normal condition or degraded condition with the above-described condition judging method, the detailed judgement of the degraded condition can be efficiently made.
- the first border value and second border value vary with the design or the like of the battery.
- the present condition judging method enables a detailed judgement of the degraded condition of the secondary battery in a short period of time and at low costs.
- the secondary battery can be subjected to a proper regenerating treatment in accordance with the degraded condition thereof.
- the battery can be used over a long period of time. Accordingly, the costs required for changing an old battery which becomes impossible to be used to a new one can be saved.
- the present inventors have obtained a first resistance component mainly composed of an ion conduction resistance of an electrolyte, and a second resistance component composed of a reaction resistance of electrodes as the internal resistance related values which are related to the internal resistance of a reference battery equivalent to the secondary battery (another secondary battery of the same type as the secondary battery, for example), plotted the internal resistance values on a plane co-ordinate of which X axis and Y axis intersect perpendicularly with the first resistance component as one axis component (X component) and the second resistance component as another axis component (Y component), and investigated the battery condition of the secondary battery in detail.
- the co-ordinate plane can be divided into a normal region as a set region of the internal resistance co-ordinates of the reference battery in a normal condition, and degraded regions as set regions of the internal resistance co-ordinates of the reference battery in a degraded condition.
- the degraded regions on the plane co-ordinate can be divided into a first degraded region which is a set region in the first degraded condition, second degraded region which is a set region in the second degraded condition, and third degraded region which is a set region in the third degraded condition.
- the part A of the curve corresponds to the part where the battery condition varies due to the activation of the battery, which is caused by the initial charging and discharging, and consequently the internal resistance co-ordinate varies. With this initial activation, the oxidized film which has existed on the surface of the negative electrode active material is removed, and consequently the second resistance component decreases.
- the present inventors have found that by obtaining the internal resistance co-ordinate of a reference battery which is equivalent to the secondary battery, and the relation between the obtained internal resistance co-ordinate and battery condition, and comparing the internal resistance co-ordinate of the secondary battery with the obtained relation, the condition of the secondary battery can be judged.
- the plane co-ordinate is not limited to that where the X axis and Y axis intersect perpendicularly, as disclosed above. Since the plane co-ordinate wherein X and Y axes intersect perpendicularly is easiest to see, thereby facilitating the judgement of the battery condition.
- the method for obtaining at least one of the first resistance component and second resistance component is not limited specifically. It is preferable to use the method disclosed in one of the forty-first through forty-seventh aspects.
- the condition of each of the electrodes and electrolyte can be judged in detail and quickly, and consequently the judgement whether the secondary battery is in a normal condition or degraded condition can be made quickly and in detail.
- the level of degradation or the reason for degradation can be judged in detail and quickly. And the judgement can be made with ease at any time as required.
- the AC impedance method requires an external power source, and consequently it is difficult to judge the battery condition during driving of a vehicle by mounting the judgement algorithm, for example, thereon.
- the judgement algorithm for example, thereon.
- the battery condition can be judged accurately.
- the power density of the secondary battery is an especially important battery performance. This power density greatly depends on the battery condition. As the battery is degraded, the power density decreases. Namely, the battery condition and power density have an extremely close relation with each other. As described above, the parameter of the maximum power density is an especially preferable parameter for use in the judgement of at least the discharging performance such as the initial activity and degradation. Accordingly, with the above-described forty-eighth aspect, the battery condition can be judged based on the power density in detail.
- the present inventors have found that the lowering of the battery performance in a nickel-hydrogen battery provided with a negative electrode wherein a hydrogen-occluding alloy is used as a negative electrode active material is mainly caused by drying up of the electrolyte, and degradation of the negative electrode due to oxidization thereof.
- the present inventors have further studied the process of lowering of the battery performance, and have found the following points.
- the negative electrode is pulverized due to the discharging reaction, and at the same time, the positive electrode is swelled to decrease the amount of the electrolyte, thereby lowering the battery capacity and increasing the internal resistance.
- the number of charging and discharging cycles is small, the variation of the battery capacity and internal resistance is small, but as the number of charging and discharging cycles increases, the battery capacity remarkably lowers and the internal resistance remarkably increases. The reason therefor is considered as follows.
- the performance of the oxidized and degraded negative electrode can be recovered by a reducing treatment using a reducing agent.
- a reducing treatment is shown in FIG. 30.
- a hydrogen-occluding alloy (MmNi 5-x-y-z Al x Mn y Co z (Mm:mishmetal)) was used as the negative electrode active material of a nickel-hydrogen battery, and an aqueous solution mainly composed of potassium hydroxide was used as the electrolyte thereof.
- the negative electrode was oxidized.
- the negative electrode thus oxidized and degraded was subjected to the reducing treatment by immersing the negative electrode in the electrolyte containing a predetermined density of reducing agent in a predetermined period of time.
- Sodium hypophosphite was used as the reducing agent.
- the remaining negative electrode was immersed in an electrolyte containing no reducing agent, and the potential thereof was measured similarly.
- FIG. 30 shows that the absolute value of the potential of the negative electrode which was immersed in the electrolyte containing the reducing agent is greater than that of the negative electrode which was immersed in the electrolyte containing no reducing agent, and consequently the negative electrode immersed in the electrolyte containing the reducing agent is activated so that the performance thereof is recovered. This is considered to be caused by the oxide on the surface of the negative electrode being reduced with the reducing agent.
- the reducing treatment was performed by immersing a positive electrode of which the active material is nickel hydroxide in the electrolyte containing a predetermined concentration of reducing agent in a predetermined period of time.
- aqueous solution mainly composed of potassium hydroxide was used as the electrolyte, and sodium hypophosphite was used as the reducing agent.
- FIG. 31 shows the variation of the potential of each positive electrode with the immersing time thereof.
- the potential of the positive electrode which was immersed in the electrolyte containing the reducing agent is less than that of the positive electrode which was immersed in the electrolyte containing no reducing agent, and consequently the positive electrode immersed in the electrolyte containing the reducing agent is made inactive so that the performance thereof lowers. This is considered to be caused by the decrease in the number of Ni valance in the positive electrode active material (self discharging).
- the kind of the secondary battery to which the present invention can be applied is not limited specifically.
- the present invention can be applied to a nickel-hydrogen battery, for example.
- the nickel-hydrogen battery provided with a negative electrode of which an active material is a hydrogen-occluding alloy, and an electrolyte which is interposed between a positive electrode and the negative electrode (which is disclosed in forty-seventh aspect) is most suitable.
- the present regenerating method is applied to the nickel-hydrogen battery provided with a negative electrode of which an active material is a hydrogen-occluding alloy, and an electrolyte which is interposed between a positive electrode and the negative electrode, in the case of the degradation level of the negative electrode being low, the electrolyte is only supplemented, and in the case of the degradation level thereof being high, a reducing agent is added to the electrolyte, thereby regenerating the battery.
- the reducing agent is added to the electrolyte so that recovering of the battery performance due to the recover of the performance of the negative electrode increases much more, as compared with lowering of the battery performance due to the decrease of the performance of the positive electrode, thereby recovering the battery performance. Consequently, the battery performance can be readily recovered by an extremely simple method of adding a reducing agent to the electrolyte without changing a degraded negative electrode to a new one.
- the present invention As described above, with the present invention, the lowering battery performance of the nickel-hydrogen battery can be recovered with ease.
- the present invention can be applied to another nickel-hydrogen battery having the following arrangement.
- the active material of the positive electrode is not limited specifically. Any well known active material for the positive electrode may be used. For example, nickel hydroxide can be used as the active material for the positive electrode. And cobalt oxide adapted to improve the using rate of the active material may be used additionally.
- a hydrogen-occluding alloy is used as the active material of the negative electrode.
- the kind of the hydrogen-occluding alloy is not limited specifically. Any well-known hydrogen-occluding alloy will do. For example, MmNi 5-x-y-z Al x Mn y Co z may be used.
- Each of the positive electrode and negative electrode may be the electrode prepared by applying a powdery electrode active material containing a tackiness agent or the like to a surface of a collector thereof, that is the electrode prepared by forming an electrode active material layer containing an electrode active material on the surface of the collector thereof.
- the configuration and arrangement of the positive electrode and negative electrode are not limited specifically. Various configurations and arrangements will do. For example, a flat positive electrode plate and flat negative electrode plate are arranged so as to be opposed to each other, flat positive electrode plates and flat negative electrode plates are layered on each other, a cylindrical positive electrode and cylindrical negative electrode having different diameters are alternately arranged coaxially, and a band-shaped positive electrode plate and a band-shaped negative electrode plate are piled on each other and wound on a central axis (will be referred to as “wound type”). A separator may be interposed between the positive electrode and negative electrode.
- the kind of the electrolyte is not limited specifically, and any well-known electrolyte may be used.
- an alkali aqueous solution such as an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide and a mixture aqueous solution of potassium hydroxide and sodium hydroxide will do.
- the degradation level due to the oxidization of the negative electrode is examined.
- the method for examining the degradation level is not limited specifically.
- the electrolyte is only supplemented.
- the method and means for supplementing the electrolyte are not limited specifically.
- the electrolyte can be supplemented by the method and means illustrated in FIG. 27. This example will be explained in detail with reference to the later-described condition judging method. Openings 40 a and 40 b are respectively provided in an upper part and lower part of a battery casing, and gas within the battery casing is sucked out via one opening 40 a while electrolyte is sucked into the battery casing via another opening 40 b , thereby supplementing the electrolyte.
- the positions of the openings provided in the battery casing are not limited to those in FIG. 27.
- a cylindrical battery (such as a wound type battery) is schematically illustrated. The battery is not limited to this type. Similar method can be applied to the layered type battery.
- a reducing agent is added to the electrolyte.
- Sodium hypophosphite, sodium borohydride, hydrazine or the like can be used as the reducing agent. Examples of the method for adding the reducing agent are as follows.
- One example is the method of directly adding the reducing agent to the electrolyte. This method is effective when there is a sufficient quantity of electrolyte within the battery so as not to require any supplement of electrolyte. With this method, after adding the reducing agent to the electrolyte, the reducing agent is dissolved in the electrolyte by a proper method. In the case of the reducing agent being the material which dissolves quickly in the electrolyte, the required operation is extremely easy. So, this method is a most effective method.
- Another example is the method of preparing an electrolyte containing a reducing agent, and supplementing the prepared electrolyte to the electrolyte within the battery.
- This method is effective when the electrolyte is dried up with the degradation of the negative electrode, and the supplement of electrolyte is needed.
- this method is also effective when the reducing agent is the material which is difficult to dissolve in the electrolyte only with the addition of the reducing agent thereto.
- the electrolyte containing the reducing agent is added to the electrolyte within the battery.
- the method for supplementing the electrolyte containing the reducing agent to the electrolyte within the battery is not limited specifically.
- the supplement of the electrolyte can be performed with the method and means illustrated in FIG. 27.
- the amount of the reducing agent is not limited specifically. But, if the amount is too small, the oxidized and degraded negative electrode cannot be reduced sufficiently. Furthermore, as shown in FIGS. 30 and 31, as the amount of the reducing agent increases, the reduction of the negative electrode is efficiently performed, but at the same time, the reduction of the positive electrode is promoted. Consequently, if the amount of the reducing agent is too great, the degraded negative electrode can be sufficiently reduced, but excess reducing agent reduces the positive electrode. And if the amount of the excess reducing agent is great, a hydrogen gas is generated and the internal pressure of the battery may increase.
- the amount of the reducing agent is properly selected. At this time, it is preferable to add the reducing agent which is enough for reducing the negative electrode sufficiently in accordance with the degradation level thereof. By limiting the amount of the reducing agent in this manner, an excess reducing agent can be prevented from existing in the electrolyte.
- the negative electrode can be reduced speedily, as compared with the positive electrode.
- the amount of the reducing agent is not limited specifically.
- the reducing agent enough for reducing the negative electrode sufficiently in accordance with the degradation level of the negative electrode.
- the electrolyte may be changed to a new one just when the negative electrode is sufficiently reduced before reducing the negative electrode.
- the electrolyte As described above, after the reducing agent is added to the electrolyte, and the negative electrode is reduced thereby, a reaction product due to the reduction remains in the negative electrode or electrolyte. If this reaction product is the material which has bad effects on the battery performance, the electrolyte is changed to new one, and removed. When the electrolyte is changed, the reaction product which has been attached to the surface of the negative electrode and cannot be removed therefrom with ease can be removed by washing away it with a proper cleaning liquid.
- the kind of the cleaning liquid is not limited specifically. It is preferable to use the electrolyte or a solvent thereof as the cleaning liquid.
- the wound type nickel-hydrogen battery including a positive electrode of which an active material was nickel hydroxide, a negative electrode of which an active material was a hydrogen-occluding alloy (MmNi 5-x-y-z Al x Mn y Co z ) and an electrolyte composed of potassium hydroxide was regenerated, as follows, by the regenerating method in accordance with the present invention.
- This battery was prepared by the following method.
- powdery nickel hydroxide was prepared as the positive electrode active material, and this positive electrode active material was applied on a belt-shaped foamed metal substrata using a proper adhesive, and pressed thereon, thereby forming a positive electrode plate.
- a powdery hydrogen-occluding alloy (MmNi 5-x-y-z Al x Mn y Co z ) was prepared as the negative electrode active material, and this negative electrode active material was applied on a belt-shaped foamed metal substrata using a proper adhesive, and pressed thereon, similarly to the case of the positive electrode, thereby forming a negative electrode plate.
- These positive electrode plate and negative electrode plate are wound with a separator interposed therebetween to form an electrode body. This electrode body and electrolyte are accommodated in a battery casing which can be readily dismantled and assembled, thus obtaining a battery.
- the wound type battery thus prepared was subjected to a predetermined number of charging and discharging cycles under predetermined charging and discharging conditions. Then, the electrode body was taken from this wound type battery and cut into a proper size to prepare a layered battery for confirmation.
- This layered battery was subjected to one of the following operations in accordance with the level of the degradation of the negative electrode, and predetermined battery performance was examined. As a result, the battery performance was confirmed to be recovered with the following operations.
- FIG. 27 When the level of the degradation of the negative electrode is low, the electrolyte was supplemented by the method and means illustrated in FIG. 27. As illustrated in FIG. 27, an inlet pipe 42 connected to a suction pump is connected to an opening 40 a adapted to discharge a gas or electrolyte from a battery. As illustrated in FIG. 28, an opening of a safety valve 100 which can be arbitrarily detached from the battery casing can be used as the opening 40 a.
- This safety valve 100 includes a cylindrical base part 110 which extends integrally from the battery casing so as to be interconnected with an opening 40 c , a rubber body (EPDM rubber) 112 which is accommodated within the base part 110 , and a cap 114 for closing an opening of the base part 110 . Screw threads are formed on each of an outer peripheral surface of the base part 110 and an inner surface of the cap for fitting them firmly in each other.
- the base part 110 and cap 114 are respectively provided with gas outlet ports 110 a and 114 a .
- O rings may be provided in predetermined positions between the base part 110 and cap 114 as sealing members.
- a safety valve 200 illustrated in FIG. 29 may be used.
- one part of the inlet pipe 42 (a built-in inlet pipe 42 a ) is provided beforehand, and a predetermined number of outlet ports 10 b , each having a predetermined size, are provided in predetermined positions of the base part 110 .
- the cap 114 By turning the cap 114 , the connection of the gas outlet port 114 a with the gas outlet ports 110 a and 110 b can be arbitrarily changed.
- the gas outlet port 114 a is previously interconnected with the gas outlet port 110 a while the outlet port 110 b of the base part 110 is closed with the cap 114 .
- the cap 114 is turned to interconnect the gas outlet port 114 a with the gas outlet prt 110 b .
- the inlet pipe 42 a is connected to the gas outlet port 114 a of the cap 114 .
- the opening 40 b adapted to introduce the electrolyte is immersed in a separately prepared electrolyte (vessel A).
- a gas within the battery is sucked by the suction pump via the opening 40 a , the electrolyte is sucked up via the opening 40 b so that the battery is charged with the electrolyte.
- an electrolyte containing a reducing agent was supplemented into the battery by the method and means illustrated in FIG. 27.
- An opening 40 a of the battery can be provided using the safety valve 100 illustrated in FIG. 28 or the safety valve 200 illustrated in FIG. 29.
- An electrolyte in which sodium hypophosphite was dissolved with a predetermined concentration was separately prepared (vessel B), and an inlet 10 b of the battery was immersed in the reducing agent-containing electrolyte within the vessel B.
- the electrolyte within the vessel A may be replaced with the reducing agent-containing electrolyte, instead of preparing of the vessel B, or the reducing agent may be dissolved in the electrolyte within the vessel A.
- the reducing agent-containing electrolyte within the vessel B was supplemented into the battery by operating the suction pump, as disclosed above.
- the opening 40 b of the battery was immersed in the electrolyte within the vessel A, and, as described above, the suction pump was operated to feed the electrolyte into the battery so that productions caused by the reduction were washed out. Then, the interior of the battery was charged with an electrolyte.
- the present inventors have also studied the effects of the degradation of the negative electrode on the battery performance. As a result, they have found that when an oxide having an average thickness of 1000 nm is formed on an active material layer of the negative electrode, the battery capacity rapidly decreases and the internal resistance rapidly increases. One example of this finding is shown in FIG. 21.
- FIG. 21 shows the result of the measurement of the thickness of the oxide layer formed on the active material of the negative electrode of the nickel-hydrogen battery identical to that used in the regenerating method 1, which was subjected to the repetition of charging and discharging cycles under predetermined charging and discharging conditions, along with variations of the battery capacity and internal resistance with respect to the thickness of the oxide layer.
- the thickness of the oxide layer of the active material of the negative electrode was measured with the Auger electron spectroscopic method.
- the battery capacity was measured by the following method.
- the battery was charged in an atmosphere of 25° C. with a current of 1/5C to the charging depth (SOC) of 110%, and discharged with a current of 1/5C to the voltage of 1V. These charging and discharging operations were repeated twice, and the battery capacity was measured. The time interval between the first and second operations was set to 30 minutes.
- the internal resistance was measured by the following method.
- the charging and discharging operation of charging in an atmosphere of 25° C. with a current of 1/5C to the charging depth (SOC) of 60%, and discharging with a predetermined current was repeated four times by varying the discharging current, 1/3C, 1C, 3C and 6C.
- the current-voltage characteristic was measured in 10 seconds after each charging and discharging operation, and the inclination thereof was calculated to obtain the internal resistance.
- the time interval between one charging and discharging operation and another one was set to 10 minutes upon measuring the current-voltage properties, and the time interval in another case was 30 minutes.
- FIG. 21 shows that when the average thickness of the oxide layer formed on the surface of the negative electrode active material is less than 1000 nm, the battery capacity and internal resistance do not greatly vary. On the other hand, when the average thickness thereof is 1000 nm or more, the battery capacity rapidly decreases and the internal resistance rapidly increases.
- the present invention when the average thickness of the oxide layer which is formed on the surface of the active material of the negative electrode of the secondary battery of which the battery condition is to be judged is less than a predetermined standard value, the level of the degradation of the negative electrode is judged low, and when the average thickness of the oxide layer is greater than the predetermined standard value, the level of the degradation is judged high.
- the standard value depends on the kind of the secondary battery, or the like.
- the average thickness of the oxide layer which was measured when the discharge capacity of the reference battery equivalent to the secondary battery rapidly decreased or the internal resistance thereof rapidly increased, as the standard value.
- the standard value thereof is 1000 nm.
- the level of the degradation of the negative electrode is judged low when the average thickness of the oxide layer which is formed on the surface of the active material of the negative electrode is less than 1000 nm, and the level of the degradation thereof is judged high when the average thickness of the oxide layer is 1000 nm or more.
- the indexes of the battery performance such as the battery capacity and internal resistance, depend on the specification of the battery. Therefore, the index of the battery performance, which greatly varies with the elevation of the level of degradation of the negative electrode, depends on the specification of the battery. In accordance with the present invention, by measuring the average thickness of the oxide layer, regardless of the specification of the battery, the level of the degradation of the negative electrode can be accurately judged.
- the reducing agent is surely prevented from adding to the electrolyte when the level of the degradation is low, or only the electrolyte is surely prevented from being supplemented when the level of the degradation is high.
- the battery performance can be recovered effectively.
- the method for measuring the average thickness of the oxide layer which is formed on the surface of the active material of the negative electrode is not limited specifically. It is preferable to measure it with the Auger electron spectroscopic method. With this method, the average thickness of the oxide layer can be measured with accuracy without damaging the negative electrode.
- the indexes of the battery performance values such as the battery capacity and internal resistance
- the level of the degradation of the negative electrode can be judged using the measured values as the standard values. When the specification and using conditions of the battery vary, the standard values thereof must be measured again.
- a nickel-hydrogen battery similar to that of the regenerating method 1 was prepared, and a predetermined number of charging and discharging cycles were performed under predetermined charging and discharging conditions.
- the negative electrode plate was taken from the battery, and subjected to the reducing treatment.
- the negative electrode was immersed in an electrolyte containing 0.2 mol/l of sodium hypophosphite at 60° C. for 2 hours, whereby the reducing treatment is performed.
- the negative electrode subjected to the reducing treatment was assembled in the battery, thereby preparing the battery again.
- the resulting battery was subjected to a predetermined number of charging and discharging cycles under predetermined charging and discharging conditions, and the variation of the charging and discharging efficiency was examined.
- the graph 1 shows the results thereof.
- FIG. 25 shows that two graphs approximately agree to each other. This result shows that the reducing treatment of the negative electrode of which the battery capacity decreases slightly and the internal resistance increases slightly, does not affect the battery performance. Accordingly, in this case, by merely supplementing the electrolyte, the battery performance can be recovered.
- the method for examining the level of the degradation of the negative electrode is not limited specifically. It is preferable to measure the average thickness of the oxide layer which is formed on the surface of the active material of the negative electrode is measured, and judge the level of the degradation of the negative electrode to be low in the case of the average thickness being less than 1000 nm while judging it to be high in the case of the average thickness being 1000 nm or more.
- the reducing treatment is not limited specifically.
- the negative electrode may be exposed to a gas containing a reducing agent, or a liquid containing a reducing agent. In the latter case, for example, the liquid containing the reducing agent may be sprayed or applied onto the negative electrode, or the negative electrode may be immersed in the liquid containing the reducing agent.
- the kind of the reducing agent is not limited specifically.
- the same reducing agent as that used in the nickel-hydrogen battery which is disclosed in the forty-first aspect can be used.
- the negative electrode is exposed to the liquid containing the reducing agent, it is preferable to use the liquid prepared by dissolving the reducing agent in the electrolyte or a solvent thereof. With this arrangement, the negative electrode can be subjected to the reducing treatment in the condition identical to that where the negative electrode is accommodated in the battery casing.
- the nickel-hydrogen battery was regenerated as follows.
- an electrode body was taken from each of the batteries 2 a and 2 b .
- the electrode body taken from the battery 2 a was dismantled to obtain a negative electrode plate.
- the negative electrode plate of the battery 2 a and the electrode body of the battery 2 b were respectively immersed in an electrolyte containing 0.2 mol/l of sodium hypophosphite at 60° C. for 2 hours for reducing treatment.
- the batteries 2 a ′, 2 b ′ and 2 c were subjected to a predetermined number of charging and discharging cycles under predetermined charging and discharging conditions, and the charging and discharging efficiency of each battery was measured. The measurement results are shown in FIG. 20.
- FIG. 20 shows that the battery 2 a ′ is most excellent in the charging and discharging efficiency, as compared with the batteries 2 b ′ and 2 c . This result shows that when the level of the degradation of the negative electrode is high, the battery performance can be recovered most effectively by taking the negative electrode from the battery and subjecting it to the reducing treatment.
- the nickel-hydrogen battery similar to that of the regenerating method 1 was examined on the effect of the concentration of the reducing agent, treating temperature and treating time in the reducing treatment on the recovery of the battery performance.
- the level of the degradation of the negative electrode was judged based on the variation of the battery capacity and internal resistance.
- an electrode body was taken from each battery, and dismantled to obtain a negative electrode plate.
- the negative electrode plate of each battery was immersed in an electrolyte containing a predetermined concentration of sodium hypophosphite at 60° C. for 2 hours for reducing treatment.
- concentration of the reducing agent in the electrolyte for each negative electrode plate was varied as follows: 0 mol/l, 0.2 mol/l, 0.3 mol/l, 0.4 mol/l, 0.5 mol/l, 1.0 mol/l and 2.0 mol/l.
- the resultant electrode body was accommodated in the battery casing to prepare a battery again.
- the resultant batteries were subjected to 10 times of charging and discharging cycles under predetermined charging and discharging conditions.
- the charging and discharging efficiency of each battery in the tenth charging and discharging cycle was shown in FIG. 22. This result shows that at the treating temperature of 60° C., the charging and discharging efficiency is the maximum and the battery performance is recovered most preferably when the concentration of the reducing agent is 0.4 mol/l.
- the remaining three negative electrode plates were immersed in an electrolyte containing 0.6 mol/l of sodium hypophosphite at predetermined treating temperatures for 2 hours for reducing treatment.
- the treating temperature for each negative electrode plate was varied as follows: 40° C., 60° C. and 80° C.
- the resultant batteries were subjected to 10 times of charging and discharging cycles under predetermined charging and discharging conditions.
- the charging and discharging efficiency of each battery in the tenth charging and discharging cycle was shown in FIG. 23. This result shows that the charging and discharging efficiency with a concentration of reducing agent of 0.2 to 0.6 mol/l is the maximum and the battery performance is recovered most preferably when the treating temperature is 40° C.
- an electrode body was taken from each battery, and dismantled to obtain a negative electrode plate.
- the resultant negative electrode plates were immersed in an electrolyte containing 0.4 mol/l of sodium hypophosphite at 60° C. for a predetermined treating time for reducing treatment.
- the treating time for each negative electrode plate was varied as follows: 0.5 hour, 1.0 hour, 2.0 hour and 3.0 hour.
- the resultant electrode body was accommodated in the battery casing to prepare a battery again.
- the resultant batteries were subjected to 10 times of charging and discharging cycles under predetermined charging and discharging conditions.
- the charging and discharging efficiency of each battery in the tenth charging and discharging cycle was shown in FIG. 24. This result shows that in the reducing treatment with a concentration of reducing agent of 0.4 mol/l and at a treating temperature of 60° C., the charging and discharging efficiency becomes especially high and the battery performance is recovered especially when the treating time is 60 minutes or more.
- the negative electrode which is prepared by applying a powdery active material of the negative electrode to the surface of a collector with a bonding agent or the like is frequently used.
- the negative electrode of such battery is oxidized to be degraded, not only the active material of the negative electrode but also the collector and bonding agent may be degraded.
- the degraded negative electrode is in an activated condition so that when the active material is separated from the negative electrode in the air, the active material may react on oxygen in the air to be further degraded.
- the active material is mechanically separated from the degraded negative electrode in a liquid having nonoxidizing properties. So, the surface of the active material of the negative electrode is prevented from being further degraded, as compared with that at the time the negative electrode is taken from the battery.
- the active material thus separated can be effectively reduced to enable decreasing of the amount of the reducing agent along with the treating time thereof. If the decreased costs with this reducing treatment are greater than the costs required to form a negative electrode again using the reduced active material, the nickel-hydrogen battery can be regenerated at low costs.
- the secondary battery can be regenerated at lower costs, as compared with the method disclosed in the fifty-fifth aspect.
- the kind of the secondary battery to which the present aspect is applicable is not limited specifically.
- the present aspect can be applied to a nickel-hydrogen battery, for example, and especially a nickel-hydrogen battery provided with a negative electrode of which the active material is a hydrogen-occluding alloy, and an electrolyte which is interposed between the positive electrode and negative electrode(fifty-seventh aspect).
- the nickel-hydrogen battery provided with a negative electrode which is prepared by applying a powdery active material to a surface of a collector with a bonding agent or the like is most suitable.
- the kind of the liquid having nonoxidizing properties is not limited specifically. Water, electrolyte, solvent of the electrolyte, for example, can be used. Especially, it is preferable to mechanically separate the active material in the liquid having reducing properties. With this method, the degraded negative electrode can be reduced during separating the active material therefrom, and consequently, the active material can be reduced. As a result, the active material can be reduced more sufficiently in addition to the succeeding reducing treatment.
- the method for separating the active material from the negative electrode is not limited specifically.
- the active material can be scraped from the negative electrode with a scraper to be separated from the negative electrode.
- the method for reducing the active material thus separated is not limited specifically.
- the treating method similar to that used in the reducing treatment disclosed in the regenerating method of the fifty-fifth aspect can be used.
- the active material thus reduced can be used again. Before using it again, it is preferable to make the powder diameter equal to one another again.
- the nickel-hydrogen battery was regenerated as follows.
- an electrode body is taken from each of the battery 3 a and battery 3 b , and dismantled to obtain a negative electrode.
- the negative electrode obtained by dismantling the battery 3 a was immersed in water, and an active material was scraped from the negative electrode with a scraper.
- the negative electrode obtained by dismantling the battery 3 b was immersed in a reducing water having reducing properties, and an active material was scraped from the negative electrode with a scraper.
- the scraped active material was dried, and pulverized in a mortar. Then the pulverized active material was sifted to make the diameter thereof equal to one another.
- the active material thus mechanically separated was immersed in an electrolyte containing sodium hypophosphite as a reducing agent at 60° C. for 2 hours for reducing treatment. Then, the active material was filtered, dried, and sifted again to make the diameter thereof equal to one another so as to become 75 ⁇ m or less.
- the resultant batteries 3 a ′ and 3 b ′ were subjected to the repetition of charging and discharging cycles with 25 mA, and the charging and discharging efficiency of each battery in a predetermined number of the charging and discharging cycle was measured.
- the measurement result is shown in FIG. 26.
- FIG. 26 shows that the charging and discharging efficiency of the battery 3 b ′ is excellent, as compared with that of the battery 3 a ′. This result shows that the active material can be reduced more sufficiently by mechanically separating the active material from the negative electrode in the liquid having reducing properties.
- the battery condition can be judged in detail with the condition judging method disclosed in each of the thirty-first through fiftieth aspects.
- the level of the degradation of the negative electrode was judged in detail.
- the level of the degradation of the negative electrode has a close relation with the second resistance component out of the first resistance component, second resistance component and resistance component ratio. So, it is preferable to judge the level of the degradation of the negative electrode based on at least the second resistance component. With this method, the level of the degradation of the negative electrode can be judged in detail.
- a proper regenerating method can be applied so that the secondary battery can be regenerated effectively. This results in the regenerating time of the secondary battery, for example, becoming short, and consequently the regenerating costs can be reduced.
- the kind of the secondary battery to which the present aspect is applicable is not limited specifically.
- the present aspect can be applied to a nickel-hydrogen battery, for example, and especially a nickel-hydrogen battery provided with a negative electrode of which the active material is a hydrogen-occluding alloy, and an electrolyte which is interposed between the positive electrode and negative electrode, With the present regenerating method, when the battery performance of the nickel-hydrogen battery decreases, it can be recovered with ease.
- the supplement of the electrolyte or the addition of the reducing agent to the electrolyte can be performed, similarly to the regenerating method disclosed in the fifty-first aspect.
- the degradation mode of the degraded secondary battery can be judged in detail with the condition judging method disclosed in the thirty-seventh aspect or fortieth aspect.
- the degradation mode is judged in detail with the condition judging method disclosed in at least one of the thirty-seventh and fortieth aspects.
- a proper regenerating method can be applied so that the secondary battery can be regenerated effectively. This results in the regenerating time of the secondary battery, for example, becoming short, and consequently the regenerating costs can be decreased.
- the kind of the secondary battery to which the present aspect is applicable is not limited specifically.
- the present aspect can be applied to a nickel-hydrogen battery, for example, and especially a nickel-hydrogen battery provided with a negative electrode of which the active material is a hydrogen-occluding alloy, and an electrolyte which is interposed between the positive electrode and negative electrode, With the present regenerating method, when the battery performance of the nickel-hydrogen battery decreases, it can be recovered with ease.
- the supplement of the electrolyte and the addition of the reducing agent to the electrolyte can be performed, similarly to the fifty-first aspect.
- the supplement of the electrolyte or the reducing treatment after taking the negative electrode from the battery casing can be performed, similarly to the forty-fifth aspect.
- condition judging method and regenerating method of the present aspect will be explained with reference to several embodiments.
- New nickel-hydrogen batteries (95 Ah layered type) were prepared as secondary batteries. These nickel-hydrogen battery were actually mounted on an electric vehicle, or simulated to be mounted thereon, and used under various environments. The battery condition of each secondary battery thus used was judged, and the regeneration thereof was performed. The results of the judgement and regeneration are as follows.
- the degraded condition is divided into a first degraded condition which is mainly caused by the increase of the ion conduction resistance, a second degraded condition which is mainly caused by the increase of both the ion conduction resistance and reaction resistance, and a third degraded condition which is mainly caused by the excess increase of the reaction resistance
- the secondary battery subjected to the charging and discharging test in Embodiment 3 was in the third degraded condition
- the secondary batteries subjected to the charging and discharging test in Embodiments 4 and 5 were in the second degraded condition
- the secondary battery subjected to the charging and discharging test in Embodiment 6 was in the first degraded condition.
- a first border value between the first degraded condition and second degraded condition in the angle ⁇ A ′ of the reference battery is ⁇ /12
- a second border value between the second degraded condition and third degraded condition in the angle ⁇ A ′ of the reference battery is ⁇ /3.
- the internal resistance co-ordinate R A ′ which indicates the co-ordinate of the internal resistance of the reference battery was plotted on a plane co-ordinate of which X axis and Y axis intersect perpendicularly with the first resistance component r 1A ′ obtained in the reference battery as the X component and the second resistance component r 2A ′ obtained in the reference battery as the Y component, and the relation between the internal resistance co-ordinate R′ and the battery condition was investigated.
- FIG. 32 shows that the battery condition of each of the secondary batteries can be judged at a glance, and consequently, the judgement of the battery condition can be performed with ease.
- a first resistance component (r 1B ), second resistance component (r 2B ) and angle ( ⁇ B ) of each of the secondary batteries subjected to the charging and discharging tests of Embodiments 1 through 6 were obtained using the AC impedance method.
- the AC impedance component Zac and DC impedance component Zdc were measured. These impedance components were used as the first resistance component r 1B and second resistance component r 2B .
- the measurement of the AC impedance component was performed four times. The average value of the measured values are shown in TABLE 3.
- the internal resistance of a reference battery of the same kind as that of the secondary battery was divided into a first resistance component (r 1B ′) and second resistance component (r 2B ′), and they were respectively measured. It has been clarified that when the sum of the first resistance component and second resistance component (r 1B ′+r 2B ′) is less than 1.2 m ⁇ , the reference battery is in a normal condition, and when the sum of the first resistance component and second resistance component (r 1B ′+r 2B ′) is 1.2 m ⁇ or more, the reference battery is in a degraded condition. Namely, it has been also clarified by the AC impedance method that the degradation judging standard value of the reference battery is 1.2 m ⁇ .
- the first border value of the angle ⁇ B ′ of the reference battery between the first degraded condition and second degraded condition is ⁇ /12
- the second border value of the angle ⁇ B ′ of the reference battery between the second degraded condition and third degraded condition is ⁇ /3.
- FIG. 33 shows that the battery condition of each of the secondary batteries can be judged at a glance, and consequently, the judgement of the battery condition can be performed with ease. And it has been clarified from FIGS. 32 and 33 that the measured values obtained with the AC impedance method do not greatly scatter and the measurement accuracy thereof is very high, as compared with those obtained with the current interrupter method.
- the secondary batteries subjected to the charging and discharging tests of Embodiments 1 through 6 were subjected to two kinds of regenerating treatments of supplementing an electrolyte, and supplementing an electrolyte to which a reducing agent was added.
- the electrolyte wherein 0.4 mol/l of sodium hypophosphite is dissolved in water was used as the reducing agent.
- This secondary battery is difficult to regenerate with a positive electrode and negative electrode held within a battery casing. So, it is necessary to take the negative electrode from the battery casing and regenerate it, or to mechanically separate an active material from the negative electrode in the liquid having nonoxidizing properties, and subject the active material to the reducing treatment.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/161,693 US6924623B2 (en) | 1998-08-10 | 2002-06-05 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/129,493 US7075305B2 (en) | 1998-08-10 | 2005-05-16 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/130,253 US7030618B2 (en) | 1998-08-10 | 2005-05-17 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/131,290 US7235326B2 (en) | 1998-08-10 | 2005-05-18 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/131,279 US7180298B2 (en) | 1998-08-10 | 2005-05-18 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-226307 | 1998-08-10 | ||
| JP22630798 | 1998-08-10 | ||
| JP35666498 | 1998-12-15 | ||
| JP3489099 | 1999-02-12 | ||
| JP11873299A JP3598873B2 (ja) | 1998-08-10 | 1999-04-26 | 二次電池の状態判定方法及び状態判定装置、並びに二次電池の再生方法 |
| PCT/JP1999/003866 WO2000010219A1 (en) | 1998-08-10 | 1999-07-16 | Method for judging state of secondary cell and device for judging state thereof, and method for regenerating secondary cell |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1999/003866 Continuation WO2000010219A1 (en) | 1998-08-10 | 1999-07-16 | Method for judging state of secondary cell and device for judging state thereof, and method for regenerating secondary cell |
Related Child Applications (1)
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|---|---|---|---|
| US10/161,693 Continuation-In-Part US6924623B2 (en) | 1998-08-10 | 2002-06-05 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
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|---|---|
| US20010028238A1 true US20010028238A1 (en) | 2001-10-11 |
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|---|---|---|---|
| US09/779,466 Abandoned US20010028238A1 (en) | 1998-08-10 | 2001-02-09 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US10/161,693 Expired - Fee Related US6924623B2 (en) | 1998-08-10 | 2002-06-05 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/129,493 Expired - Fee Related US7075305B2 (en) | 1998-08-10 | 2005-05-16 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/130,253 Expired - Fee Related US7030618B2 (en) | 1998-08-10 | 2005-05-17 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/131,290 Expired - Fee Related US7235326B2 (en) | 1998-08-10 | 2005-05-18 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/131,279 Expired - Fee Related US7180298B2 (en) | 1998-08-10 | 2005-05-18 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
Family Applications After (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/161,693 Expired - Fee Related US6924623B2 (en) | 1998-08-10 | 2002-06-05 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/129,493 Expired - Fee Related US7075305B2 (en) | 1998-08-10 | 2005-05-16 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/130,253 Expired - Fee Related US7030618B2 (en) | 1998-08-10 | 2005-05-17 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/131,290 Expired - Fee Related US7235326B2 (en) | 1998-08-10 | 2005-05-18 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
| US11/131,279 Expired - Fee Related US7180298B2 (en) | 1998-08-10 | 2005-05-18 | Method and device for judging the condition of secondary batteries and method for regenerating secondary batteries |
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| US (6) | US20010028238A1 (ko) |
| EP (2) | EP1115171A4 (ko) |
| JP (1) | JP3598873B2 (ko) |
| KR (1) | KR100447461B1 (ko) |
| CN (2) | CN1203320C (ko) |
| CA (1) | CA2340207A1 (ko) |
| WO (1) | WO2000010219A1 (ko) |
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|---|---|
| US20050214633A1 (en) | 2005-09-29 |
| JP3598873B2 (ja) | 2004-12-08 |
| US20050206390A1 (en) | 2005-09-22 |
| US7030618B2 (en) | 2006-04-18 |
| WO2000010219A1 (en) | 2000-02-24 |
| CN1260851C (zh) | 2006-06-21 |
| US7075305B2 (en) | 2006-07-11 |
| US20050206389A1 (en) | 2005-09-22 |
| US7235326B2 (en) | 2007-06-26 |
| EP1115171A1 (en) | 2001-07-11 |
| US6924623B2 (en) | 2005-08-02 |
| KR100447461B1 (ko) | 2004-09-07 |
| JP2000299137A (ja) | 2000-10-24 |
| US20030062875A1 (en) | 2003-04-03 |
| CN1549386A (zh) | 2004-11-24 |
| EP1115171A4 (en) | 2004-09-29 |
| CA2340207A1 (en) | 2000-02-24 |
| CN1203320C (zh) | 2005-05-25 |
| US7180298B2 (en) | 2007-02-20 |
| EP2287958A1 (en) | 2011-02-23 |
| KR20010082115A (ko) | 2001-08-29 |
| CN1320286A (zh) | 2001-10-31 |
| US20050208368A1 (en) | 2005-09-22 |
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