CN102428379B - State detection method for electric storage device, and apparatus therefor - Google Patents

State detection method for electric storage device, and apparatus therefor Download PDF

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CN102428379B
CN102428379B CN201080002326.8A CN201080002326A CN102428379B CN 102428379 B CN102428379 B CN 102428379B CN 201080002326 A CN201080002326 A CN 201080002326A CN 102428379 B CN102428379 B CN 102428379B
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energy storage
electric energy
discharge
storage device
voltage
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CN102428379A (en
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温井克弥
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • 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

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  • Charge And Discharge Circuits For Batteries Or The Like (AREA)
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Abstract

Provided are a state detection method for an electric storage device, which is capable of determining whether the appropriate capability of discharge is maintained regardless of whether charge/discharge is being performed or charge/discharge is stopped, and an apparatus therefor. In step (S7), the voltage change amount ( Va_n) is calculated from a voltage (V_end) when charge/discharge is stopped, said voltage being stored in a storage unit (120), and a current voltage (V_now). In step (S9), a capability-of-discharge correction function ((F) (SOH_n1, x)) corresponding to a state of health (SOH_n1) read in step (S8) is read from the storage unit (120), and in step (S10), the capability-of-discharge correction amount (COD_SOH_n) is calculated by assigning Va_n to a variable (x). In step (S11), the current capability of discharge (COD_now) is calculated from the current voltage (V_now) and the capability-of-discharge correction amount (COD_SOH_n) calculated in step (S10).

Description

The condition detection method of electric energy storage device and device thereof
Technical field
The present invention relates to condition detection method and the device thereof of electric energy storage device, particularly relate to the condition detection method relevant to the discharge capability of electric energy storage device and device thereof.
Background technology
In recent years, very large to the demand of electric energy storage device, such as, installed in a lot of automobile and accepted from the accumulator as electric energy storage device the electric machine that action is carried out in power supply, the importance of accumulator uprises day by day.In recent years, line traffic control is developed, with electronic brake system (EPB) for representative also carries out Electronic Control to the parts of security system.In addition, along with the energy-conservation discharge with carbon dioxide limits, the idle stop function had when the places such as intersection stop temporarily being required to reset ability with it.
Field beyond automobile, such as, in order to promote the utilization of the natural energy such as solar electrical energy generation or wind-power electricity generation, also uses electric energy storage device, and can store dump energy for equilibrium generating.In addition, be used for when power failure grade also using electric energy storage device in the standby power supply such as stabilized power source, accessory power supply carrying out to electric machine powering.Such electric energy storage device adopts secondary cell or capacitor etc. with the electric energy storage device of electrolytic solution movement.
Usually, under condition highly stable after electric energy storage device stops discharge and recharge, there is between its open-circuit voltage (OCV) and residual capacity (SOC:State of charge) relation by 1: 1 correspondence as shown in the label 81 of Figure 35.But the relation of this 1: 1 obtains under condition stable as laboratory.Electric energy storage device after discharge and recharge, such as when it is containing the accumulator of electrolytic solution, can be subject to the generation of the ion caused on polar board surface by electrochemical reaction and annihilation reaction respectively and be spread by electrolytic solution or the impact of movement of ion that convection current etc. causes.
Above-mentioned impact will inevitably be produced in the electric energy storage device of the movement in the electrolytic solution of the ion as lithium ion battery or lead accumulator.In addition, even if capacitor and so on, when using electrolytic solution as storage medium, because the concentration of this medium changes, the impact of ion diffuse etc. can be therefore also subject to.Even if when using solid electrolyte as medium when replacing electrolytic solution, the ion in this electrolyte also can offset under electric power storage effect.Therefore, reaching steady state (SS) according to medium or medium needs certain hour, obtain stable OCV, needs the convergence time (such as, pregnant solution type lead acid accumulator needs 20 hours) corresponding to the characteristic of various electric energy storage device.
As mentioned above, when ion concentration transient changing in electrolyte or electrolytic solution, need the long period just can reach the very uniform state of ion concentration, therefore according to the result measuring cell voltage in limited minute, between OCV and SOC, the relation of 1: 1 is false.Figure 36, Figure 37 are the figure of an example of the transient changing of OCV when illustrating that the SOC of accumulator and temperature are fixed.Even if Figure 36 shows SOC and fixes, OCV (label 82) will be stabilized to fixed value also needs the time.In addition, Figure 37 shows in SOH (impairment grade, State of health) change of OCV (label 83,84,85) in asynchronous accumulator, even if illustrated therein is when SOC and temperature being adjusted to the same terms and nearest discharge and recharge condition being also set to identical, as long as SOH is different, identical OCV would not be converged to.
So, in order to obtain SOC accurately based on OCV, need to use the SOC reflecting the SOH of electric energy storage device rightly.In addition, discharge and recharge stop after transient changing comprise as ion generation and eliminate the reaction time reaction short, change fast change and the reaction time is grown, changes slow change as the diffusion of electrolytic solution or convection current etc.Different transient changing of such reaction time is also different according to SOC or SOH respectively.
To make, electric energy storage device is stable can be used, and needs to carry out its state-detection accurately, to detect that this situation is tackling in advance when discharge capability occurring be not enough etc.In the system using electric energy storage device, in order to make the regular events such as intrasystem electric machine, electric energy storage device is set to the lower voltage limit (critical point of discharge capability) also requiring to maintain in charge and discharge process.Therefore, in the state-detection of electric energy storage device, as the judgement of its discharge capability (COD:Capability of Discharge), importantly judge that whether the voltage of electric energy storage device is higher than above-mentioned lower voltage limit accurately.
The COD of electric energy storage device determines whether the voltage that always can maintain electric energy storage device than lower voltage limit higher for any load.An example of the change in voltage of electric energy storage device when Figure 38 shows electric discharge.Figure 38 schematically shows and on accumulator, to connect when load is discharged cell voltage 33 over time.Cell voltage 33 during electric discharge declines with the passing of time and gradually, if but drop to the critical point of lower voltage limit, the i.e. discharge capability of system requirements, just cannot provide appropriate electric energy to the electric machine etc. of system.
The falling quantity of voltages of starting at from initial cell voltage 31 can represent as the following formula.
Falling quantity of voltages=reaction resistance (increase) × electric current+built-in potential (decline)
Here, the voltage drop (arrow D) caused by reaction resistance is the voltage drop with the energy caused needed for electrochemical reaction, its deterioration according to electric energy storage device (SOH) and changing.In addition, built-in potential decline (arrow C) be that the change etc. of the active substance caused by the carrying out along with electrochemical reaction causes, its residual capacity according to electric energy storage device (SOC) and changing.As can be seen from Figure 38, even if built-in potential 34 is higher than drop-out voltage 35, if the slippage caused by exoelectrical reaction resistance is large, the critical point of discharge capability also can be dropped to.So, with in the electric energy storage device of electrochemical reaction, discharge capability COD is determined by the lower voltage limit 35 specified in built-in potential C, the exoelectrical reaction resistance D of accumulator and system definition, therefore to judge discharge capability accurately, differentiation exoelectrical reaction resistance D (deterioration) and built-in potential C (residual capacity) is needed to judge.
As the method for discharge capability judging electric energy storage device, can consider system is stopped making discharge equipment discharge completely, then by again carrying out full charge and directly measure residual capacity and carrying out the method that judges.But in the method, in order to measure residual capacity, electric energy storage device becomes disabled state.Especially in system for subsequent use, be there is the danger that can not realize original function in electric energy storage device.In addition, when bleeding off all told to carry out practical measurement, discharge time and duration of charging both all need the suitable time, thus reduce the operational efficiency of system significantly.
As the method for deterioration state judging electric energy storage device, there will be a known and estimate internal state by impedance method and the method estimating discharge capability based on its information.But, though the method can be applied to electric energy storage device full charge or close to the state of full charge under used in, cannot be applied in electric energy storage device used under part charged state (PSOC:Partial State of charge).In recent years, electric energy storage device is used in the purposes of balanced natural energy, but in such purposes, to use electric energy storage device under the part charged state that residual capacity compared with full charge is mutually far short of what is expected.
The difference of the application mode using Figure 39 to illustrate when being applied with full charge by electric energy storage device and when applying with PSOC.Figure 39 (a) shows the state-detection in existing application process, and Figure 39 (b) shows the state-detection in the application process of PSOC.In existing application process, require the reduction 42a detecting the deteriorated allowance 42 caused by deterioration, to judge remaining deteriorated allowance 42b.On the other hand, need to carry out following control in the application process of PSOC: detect the charged area 44 that caused by deterioration and respective reduction 44a, the 45a of deteriorated allowance 45, and in order to ensure necessary charging capacity and discharge capacity, charged area 44 and deteriorated allowance 45 are set again by the scope changing deployment area 43.
Always with the state of basic full charge by the application process of existing electric energy storage device that uses, can think that the impedance of electric energy storage device only changes by the impact of deterioration.Therefore, by measuring impedance, the impairment grade (SOH) of electric energy storage device can be known.On the other hand, based in the application of PSOC, impedance, by deterioration and the impact both residual capacity, therefore cannot obtain impairment grade based on impedance.
Foregoing describe the different transient changing of the reaction time in electric energy storage device after discharge and recharge, but in order to reflect the difference in this reaction time, such as, in patent documentation 1, describe the method that component transient changing being divided into three time constants carries out evaluating.In patent documentation 1, transient response changed according to the discharge and recharge time, in addition, it is mentioned that transient response is relevant to the rate of propagation of resistive component, the polarization components corresponding with the internal-response of battery and electrolytic solution.
At first technical literature
[patent documentation 1] No. JP2005-106615, Japanese Patent Application Laid-Open (Japanese Unexamined Patent Publication 2005-106615).
Brief summary of the invention
Invent technical matters to be solved
But, the method for the state-detection of electric energy storage device when still not carrying out system discharge and recharge just in the application so far accurately.As the means of supplementing out economy for decision-making system residual capacity just in the application, electric current aggregate-value when there will be a known the discharge and recharge based on electric energy storage device estimates current remaining capacity and uses this residual capacity to judge the method for discharge capability.But, aggregate-value by means of only charging current and discharge current is the decline that cannot reflect the efficiency for charge-discharge caused by the change of the internal state amounts such as the deterioration of electric energy storage device, there are differences between the residual capacity of the residual capacity of the electric energy storage device calculated based on electric current aggregate-value and the available electric energy storage device of reality, thus correctly cannot calculate discharge capability.In addition, only monitor that can residual capacity cannot judge discharge capability, namely cannot judge the voltage that maintain electric energy storage device than the voltage of system requirements higher.
Below, Figure 40 is used to illustrate that electric current aggregate-value is identical but the example that the voltage of electric energy storage device is different.This Figure 40, by follow-up for transverse axis periodicity, shows the voltage at the end of the charging repeated under electric current aggregate-value is identical in charging and discharging charge status.Make the charging cumulative amount in one-period and electric discharge cumulative amount be 5% (Δ SOC=5%), and the discharge and recharge cumulative amount in each cycle is 0.In addition, the residual capacity (SOC) when the discharge and recharge that Figure 40 shows electric energy storage device starts is the situation of 90% (label 51 ~ 53), 80% (label 54), 70% (label 55 ~ 60), 60% (label 61).
As can be seen from Figure 40, along with charging-discharging cycle number increases, the voltage at the end of charging also rises.This represents that the quantity of state of electric energy storage device inside changes along with the repetition of charging-discharging cycle.In addition, even if the variable quantity of electric current aggregate-value is 0, the quantity of state of electric energy storage device also there occurs change.Data shown in Figure 40 are the experimental datas using the pregnant solution type lead acid accumulator (JIS standard 55D23) of Furukawa battery manufacture to carry out.
On the other hand, due to the time different transient changing that yet can react in the inside of electric energy storage device in the state-detection after discharge and recharge stops, therefore still do not estimate the impact brought by these transient changing so far rightly and carry out the method for state-detection.Even if such at condition detection method as described in Patent Document 1, the transient changing after discharge and recharge stopping to be divided into different time constants component is to carry out state-detection, if SOC or SOH of electric energy storage device changes, then also need correspondingly to regulate each time constant, therefore there is following problem: be difficult to obtain the time constant for different SOC or SOH accurately, thus be difficult to the state-detection of carrying out accumulator accurately.In view of above-mentioned technical matters, the object of the invention is to, provide and no matter be in the middle of discharge and recharge or stopped discharge and recharge all can determining whether condition detection method and the device thereof of the electric energy storage device that maintain appropriate discharge capability.
The technical scheme that technical solution problem adopts
The condition detection method of the electric energy storage device involved by first aspect present invention be judge in the middle of discharge and recharge for the cycle that correspondence is predetermined and discharge and recharge stop in the middle of the condition detection method of electric energy storage device of discharge capability, voltage V_end when the voltage determination value of the described electric energy storage device and then measured after last discharge and recharge stops stops as discharge and recharge is also stored in predetermined storage part, voltage V_end when described discharge and recharge stops is read in from described storage part, deduct in voltage V_end during by stopping from described discharge and recharge that current (being set to periodicity is voltage determination value V_now n), and calculate as forehead voltage variety Δ Va_n, based on impairment grade SOH and the described voltage variety Δ Va_n also prior discharge capability correction function F (SOH worked out of use of described electric energy storage device, Δ Va_n) calculate the discharge capability correction COD_SOH_n of described electric energy storage device, by formula below, calculate the present discharge ability COD_now of described electric energy storage device,
COD_now＝V_now-COD_SOH_n
And when described discharge capability COD_now is greater than predetermined threshold COD_Th, be judged to be that the discharge capability of described electric energy storage device is maintained.
In the condition detection method of the electric energy storage device involved by other side of the present invention, (SOH_n1, x) (x is variable) being substituted in described variable x by described voltage variety Δ Va_n calculates by reading in the described discharge capability correction function F corresponding with described impairment grade SOH_n1 from described storage part for the impairment grade SOH_n1 that described impairment grade SOH is the periodicity in the middle of stopping from current nearest discharge and recharge to be calculated when being n1 (n1≤n), described discharge capability correction COD_SOH_n.
In the condition detection method of the electric energy storage device involved by other side of the present invention, described discharge capability correction function F (SOH, Δ Va) the incompatible expression of linear junction of the relaxation function fi (i=1 ~ m) of two or more (being set to m) each reaction velocity worked out in advance accordingly by the speed of the transient changing with described electric energy storage device inside, in the middle of the discharge and recharge of described electric energy storage device stops, described voltage determination value is kept in described storage part, and the relaxation function fi of described each reaction velocity also uses the described voltage determination value be kept in described storage part to be optimised according to the elapsed time stopping from described discharge and recharge starting at.
In the condition detection method of the electric energy storage device involved by other side of the present invention, when described electric energy storage device is in the middle of discharge and recharge stopping, and when stopping the elapsed time of starting to exceed the schedule time (being set to for the first slack time) from discharge and recharge, the relaxation function fi of the described voltage determination value pair described each reaction velocity corresponding with transient changing be fast kept in described storage part is used to carry out optimization, the relaxation function fi of each reaction velocity after described optimization is used to calculate the impairment grade SOH_fast_n depending on transient changing fast, the impairment grade SOH_slow_n2 depending on transient changing slowly calculated when being n2 (n2≤n) based on the periodicity in the middle of stopping from current nearest discharge and recharge and described impairment grade SOH_fast_n, and utilize predefined function G, current impairment grade SOH_n is calculated by formula below,
SOH_n＝G(SOH_fast_n，SOH_slow_n2)
Further, described discharge capability correction COD_SOH_n is by reading in the described discharge capability correction function F corresponding with described impairment grade SOH_n (SOH_n, x) and substituted in described variable x by described voltage variety Δ Va_n and calculate from described storage part.
In the condition detection method of the electric energy storage device involved by other side of the present invention, when described electric energy storage device is in the middle of discharge and recharge stopping, and when stopping the elapsed time of starting to exceed longer than described first slack time the second predetermined slack time from discharge and recharge, the relaxation function fi of described voltage determination value to the described each reaction velocity depending on transient changing slowly that further use is kept in described storage part carries out optimization, the relaxation function fi of each reaction velocity after described optimization is used to calculate the impairment grade SOH_slow_n depending on transient changing slowly, the impairment grade SOH_fast_n of the transient changing fast and described impairment grade SOH_slow_n depending on transient changing is slowly depended on described in calculating, and utilize described function G, current impairment grade SOH_n is calculated by formula below,
SOH_n＝G(SOH_fast_n，SOH_slow_n)。
In the condition detection method of the electric energy storage device involved by other side of the present invention, after discharge and recharge stops, and then described electric energy storage device being carried out to the charging (state-detection before charge) of predetermined volumes, and described voltage determination value charging before described state-detection and then measured after terminating is saved in described storage part as voltage V_end during described discharge and recharge stopping.
The condition checkout gear of the electric energy storage device involved by first aspect present invention be judge in the middle of discharge and recharge for the cycle that correspondence is predetermined and discharge and recharge stop in the middle of the condition checkout gear of electric energy storage device of discharge capability, it is characterized in that, comprise: storage part, for preserving the voltage determination value of described electric energy storage device, state detecting section, reads in for the correspondence described cycle and is kept at data in described storage part to judge the discharge capability of described electric energy storage device, and State-output unit, for inputting result of determination from described state detecting section, and externally export, wherein, described storage part is kept at the described voltage determination value of the described electric energy storage device and then measured after last discharge and recharge stops, voltage V_end when stopping as discharge and recharge, described state detecting section reads in voltage V_end when described discharge and recharge stops from described storage part, deduct in voltage V_end during by stopping from described discharge and recharge that current (being set to periodicity is that voltage determination value V_now n) calculates current voltage variation delta Va_n, based on impairment grade SOH and the described voltage variety Δ Va_n also prior discharge capability correction function F (SOH worked out of use of described electric energy storage device, Δ Va_n) calculate the discharge capability correction COD_SOH_n of described electric energy storage device, the present discharge ability COD_now of described electric energy storage device is calculated by formula below,
COD_ow＝V_ow-COD_SOH_n
And when described discharge capability COD_now is greater than predetermined threshold COD_Th, be judged to be that the discharge capability of described electric energy storage device is maintained.
In the condition detection method of the electric energy storage device involved by other side of the present invention, the condition detection method of electric energy storage device, described electric energy storage device is stopped discharge and recharge and the voltage of described electric energy storage device when reaching the state meeting predetermined stable condition as burning voltage during stopping, using voltage when have passed through time t after stopping discharge and recharge from described electric energy storage device relative to the variable quantity of burning voltage during described stopping as voltage variety during stopping, now, relaxation function F (t) of voltage variety when being used for calculating described stopping is worked out in advance as the function of the predetermined quantity of state of described electric energy storage device, measure described electric energy storage device will stop charge before charging at the end of voltage, or voltage at the end of the electric discharge before will stopping discharging, measure the described charging of described electric energy storage device or described electric discharge stop after voltage, relaxation function F (t) described in voltage variety when calculating described stopping according to described voltage determination value optimization, described quantity of state is estimated according to described relaxation function F (t) be optimised, voltage at the end of voltage or described charging at the end of utilizing described electric discharge, and described by the quantity of state that estimates to judge the discharge capability (COD) of described electric energy storage device.
In the condition detection method of the electric energy storage device involved by other side of the present invention, the relaxation function f of each reaction velocity of two or more (be set to m) of described relaxation function F (t) by working out in advance accordingly with the reaction velocity of described electric energy storage device inside it the linear combination of () (i=1 ~ m) represents, the relaxation function f of described each reaction velocity it voltage variety during the described stopping calculated according to described voltage determination value is separated into the component corresponding with described reaction velocity and has carried out optimization by () (i=1 ~ m).
In the condition detection method of the electric energy storage device involved by other side of the present invention, when the impact that the electric current caused by described discharge and recharge is small or bring for fixed value thus to the transient changing of described electric energy storage device inside is limited in predetermined scope, judge that described electric energy storage device stopped discharge and recharge.
In the condition detection method of the electric energy storage device involved by other side of the present invention, prior establishment is for revising the voltage increment of the change in voltage caused by described electric current, utilize the voltage adding described voltage increment gained in described voltage determination value, relaxation function F (t) described in optimization.
In the condition detection method of the electric energy storage device involved by other side of the present invention, according to accumulative will discharge and recharge stop before discharge and recharge in electric current and the electric current aggregate-value that obtains calculates residual capacity increase and decrease amount (Δ SOC) when discharge and recharge stops, residual capacity when upper once discharge and recharge stops adds described residual capacity increase and decrease amount and calculates residual capacity when current discharge and recharge stops, based on voltage at the end of voltage at the end of described electric discharge or described charging, from the quantity of state that described relaxation function F (t) estimates, and described SOC judges described COD.
In the condition detection method of the electric energy storage device involved by other side of the present invention, prior establishment using voltage at the end of predetermined quantity of state and charging as the charge efficiency calculating formula of variable, SOC when described discharge and recharge stops utilizes residual capacity increase and decrease amount described in charge efficiency correction and calculates, and voltage at the end of the described quantity of state utilizing described relaxation function F (t) to calculate and described charging is substituted into described charge efficiency calculating formula and calculates by described charge efficiency.
In the condition detection method of the electric energy storage device involved by other side of the present invention, described quantity of state is the residual capacity of described electric energy storage device.
In the condition detection method of the electric energy storage device involved by other side of the present invention, described quantity of state is the impairment grade (SOH) of described electric energy storage device.
In the condition detection method of the electric energy storage device involved by other side of the present invention, described relaxation function F (t) has the fast component f of relaxation velocity fastt component f that () and relaxation velocity are slow slow(t), the in advance described f of establishment fast(t), described f slow(t) and both ratio f fast(t)/f slowt reference value that () is respective, utilizes the described f that the F (t) be optimised described in basis calculates fast(t), described f slow(t) and described f fast(t)/f slow, and respective described reference value judge described COD.
In the condition detection method of the electric energy storage device involved by other side of the present invention, described quantity of state is the impairment grade SOH of described electric energy storage device, utilizes described f fast(t), described f slow(t) and described f fast(t)/f slow, and respective described reference value calculate described impairment grade.
In the condition detection method of the electric energy storage device involved by other side of the present invention, voltage at the end of residual capacity during described discharge and recharge stopping and described charging, using the High-speed transient change correction calculating formula of voltage at the end of residual capacity and charging as variable, is substituted into described High-speed transient change correction calculating formula and calculates relative to described f by prior establishment fastthe correction of (t), and utilize with the described f of described correction correction fastt () calculates described impairment grade.
In the condition detection method of the electric energy storage device involved by other side of the present invention, establishment concentration change gauge formula in advance, described concentration change gauge formula is used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slow, the concentration change amount of the electrolytic solution of described electric energy storage device, relaxation function F (t) be optimised described in utilization and according to described concentration change gauge formula calculate described electrolytic solution concentration change amount and for described quantity of state.
In the condition detection method of the electric energy storage device involved by other side of the present invention, establishment is in advance used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slowthe stratification variable quantity calculating formula of stratification variable quantity, in described stratification variable quantity calculating formula, using CONCENTRATION DISTRIBUTION bias (stratification) variable quantity of the electrolytic solution of described electric energy storage device as described stratification variable quantity, described relaxation function F (t) be optimised described in utilization also calculates described stratification variable quantity according to described stratification variable quantity calculating formula and for described quantity of state.
In the condition detection method of the electric energy storage device involved by other side of the present invention, establishment is in advance used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slowthe horizontal stratification variable quantity calculating formula of horizontal stratification variable quantity, in described horizontal stratification variable quantity calculating formula, using the variable quantity of the liquid level of the electrolytic solution for described electric energy storage device CONCENTRATION DISTRIBUTION bias in the horizontal (horizontal stratification) as described horizontal stratification variable quantity, described relaxation function F (t) be optimised described in utilization also calculates described horizontal stratification variable quantity according to described horizontal stratification variable quantity calculating formula and for described quantity of state.
In the condition detection method of the electric energy storage device involved by other side of the present invention, establishment is in advance used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slowthe portraitlandscape stratification variable quantity calculating formula of portraitlandscape stratification variable quantity, in described portraitlandscape stratification variable quantity calculating formula, using the variable quantity of the CONCENTRATION DISTRIBUTION bias (horizontal stratification, longitudinal stratification) of the liquid level of the electrolytic solution for described electric energy storage device on horizontal and vertical as described portraitlandscape stratification variable quantity, described relaxation function F (t) be optimised described in utilization also calculates described horizontal stratification variable quantity and longitudinal stratification variable quantity according to described portraitlandscape stratification variable quantity calculating formula and for described quantity of state.
In the condition detection method of the electric energy storage device involved by other side of the present invention, the function that described relaxation function F (t) is further used as the temperature of described electric energy storage device is worked out in advance, measure described electric energy storage device temperature and for the calculating of described relaxation function F (t).
In the condition detection method of the electric energy storage device involved by other side of the present invention, OCV when burning voltage is stable during described stopping, from described voltage determination value deduct according to OCV calculating formula during in advance establishment stable calculate described stable time OCV calculate described OCV variable quantity, using described OCV variable quantity as voltage variety during described stopping.
In the condition detection method of the electric energy storage device involved by other side of the present invention, according to the relaxation function f of described each reaction velocity it () estimates the quantity of state of corresponding each described reaction velocity, and the quantity of state amounting to each described reaction velocity is to calculate described quantity of state.
In the condition detection method of the electric energy storage device involved by other side of the present invention, at the relaxation function f by the described each reaction velocity under predetermined state it the described SOH of (), described SOC and each reaction velocity is set to fi respectively ref(t), SOC ref, and SOHi ref, by described electric energy storage device be set to G (T) relative to the dependence of temperature T time, the relaxation function fi of the described each reaction velocity after the discharge and recharge of n-th time terminates nt () is expressed as:
fi n(t)＝fi ref(t)*{SOC n/SOC ref}
*{SOHi n/SOHi ref}*g(T)
(here, SOHi nrepresent the SOH of described each reaction velocity).
In the condition detection method of the electric energy storage device involved by other side of the present invention, measure the voltage and current of described electric energy storage device, when being judged to be that described electric energy storage device stopped discharge and recharge according to described electric current or predetermined discharge and recharge stop signal, according to described voltage determination value calculate corresponding with the elapsed time stopping from described discharge and recharge starting at described stop time voltage variety, voltage variety when utilizing described stopping, the relaxation function f of the described each reaction velocity corresponding to the described reaction velocity short to time constant compared with the described elapsed time it () carries out optimization, the relaxation function f of the described each reaction velocity corresponding to described reaction velocity that time constant is long compared with the described elapsed time it relaxation function that () uses it previous, and according to its previous relaxation function described, described in the relaxation function f of described each reaction velocity that is optimised it at the end of (), described electric discharge, at the end of voltage and described charging, voltage estimates described quantity of state.
In the condition detection method of the electric energy storage device involved by other side of the present invention, described described voltage when stopping during burning voltage to be voltage after the discharge and recharge of described electric energy storage device stops the be variation of every 1 hour becomes below 5mv.
In the condition detection method of the electric energy storage device involved by other side of the present invention, the condition detection method of electric energy storage device, charge before the state-detection of predetermined volumes is carried out to the described electric energy storage device that stopped discharge and recharge, the voltage of described electric energy storage device when charging have passed through time t after terminating before measuring described state-detection with predetermined period, with the variable quantity (during stopping voltage variety) of voltage determination value described in relaxation function F (t) best fit approximation relative to burning voltage when making the discharge and recharge of described electric energy storage device stop and being reached for stopping when roughly fixing, described relaxation function F (t) is the function of the predetermined quantity of state of described electric energy storage device, described quantity of state is estimated by relaxation function F (t) of best fit approximation according to described, by being compared with predetermined threshold value the discharge capability judging described electric energy storage device by the quantity of state estimated by described.
In the condition detection method of the electric energy storage device involved by other side of the present invention, before described state-detection in charging, carry out the charging of the rated capacity 5% of described electric energy storage device.
In the condition detection method of the electric energy storage device involved by other side of the present invention, when terminate charging before described state-detection and the described voltage determination value obtained at first lower than during described stopping during burning voltage, be judged to be that the discharge capability of described electric energy storage device have dropped.
In the condition detection method of the electric energy storage device involved by other side of the present invention, during described stopping, burning voltage uses described relaxation function F (t) by best fit approximation to upgrade.
In the condition detection method of the electric energy storage device involved by other side of the present invention, the relaxation function f of each reaction velocity of two or more (be set to m) of described relaxation function F (t) by working out in advance accordingly with the reaction velocity of described electric energy storage device inside it the linear combination of () (i=1 ~ m) represents, the relaxation function f of described each reaction velocity it voltage variety during described stopping is separated into the component corresponding with described reaction velocity and has carried out optimization by () (i=1 ~ m).
In the condition detection method of the electric energy storage device involved by other side of the present invention, described quantity of state is the residual capacity (SOC) of described electric energy storage device.
In the condition detection method of the electric energy storage device involved by other side of the present invention, described quantity of state is the impairment grade (SOH) of described electric energy storage device.
In the condition detection method of the electric energy storage device involved by other side of the present invention, at the relaxation function f by the described each reaction velocity under predetermined normal condition it the described impairment grade of (), described residual capacity and each reaction velocity is set to f respectively i ref(t), SOC ref, and SOH i ref, by described electric energy storage device be set to G (T) relative to the dependence of temperature T time, best fit approximation is to the relaxation function f of described each reaction velocity in the n-th cycle of described voltage determination i n(t) with in described n-th cycle by the described residual capacity SOC estimated n, described each reaction velocity impairment grade SOH i nbetween there is relation below represented by formula:
f i n(t)＝f i ref(t)*{SOC n/SOC ref}
*{SOH i n/SOH i ref}*g(T)。
In the condition detection method of the electric energy storage device involved by other side of the present invention, before carrying out described state-detection before charging, pulsed discharge is carried out to described electric energy storage device and carries out other state-detection.
In the condition detection method of the electric energy storage device involved by other side of the present invention, before carrying out described state-detection before charging, carry out the impedance measuring of described electric energy storage device, and carry out other state-detection further.
In the condition checkout gear of the electric energy storage device involved by other side of the present invention, consist of and the internal charger controlled by control module can be used to charge, the feature of described condition checkout gear is, comprising: signal input unit, for input state detecting pattern commencing signal, output display unit, for externally exporting predetermined information, determination unit, for measuring the voltage of described electric energy storage device, and state detecting section, described state detecting section has state-detection mode switch, and with described control module, described signal input unit, described output display unit, and described determination unit connects, wherein, described state detecting section is when have input described state-detection pattern commencing signal from described signal input unit, the voltage of the described electric energy storage device of the elapsed time t before described electric energy storage device being carried out to state-detection from described determination unit input after charging, with the variable quantity (during stopping voltage variety) of voltage determination value described in relaxation function F (t) best fit approximation relative to burning voltage when making the discharge and recharge of described electric energy storage device stop and reaching stopping when roughly fixing, described relaxation function F (t) is the function of the predetermined quantity of state of described electric energy storage device, described quantity of state is estimated by relaxation function F (t) of best fit approximation according to described, by being compared with predetermined threshold value the discharge capability judging described electric energy storage device by the quantity of state estimated by described, and result of determination is exported to described output display unit.
In the condition checkout gear of the electric energy storage device involved by other side of the present invention, charging exports predetermined request signal by described state detecting section to described control module before described state-detection, and control described internal charger by described control module and carry out.
In the condition checkout gear of the electric energy storage device involved by other side of the present invention, before described state-detection, charging is undertaken by connecting external charger on described electric energy storage device.
Invention effect
According to the present invention, can provide and no matter be in the middle of discharge and recharge or stopped discharge and recharge all can determining whether condition detection method and the device thereof of the electric energy storage device that maintain appropriate discharge capability.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of first embodiment of the invention;
Fig. 2 is the block diagram of the structure of the electric energy storage device that the first embodiment is shown;
Fig. 3 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of second embodiment of the invention;
The curve map of the relation of voltage and SOH when Fig. 4 is the electric discharge of electrical storage device when illustrating stable;
Fig. 5 be illustrate stopping first discharging after the curve map of transient changing of OCV;
Fig. 6 is the curve map of the timeliness of falling quantity of voltages when illustrating that the elapsed time different time point place after the first electric discharge stops has carried out the second electric discharge;
Fig. 7 is OCV and the OCV variable quantity curve map over time after charging stopping is shown;
Fig. 8 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of third embodiment of the invention;
Fig. 9 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of fourth embodiment of the invention;
Figure 10 is the process flow diagram of the condition detection method that the first reference example is described;
Figure 11 is the block diagram of the Sketch of the condition checkout gear that the condition detection method employing the first reference example is shown;
Figure 12 is the process flow diagram that the timing (timing, sequential) to the data determination carried out needed for state-detection is carried out judging;
Figure 13 is the process flow diagram for illustration of judging the method that discharge and recharge stops;
Figure 14 is for illustration of OCV 20hrthe process flow diagram of system of selection;
Figure 15 is the optimized process flow diagram for illustration of carrying out F (t);
Figure 16 is the optimized process flow diagram for illustration of carrying out F (t);
Figure 17 is the process flow diagram of the method for illustration of computing mode amount SOH, SOC;
Figure 18 is the curve map of an example of the relaxation function that relaxation function and each reaction velocity are shown;
Figure 19 is the curve map that the relaxation function of each reaction velocity and an example of ratio thereof are shown;
Figure 20 is the curve map of the example that stable OCV derived formula is shown;
Figure 21 is the process flow diagram of the condition detection method that the second reference example is described;
Figure 22 is the curve map of the example that charge efficiency η 1, η 2 are shown;
Figure 23 is the process flow diagram of the condition detection method that the 3rd reference example is described;
Figure 24 is the curve map of an example of the change of the relaxation function that each reaction velocity is shown;
Figure 25 is the curve map of the example that SOH changes relative to fast reaction velocity;
Figure 26 illustrates the curve map of correction factor relative to an example of SOH;
Figure 27 is the process flow diagram of the decision method for illustration of the quantity of state in the 3rd reference example;
Figure 28 is the mode chart of the stratification for illustration of electric energy storage device;
Figure 29 is the process flow diagram of the summary of condition detection method for illustration of the electric energy storage device according to the 4th reference example;
Figure 30 is the block diagram of the condition checkout gear of electric energy storage device according to the 4th reference example;
Figure 31 be illustrate caused by the discharge and recharge in the middle of running and charging before state-detection electric current, voltage the curve map of change;
Figure 32 is for illustration of from the requested process flow diagram playing process till the charging before state-detection terminates of state-detection pattern;
Figure 33 is the process flow diagram of process when setting up for illustration of state-detection pattern;
Figure 34 is the process flow diagram of the summary of condition detection method for illustration of the electrical storage device according to other embodiments of the invention;
Figure 35 is the curve map of the relation that stable open-circuit voltage and SOC are shown;
Figure 36 is the curve map of the change of OCV when illustrating that SOC fixes;
Figure 37 is the curve map of the change that the asynchronous OCV of SOH is shown;
Figure 38 illustrates to connect cell voltage mode chart over time when load is discharged on accumulator;
Figure 39 is the different key diagram for illustration of application mode when being applied with full charge by electric energy storage device and when applying with PSOC;
Figure 40 is the curve map of the voltage illustrated at the end of the discharge and recharge that repeats in the identical charging and discharging situation of electric current aggregate-value.
Embodiment
With reference to accompanying drawing, the condition detection method of the electric energy storage device in the preferred embodiment of the present invention and device thereof are described.Identical label is marked, with simplicity of illustration and explanation for each component part with identical function.Below, using the example of the accumulators such as pregnant solution type lead acid accumulator mounted on a vehicle as electric energy storage device, the condition detection method of electric energy storage device of the present invention and condition checkout gear are described.But content described below is not limited to Vehicular accumulator cell, can be applicable to too for the electric energy storage device of solar electrical energy generation or wind-power electricity generation etc. or the electric energy storage device for the standby power supply such as stabilized power source, accessory power supply.
No matter electric energy storage device is in the middle of discharge and recharge or in discharge and recharge stopping, all can judges the discharge capability of electric energy storage device for the condition detection method of electric energy storage device of the present invention and device thereof.First, the situation of state-detection (state-detection hereinafter referred to as time lax) when relaxing with the transient changing after discharge and recharge stops, for object, is described the base conditioning content involved by the condition detection method of electric energy storage device of the present invention.Below, burning voltage when voltage when electric energy storage device being stopped discharge and recharge and reaches the state meeting predetermined stable condition is set to stopping, voltage variety when voltage determination value when have passed through time t after electric energy storage device stops discharge and recharge being set to stopping relative to the variable quantity of burning voltage when stopping.
Prior establishment depend on the predetermined quantity of state of electric energy storage device relaxation function F (t) and used as calculate above-mentioned stopping time voltage variety function.In addition, when using the stopping obtained based on voltage determination value, voltage variety carries out optimization to relaxation function F (t), estimates predetermined quantity of state carry out state-detection from relaxation function F (t) after optimization.In the condition detection method of electric energy storage device of the present invention, use above-mentioned relaxation function F (t) to estimate discharge capability (COD), and whether maintained rightly by the COD of this presumption is compared with the threshold value preset the discharge capability judging electric energy storage device.
In the present invention, use relaxation function F (t) estimates cell voltage when electric energy storage device is stablized, as the COD for judging discharge capability.In addition, threshold value adopts and is set to such magnitude of voltage: also make cell voltage not drop to below lower voltage limit required system even if carry out discharge and recharge from this state when the COD estimated is greater than threshold value.This threshold value at least sets according to the variation in voltage amount caused by common discharge and recharge, does not drop to below the lower voltage limit of system requirements to make cell voltage.In addition, as the quantity of state that can estimate based on relaxation function F (t), such as, the SOH (State of health) or residual capacity etc. of the impairment grade index as electric energy storage device is had.
The transient changing of electric energy storage device after discharge and recharge stops comprise from as ion generation and eliminate the fast change that like this reaction velocity is slow such as movement be changed to as electrolytic solution of reaction velocity reaction, these variable effects the change of the above-mentioned quantity of state after discharge and recharge stopping.Therefore, in the condition detection method of electric energy storage device of the present invention, use relaxation function F (t) to estimate the change of the quantity of state of each reaction velocity, and comprehensively the judgement of quantity of state is carried out in these changes.
As burning voltage during above-mentioned stopping, the open-circuit voltage (hereinafter referred to as OCV time stable) of the electric energy storage device stopped when have passed through time enough after discharge and recharge can be used in.Open-circuit voltage OCV is that the terminal of electric energy storage device is open thus the voltage between terminals of discharging when stopping.During the stopping used in the condition detection method of electric energy storage device of the present invention, burning voltage is not limited to stable OCV, also can use burning voltage at that time in the limited situation of the transient effect of electric energy storage device.As an example, from electric energy storage device to during load is stopped power supply, sometimes the control device etc. to load provides Weak current (dark current), when providing such dark current etc., also can using voltage when have passed through time enough after stopping load as burning voltage during stopping.
In addition, when the discharge and recharge of electric energy storage device is always fixed value, also can think that the transient effect brought to electric energy storage device is very little, therefore can using voltage when have passed through time enough after stopping load as burning voltage during stopping.So, when the impact that the electric current caused by discharge and recharge is small or bring for fixed value thus to the transient changing of electric energy storage device inside is limited in predetermined scope, can be judged to when stopped the power supply to load to stopped the electric discharge from electric energy storage device, and by voltage when have passed through long-time using the state maintaining Weak current or fixed current after discharge and recharge stops as burning voltage during stopping.Now preferably determine the voltage increment revising the change in voltage caused by Weak current or fixed current in advance, and use this voltage increment to revise voltage determination value.
Below, as an example of burning voltage when stopping, when using stable, OCV is described.When use is stablized during OCV, the relation shown in applicable Figure 35 represents quantity of state SOC as the following formula.
SOC＝FS(OCV S’(SOC’，SOH，T)) (1)
OCV s(SOC，SOH，T)＝Lim(V mes(t)) (2)
Here, OCV srepresent calculate specifically stable time OCV, OCV ' represent last calculate stable time OCV, t represent from discharge and recharge and stop elapsed time of starting at, SOC ' represents the residual capacity that the last time calculates, V mest () represents the voltage determination value at elapsed time t place, T represents the temperature of electric energy storage device.The Lim of formula (2) represents and will the elapsed time of starting at be stopped from discharge and recharge to be set to infinity, the right of formula (2) represent discharge and recharge stop after the voltage determination value V of elapsed time t electric energy storage device when being infinity mes(t).When use stablize time OCV beyond stopping time burning voltage time, also can work out above-mentioned same relational expression in advance and use between SOC.
Illustrate in above formula that SOC depends on the OCV that the last time calculates s' and determined, OCV simultaneously salso depend on SOC, but also depend on as the SOH of other quantity of state and the temperature T of electric energy storage device and change.In addition, due to OCV sdepend on quantity of state SOH, therefore quantity of state SOC also depends on SOH, thus needs to carry out respective renewal with appropriate timing.
As shown in formula (2), OCV sv when be the elapsed time t that stops starting at from discharge and recharge being infinity mes(t), but can V be set as in practical application mest the change of () is considered to the V at the time point place of very little elapsed time t mes(t).In addition, when electric energy storage device is pregnant solution type lead acid accumulator, OCV scan be set as that OCV is below 5mV every the variable quantity of hour or have passed through 20 little V constantly from discharge and recharge stops mes(t).Below, by accumulator from discharge and recharge stop have passed through 20 little V constantly mest () is set to the OCV of formula below 20hr, and use it for OCV s.
OCV 20hr＝V mes(t＝20hr)
OCV s(SOC，SOH，T)≒OCV 20hr(3)
Voltage determination value V after discharge and recharge is stopped meswhen () is set to Δ V (t) relative to the variable quantity of OCV time stable, OCV variable quantity (during stopping voltage variety) t, can represent as follows:
ΔV(t)＝V mes(t)-OCV 20hr(4)
This OCV variation delta V (t) uses the term of " polarization " always and is considered and comprises all transient changing in existing galvanochemistry definition.But Δ V (t) is by until the change in voltage produced close to the relaxation till stablize OCV, is therefore subject to the impact of the following change in voltage factor enumerated.
As the factor of change in voltage, there are polar plate status, the ion concentration of pole plate vicinity, their solid phase reaction, solid-liquid reaction and by the precipitation of electrolytic solution, convection current or spread the ionic transfer etc. caused.OCV variation delta V (t) can be considered to be combined by the different relaxation of these reaction velocitys cause.So, transient changing after the discharge and recharge stopping of electric energy storage device comprises the different course of reaction of speed, therefore in order to judge accurately discharge and recharge stop after the discharge capability of electric energy storage device, preferably adopt and the method evaluated changed to carry out state-detection to the state of each reaction velocity.
According to the difference of reaction velocity, the function F (t) be made up of m polynomial expression is used to represent OCV variation delta V (t) as the following formula.
ΔV(t)＝F(t)
＝f 1(t)+f 2(t)+…f m(t)＝∑f i(t) (5)
In above-mentioned relaxation function F (t), every f it () represents that each relaxation that the reaction velocity of electric energy storage device is different is to the contribution amount of change in voltage, is below set to the relaxation function f of each reaction velocity i(t).Every f it () is impairment grade SOH, the residual capacity SOC of the quantity of state depended on as electric energy storage device and the function of temperature T.The relaxation function f of each reaction velocity of formula (5) it () can use the voltage determination value V after stopping based on discharge and recharge mest OCV variation delta V (t) that () calculates determines, is optimised to this OCV variation delta V (t) to make it.
In the condition checkout gear employing condition detection method of the present invention, SOC, SOH, OCV before initial state is detected 20hrrespective initial value SOC 0, SOH i 0, OCV 20hr 0, the respective reference value SOC be kept in advance in condition checkout gear can be used ref (0), SOH i ref (0), OCV 20hr ref (0)set as follows.
SOC 0＝SOC ref(0)
SOH i 0＝SOH i ref(0)
OCV 20hr 0＝OCV 20hr ref(0)
After the discharge and recharge stopping of n-th time (n is the integer of more than 1) after the state-detection of electric energy storage device by condition checkout gear, when representing relaxation function F (t) of formula (5) and the relaxation function f of each reaction velocity of OCV variation delta V (t) it () is set to F respectively n(t), f i ntime (t), the relaxation function f of each reaction velocity i nt () (is set to SOC respectively based on SOC and the SOH corresponding with i-th reaction velocity n, SOH i n) can represent as the following formula.
f i n(t)＝f i ref(t)*{SOC n/SOC ref}
*{SOH i n/SOH i ref}*g(T) (6)
Here, f i ref(t), SOC ref, SOH i refthe f under the original state (such as unused state) preset i(t), SOC, SOH i, g (T) represents temperature dependent function.
In formula (6), time fixing when supposing temperature T and SOC and time to have nothing to do, SOH i nby formulae discovery below.
SOH i n＝{f i n(t)/f i ref(t)}*SOH i ref(7)
Thereby, it is possible to by the f of formula (5) i nt () optimum turns to based on voltage determination value V mest Δ V (t) that () calculates, and use this Δ V (t) to calculate SOH by formula (7) i n.
The SOH of the different various transient responses of reaction velocity is being calculated by formula (7) i ntime, these are integrated whole SOH of calculating npredetermined function G can be used to represent as follows.
SOH n＝G(SOH 1 n、SOH 2 n、…、SOH m n) (8)
Such as, when by m SOH irespective coefficient when being set to A ~ M respectively, can represent as follows.
SOH n＝A*SOH 1 n+B*SOH 2 n+…+M*SOH m n
＝A*{f 1 n(t)/f 1 ref(t)}SOH 1 ref+
B*{f 2 n(t)/f 2 ref(t)}SOH 2 ref+…+
M*{f m n(t)/f m ref(t)}SOH m ref(8-1)
Wherein, formula (8-1) is an example of the relational expression of representation formula (8), and the relational expression of formula (8) is not limited thereto.The SOH as above calculated can be used ncarry out the detection of the deterioration state of electric energy storage device.Similarly, relaxation function F (t) after using optimization also can calculate the SOC as other quantity of state n.
Use the SOH calculated by formula (7) i nand by the f of formula renewal below i n(t), and by the f after renewal i nt () is for SOC i ncalculating in.
f i n(t)＝f i ref(t)*{SOC i n-1/SOC ref}
*{SOH i n/SOH i ref}*g(T) (6-1)
Based on formula (4) and formula (6-1), OCV 20hrcalculate by formula below.
OCV 20hr＝V mes(t)-∑[f i ref(t)*{SOC n-1/SOC ref}
*{SOH i n/SOH i ref}]*g(T) (9)
By by this OCV 20hrsubstitute in formula (1), can SOC be calculated n, thus can be used in the state-detection of SOC.
As mentioned above, can based on m the reference value f corresponding with m kind reaction velocity i refthe reference value SOH of (t) (i=1 ~ m), a m impairment grade i refthe reference value SOC of (i=1 ~ m) and 1 residual capacity ref, calculate the relaxation function f of m each reaction velocity after n-th discharge and recharge stopping i n(t) (i=1 ~ m).And obtain based on this OCV, SOC and SOH of reflecting the impairment grade corresponding from different reaction velocitys, can high-precision state-detection be carried out.
In above-mentioned, with discharge and recharge stop after lax time state-detection for object, describe the basic contents processing involved by condition detection method, but state-detection when the condition detection method of electric energy storage device of the present invention is not defined to lax, also can carry out the state-detection of electric energy storage device in charge and discharge process.Below, system is in run in the middle of and electric energy storage device is just carrying out discharge and recharge time state-detection state-detection when being set to discharge and recharge.In the above description, due to only with state-detection time lax for object, therefore the periodicity n of state-detection is set to the number of times that discharge and recharge stops, but when comprising discharge and recharge state-detection state-detection in, preferably periodicity n is set to periodicity when such as carrying out state-detection periodically with predetermined time interval.
In addition, because state-detection time lax is limited to OCV along with the elapsed time t stopping from discharge and recharge starting to the state-detection in the relaxation of OCV convergence time stable (OCV variation delta V (t) is to 0 convergence), therefore, it is possible to relaxation function to be only expressed as the function F (t) of elapsed time t.But, the discharge capability COD of the electric energy storage device in charge and discharge process affects the very large of voltage variety that the elapsed time stopping from nearest discharge and recharge starting at starts at by voltage when stopping from discharge and recharge in short-term, and along with the elapsed time elongated, affect by the very large of impairment grade SOH.
Therefore, using be used as relaxation function in state-detection during lax after discharge and recharge stops function F following as discharge capability correction function F, using the function used in state-detection when state-detection when lax and discharge and recharge.In addition, in order to differentiate with OCV variation delta V (t) of formula (4), the voltage variety that voltage when stopping from discharge and recharge is started at is set to Δ Va (t).Now, discharge capability correction function F can be expressed as F (SOH, Δ Va), as the function of voltage variety Δ Va (t) with impairment grade SOH.Here, the dependence of elapsed time t is comprised in the time dependence of voltage variety Δ Va (t).
Voltage when nearest discharge and recharge being stopped, be set to voltage when discharge and recharge stops from the voltage finally carried out state-detection time point (current) when discharge and recharge stops, and be expressed as V_end.In addition, when by stopping the elapsed time of playing till state-detection time point (current) to be set to t from last discharge and recharge, current voltage is set to V_now time, voltage variety Δ Va (t) calculates by formula below.
ΔVa(t)＝V_end-V_now (10)
Here, when discharge and recharge stops, voltage V_end is set to V_cha_end when charging and stopping, and is set to V_dis_end when discharging and stopping.
OCV variation delta V (t) in stopping discharge and recharge below and the relation of above-mentioned voltage variety Δ Va (t) are described.The V of formula (4) mest () is here V_now, therefore the computing formula of OCV variation delta V (t) shown in formula (4) can be rewritten as the following formula.
ΔV(t)＝V_now-OCV 20hr(4-1)
＝F(SOH，ΔVa)
From formula (10) and formula (4-1), there is between voltage variety Δ Va (t) and OCV variation delta V (t) relation below shown in formula.
ΔVa(t)+ΔV(t)＝V_end-OCV 20hr(11)
OCV, OCV when discharge capability (being set to COD_now) during discharge and recharge stops equals stable 20hr, therefore can be provided by formula below by formula (4-1).
COD_now＝OCV 20hr＝V_now-ΔV(t)
＝V_now-F(SOH，ΔVa) (12)
That is, discharge capability COD_now deducts the value of discharge capability correction, i.e. discharge capability correction function F (SOH, Δ Va) and the value obtained from current voltage V_now.
Identical in stopping with above-mentioned discharge and recharge, the discharge capability COD_now in charge and discharge process also can use formula (12) to calculate.When will as discharge capability correction function F (SOH, Δ Va) the discharge capability correction of value when being expressed as COD_SOH, in the condition detection method of electric energy storage device of the present invention, during discharge and recharge state-detection and lax time state-detection in the discharge capability COD_now of electric energy storage device all by formulae discovery below.
ΔVa(t)＝V_end-V_now
COD_SOH＝F(SOH，ΔVa)
COD_now＝V_now-COD_SOH
Being judged to maintain discharge capability when the discharge capability calculated in above formula COD_now is greater than threshold value COD_Th, being judged to be that when being less than or equal to threshold value COD_Th discharge capability is not enough.
(the first embodiment)
Use Fig. 1, Fig. 2, the condition detection method of the electric energy storage device that first embodiment of the invention relates to and device thereof are described.Fig. 1 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of the present embodiment, and Fig. 2 is the block diagram of the structure of the condition checkout gear of the electric energy storage device that the present embodiment is shown.
The condition checkout gear 100 of the present embodiment shown in Fig. 2 is for carrying out state-detection to the electric energy storage device be arranged on the vehicle 1 of objective system (accumulator) 10.Vehicle 1 comprises: for the control module 12 of the charging that the charhing unit (alternator, alternator) 11 that charges to accumulator 10 in the middle of running at engine and controlling is undertaken by charhing unit 11 etc.In addition, vehicle 1 is provided with the load 2 of various electronic devices and components, these loads 2 to be connected on accumulator 10 thus can to accept power supply.In accumulator 10, be provided with voltage measuring unit for measuring 20, amperometric determination unit 21 and temperature measurement unit 22, condition checkout gear 100 inputs the measured value of each in these determination units and carries out state-detection.
Condition checkout gear 100 comprises: state detecting section 110, storage part 120 and State-output unit 130.State detecting section 110 inputs the voltage determination value of accumulator 10, amperometric determination value and temperature measuring value respectively from voltage measuring unit for measuring 20, amperometric determination unit 21 and temperature measurement unit 22, and carries out the state-detection of carrying out accumulator 10 based on the process of the condition detection method of the present embodiment.The various reference data needed for process that storage part 120 preservation state detects and determination data etc.In addition, State-output unit 130 is the unit waiting notify status testing result etc. to driver.
No matter whether accumulator 10 is in the middle of discharge and recharge the condition detection method of the electric energy storage device of the present embodiment, is all performed periodically with predetermined time interval in state detecting section 110 after condition checkout gear 100 starts.In FIG, after starting the state-detection of n-th time in step sl, voltage measuring unit for measuring 20 is used to obtain the voltage determination value of accumulator 10 in step s 2, and using this voltage determination value as current voltage V_now.
In step s3, judge that accumulator 10 to be in the middle of discharge and recharge (result of determination as "Yes"), still be in discharge and recharge to stop central (result of determination is "No"), and when result of determination is "Yes", enter step S8, enter step S4 when result of determination is "No".About this judgement, amperometric determination unit 21 can be used to obtain the amperometric determination value of accumulator 10, and in the middle of being judged to be that when this value is 0 discharge and recharge stops, the value beyond for 0 is judged to be in the middle of discharge and recharge.Or, in the middle of being judged to be when also the absolute value of amperometric determination value can be less than or equal to predetermined current threshold that discharge and recharge stops, in time beyond it, is judged to be in the middle of discharge and recharge.
When being judged to be that discharge and recharge stops central (result of determination is "No") in step s3, then after judging whether accumulator 10 is in just stopping discharge and recharge in step s 4 which, step S5 is entered, when entering step S7 for during "No" when result of determination is "Yes".About this judgement, can be judged to be in just stopping discharge and recharge when being judged to be in the middle of discharge and recharge in the state-detection in front once ((n-1)th time) after.After being judged to be in just stopping discharge and recharge in step s 4 which time (result of determination is "Yes"), in step s 5 current voltage V_now is set as that voltage V_end when discharge and recharge stops (is V_cha_end when charging stops, electric discharge is V_dis_end when stopping), and be stored in storage part 120, then charge to step S7.
In the step s 7, the voltage V_end when discharge and recharge be stored in storage part 120 stops is read.Voltage V_end when this discharge and recharge stops is stored in storage part 120 by step S5 when stopping from current nearest discharge and recharge.Voltage V_end when stopping based on this discharge and recharge and current voltage V_now, and pass through formulae discovery voltage variety Δ Va_n below.
ΔVa_n＝V_end-V_now
In step s 8, the impairment grade SOH_n1 be stored in storage part 120 is read in.Here, n1 represents that SOH is by the periodicity (n1≤n) during final updating, and impairment grade SOH_n1 is the previous SOH of final updating.The characteristic value of the accumulator 10 during new product is kept in storage part 120 as with reference to data in advance, and from this reference data, reads in SOH to be used as the initial value SOH_0 of SOH_n.Or, the characteristic value of general electric energy storage device is kept in storage part 120 as with reference to data in advance, and using the SOH of this reference data as SOH_0.This SOH_0 is rewritten by SOH_1, the value calculated when SOH_1 is and carries out state-detection first after installing accumulator 10.In step s 9, from storage part 120, read in the discharge capability correction function F corresponding with the impairment grade SOH_n1 read in step s 8 (SOH_n1, x).
In step slo, the Δ Va_n that calculates in the step s 7 is substituted into discharge capability correction function F and (in SOH_n1, variable x x), calculate discharge capability correction COD_SOH_n.
COD_soh_n＝F(SOH_n1，ΔVa_n)
In step s 11, based on current voltage V_now and the discharge capability correction COD_SOH_n that calculates in step slo, by formulae discovery present discharge ability COD_now below.
COD_now＝V_now-COD_SOH_n
In step s 12, the threshold value COD_Th of the present discharge ability COD_now calculated in step s 11 and discharge capability is compared, when present discharge ability COD_now is greater than threshold value COD_Th, be judged to be the discharge capability (step S13) that maintain accumulator 10, on the other hand, when present discharge ability COD_now is less than or equal to threshold value COD_Th, be judged to be discharge capability deficiency (step S14).This result of determination, by suitably exporting to appropriate state output unit 130, can notify to driver etc.
As mentioned above, according to condition detection method and the condition checkout gear of the electric energy storage device of the present embodiment, no matter be in the middle of discharge and recharge or be in the middle of discharge and recharge stopping, all can judging whether discharge capability is maintained rightly.In the present embodiment, as the impairment grade SOH calculated needed for discharge capability correction, employ the SOH_n1 from the current last time be recently stored in storage part, but because the change of SOH is very little at short notice, even if therefore use SOH_n1 also can estimate present discharge ability COD_now accurately.
(the second embodiment)
Use Fig. 3, the condition detection method of the electric energy storage device that second embodiment of the invention relates to is described.Fig. 3 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of the present embodiment.The present embodiment can carry out in the state-detection when discharge and recharge stops reflecting discharge and recharge stop after short time in the judgement of discharge capability of transient changing.
Below, the impact suffered by the transient changing after first stopping from discharge and recharge the COD of electric energy storage device is described.SOH when Fig. 4 shows electric discharge and the relation of discharge capability COD.In the diagram, using discharge stop after have passed through that electric energy storage device reached stable in 20 hours time voltage determination value (D1) represent on the longitudinal axis as discharge capability COD, the SOH calculated with condition is now represented on transverse axis.In addition, show the dotted line L1 of approximate voltage measured value in the lump, as shown in dotted line L1, there is between known SOH and COD the relation of basic 1 to 1.Based on this, by SOH during calculation stability accurately, COD can be obtained accurately.
On the other hand, below, the impact of the transient changing when electric energy storage device after research charging stopping not being stablized.Fig. 5 shows the transient changing of the OCV after charging stopping.(a) of Fig. 5 shows the change of OCV when being illustrated with logarithmic scale by the time shaft of transverse axis, and Fig. 5 (b) schematically shows the change of the OCV of Fig. 5 (a) when being illustrated with linear graduation by the time shaft of transverse axis.As shown in Figure 5, after stopping charging, the transient changing caused by charging slowly relaxes, and OCV restrains to stable OCV gradually.
But the elapsed time after charging stops is shorter, and the impact of the transient changing caused by charging is larger, if therefore discharged at this time point, that will be charged before affects very greatly.Therefore, figure 6 illustrates and carried out falling quantity of voltages when discharging over time at the elapsed time different multiple time points after stopping that charging.There is illustrated stop elapsed time of starting to be 30 seconds (label t1) from charging, 100 seconds (label t2), 300 seconds (label t3), 3600 seconds (label t4), 36000 seconds (label t5) and 72000 seconds (label t6) time point carried out falling quantity of voltages when discharging over time.Here, as electric discharge, make the discharge sustain of 100 [A] carry out 30 seconds.
As can be seen from Figure 6, the elapsed time after charging stops is shorter, and falling quantity of voltages is larger.Especially the falling quantity of voltages when the time point that have passed through 30 seconds after stopping of the charging falling quantity of voltages (label t1) of having carried out when discharging is greater than the elapsed time till more extending from electric discharge is played in charging stopping.If will the elapsed time of starting at be stopped to extend to a certain degree from charging, falling quantity of voltages almost see any difference.Because the missionary society of such falling quantity of voltages Δ va affects COD, therefore when the time point short in the elapsed time stopping from charging starting at judges COD, preferably carry out the correction with the poor corresponding COD of falling quantity of voltages Δ va.
In the present embodiment, think that the difference of above-mentioned falling quantity of voltages Δ va is caused by the change along with the impairment grade SOH_fast fast caused by transient changing, thus calculate SOH_fast based on formula (7), and use prepared in advance and the function G (SOH_fast, SOH_slow) shown in formula (8) be stored in storage part 120 calculates SOH.Here, SOH_slow represents the impairment grade caused by transient changing slowly calculated when nearest discharge and recharge stops.In order to calculate the impairment grade SOH_fast caused by transient changing fast accurately, use voltage determination value to the relaxation function f of each reaction velocity of discharge capability correction function F (SOH, Δ Va) it relaxation function f that in (), reaction velocity is fast it () carries out optimization.This optimization can be carried out after have passed through the schedule time (being set to for the first slack time) stopping from discharge and recharge.
In contrast, when the time point long in the elapsed time stopping from electric discharge starting at judges COD, the impact that falling quantity of voltages Δ va brings is little, and the impact of the precision of the SOH using Fig. 4 to be described is very large.In addition, in above-mentioned Fig. 4 ~ Fig. 6, the impact of the transient changing after stopping charging is illustrated, but the impact of the transient changing after stopping of discharging too.
In the condition detection method of the electric energy storage device of the present embodiment, when the elapsed time stopping from discharge and recharge starting in short-term, calculate the poor corresponding SOH_fast with the voltage variety Δ va produced along with transient changing fast accurately, and use this SOH_fast to estimate discharge capability COD.Here, below, use Fig. 7 to stopping the elapsed time of starting to be described for what distinguish transient changing fast from discharge and recharge.The first above-mentioned slack time can as the elapsed time distinguishing above-mentioned transient changing fast.Fig. 7 (a) shows the OCV (label 71) of pregnant solution type lead acid accumulator (battery capacity is 48 [Ah]) after charging stops and the time variations of OCV variation delta V (label 72), and Fig. 7 (b) shows the OCV (label 73) of small size closed lead-acid accumulator (battery capacity I 5.5 [Ah]) after charging stops and the time variations of OCV variable quantity (label 74).
In the pregnant solution type accumulator shown in Fig. 7 (a), reach stable required time from electrolytic solution its structure long, if the absolute value of OCV variation delta V is not less than 0.2V, can not be called to reach and stabilizes.Therefore, in Fig. 7 (a), when the absolute value of OCV variation delta V being dropped to roughly 0.2V, stop the elapsed time t_fast started at as the elapsed time corresponding with transient changing fast from discharge and recharge.On the other hand, in the sealed type battery shown in Fig. 7 (b), reach stable required time from electrolytic solution its structure short, when the absolute value of OCV variation delta V being dropped to 0.3V, stop the elapsed time t_fast started at as the elapsed time corresponding with transient changing fast from discharge and recharge.Below, the elapsed time t_fast corresponding with transient changing was fast used as the first slack time.
Below, use the process flow diagram shown in Fig. 3, the condition detection method of the electric energy storage device of the present embodiment is described.Play from the state-detection of n-th time step S3 whether be in discharge and recharge stop in the middle of judgement till, carry out the process identical with the step S1 ~ S3 shown in the process flow diagram of Fig. 1.In addition, when being judged in step s3 to be in the middle of discharge and recharge, carry out the process identical with the step S7 of Fig. 1 ~ S10 (by above as processing module A), step S11 and step S12 ~ S14 (will be above as processing module B).
On the other hand, when being judged to not to be in (being in discharge and recharge stops central) in the middle of discharge and recharge in step s3, after carrying out the process identical with the step S4 of Fig. 1, S5, judge to stop the elapsed time of starting at whether to be greater than for the first slack time from discharge and recharge in step S20.Then, when the elapsed time was less than or equal to for the first slack time, identical with the first embodiment, carry out the process of processing module A, step S11 and processing module B.On the other hand, when being judged to stop the elapsed time of starting to be greater than for the first slack time from discharge and recharge in step S20, the process of following steps S21 ~ S27 is carried out in the present embodiment.
In the step s 21, with the step S7 identical calculations voltage variety Δ Va_n of processing module A.In following step S22, formula (7) is used to calculate the impairment grade SOH_fast_n caused by transient changing fast.In step S23, read in the impairment grade SOH_slow_n caused by transient changing be slowly stored in storage part 120, from storage part 120, read in SOH calculating formula G (SOH_fast, SOH_slow) in step s 24 which.In step s 25, by SOH_fast and SOH_slow that the above-mentioned SOH_fast_n calculated and the SOH_slow_n read in are substituted into SOH calculating formula G (SOH_fast, SOH_slow) respectively, current SOH_n is calculated.
In step S26, identical with step S9, from storage part 120, read in the discharge capability correction function F corresponding with the impairment grade SOH_n calculated in step s 25 (SOH_n, x).Then, in step s 27, substitute into discharge capability correction function F by the Δ Va_n that will calculate in the step s 21 and (in SOH_n, variable x x), calculate discharge capability correction COD_SOH_n.
COD_soh_n＝F(SOH_n1，ΔVa_n)
Afterwards, in step s 11, present discharge ability COD_now is calculated based on current voltage V_now and the discharge capability correction COD_SOH_n that calculates in step s 27.And use present discharge ability COD_now to carry out the process of processing module B.
According to the condition detection method of the electric energy storage device of the present embodiment and the condition checkout gear of electric energy storage device of the present embodiment employing this condition detection method, except no matter be in the middle of discharge and recharge or be in discharge and recharge stop in the middle of all can judging whether discharge capability is maintained rightly except, also calculate impairment grade SOH based on fast transient response in short-term in discharge and recharge stand-by time, thus can more precisely estimate present discharge ability COD_now than the occasion of the SOH_n1 of use first embodiment.
(the 3rd embodiment)
Use Fig. 8, the condition detection method of the electric energy storage device that third embodiment of the invention relates to is described.Fig. 8 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of the present embodiment.The discharge capability of the transient changing after the present embodiment makes state-detection when stopping as discharge and recharge to calculate to reflect discharge and recharge to stop.Namely, in the middle of the discharge and recharge of electric energy storage device stops, not only calculate the impairment grade SOH_slow also calculated by transient changing causes slowly by the impairment grade SOH_fast that transient changing causes fast and obtain impairment grade SOH accurately, and use this impairment grade SOH to estimate accurately and judge the discharge capability of electric energy storage device.Below, using the elapsed time corresponding with transient changing slowly as the second slack time.
In the process flow diagram shown in Fig. 8, the elapsed time of playing step S20 from the state-detection of n-th time carries out the process identical with the condition detection method of the second embodiment shown in the process flow diagram of Fig. 3 till whether being greater than the judgement of the first slack time.In addition, when being judged to be that the elapsed time was less than or equal to for the first slack time in step S20, the process of the processing module A of Fig. 3, step S11 and processing module B is carried out.On the other hand, when being judged to be that the elapsed time was greater than for the first slack time in step S20, identical with the second embodiment, in rapid 21, calculate voltage variety Δ Va_n, then enter the process of step S30.
In step s 30, judge to stop the elapsed time of starting at whether to be greater than for the second slack time from discharge and recharge.Its result, when the elapsed time was less than or equal to for the second slack time, identical with the second embodiment, carry out the process of step S22 ~ S27 (as processing module C).On the other hand, when being judged in step s 30 to stop the elapsed time of starting to be greater than for the second slack time from discharge and recharge, the process of following steps S31 ~ S34 is carried out in the present embodiment.
In step S31, OCV variation delta V_n is calculated based on formula (4), and use this OCV variation delta V_n to carry out optimization according to the relation of formula (5) to discharge capability correction function F (SOH, Δ Va) in step s 32.In step S33, formula (7) and formula (8) is used to calculate current impairment grade SOH_n.Further, in step S34, by the Δ calculated in the step s 21 Va_n and the SOH_n that calculates in step S33 is substituted into the discharge capability correction function F (SOH, Δ Va) after optimization, discharge capability correction COD_SOH_n is calculated.
Afterwards, in step s 11, present discharge ability COD_now is calculated based on current voltage V_now and the discharge capability correction COD_SOH_n that calculates in step s 27.Further, present discharge ability COD_now is used to carry out the process of processing module B.
According to the condition detection method of the electric energy storage device of the present embodiment and the condition checkout gear of electric energy storage device of the present embodiment employing this condition detection method, except no matter be in the middle of discharge and recharge or be in discharge and recharge stop in the middle of all can judging whether discharge capability is maintained rightly except, also by when discharge and recharge stops by with stopping after elapsed time independently calculate impairment grade SOH accurately, thus can more precisely estimate present discharge ability COD_now.
(the 4th embodiment)
Use Fig. 9, the condition detection method of the electric energy storage device that fourth embodiment of the invention relates to is described.Fig. 9 is the process flow diagram of the treatment scheme of the condition detection method of electric energy storage device for illustration of the present embodiment.
When carrying out the state-detection of electric energy storage device after stopping in discharge and recharge, because of differences such as discharge and recharge history before this, there is very big-difference in transient changing.Such as, the accumulator be arranged on automobile carries out various discharge and recharge in the middle of travelling at vehicle, and the migration therefore produced in the electrolytic solution of accumulator, precipitation, convection current, diffusion etc. are also various because of the difference of vehicle operating condition.Therefore, the transient changing of accumulator after discharge and recharge stops is different because of the difference of vehicle operating condition before this, cannot produce identical or can think trend identical there is reproducible halted state.
The present embodiment is made to address these problems, for providing the impact of the discharge and recharge before reducing electric energy storage device stopping carrying out condition detection method and the device thereof of the electric energy storage device of state-detection.In the present embodiment, when carrying out state-detection after stopping in discharge and recharge, accumulator 10 is carried out to the charging (charging hereinafter referred to as before state-detection) of predetermined volumes after discharge and recharge just stops, and the state-detection of electric energy storage device is carried out in charging after terminating before state-detection.Charge as before state-detection, preference is as carried out the charging of rated capacity 5%.
Process flow diagram shown in Fig. 9 is except the process after discharge and recharge just stops, there is the treatment scheme that the condition detection method of the 3rd embodiment shown in Fig. 8 is identical, in the present embodiment, can with stop after elapsed time independently calculate impairment grade SOH accurately, thus present discharge ability COD_now can be estimated accurately.And, in the present embodiment, be after discharge and recharge has just stopped when determining in step s 4 which, then charge before carrying out state-detection in step s 40.Charge before carrying out such state-detection, electric energy storage device transfers to the state with reproducible transient changing.Thus, can identical or can think trend identical there is reproducible halted state under carry out state-detection, thus more precisely can carry out the state-detection of electric energy storage device.
The condition detection method of the electric energy storage device of the present invention of above-mentioned explanation and device thereof are not limited to the existing electric energy storage device be arranged on engine-driven vehicle, the reserve battery worked when being applicable to electric automobile, portable phone, power failure, with in the cooperation of electric system for the electrical storage device of the balanced electric power utilizing the natural the subject of knowledge and the object of knowledge of sun power or wind-force to send and system that they are combined with.Condition detection method and the device thereof of electric energy storage device of the present invention are not limited to such use, can be applicable to have installed electric energy storage device and need to carry out to monitor or any device of condition adjudgement.As electric energy storage device, have accumulator or capacitor etc., be about to make the energy of device interior increase via electronics or moving of ion or reduce and the device that its internal energy can be obtained by outside with electric-powered manner for object.Such as there are lithium (Li) ion battery, nickel (Ni) hydrogen battery, sodium-sulphur battery, lead-acid battery, capacitor etc., the accumulating system they be combined with can also be applied to.An example just part for above-mentioned electric energy storage device, is not limited to above-mentioned accumulator or capacitor.
According to condition detection method and the device thereof of electric energy storage device of the present invention, even if system is not necessarily in the discharge capability that also can judge electric energy storage device in the middle of stopping, the misoperation of electric energy storage device installation system therefore can not be caused because the mistake of discharge capability judges.In addition, the discharge capability decision method due to electric energy storage device constructs to distinguish and is subject to the very large condition affected of electric energy storage device external factor and the condition beyond it to carry out the algorithm calculated, and therefore can use respectively according to state.Its result, the range of choice based on the control method of result of determination broadens, and the system more flexibly that can realize is used.
(the 5th embodiment)
The condition detection method of the electric energy storage device that fifth embodiment of the invention relates to is described.
In the condition detection method of the electric energy storage device of the present embodiment, detected the transient changing of the electric energy storage device after discharge and recharge stopping by the change of the voltage that can measure from electric energy storage device.Namely, voltage when electric energy storage device being stopped discharge and recharge and reaches the state meeting predetermined stable condition is as burning voltage during stopping, and the voltage determination value after utilizing discharge and recharge to stop carries out the state-detection under the transient behaviour of electric energy storage device relative to the variable quantity of burning voltage when stopping.Below, using voltage determination value when have passed through time t after electric energy storage device stops discharge and recharge relative to the variable quantity of burning voltage when stopping as voltage variety during stopping.
In the condition detection method and device thereof of the electric energy storage device of the present embodiment, in advance establishment depends on relaxation function F (t) of the predetermined state amount of electric energy storage device, and used as the function of voltage variety when calculating above-mentioned stopping.Further, when using the stopping obtained by voltage determination value, voltage variety carries out optimization to relaxation function F (t), estimates predetermined quantity of state and carried out state-detection from relaxation function F (t) after optimization.In the condition detection method of the present embodiment, voltage status before detection discharge and recharge just stops, and use above-mentioned relaxation function F (t) to estimate predetermined quantity of state, and compare with each determinating reference preset the discharge capability (COD) judging electric energy storage device by the quantity of state of described presumption and whether maintained rightly.As predetermined quantity of state, such as, can be used as the SOH (State of health) of the index of the impairment grade of electric energy storage device or represent the SOC etc. of residual capacity.
The transient changing of electric energy storage device after discharge and recharge stops comprise from as ion generation and eliminate the fast change that like this reaction velocity is slow such as movement be changed to as electrolytic solution of reaction velocity reaction, these variable effects the change of the above-mentioned quantity of state after discharge and recharge stopping.Therefore, in the condition detection method of the electric energy storage device of the present embodiment, use relaxation function F (t) to estimate the change of the quantity of state of each reaction velocity, and comprehensively the judgement of quantity of state is carried out in these changes.Such as, also consider that the impact of slow reaction velocity is to the quantity of state at the short time point place of the elapsed time after judging discharge and recharge and terminating.
As burning voltage during above-mentioned stopping, there will be a known at the open-circuit voltage OCV (hereinafter referred to as OCV time stable) stopping electric energy storage device when have passed through time enough after discharge and recharge.OCV is that the terminal of electric energy storage device is open thus the voltage between terminals of discharging when stopping.During the stopping used in the condition detection method of the electric energy storage device of the present embodiment, burning voltage is not limited to OCV, when defining the transient effect to electric energy storage device, also can use burning voltage at that time.As an example, from electric energy storage device to during load is stopped power supply, sometimes the control device etc. to load provides Weak current (dark current), when providing such dark current etc., also can using voltage when have passed through time enough after stopping load as burning voltage during stopping.
In addition, even if when the discharge and recharge of electric energy storage device is always fixed value, also can think that the transient effect brought to electric energy storage device is very little, therefore can using voltage when have passed through time enough after stopping load as burning voltage during stopping.So, when the impact that the electric current caused by discharge and recharge is small or bring to the transient changing of electric energy storage device inside for fixed value is limited in predetermined scope, can be judged to when stopped the power supply to load to stopped the electric discharge from electric energy storage device, and by voltage when have passed through long-time using the state maintaining Weak current or fixed current after discharge and recharge stops as burning voltage during stopping.Now preferably determine the voltage increment revising the change in voltage caused by Weak current or fixed current in advance, and use this voltage increment to revise voltage determination value.
Below, as an example of burning voltage when stopping, when using stable, OCV is described.When use is stablized during OCV, the relation shown in applicable Figure 35 represents quantity of state SOC as the following formula.
SOC＝FS(OCV S’(SOC’，SOH，T)) (1-1)
OCV s(SOC，SOH，T)＝Lim(V mes(t)) (1-2)
Here, OCV srepresent calculate specifically stable time OCV, OCV ' represent last calculate stable time OCV, SOC ' represent the last residual capacity calculated, T represents the temperature of electric energy storage device.Further, the Lim of above formula represents and will the elapsed time of starting at be stopped from discharge and recharge to be set to infinity, the right of formula (1-2) represent discharge and recharge stop after the voltage determination value V of elapsed time electric energy storage device when being infinity mes(t).Similarly, when use stablize time OCV beyond stopping time burning voltage time, also can work out above-mentioned same relational expression in advance between SOC.
Illustrate in above formula that SOC depends on the OCV that the last time calculates s' and determined, OCV simultaneously salso depend on SOC, but also depend on as the SOH of other quantity of state and the temperature T of electric energy storage device and change.In addition, due to OCV sdepend on other quantity of state SOH, quantity of state SOC also depends on SOH, thus needs to carry out respective renewal with appropriate timing.
As shown in formula (1-2), OCV sv when be the elapsed time t that stops starting at from discharge and recharge being infinity mes(t), but also can V be set as in practical application mest the change of () is considered to the V at the time point place of very little elapsed time t mes(t).In addition, when electric energy storage device is pregnant solution type lead acid accumulator, OCV scan be set as that OCV is below 5mV every the variable quantity of hour or have passed through 20 little V constantly from discharge and recharge stops mes(t).Below, using electric energy storage device be the occasion of the accumulators such as pregnant solution type lead acid accumulator as an example, the condition detection method of electric energy storage device of the present invention is described.
Below, by accumulator have passed through from discharge and recharge stops 20 little Vmes (t) be constantly set to below the OCV of formula 20hr, and use it for OCV s.
OCV 20hr＝V mes(t＝20hr)
OCV s(SOC，SOH，T)≒OCV 20hr(1-3)
Voltage determination value V after discharge and recharge is stopped meswhen () is set to Δ V (t) relative to the variable quantity of OCV time stable, OCV variable quantity (during stopping voltage variety) t, can represent as follows:
ΔV(t)＝V mes(t)-OCV 20hr(1-4)
This OCV variation delta V (t) uses the term of " polarization " always and is considered and comprises all transient changing in existing galvanochemistry definition.But Δ V (t) is by until the change in voltage produced close to the relaxation till stablize OCV, is therefore subject to the impact of the following change in voltage factor enumerated.As the factor of change in voltage, there are polar plate status, the ion concentration of pole plate vicinity, their solid phase reaction, solid-liquid reaction and by the precipitation of electrolytic solution, convection current or spread the ionic transfer etc. caused.Δ V (t) can be considered to be combined by the different relaxation of these reaction velocitys cause.So, transient changing after the discharge and recharge stopping of electric energy storage device 11 comprises the different course of reaction of speed, therefore in order to judge accurately discharge and recharge stop after the discharge capability of electric energy storage device 11, preferably adopt and the method evaluated changed to carry out state-detection to the state of often kind of reaction velocity.
According to the difference of reaction velocity, the function F (t) be made up of m polynomial expression is used to represent Δ V (t) as the following formula.
ΔV(t)＝F(t)
＝f 1(t)+f 2(t)+…f m(t)＝∑f i(t) (1-5)
In above-mentioned relaxation function F (t), every f it () represents that relaxation that the reaction velocity of electric energy storage device is different is to the contribution amount of change in voltage, is below set to the relaxation function f of each reaction velocity i(t).Every f it () is impairment grade SOH, the residual capacity SOC (ion concentration) of the quantity of state depended on as accumulator and the function of temperature T.The relaxation function f of each reaction velocity of formula (1-5) it () can use the voltage determination value V after stopping according to discharge and recharge mest Δ V (t) that () calculates is determined, is optimised to this Δ V (t) to make it.
In the condition detecting system of the condition detection method of the present embodiment, SOC, SOH, OCV before state-detection is started 20hrrespective initial value SOC 0, SOH i 0, OCV 20hr 0, the respective reference value SOC be kept in advance in condition detecting system can be used ref (0), SOH i ref (0), OCV 20hr ref (0)set as follows.
SOC 0＝SOC ref(0)
SOH i 0＝SOH i ref(0)
OCV 20hr 0＝OCV 20hr ref(0)
Here, reference value SOC ref (0), SOH i ref (0), OCV 20hr ref (0)the value obtained in other battery respectively.
After the discharge and recharge stopping of n-th time (n is the integer of more than 1) after being detected by condition detecting system initial state, when representing relaxation function F (t) of formula (1-5) and the relaxation function f of each reaction velocity of OCV variation delta V (t) it () is set to F respectively n(t), f i ntime (t), the relaxation function f of each reaction velocity i nt () (is set to SOC respectively based on SOC and the SOH corresponding with i-th reaction velocity n, SOH i n) can represent as the following formula.
f i n(t)＝f i ref(t)*{SOC n/SOC ref}
*{SOH i n/SOH i ref}*g(T) (1-6)
Here, f i ref(t), SOC ref, SOH i refthe f under the original state (such as unused state) preset i(t), SOC, SOH i, g (T) represents temperature dependent function.
In formula (1-6), when temperature T and SOC and time have nothing to do and fix, SOH i nby formulae discovery below.
SOH i n＝{f i n(t)/f i ref(t)}*SOH i ref(1-7)
Thereby, it is possible to by the f of formula (1-5) i nt () optimum turns to based on voltage determination value V mest Δ V (t) that () calculates, and use this Δ V (t) to calculate SOH by formula (1-7) i n.
The SOH of the different each transient response of reaction velocity is being calculated by formula (1-7) i nafter, these are integrated whole SOH of calculating ncan represent as follows.
SOH n＝G(SOH 1 n、SOH 2 n、…、SOH m n) (1-8)
Such as, when by m SOH ithe coefficient of each when being set to A ~ M, can represent as follows.
SOH n＝A*SOH 1 n+B*SOH 2 n+…+M*SOH m n
＝A*{f 1 n(t)/f 1 ref(t)}SOH 1 ref+
B*{f 2 n(t)/f 2 ref(t)}SOH 2 ref+…+
M*{f m n(t)/f m ref(t)}SOH m ref(1-8-1)
Wherein, formula (1-8-1) is an example of the relational expression of representation formula (1-8), and the relational expression of formula (1-8) is not limited thereto.The SOH as above calculated can be used ncarry out the detection of the deterioration state of accumulator.Similarly, relaxation function F (t) after using optimization also can calculate the SOC as other quantity of state n.
Relaxation function F (t) shown in formula (1-5) is owing to having the relaxation function f of the different each reaction velocity of reaction velocity it (), therefore after the discharge and recharge stopping of n-th time, if the elapsed time is short, then cannot pass through the f corresponding with slow reaction velocity i nt () optimization is obtained.Its result, cannot use relaxation function F (t) to upgrade SOC n, SOH i n.Therefore, at the f corresponding with slow reaction velocity i nt () becomes and before optimization, can replace SOC n, SOH i nand value SOC when using last discharge and recharge to stop n-1, SOH i n-1, and be formula below by formula (1-6) approximate representation.
f i n(t)＝f i ref(t)*{SOC n-1/SOC i ref}
*{SOH i n-1/SOH i ref}*g(T) (1-6-1)
For the f corresponding with slow reaction velocity i nt when () can use formula (1-6-1), state-detection can be carried out from have passed through the time point of short time after discharge and recharge stops.Especially, when only carrying out the discharge and recharge of below predetermined threshold, the SOC after can terminating make use of last discharge and recharge n-1, SOH i n-1relaxation function F nt () is used in state-detection.
On the other hand, about the residual capacity SOC of accumulator, discharge and recharge in during can stopping for the discharge and recharge playing current (n-th time) from the discharge and recharge stopping terminating last ((n-1)th time), residual capacity variation delta SOC is calculated by the charging and discharging currents in accumulative this period, and by revising last residual capacity SOC with this residual capacity variation delta SOC n-1calculate SOC n.Namely set as the following formula.
SOC n-1’＝SOC n-1+ΔSOC
Use this SOC n-1' replace SOC n, can be formula below by formula (1-6) approximate representation.
f i n(t)＝f i ref(t)*{SOC n-1’/SOC ref}
*{SOH i n-1/SOH i ref}*g(T) (1-6-2)
Use the SOH calculated by formula (1-7) i nand by the f of formula renewal below i n(t), and by the f after renewal i nt () is for SOC i ncalculating in.
f i n(t)＝f i ref(t)*{SOC i n-1/SOC ref}
*{SOH i n/SOH i ref}*g(T) (1-6-3)
Based on formula (1-4) and formula (1-6-3), OCV 20hrcalculate by formula below.
OCV 20hr＝V mes(t)-∑[f i ref(t)*{SOC n-1/SOC ref}
*{SOH i n/SOH i ref}]*g(T) (1-9)
By by this OCV 20hrsubstitute in formula (1-1), can SOC be calculated n, thus can be used in the state-detection of SOC.
As mentioned above, can based on m the reference value f corresponding with m kind reaction velocity i refthe reference value SOH of (t) (i=1 ~ m), a m impairment grade i refthe reference value SOC of (i=1 ~ m) and 1 residual capacity ref, calculate the relaxation function f of m each reaction velocity after n-th discharge and recharge stopping i n(t) (i=1 ~ m).And obtain based on this OCV, SOC and SOH of reflecting the impairment grade corresponding from different reaction velocitys, can high-precision state-detection be carried out.
Below, Figure 10, Figure 11 condition detection method to the electric energy storage device of the fifth embodiment of the present invention is used to be described.Figure 10 is the process flow diagram of the treatment scheme of carrying out for illustration of the condition detection method by the present embodiment.In addition, Figure 11 is the block diagram of the Sketch of the condition checkout gear that the condition detection method employing the present embodiment is shown.Condition checkout gear 210 shown in Figure 11 carries out the state-detection of the accumulator 201 be arranged on vehicle as an example.Accumulator 201 is connected with charhing unit 202 and load 203, thus is undertaken charging and discharging to load 203 by charhing unit 202.In addition, be provided with temperature measurement unit 201a, voltage measuring unit for measuring 201b and amperometric determination unit 201c in accumulator 201, these unit can input respective measured value via input block 204 to condition checkout gear 210.And be provided with the control device 205 that the discharge and recharge of accumulator 201 is controlled.Also can from control device 205 via input media 204 to condition checkout gear 210 input control information.
Condition checkout gear 210 comprises: arithmetic unit 211, static memory cell (ROM) 212 and temporary storage cell (RAM) 213, timer 2 14 and State-output unit 215.Arithmetic unit 211 uses input block 204 to input the temperature measuring value of accumulator 201, voltage determination value and amperometric determination value, and these measured values is saved in temporary storage cell 213.In addition, the relaxation function f of each reaction velocity is preserved in static memory cell 212 ithe initial value of (t), various quantity of state or reference value.Arithmetic unit 211 uses the initial value or reference value that are kept in static memory cell 212 and the voltage determination value etc. be kept in temporary storage cell 213, and the state-detection of accumulator 201 is carried out with cycle predetermined time counted by timer 2 14, then result is inputed to State-output unit 215.The output information of State-output unit 215 also can be provided for the information of the controling parameters for control device 205.
Below, use the process flow diagram shown in Figure 10, the condition detection method of this reference example is described.First, in step s 201, input block 204 is used to input voltage determination value and the amperometric determination value of accumulator.In following step S202, judge that discharge and recharge stops whether starting based on inputted amperometric determination value.When be judged to be discharge and recharge stop starting time, in step S203 using voltage determination value before as electric discharge at the end of voltage V dEor voltage V at the end of charging cEbe saved in temporary storage cell 213.Then, in step S204, voltage V at the end of discharging dEor voltage V at the end of charging cEwith the V of the reference value be kept in static memory cell 212 refrelatively, and higher than reference value V refin time, enters in following step S205.On the other hand, voltage V at the end of electric discharge dEor voltage V at the end of charging cElower than reference value V reftime, be judged to be that discharge capability COD is not enough, enter in step S213 and export COD deficiency to State-output unit 215, then terminate.
Here, V refit is the value (such as, 12.8V) measured in other battery in advance.
Voltage V at the end of be judged to be electric discharge in step S204 dEor voltage V at the end of charging cEbe more than or equal to V reftime, in step S205, judgement is in discharge and recharge and stops central or restarted discharge and recharge.When being judged to have restarted discharge and recharge, done state detects.On the other hand, when discharge and recharge stops continue, in step S206, voltage determination value is set as V mesand be saved in temporary storage cell 213.In following step S207, select the OCV as burning voltage when stopping 20hr, and use this OCV 20hrwith voltage determination value V mesΔ V (t) is calculated in step S208.
In step S209, be used in Δ V (t) calculated in step S208 and optimization is carried out to relaxation function F (t).About approximating method, can consider that the utilization of least square method etc. returns the various computing method calculated, but due to Δ V (20hr)=0 in this matching, if that therefore use exponential function simply and carry out recurrences calculating, error will become large.Therefore, the inclination of the tangent line near preferred introducing and Δ V (20hr)=0 offset and the function always set up of Δ V (20hr) > 0 (such as, formula described later (1-10-4)), and to its residual quantity carry out based on exponential function and matching.
In step S210, relaxation function F (t) after optimization is used to estimate predetermined quantity of state (representing with S below).In step S211, by the quantity of state S of presumption and the reference value S be kept in static memory cell 212 refrelatively, and entering step S212 when being judged to be that quantity of state S meets predetermined condition, exporting the guaranteed thing of COD to State-output unit 215.On the other hand, when being judged to be in the judgement in step S211 that quantity of state S enters in step S213 when not meeting predetermined condition, the thing of COD deficiency is exported to State-output unit 215.
In the condition detection method of the accumulator of the present embodiment, by the SOC calculating formula of formula (1-1) and with SOC, SOH, OCV 20hrreference value SOC corresponding to initial value ref (0), SOH i ref (0), OCV 20hr ref (0)be kept in advance in static memory cell 212, and use them that respective initial value is set as SOC 0=SOC ref (0), SOH i 0=SOH i ref (0), OCV 20hr 0=OCV 20hr ref (0).
Figure 12 shows the process details of step S201.In fig. 12, timer count value is confirmed in predetermined confirmation timing, and for the mensuration timing specified, if timer count value (t_count) has exceeded it measure timing value (step S201-2), then voltage, the electric current (step S201-4) of accumulator 201 are inputted from input block 214.
Figure 13 shows the example judging the method that the discharge and recharge of accumulator 201 stops in step S202.Be judged to be that when the amperometric determination value measured in step S202-2 is less than or equal to the predetermined threshold be kept in static memory cell 212 discharge and recharge stopped (step S202-4), but, such as when control device 205 is judged as that automobile is in parking or temporary parking, or when the information representing that condition checkout gear 210 has been connected with accumulator 201 is imported in arithmetic unit 211 (step S202-1), these information also can be used to judge that discharge and recharge stopped (step S202-3).
The OCV of step S207 is shown at the process flow diagram of Figure 14 20hrsystem of selection.Start to calculate OCV for n-th time 20hrtime SOC n, SOH nuse last calculated value SOC n-1, SOH n-1(step S207-1).The Current Temperatures T of accumulator 201 uses the measured value (step S207-2) inputted from input block 204.If by the OCV selected thus 20hrbe set to OCV 20hr temp, then the relational expression in advance worked out under being used in the h kind condition value of multiple SOC, SOH and temperature combined:
H (SOC_j, SOH_k, T_l)=OCV 20hr ref (h)(h, j, k, l are natural number) (step S207-4), by the OCV of formula setting below 20hr temp(step S207-5).
OCV 20hr temp＝OCV 20hr ref(h)
Below, in order to simplify, postulation formula (1-5) is formed by following 4.
F(t)＝f fast(t)+f slow(t)
＝{f fast1(t)+f fast2(t)}+
{f slow1(t)+f slow2(t)} (1-10)
As an example, such as, formula (1-10) is expressed as formula below:
The function 1:f of fast relaxation velocity fast1(t)=A*exp (-B*t^C) (1-10-1)
The function 2:f of fast relaxation velocity fast2(t)=D*exp (-E*t^F) (1-10-2)
The function 1:f of slow relaxation velocity slow1(t)=G*exp (-H*t^I) (1-10-3)
The function 2:f of slow relaxation velocity slow2(t)=-a/72000*t+b (1-10-4)
Easily work out optimized for Δ V (t) function thus.But the memory span of the arithmetic speed according to arithmetic unit 211, static memory cell 212 and temporary storage cell 213 and the precision conditions required by determination sensor etc. also can be used complicated for this function or after simplifying function.
Use Figure 15 and Figure 16, based on Δ V (t), F is obtained to the elapsed time based on timer count nt the method for () is described (step S209).Function shown in formula (1-10-1) ~ formula (1-10-4) by the interval that 4 reference times, (10 seconds, 1000 seconds, 36000 seconds, 72000 seconds) divided to make the mode becoming ascendancy separately determine each coefficient by matching.Here, reference time, (10 seconds, 1000 seconds, 36000 seconds, 72000 seconds) were an example, can set according to the relaxation property of the reaction velocity of accumulator.In addition, not only according to the reaction velocity of internal storage battery, and driving conditions in the vehicle that can use according to reality or stall condition, precision etc. required by sensor change the above-mentioned time as benchmark.
The elapsed time after discharge and recharge stops is less than 20 and littlely obtains F based on Δ V (t) constantly to use Figure 15 to illustrate nthe method of (t).When the time t of determining is less than the first reference time (10 seconds) (step S209-1), the calculated value F after stopping based on last discharge and recharge n-1t () passes through formulae discovery F below n(t) (step S209-2).
F n(t)＝f fast1 n-1(t)+f fast2 n-1(t)+
f slow1 n-1(t)+f slow2 n-1(t) (1-11)
Below, similarly when time t was more than or equal to for the first reference time and be less than the second reference time (1000 seconds) (step S209-3), the F after terminating based on last discharge and recharge n-1t () and up-to-date data pass through formulae discovery F below n(t) (step S209-4).
F n(t)＝f fast1 n(t)+f fast2 n-1(t)+
f slow1 n-1(t)+f slow2 n-1(t) (1-12)
In addition, when the time t of determining was more than or equal to for the second reference time and is less than the 3rd reference time (36000 seconds) (step S209-5), the F after terminating based on last discharge and recharge n-1t () and up-to-date data pass through formulae discovery F below n(t) (step S209-6).
F n(t)＝f fast1 n(t)+f fast2 n(t)+
f slow1 n-1(t)+f slow2 n-1(t) (1-13)
In addition, when the time t of determining was more than or equal to for the 3rd reference time and is less than the 4th reference time (72000 seconds) (step S209-7), the F after terminating based on last discharge and recharge n-1t () and up-to-date data pass through formulae discovery F below n(t) (step S209-8).
F n(t)＝f fast1 n(t)+f fast2 n(t)+
f slow1 n(t)+f slow2 n-1(t) (1-14)
The F obtained based on above-mentioned formula (1-11) ~ (1-14) is substituted into by t=20 hour nt (), can obtain formula (step S209-11) below.
OCV 20hr n＝F n(20hr)
When the time t of determining is more than or equal to the 4th reference time (such as, 20 hours) (step S209-7), as shown in figure 16, based on based on up-to-date V mes(20hr) OCV obtained 20hr tempΔ V (t) recorded up to now is (as Δ V (t) temp), calculate Δ V as the following formula n(t) (step S209-13).
ΔV n(t)＝ΔV(t) temp+OCV 20hr temp-OCV 20hr n(1-15)
Further, by formulae discovery F below n(t) (step S209-15).
F n(t)＝f fast1 n(t)+f fast2 n(t)+
f slow1 n(t)+f slow2 n(t) (1-16)
Figure 17 is shown use and is calculated by the process of Figure 15 and Figure 16 and be saved in the f in temporary storage cell 213 i(t) and the reference value f be kept in advance in static memory cell 212 i ref(t), SOH i refcalculate SOH i n, SOC the treatment scheme of step S210.The above-mentioned OCV drawn is read from each storage unit 212,213 20hr n, reference value f i ref(t) and SOH i ref, and temperature T n(step S210-1,2), by importing the function I (OCV be kept in static memory cell 212 by respective value 20hr_ n, SOH i n, T n)=SOC ref_nrelational expression in calculate SOC ref_n(step S210-6), and from this SOC ref_ncalculate SOC n=SOC ref_n(step S210-7).
An example of change every when Figure 18 shows an optimized example of relaxation function F (t) in the condition detection method as the accumulator of this reference example and represented as formula (1-10) by relaxation function F (t).Figure 18 is the curve map that change transverse axis being set to Δ V (t) (=F (t)) when terminating the elapsed time of starting at from discharge and recharge is shown, label 251 ~ 254 respectively illustrates every (f of formula (1-10) fast1(t), f fast2(t), f slow1(t), f slow2(t)) change.In addition, label 250 shows true value, and label 255 shows the value of the F (t) calculated from formula (1-10).The figure shows by using the F (t) of this reference example can predict Δ V (t) accurately.
Below, the stratification degree (diffusion etc. of electrolytic solution) of long response time speed is set to the SOH of formula (1-7) 1(i=1) SOH, and after supposing n-th discharge and recharge 1 nby formulae discovery below.
SOH 1 n＝f slow n(t)/f slow ref*SOH 1 ref
＝{f slow1 n(t)+f slow2 n(t)}/
{f slow1 ref(t)+f slow2 ref(t)}*SOH 1 ref(1-17)
In above-mentioned, by the f of formula (1-7) i n(t), f i reft () is assumed to further can based on two sum { f slow1 n(t)+f slow2 n(t) }, { f slow1 ref(t)+f slow2 ref(t) } calculate.
As an example, use the size model that Furukawa battery formula manufactures: the pregnant solution type lead acid accumulator of 55D23 is at environment temperature 25 DEG C, DOD (Depth of discharge, depth of discharge) 10% condition under, from unused state, charging-discharging cycle is implemented 20 times, 50 times and 100 times.Determination data after discharge and recharge based on 20 cycles, after the discharge and recharge in 50 cycles and after the discharge and recharge in 100 cycles, and according to during 20 cycles for OCV variable quantity f when benchmark have passed through 5 hours (t=5 hour) from discharge and recharge stops i n(5hr) SOH can be calculated as the following formula 1 n.
SOH 1 50＝{f slow1 50(5hr)+f slow2 50(5hr)}/
{f slow1 20(5hr)+f slow2 20(5hr)}*SOH 1 20(1-18)
SOH 1 100＝{f slow1 100(5hr)+f slow2 100(5hr)}/
{f slow1 20(5hr)+f slow2 20(5hr)}*SOH 1 20(1-19)
Figure 19 shows the f calculated based on determination data slow n(t)/f slow 20(t).Label 261,262,263 respectively illustrates f slow 20(t), f slow 50(t), f slow 100t (), label 264,265 respectively illustrates f slow 50(t)/f slow 20(t), f slow 100(t)/f slow 20(t).As can be seen from Figure 19, such as can draw at the time point of t=18000 second:
{f slow1 50(5hr)+f slow2 50(5hr)}/
{f slow1 20(5hr)+f slow2 20(5hr)}
＝F slow50(5hr)/F slow 20(5hr)
＝1.52，
Similarly, can draw:
f slow 100(5hr)/f slow 20(5hr)
＝1.63。
So, the change of the battery status corresponding to charging-discharging cycle number can be grasped from variable quantity F (t) of OCV.
In addition, as an example, have passed through 20 little OCV constantly after discharge and recharge terminates relative to charging-discharging cycle number 20,50,100 is:
OCV 20hr 20＝12.896[V]
OCV 20hr 50＝13.032[V]
OCV 20hr 100＝13.036[V]，
Figure 20 illustrates above-mentioned f slow n(t)/f slow 20(t) and OCV 20hr 20relation.Result shown in Figure 20 can be used in the OCV estimating similar accumulator 20hrstable OCV presumption formula in.
As mentioned above, according to the present invention, the condition detection method carrying out the accumulator of state-detection by evaluating the deterioration caused by the course of reaction of friction speed can be provided.By detecting the impairment grade SOH of battery, residual capacity SOC can be detected accurately.
(the 6th embodiment)
The condition detection method of Figure 21 to the electric energy storage device that the 6th embodiment relates to below is used to be described.Figure 21 is the process flow diagram that the treatment scheme of being undertaken by the condition detection method of the present embodiment is shown.The present embodiment in the step S204 of the 5th embodiment based on electric discharge at the end of voltage V dEor voltage V at the end of charging cEjudge COD, then in step S221, residual capacity SOC when using discharge and recharge to stop stop njudge COD.That is, in step 221, by residual capacity SOC stop nwith the SOC of the reference value be kept in static memory cell 212 stop refcompare, as residual capacity SOC stop nbe more than or equal to reference value SOC stop reftime, enter following step S205 and later step thereof, when being less than reference value SOC stop reftime, be judged to be that COD is not enough, enter in step S213.Thereby, it is possible to more precisely judge the discharge capability of accumulator 201.
Residual capacity SOC when using Figure 22 to stop discharge and recharge stop ncomputing method be described.The SOC calculated during by stopping above-mentioned discharge and recharge stop n-1be used in after this to restart discharge and recharge until current discharge and recharge stop during in the SOC (this is increased decrement Δ SOC as residual capacity) that increases and decreases revise, residual capacity SOC when current discharge and recharge stops can being calculated stop n.Residual capacity increases decrement Δ SOC and calculates by the charging and discharging currents adding up the accumulator 201 from last discharge and recharge is restarted until in during current discharge and recharge stopping.
In this reference example, by carrying out predetermined correction further to the Δ SOC as above calculated, more precisely can calculate residual capacity increase and decrease amount.In the condition detection method of this reference example, residual capacity SOC when being stopped by formulae discovery discharge and recharge below stop n.
SOC stop n＝SOC stop n-1+ΔSOC*η 1 n-1*η 2 n-1(1-20)
Here, as shown in Figure 22 (a), η 1 n-1it is the function f depending on slow relaxation velocity slow(10hr) (the f of formula (1-10-3) slow1or the f of formula (1-10-4) slow2) and the correction factor determined, as shown in Figure 22 (b), η 2 n-1be depend on charging at the end of voltage V cE nand the correction factor determined.These correction factors are for revising the charge efficiency of accumulator 201.
(the 7th embodiment)
Below, the condition detection method of Figure 23 to the electric energy storage device that the seventh embodiment of the present invention relates to is used to be described.Figure 23 is the process flow diagram of the treatment scheme of the condition detection method that the present embodiment is shown.In this reference example, change the 6th embodiment shown in Figure 21 process in step S210, S211 disposal route and as step S230.In step S210, the S211 of the 6th embodiment (in the 5th embodiment too), by calculate predetermined quantity of state S and by its be kept at reference value S in static memory cell 212 refcompare, determined quantity of state S and whether meet the condition representing and maintain discharge capability.On the other hand, in the step S230 of this reference example, evaluate quantity of state S for often kind of reaction velocity, and determine whether according to often kind of reaction velocity to meet the condition representing and maintain discharge capability.In addition, the judgement of the ratio based on slow reaction velocity and fast reaction velocity is also carried out.
Below, using the example of impairment grade SOH as quantity of state S, be described to the decision method carried out according to each reaction velocity and based on the decision method of the ratio of slow reaction velocity and fast reaction velocity.The impairment grade SOH of each reaction velocity fast n, SOH slow ncalculate as follows by formula (1-7).
SOH fast n’＝{f fast n(t)/f fast ref_n(t)}*SOH fast ref(1-21)
SOH slow n＝{f slow n(t)/f slow ref_n(t)}*SOH slow ref(1-22)
Further, the impairment grade SOH of each reaction velocity is combined fast n, SOH slow ntotal SOH nrepresent as formula (1-8), such as, calculate by formula (1-8-1).
Based on the impairment grade SOH that the ratio of slow reaction velocity and fast reaction velocity calculates fast/slow nalso same as described above by formulae discovery below.
SOH fast/slow n＝{f fast/slow n(t)/f fast/slow ref-n(t)}
*SOH fast/slow _ref(1-23)
Example is such as of fig. 24, the impairment grade SOH that the ratio based on slow reaction velocity and fast reaction velocity calculates fast/slow nby using the ratio of slow reaction velocity and fast reaction velocity, can evaluate by the change changing the impairment grade that a large phenomenon causes in the transient phenomenon of fast reaction velocity or the transient phenomenon of slow reaction velocity.
In order to the SOH calculated above by formula (1-21) fast n', revise by the residual capacity SOC of quantity of state when stopping as discharge and recharge stop nand voltage V at the end of charging cE nthe impact brought, by the revised impairment grade SOH of formulae discovery below fast n.This correction is for revising SOH fast nthe change demonstrated as shown in Figure 25 relative to fast reaction velocity.
SOH fast n＝SOH fast n’*α 1 n*α 2 n(1-24)
Corrected parameter α 1 n, α 2 nrelative to residual capacity SOC stop nand voltage V at the end of charging cE nsuch as, shown in Figure 26 (a), Figure 26 (b) such change is shown.Therefore, represent the change shown in Figure 26 (a), Figure 26 (b) by predefined function (High-speed transient change correction calculating formula), can based on residual capacity SOC stop nand voltage V at the end of charging cE ncalculate corrected parameter α 1 n, α 2 n.
Above to SOH fast ncorrection be illustrated, but about SOH slow n, also can work out in advance and such as calculate corrected parameter β 1 n, β 2 nformula and use this formula similarly to revise.
By using the SOH as above calculated fast n, SOH slow n, and SOH fast/slow nand compare with respective reference value like that as shown in figure 27, the COD of accumulator 201 can be judged.In figure 27, S is used fastetc. illustrating quantity of state, but when evaluating SOH, use SOH fast ndeng replacement S fastetc. being used as quantity of state.In step S231, formula (1-22) is used to calculate SOH slow n, and in step S232 with reference value SOH slow ref_ncompare.Its result, works as SOH slow nbe less than SOH slow ref_ntime, be judged to be that COD is not enough, and enter in step S213, then enter in following step S233 in the rest of the cases.
Similarly, in step S233, S234, SOH is judged fast n, judge SOH in step S235, the S236 fast/slow n.Further, if all meet predetermined condition, then to enter in step S212 and to be judged to be that COD is maintained.In this reference example, by carrying out Figure 23 and process as shown in Figure 27, the state-detection of accumulator 201 can be carried out accurately.
In above-mentioned, to obtain SOC, SOH as the quantity of state of electric energy storage device and the reference example using these quantity of states to carry out state-detection be illustrated.The condition detection method of electric energy storage device of the present invention is not limited thereto, and also can use other quantity of state relevant to the discharge capability of electric energy storage device.Except SOC, SOH, as the quantity of state that can use in the judgement of the discharge capability of electric energy storage device, also has the concentration change amount of the electrolytic solution in electric energy storage device.The concentration of electrolytic solution changes along with discharge and recharge, and from reach after discharge and recharge stops stable till need the time.
Therefore, in order to concentration of electrolyte variable quantity is used for state-detection, establishment is in advance used for calculating the every f relative to relaxation function F (t) fast(t), f slow(t) and f fast(t)/f slowthe concentration change gauge formula of the concentration of electrolyte variable quantity of (t), and this calculating formula is kept in static memory cell 212.Further, relaxation function F (t) after optimization can be used and calculate concentration of electrolyte variable quantity by concentration change gauge formula, and by judging whether this concentration of electrolyte variable quantity meets predetermined condition, carries out state-detection.By also using concentration of electrolyte variable quantity in the condition detection method of electric energy storage device, high-precision state-detection can be carried out.
As another quantity of state that can use in the judgement of the discharge capability of electric energy storage device, there is the change of the CONCENTRATION DISTRIBUTION bias (stratification) of electrolytic solution.Figure 28 shows an example of the CONCENTRATION DISTRIBUTION of the electrolytic solution of electric energy storage device.The CONCENTRATION DISTRIBUTION that Figure 28 shows electrolytic solution 293 changes and defines the mode chart of the state of stratification 294 centered by positive pole 291 and negative pole 292.In electric energy storage device, the CONCENTRATION DISTRIBUTION of electrolytic solution changes along with discharge and recharge and forms stratification 294 as shown in figure 28.This stratification comprises horizontal stratification and longitudinal stratification, horizontal stratification is the CONCENTRATION DISTRIBUTION bias of liquid level in transverse direction (arrow 295) for electrolytic solution, and longitudinal stratification is the CONCENTRATION DISTRIBUTION bias of liquid level in longitudinal direction (arrow 296) for electrolytic solution.The change of this stratification occurs along with the change of the concentration of electrolyte caused by discharge and recharge, and the same with the change of concentration of electrolyte, reaches till stablizing and need the time after discharge and recharge stopping.
Therefore, in order to stratification variable quantity is used for state-detection, establishment is in advance used for calculating the every f relative to relaxation function F (t) fast(t), f slow(t) and f fast(t)/f slowthe stratification variable quantity calculating formula of the stratification variable quantity of (t), and this calculating formula is kept in static memory cell 212.Further, relaxation function F (t) after optimization can be used and calculate stratification variable quantity by stratification variable quantity calculating formula, and by judging whether this stratification variable quantity meets predetermined condition, carries out state-detection.By also using stratification variable quantity in the condition detection method of electric energy storage device, high-precision state-detection can be carried out.
As the another quantity of state that can use in the judgement of the discharge capability of electric energy storage device, there is the change of (the horizontal stratification) of the liquid level CONCENTRATION DISTRIBUTION bias in the horizontal for electrolytic solution.The change of this horizontal stratification occurs along with the change of the concentration of electrolyte caused by discharge and recharge, and the same with the change of concentration of electrolyte, reaches till stablizing and need the time after discharge and recharge stopping.
Therefore, in order to horizontal stratification variable quantity is used for state-detection, establishment is in advance used for calculating the every f relative to relaxation function F (t) fast(t), f slow(t) and f fast(t)/f slowthe horizontal stratification variable quantity calculating formula of the horizontal stratification variable quantity of (t), and this calculating formula is kept in static memory cell 212.Further, relaxation function F (t) after optimization can be used and calculate horizontal stratification variable quantity by horizontal stratification variable quantity calculating formula, and by judging whether this horizontal stratification variable quantity meets predetermined condition, carries out state-detection.By also using horizontal stratification variable quantity in the condition detection method of electric energy storage device, high-precision state-detection can be carried out.
As another quantity of state that can use in the judgement of the discharge capability of electric energy storage device, there is the change of the CONCENTRATION DISTRIBUTION bias (horizontal stratification, longitudinal stratification) of liquid level in transverse direction and longitudinal direction for electrolytic solution.When it can be used as portraitlandscape stratification variable quantity, portraitlandscape stratification variable quantity produces along with the change of the concentration of electrolyte caused by discharge and recharge, and the same with the change of concentration of electrolyte, reaches till stablizing and need the time after discharge and recharge stopping.
Therefore, in order to portraitlandscape stratification variable quantity is used for state-detection, establishment is in advance used for calculating the every f relative to relaxation function F (t) fast(t), f slow(t) and f fast(t)/f slowthe portraitlandscape stratification variable quantity calculating formula of the portraitlandscape stratification variable quantity of (t), and this calculating formula is kept in static memory cell 212.Further, relaxation function F (t) after optimization can be used and calculate portraitlandscape stratification variable quantity by portraitlandscape stratification variable quantity calculating formula, and by judging whether this portraitlandscape stratification variable quantity meets predetermined condition, carries out state-detection.By also using portraitlandscape stratification variable quantity in the condition detection method of electric energy storage device, high-precision state-detection can be carried out.
(the 8th embodiment)
Another condition detection method after discharge and recharge stops is described in more details.
When carrying out the state-detection of electric energy storage device after stopping in discharge and recharge, according to discharge and recharge history etc. before this, there is very big-difference in transient changing, therefore there is the problem being difficult to judge accurately discharge capability etc. due to very large impact the by discharge and recharge history.
Such as, the accumulator be arranged on automobile repeatedly carries out various discharge and recharge in the middle of travelling at vehicle, and the migration therefore produced in the electrolytic solution of accumulator, precipitation, convection current, diffusion etc. are also various because of the difference of vehicle operating condition.Therefore, the transient changing of the accumulator after discharge and recharge stops is different according to the vehicle operating condition arrived before this, cannot produce identical or can think trend identical there is reproducible halted state.Even if the component that the transient changing after discharge and recharge being stopped when the condition detection method as recorded in patent documentation 1 is divided into different time constants is to carry out state-detection, if the transient changing of the accumulator after discharge and recharge stops is widely different, also be difficult to obtain each time constant component accurately, thus still exist and be difficult to high-precision problem of carrying out the state-detection of accumulator.
Therefore, in order to address these problems, provide the impact of the discharge and recharge before reducing electric energy storage device stopping carrying out condition detection method and the device thereof of the electric energy storage device of state-detection.
In the condition detection method of the electric energy storage device of the 8th embodiment, in order to maintain the discharge capability of electric energy storage device rightly, be provided with the state-detection state-detection pattern for suitably carrying out electric energy storage device.In the system possessing electric energy storage device, such as, at out of service thus the reasonable time in of stopped the time point of the discharge and recharge of electric energy storage device or have passed through after discharge and recharge stops time point etc., by user or maintainer's executing state detecting pattern.When for electric energy storage device solicited status detecting pattern, the state-detection of this electric energy storage device can be carried out accurately.
Below, using the battery that is arranged on a vehicle example as electric energy storage device, the condition detection method of the electric energy storage device of this reference example and condition checkout gear are described.But the content below illustrated is not limited to on-vehicle battery, can be applicable to too for the electric energy storage device of solar electrical energy generation or wind-power electricity generation etc., the electric energy storage device for the standby power supply such as stabilized power source, accessory power supply.
Below, Figure 29, Figure 30 is used to be described the condition detection method of the electric energy storage device of this reference example and device thereof.Figure 29 is the process flow diagram of the summary of the condition detection method of electric energy storage device for illustration of this reference example, and Figure 30 is the block diagram of the condition checkout gear of the electric energy storage device that this reference example is shown.
The condition checkout gear 400 of this reference example to be installed on vehicle 310 and state-detection for carrying out electric energy storage device (accumulator) 311, and it comprises: signal input unit 401, output display unit 402, determination unit 403 and state detecting section 410.Electric energy storage device 311 is connected with onboard electrical machine even load 312, and is connected with onboard chargers 314 such as alternators.Signal input unit 401 is for inputting the signal (hereinafter referred to as state-detection pattern commencing signal) for user's solicited status detecting patterns such as drivers, and output display unit 402 has carried out the result etc. of state-detection for informing the user.Signal input unit 401 and output display unit 402 owing to being all for driver, be therefore preferably arranged on driver's seat or its near.
State detecting section 410 inputs the measured value such as voltage, electric current of electric energy storage device 311 from determination unit 403, goes forward side by side and exercises the process of the state-detection of carrying out electric energy storage device 311 by these measured values accurately.In addition, state detecting section 410 has state-detection mode switch 411, thus replace from signal input unit 401 input state detecting pattern commencing signal, by opening detecting pattern switch 411, state-detection pattern commencing signal is exported to state detecting section 410.State-detection mode switch 411 is in order to arrange when the state-detection of carrying out making maintainer etc. carry out electric energy storage device 311 fast when making regular check on etc. and safeguard.
State detecting section 410 carries out the charging (charging before hereinafter referred to as state-detection) of predetermined volumes before carrying out state-detection to electric energy storage device 311.That is, when charging before state detecting section 410 pairs of control modules 313 request the state-detection of electric energy storage device 311, control module 313 controls, and makes engine start, makes onboard charger 314 action, thus electric energy storage device 311 is carried out to the charging of predetermined volumes.Or, charge before also can carrying out the state-detection of above-mentioned electric energy storage device 311 by maintainer etc.Now, before state-detection, by maintainer etc., external charger 320 is connected on electric energy storage device 311 and charges.State detecting section 410 after charging, carries out the state-detection of electric energy storage device 311 before having carried out the state-detection by onboard charger 314 or external charger 320.In addition, as state detecting section 410 and the communication unit between signal input unit 401, output display unit 402, determination unit 403 and control module 313, LIN (Local Interconnect Network can be used, local internet) or the communication bus such as CAN (Controller Area Network, controller local area network).
Then, use the process flow diagram shown in Figure 29, the summary of the condition detection method of this reference example is described.When using the condition checkout gear 400 of this reference example to carry out the state-detection of electric energy storage device 311, first to state detecting section 410 input state detecting pattern commencing signal (step S301).Thus, in state detecting section 410, judge whether predetermined state-detection enabled condition is set up (step S302).As this state-detection enabled condition, at least comprise electric energy storage device 311 and stop discharge and recharge.
When being judged to be that state-detection enabled condition is set up in step s 302, in step S303, state-detection pattern is set to open (ON), charges before carrying out state-detection in following step S304 to electric energy storage device 311.Once charging terminates before state-detection, in state detecting section 410, just carry out the state-detection (step S305) of electric energy storage device 311.State-detection can be carried out as follows: the residual capacity SOC such as estimating electric energy storage device 311, and the discharge capability judging electric energy storage device 311 based on this.Judge the discharge capability of electric energy storage device 311 in the process by state-detection after, its result is exported to output display unit 402, and is notified to user or maintainer etc.(step S306).On the other hand, when being judged to be that state-detection enabled condition is false in step s 302, terminate when not carrying out the process of step S303 ~ S306.
Below, the condition detection method of the electric energy storage device 311 performed in state detecting section 410 is described.Transient changing after the discharge and recharge stopping of battery 311 comprises the different course of reaction of speed, therefore in order to judge accurately discharge and recharge stop after the discharge capability of battery 311, preferably use and can change the method evaluated to carry out state-detection to the state of each reaction velocity.Such as, the difference according to reaction velocity and function (hereinafter referred to as the relaxation function) F (t) that is made up of M polynomial expression can be used, change in voltage Δ V (t) of the battery after discharge and recharge stopping is represented as the following formula.
ΔV(t)＝F(t)
＝f 1(t)+f 2(t)+…f m(t)＝∑f i(t) (2-1)
Here, voltage variety Δ V (t) represents voltage determination value V when have passed through time t from charging before state-detection terminates mest () and burning voltage when stopping are (hereinafter referred to as OCV 20hr) difference, wherein, during stopping burning voltage be after discharge and recharge stops through enough time (such as, 20 hours) thus voltage becomes basic fixing time voltage (hereinafter referred to as OCV 20hr).
ΔV(t)＝V mes(t)-OCV 20hr(2-2)
In this reference example, above formula is used to carry out state-detection.
In above-mentioned relaxation function F (t), every f it () represents that relaxation that the reaction velocity of battery 311 is different is to the contribution amount of change in voltage, is below set to the relaxation function f of each reaction velocity i(t).Every f it () is impairment grade SOH, the residual capacity SOC (ion concentration) of the quantity of state depended on as battery 311 and the function of temperature T.By from voltage determination value V mest () calculates Δ V (t), and use from voltage determination value V mest Δ V (t) that () calculates carries out optimization to formula (2-1), can determine the relaxation function f of each reaction velocity i(t).
With the voltage determination value of predetermined periodical input electric energy storage device 311 after the condition detection method of this reference example charges and terminates before state-detection, and carry out the optimization of relaxation function F (t) and upgrade whenever input voltage measured value.The relaxation function of each reaction velocity when the voltage determination value that use measures for n-th time has carried out optimization is set to f i ntime (t), f i nt () can represent as the following formula.
f i n(t)＝f i ref(t)*{SOC n/SOCref}
*{SOH i n/SOH i ref}*G(T) (2-3)
Here, f i ref(t), SOC ref, and SOH i refrepresent the impairment grade SOH of the relaxation function of each reaction velocity under predetermined normal condition, residual capacity SOC and each reaction velocity respectively, G (T) represents the dependence to the temperature T of electric energy storage device.From formula (2-3), can be regarded as out the residual capacity SOC of the voltage determination value presumption of use n-th time nand the impairment grade SOH of each reaction velocity i n.From SOC nthe discharge capability of electric energy storage device 311 can be judged.In addition, based on the impairment grade SOH of each reaction velocity accumulative for all reaction velocitys i nand the impairment grade SOH obtained, the impairment grade of electric energy storage device 311 can be judged.
In order to carry out the optimization of relaxation function F (t) shown in formula (2-1) accurately, the transient changing of carrying out the time point of state-detection preferably always identical or can think trend identical there is reproducible state.Therefore, in the condition detection method of the electric energy storage device 311 of this reference example, before carrying out state-detection, make its charging and discharging state transfer to as far as possible there is reproducible state, then carry out state-detection.Charging and discharging state before starting to make state-detection is transferred to as far as possible has reproducible state, this reference example carries out the charging (charging before state-detection) of predetermined volumes in the step S304 of Figure 29, then carries out the mensuration of change in voltage etc. and carries out state-detection.
Capacity for charging before making electric energy storage device 311 transfer to have the appropriate state-detection of reproducible state is preferably set to the capacity being enough to the impact eliminating the electrophoresis occurred with electric discharge in the electrophoresis of the electrolytic solution occurred along with the discharge and recharge in vehicle operating.Thus, before state-detection, charging reduces the impact caused by the electric discharge in vehicle operating, can measure the change in voltage occurred with charging polarization when carrying out state-detection.Below, with the accumulator of automobile for object, to as charging before state-detection, appropriate capacity is described.
In automobile actual travel, charge/discharge capacity arbitrarily and change continually, therefore can be considered to measure and charge/discharge capacity in adding up to travel determine the method for charging capacity before state-detection based on this.But, in the method for the charge/discharge capacity in accumulative traveling, not necessarily can obtain high-precision charge/discharge capacity, be difficult to determine to be suitable for charging capacity when transferring to state-detection pattern.In addition, when transferring to state-detection pattern after having carried out Large Copacity electric discharge as repeated idle stop etc., the capacity before state-detection required for charging may become large, now there is the problem that charging required time is elongated.
Therefore, in the condition detection method of this reference example, not the capacity charged before determining state-detection by the discharge and recharge in accumulative traveling, but transient changing when charging investigated in advance to each object electric energy storage device, and the capacity charged before carrying out predefined state-detection based on this.As an example, when having installed the vehicle of accumulator 55B24 (36 [Ah]) of Furukawa battery manufacture, when normally having travelled 1 ~ 2 hours, the size (absolute value) of the charge/discharge capacity (Δ SOC) of the accumulator in traveling has been less than 0.5%.
Therefore, it is possible to by the capacity charged before state-detection is set as the capacity fully larger than discharge and recharge during above-mentioned traveling, fully reduce the impact of the discharge and recharge transferred to before state-detection pattern.Its result, in the condition detection method of this reference example, battery condition when carrying out state-detection is subject to, by the domination of the transient changing caused of charging before state-detection, therefore to become and have reproducible transient behaviour.How the transient changing using Figure 31 that the accumulator after charging before state-detection is described changes according to the size of charge/discharge capacity when travelling before.Figure 31 illustrates from running status to the electric current of accumulator when carrying out state-detection after stopping and the change of voltage and magnitude relationship according to charging capacity before operating charge/discharge capacity and state-detection is schematically shown and curve map that how transient changing changes.Here, charging capacity before state-detection is set to 5% of rated capacity.
Electric current when charging capacity is greater than operating charge/discharge capacity before Figure 31 (a) shows state-detection, the change of voltage, electric current when charging capacity is in same degree before Figure 31 (b) shows operating charge/discharge capacity and state-detection, the change of voltage, Figure 31 (c) shows the change of electric current when operating charge/discharge capacity is greater than charging capacity before state-detection, voltage.As the situation that charging capacity before the state-detection shown in Figure 31 (a) is larger, operating charge/discharge capacity is set to less than 1%.In the case, the impact of operating discharge and recharge is lowered by charging before state-detection, thus change in voltage monotone decreasing before state-detection after charging the trend demonstrated to burning voltage convergence.
In addition, be in the situation of same degree as charging capacity before the operating charge/discharge capacity shown in Figure 31 (b) and state-detection, operating charge/discharge capacity be set to more than 1% and less than 5%.In the case, also can reduce the impact of operating discharge and recharge by charging before state-detection, the monotone decreasing demonstrate the trend restrained to burning voltage with Figure 31 (a) in the same manner as of the change in voltage before state-detection after charging.In addition, when before the operating charge/discharge capacity shown in Figure 31 (c) is greater than state-detection when charging capacity, even if charge before state-detection, voltage after terminating also has the trend of monotone increasing, demonstrates and Figure 31 (a), (b) diverse trend.
Charge/discharge capacity when vehicle travels, usually below about 1%, when charging capacity is set to 5% before by state-detection, fully can reduce the electropolarized impact of charge and discharge that discharge and recharge when usually being travelled by vehicle causes.Its result, in the state-detection before carrying out state-detection after charging, detects discharge capability by the such transient changing Figure 31 (a) caused based on the charging by 5% capacity, Figure 31 (b) Suo Shi.By using the functional form that can be most suitable for the approximate transient changing caused by the charging of 5% capacity as relaxation function F (t) of formula (2-1), the state-detection that make use of relaxation function F (t) can be carried out accurately.
On the other hand, before operating charge/discharge capacity such when Figure 31 (c) Suo Shi is greater than state-detection when charging capacity, making because the voltage forced down than stable electrical is tested, therefore by this voltage being detected, can have dropped to notice discharge capabilities such as users.The situation that stopped operation after repeating idle stop is at short notice the example that operating discharge capacity becomes large.Voltage determination value except the king-sized situation of operating discharge capacity, also has the deterioration of accumulator 311 to increase the weight of or by the situation etc. of placing for a long time than the situation of burning voltage step-down.Under these circumstances, also can carry out decline (off-capacity) or deterioration of measurement capacity by the condition detection method of this reference example to increase the weight of.
Before state-detection, the capacity of charging can set different values according to which kind of driving mode travelled by general vehicle as object, and preferably considers that the size, characteristic etc. of the accumulator be installed on vehicle are determined.Such as, when the capacity of charging before the electric discharge occurred by idle stop being carried out set condition as object and detecting, preferably set the charging capacity of the capacity discharged when being more than or equal to idle stop.By making to carry out the charging larger than operating discharge capacity, as shown in Figure 31 (a), Figure 31 (b), state-detection can be carried out under the transient behaviour of voltage monotone decreasing when state-detection.
Below, use Figure 32, Figure 33, the condition detection method using Figure 29 to carry out this reference example of summary description is described in more details.Figure 32 is the process flow diagram for illustration of the process terminated of charging from state-detection pattern is requested until before state-detection.Figure 32 (a) shows treatment scheme when have input state-detection pattern commencing signal by driver etc. from signal input unit 401, and Figure 32 (b) shows treatment scheme when opening state-detection mode switch 411 by maintainer etc.
When from signal input unit 401 input state detecting pattern commencing signal, or when opening detecting pattern switch 411, all there is the possibility that signal input occurs due to maloperation.Therefore, in Figure 32 (a), treatment scheme during so that the mode of maloperation can be prevented to be formed is described, in Figure 32 (b), treatment scheme when not considering the preventing of maloperation is described.But, also can so that the mode of maloperation can be prevented to be formed in the same manner as Figure 32 (a) in Figure 32 (b), and, in Figure 32 (a), also can omit the process preventing maloperation.
In Figure 32 (a), when have input state-detection pattern commencing signal from signal input unit 401 (step S311), this signal is exported to state detecting section 410.State detecting section 410, after input state detecting pattern commencing signal, output display portion 402 shows the acknowledge message (step S312) for confirming to request state-detection.Based on acknowledge message, if such as have input confirmation signal (step S313) from signal input unit 401, then next judge whether predetermined state-detection enabled condition is set up (step S314).
As above-mentioned state-detection enabled condition, at least require that accumulator 311 does not carry out discharge and recharge.As judging that accumulator 311 does not carry out the method for discharge and recharge, such as, confirm that vehicle 310 is in halted state (key switch is in closed condition).In addition, also can acknowledgement state test section 410 could communicate with peripheral device, the value whether illustrated from the measured value of determination unit 403 in normal range, whether can starting engine to make onboard charger 314 regular event etc., and no matter in which exception, all think that state-detection enabled condition is false.
In step S314, carry out the result judged, when state-detection enabled condition is set up, state-detection pattern is set as opening in step S315.Now, output display unit 402 also can be made to show state-detection pattern to be unlocked.In step S316, charge before using onboard charger 314 pairs of accumulators 311 to start to carry out state-detection.Before the state-detection employing onboard charger 314, charging is by asking the charging of predetermined volumes and by control module 313 starting engine to make onboard charger 314 action to carry out by state detecting section 410 to control module 313.
On the other hand, when in the judgement in step S314, state-detection enabled condition is false, when do not carry out step S315, S316 process terminate.Now, which condition that output display unit 402 also can be made to show in state-detection enabled condition is false.
Then, Figure 32 (b) is used to be described the treatment scheme of opening the detection of state-detection mode switch 411 initial state.When maintainer etc. opens state-detection mode switch 411 (step S321), state-detection pattern commencing signal is exported to state detecting section 410.State detecting section 410 then judges after input state detecting pattern commencing signal whether predetermined state-detection enabled condition is set up (step S322).State-detection enabled condition can be identical with the situation of Figure 32 (a).
In step S322, carry out the result judged, when state-detection enabled condition is set up, state-detection pattern is set as opening in step S323, in step S324, charge before using external charger 320 pairs of accumulators 311 to start to carry out state-detection.The charging undertaken by external charger 320 is undertaken by maintainer etc.Therefore, in step S324, the message that request charging starts can be shown on output display unit 402, and charge after confirming this message by maintainer etc.In addition, after the charging of predetermined volumes terminates, mode of operation detecting pattern switch 411 can be waited by maintainer, or also can be used for charging before notify status detects from signal input unit 401 input the signal finished.
On the other hand, when in the judgement in step S322, state-detection enabled condition is false, when do not carry out step S323, S324 process terminate.Now, which condition that output display unit 402 also can be made to show in state-detection enabled condition is false.
Then, treatment scheme when using Figure 33 to set up state-detection pattern is described.Process shown in Figure 33 performed with the predetermined cycle.First, in step S331, whether decision state detecting pattern starts.Its result, enters when state-detection pattern starts in step S332, when state-detection pattern is closed, terminates when not carrying out subsequent treatment.In following step S332, judge whether above-mentioned state-detection enabled condition is set up.The confirmation of state-detection enabled condition supposes often to carry out in during state-detection pattern.Its result, when state-detection enabled condition is set up, enters in following step S333, on the other hand when state-detection enabled condition is false, enters in step S339.Now, which condition that output display unit 402 also can be made to show in state-detection enabled condition is false.
In step S333, before decision state detects, whether charging terminates.When charging before using onboard charger 314 to carry out state-detection, can by confirming whether charging has terminated to judge to control module 313.Or the elapsed time of starting at from charging also can be used to judge.In addition, when charging before using external charger 320 to carry out state-detection, the signal according to have input charging end from state-detection mode switch 411 or signal input unit 401 judges.In step S333, carry out the result judged, at the end of charging before state-detection, enter in following step S334.On the other hand, at the end of charging before being judged to be state-detection does not have, end process when not carrying out subsequent treatment.
In step S334, determination unit 403 is used to input the voltage determination value V of current point in time mest (), uses the voltage determination value V of input so far in step S335 mest () carries out optimization to relaxation function F (t).In following step S336, the F (t) after optimization is used to estimate the discharge capability of accumulator 311.As discharge capability, such as, can use burning voltage OCV when upgrading stopping by formula (2-1), (2-2) 20hrpresumed value and based on this presumed value and OCV as shown in Figure 35 20hrthe SOC obtained with the relation of SOC.In step S337, the SOC so estimated is saved in predetermined storage part temporarily.
In step S338, judge that detecting from initial state the elapsed time t started at noly reaches the schedule time, when elapsed time t has reached the schedule time, enters in step S339.On the other hand, when elapsed time t does not reach the schedule time, terminate when not carrying out subsequent treatment.In step S339, read the interim discharge capability preserved in step S337, time this discharge capability is more than or equal to predetermined threshold, be judged to be that discharge capability is normal, when this discharge capability is less than predetermined threshold time, be judged to be that discharge capability is abnormal.In step S340, the result that determined discharge capability is exported to output display unit 402.Then, in step S341, closed condition detecting pattern also ends process.
(the 9th embodiment)
Below, use the process flow diagram shown in Figure 34, another reference example of the condition detection method of electric energy storage device is described.In the condition detection method of this reference example, before the state-detection of being carried out accumulator 311 by state-detection pattern, carry out the state-detection (step S351) based on pulsed discharge and the state-detection (step S352) based on impedance measuring.State-detection based on pulsed discharge measures electric current when making accumulator 311 pulsed discharge, voltage detect the discharge capability of accumulator 311 or the method for deterioration state based on these electric currents, voltage.In addition, be internal driving from the measured value presumption accumulator 311 of electric current, voltage based on the state-detection of impedance measuring and detect the method for the deterioration state of accumulator 311 based on internal driving.
The condition detection method based on state-detection pattern of this reference example both can carry out separately as the 4th reference example, or also as this reference example, can combine carry out with the state-detection based on pulsed discharge and the state-detection based on impedance measuring.In addition, not the state-detection based on pulsed discharge and both the state-detection based on impedance measuring must be combined, also in the state-detection based on pulsed discharge and the state-detection based on impedance measuring can be combined with the state-detection based on state-detection pattern and carry out.
In above-mentioned, describe the situation of carrying out state-detection after the discharge and recharge stopping accumulator 311 at once, but be not limited thereto, such as, under the discharge and recharge of accumulator 311 stopped long situation, also can carry out state-detection.Such as, by with one month once left and right frequency executing state detecting pattern, the discharge capability of accumulator 311 can be confirmed.Meanwhile, by charging before the state-detection based on state-detection pattern, even if also can safely and the recovery of enforcement accumulator 311 be efficiently charged (5% charging) when long-time parking.
In this reference example, as the method for charging before carrying out state-detection, make control module 313 according to the request from state detecting section 410, starting engine is to make onboard charger 314 action, thus accumulator 311 is charged, but, replace the method, driver also can be made will to terminate to travel and input state detecting pattern commencing signal before stopping engine.Now, even if such as close key switch, also do not make engine stop but carry out utilizing the front charging of the state-detection of onboard charger 314 at once, and make engine automatic stop after charging terminates.
In addition, in above-mentioned reference example, the state-detection as electric energy storage device is detected to the situation whether discharge capability be guaranteed and be illustrated, but be not limited thereto, also easily can judge the deterioration of SOH etc. further.Relaxation function F (t), owing to also having dependence to SOH, therefore, can derive the formula for calculating SOH from relaxation function F (t).By using such formula, can SOH be estimated and judge the deterioration state of electric energy storage device.
As mentioned above, according to condition detection method and the condition checkout gear of the electric energy storage device of this reference example, by carrying out the charging of predetermined volumes before carrying out state-detection, electric energy storage device transfers to the state with reproducible transient changing.Thus, can identical or can think trend identical there is reproducible transient behaviour under carry out state-detection, thus more precisely can carry out the state-detection of electric energy storage device.Its result, can detect the undercharge or fault etc. of electric energy storage device in advance, can improve vehicle operating and auxiliary engine as reliability for subsequent use.Further, by charging before state-detection, capacity wretched insufficiency can be prevented and reduce the deterioration of electric energy storage device, going back the stable utilization of feasible system, and the life-span of electric energy storage device can be extended.
Record in embodiment is for illustrating the example of the condition detection method according to electric energy storage device of the present invention, and the present invention is not limited thereto.The structure of the detail section of the condition detection method of the electric energy storage device in embodiment and detailed action etc. can suitably change without departing from the scope of the subject in the invention.
Description of reference numerals
1: vehicle
2: load
10: accumulator
11: charhing unit
12: control module
20: voltage measuring unit for measuring
21: amperometric determination unit
22: temperature measurement unit
100: condition checkout gear
110: state detecting section
120: storage part
130: State-output unit

Claims (41)

1. a condition detection method for electric energy storage device, for the discharge capability in the middle of the cycle judgement discharge and recharge that correspondence is predetermined and in the middle of discharge and recharge stopping, is characterized in that,
Voltage V_end when the voltage determination value of the described electric energy storage device and then measured after last discharge and recharge stops being stopped as discharge and recharge is also stored in predetermined storage part,
Voltage V_end when described discharge and recharge stops is read in from described storage part,
Deduct current voltage determination value V_now voltage V_end when stopping from described discharge and recharge, and calculate current voltage variety Δ Va_n, wherein, the periodicity of current voltage variety Δ Va_n is set to n,
The discharge capability correction function F (SOH, Δ Va_n) of establishment is in advance used to calculate the discharge capability correction COD_SOH_n of described electric energy storage device based on the impairment grade SOH of described electric energy storage device and described voltage variety Δ Va_n,
By formula below, calculate the present discharge ability COD_now of described electric energy storage device,
COD_now＝V_now－COD_SOH_n
Further, when described discharge capability COD_now is greater than predetermined threshold COD_Th, be judged to be that the discharge capability of described electric energy storage device is maintained.
2. the condition detection method of electric energy storage device as claimed in claim 1, is characterized in that,
Described impairment grade SOH is the impairment grade SOH_n1 calculated when being n1 from the periodicity in the middle of current nearest discharge and recharge stopping, wherein n1≤n,
By reading in the described discharge capability correction function F corresponding with described impairment grade SOH_n1 from described storage part, (SOH_n1, x) wherein, x is variable and is substituted in described variable x by described voltage variety Δ Va_n and calculate described discharge capability correction COD_SOH_n.
3. the condition detection method of electric energy storage device as claimed in claim 1 or 2, is characterized in that,
The incompatible expression of linear junction of the relaxation function fi of plural each reaction velocity that described discharge capability correction function F (SOH, Δ Va) is worked out accordingly in advance by the speed of the transient changing with described electric energy storage device inside, wherein, i=1 ~ m,
In the middle of the discharge and recharge of described electric energy storage device stops, described voltage determination value is kept in described storage part,
The relaxation function fi of described each reaction velocity stops the elapsed time of starting at also to use the described voltage determination value be kept at described storage part to be optimised according to described from discharge and recharge.
4. the condition detection method of electric energy storage device as claimed in claim 3, is characterized in that,
Stop central when described electric energy storage device is in discharge and recharge and stops the elapsed time of starting to exceed the schedule time from discharge and recharge, wherein, the schedule time was set to for the first slack time,
The relaxation function fi of the described voltage determination value pair described each reaction velocity corresponding with transient changing be fast kept in described storage part is used to carry out optimization,
The relaxation function fi of each reaction velocity after described optimization is used to calculate the impairment grade SOH_fast_n depending on transient changing fast,
The impairment grade SOH_slow_n2 depending on transient changing slowly calculated when being n2 based on the periodicity in the middle of stopping from current nearest discharge and recharge and described impairment grade SOH_fast_n, wherein, n2≤n, and utilize predefined function G, by formula below, calculate current impairment grade SOH_n
SOH_n＝G(SOH_fast_n，SOH_slow_n2)
Further, described discharge capability correction COD_SOH_n is by reading in the described discharge capability correction function F corresponding with described impairment grade SOH_n (SOH_n, x) and substituted in described variable x by described voltage variety Δ Va_n and calculate from described storage part.
5. the condition detection method of electric energy storage device as claimed in claim 4, is characterized in that,
When described electric energy storage device be in discharge and recharge stop in the middle of and stops the elapsed time of starting to exceed predetermined second slack time grown than described first slack time from discharge and recharge time,
The relaxation function fi of described voltage determination value to the described each reaction velocity depending on transient changing slowly that further use is kept in described storage part carries out optimization,
The relaxation function fi of each reaction velocity after described optimization is used to calculate the impairment grade SOH_slow_n depending on transient changing slowly,
Described in calculating, depend on the impairment grade SOH_fast_n of the transient changing fast and described impairment grade SOH_slow_n depending on transient changing slowly, and utilize described predefined function G, by formula below, calculate current impairment grade SOH_n,
SOH_n＝G(SOH_fast_n，SOH_slow_n)。
6. the condition detection method of electric energy storage device as claimed in claim 1, is characterized in that,
After discharge and recharge stops, and then described electric energy storage device being carried out to the charging of predetermined volumes, i.e. charging before state-detection, and voltage V_end being saved in described storage part when described voltage determination value charging before described state-detection and then measured after terminating stops as described discharge and recharge.
7. a condition checkout gear for electric energy storage device, for the discharge capability in the middle of the cycle judgement discharge and recharge that correspondence is predetermined and in the middle of discharge and recharge stopping, is characterized in that, comprising:
Storage part, for preserving the voltage determination value of described electric energy storage device;
State detecting section, reads in for the corresponding cycle described in each data that are kept in described storage part and judges the discharge capability of described electric energy storage device; And
State-output unit, for inputting result of determination from described state detecting section, and externally exports,
Wherein, described storage part is kept at the described voltage determination value of the described electric energy storage device and then measured after last discharge and recharge stops, voltage V_end when stopping as discharge and recharge,
Described state detecting section reads in voltage V_end when described discharge and recharge stops from described storage part, current voltage determination value V_now is deducted in voltage V_end during by stopping from described discharge and recharge, calculate current voltage variation delta Va_n, wherein, the periodicity of current voltage variety Δ Va_n is set to n, and use the discharge capability correction function F (SOH, Δ Va_n) of establishment in advance to calculate the discharge capability correction COD_SOH_n of described electric energy storage device based on the impairment grade SOH of described electric energy storage device and described voltage variety Δ Va_n
Described state detecting section passes through formula below, calculates the present discharge ability COD_now of described electric energy storage device,
COD_ow＝V_ow－COD_SOH_n
Further, when described discharge capability COD_now is greater than predetermined threshold COD_Th, be judged to be that the discharge capability of described electric energy storage device is maintained.
8. a condition detection method for electric energy storage device, is characterized in that,
Described electric energy storage device is stopped discharge and recharge and the voltage of described electric energy storage device when reaching the state meeting predetermined stable condition as burning voltage during stopping, using voltage when have passed through time t after stopping discharge and recharge from described electric energy storage device relative to the variable quantity of burning voltage during described stopping as voltage variety during stopping, now
Relaxation function F (t) of voltage variety when being used for calculating described stopping is worked out in advance as the function of the predetermined quantity of state of described electric energy storage device,
Measure described electric energy storage device will stop charge before charging at the end of voltage or will stop discharge before electric discharge at the end of voltage,
Measure the described charging of described electric energy storage device or described electric discharge stop after voltage,
Relaxation function F (t) described in voltage variety when calculating described stopping according to described voltage determination value optimization,
Described quantity of state is estimated according to described relaxation function F (t) be optimised,
At the end of utilizing described electric discharge at the end of voltage or described charging voltage and described by the quantity of state that estimates to judge the discharge capability COD of described electric energy storage device.
9. the condition detection method of electric energy storage device as claimed in claim 8, is characterized in that,
When the impact that the electric current caused by described discharge and recharge is small or bring for fixed value thus to the transient changing of described electric energy storage device inside is limited in predetermined scope, judge that described electric energy storage device stopped discharge and recharge.
10. the condition detection method of electric energy storage device as claimed in claim 9, is characterized in that,
Prior establishment for revising the voltage increment of the change in voltage caused by described electric current,
Utilize the voltage adding described voltage increment gained in described voltage determination value, relaxation function F (t) described in optimization.
The condition detection method of 11. electric energy storage devices according to any one of claim 8 to 10, is characterized in that,
According to accumulative will discharge and recharge stop before discharge and recharge in electric current and the electric current aggregate-value SOC calculated when discharge and recharge stops that obtains increases decrement Δ SOC, SOC when upper once discharge and recharge stops adds described SOC increase and decrease amount and calculates SOC when current discharge and recharge stops
SOC when stopping based on voltage at the end of voltage at the end of described electric discharge or described charging, the quantity of state estimated from described relaxation function F (t), described current discharge and recharge judges described COD.
The condition detection method of 12. electric energy storage devices as claimed in claim 11, is characterized in that,
Prior establishment using voltage at the end of predetermined quantity of state and charging as the charge efficiency calculating formula of variable,
SOC when described discharge and recharge stops utilizes SOC increase and decrease amount described in charge efficiency correction and calculates, and voltage at the end of the described quantity of state utilizing described relaxation function F (t) to calculate and described charging is substituted into described charge efficiency calculating formula and calculates by described charge efficiency.
The condition detection method of 13. electric energy storage devices as claimed in claim 12, is characterized in that,
Described quantity of state is the SOC of described electric energy storage device.
The condition detection method of 14. electric energy storage devices as claimed in claim 12, is characterized in that,
Described quantity of state is the SOH of described electric energy storage device.
The condition detection method of 15. electric energy storage devices as claimed in claim 14, is characterized in that,
Described relaxation function F (t) has the fast component f of relaxation velocity fastt component f that () and relaxation velocity are slow slow(t),
The described f of prior establishment fast(t), described f slow(t) and both ratio f fast(t)/f slowt reference value that () is respective,
Utilize the described f that the F (t) be optimised described in basis calculates fast(t), described f slow(t) and described f fast(t)/f slow, and respective described reference value judge described COD.
The condition detection method of 16. electric energy storage devices as claimed in claim 15, is characterized in that,
Described quantity of state is the impairment grade SOH of described electric energy storage device,
Utilize described f fast(t), described f slow(t) and described f fast(t)/f slow, and respective described reference value calculate described SOH.
The condition detection method of 17. electric energy storage devices as claimed in claim 16, is characterized in that,
Prior establishment using the High-speed transient change correction calculating formula of voltage at the end of SOC and charging as variable,
Voltage at the end of SOC during described discharge and recharge stopping and described charging is substituted into described High-speed transient change correction calculating formula calculate relative to described f fastthe correction of (t), and utilize with the described f of described correction correction fastt () calculates described SOH.
The condition detection method of 18. electric energy storage devices as claimed in claim 15, is characterized in that,
Prior establishment concentration change gauge formula, described concentration change gauge formula is used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slow, the concentration change amount of the electrolytic solution of described electric energy storage device,
Relaxation function F (t) be optimised described in utilization and according to described concentration change gauge formula calculate described electrolytic solution concentration change amount and for described quantity of state.
The condition detection method of 19. electric energy storage devices as claimed in claim 15, is characterized in that,
Prior establishment is used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slowthe stratification variable quantity calculating formula of stratification variable quantity, in described stratification variable quantity calculating formula, using the CONCENTRATION DISTRIBUTION bias variable quantity of the electrolytic solution of described electric energy storage device as described stratification variable quantity,
Described relaxation function F (t) be optimised described in utilization also calculates described stratification variable quantity according to described stratification variable quantity calculating formula and for described quantity of state.
The condition detection method of 20. electric energy storage devices as claimed in claim 15, is characterized in that,
Prior establishment is used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slowthe horizontal stratification variable quantity calculating formula of horizontal stratification variable quantity, in described horizontal stratification variable quantity calculating formula, using the variable quantity of the liquid level of the electrolytic solution for described electric energy storage device CONCENTRATION DISTRIBUTION bias in the horizontal as described horizontal stratification variable quantity,
Described relaxation function F (t) be optimised described in utilization also calculates described horizontal stratification variable quantity according to described horizontal stratification variable quantity calculating formula and for described quantity of state.
The condition detection method of 21. electric energy storage devices as claimed in claim 15, is characterized in that,
Prior establishment is used for calculating the described f relative to described relaxation function F (t) fast(t), described f slow(t) and described f fast(t)/f slowthe portraitlandscape stratification variable quantity calculating formula of portraitlandscape stratification variable quantity, in described portraitlandscape stratification variable quantity calculating formula, using the variable quantity of the CONCENTRATION DISTRIBUTION bias of the liquid level of the electrolytic solution for described electric energy storage device on horizontal and vertical as described portraitlandscape stratification variable quantity
Described relaxation function F (t) be optimised described in utilization also calculates described horizontal stratification variable quantity and longitudinal stratification variable quantity according to described portraitlandscape stratification variable quantity calculating formula and for described quantity of state.
The condition detection method of 22. electric energy storage devices as claimed in claim 21, is characterized in that,
The temperature funtion that described relaxation function F (t) is further used as described electric energy storage device is worked out in advance,
Measure described electric energy storage device temperature and for the calculating of described relaxation function F (t).
The condition detection method of 23. electric energy storage devices as claimed in claim 22, is characterized in that,
OCV when burning voltage is stable during described stopping, from described voltage determination value deduct according to OCV calculating formula during in advance establishment stable calculate described stable time OCV calculate described OCV variable quantity,
Using described OCV variable quantity as voltage variety during described stopping.
The condition detection method of 24. electric energy storage devices as claimed in claim 8, is characterized in that,
The relaxation function f of plural each reaction velocity of described relaxation function F (t) by working out in advance accordingly with the reaction velocity of described electric energy storage device inside it the linear combination of () represents, wherein, and i=1 ~ m,
The relaxation function f of described each reaction velocity it voltage variety during the described stopping calculated according to described voltage determination value is separated into the component corresponding with described reaction velocity and has carried out optimization by ().
The condition detection method of 25. electric energy storage devices as claimed in claim 24, is characterized in that,
According to the relaxation function f of described each reaction velocity it () estimates the quantity of state of corresponding each described reaction velocity, and the quantity of state amounting to each described reaction velocity is to calculate described quantity of state.
The condition detection method of 26. electric energy storage devices as claimed in claim 25, is characterized in that,
At the relaxation function f by the described each reaction velocity under predetermined state it the SOH of the SOC of (), described electric energy storage device and the described electric energy storage device of each reaction velocity is set to fi respectively ref(t), SOC ref, and SOHi ref, by described electric energy storage device be set to G (T) relative to the dependence of temperature T time, the relaxation function fi of the described each reaction velocity after the discharge and recharge of n-th time terminates nt () is expressed as:
fi n(t)＝fi ref(t)*{SOC n/SOC ref}
*{SOHi n/SOHi ref}*g(T)
Wherein, SOHi nrepresent the SOH of described each reaction velocity.
The condition detection method of 27. electric energy storage devices as claimed in claim 24, is characterized in that,
Measure the voltage and current of described electric energy storage device,
When being judged to be that described electric energy storage device stopped discharge and recharge according to described electric current or predetermined discharge and recharge stop signal,
According to described voltage determination value calculate corresponding with the elapsed time stopping from described discharge and recharge starting at described stop time voltage variety,
Voltage variety when utilizing described stopping, the relaxation function f of the described each reaction velocity corresponding to the described reaction velocity short to time constant compared with the described elapsed time it () carries out optimization,
The relaxation function that relaxation function fi (t) of the described each reaction velocity corresponding to described reaction velocity that time constant is long uses it previous compared with the described elapsed time, and according to its previous relaxation function described, described in the relaxation function f of described each reaction velocity that is optimised it at the end of (), described electric discharge, at the end of voltage and described charging, voltage estimates described quantity of state.
The condition detection method of 28. electric energy storage devices as claimed in claim 27, is characterized in that,
Described described voltage when stopping during burning voltage to be voltage after the discharge and recharge of described electric energy storage device stops the be variation of every 1 hour becomes below 5mv.
The condition detection method of 29. 1 kinds of electric energy storage devices, is characterized in that,
Charge before the state-detection of predetermined volumes is carried out to the described electric energy storage device that stopped discharge and recharge,
The voltage of described electric energy storage device when charging have passed through time t after terminating before measuring described state-detection with predetermined period,
With the variable quantity of voltage determination value described in relaxation function F (t) best fit approximation relative to burning voltage when making the discharge and recharge of described electric energy storage device stop and being reached for stopping when roughly fixing, described relaxation function F (t) is the function of the predetermined quantity of state of described electric energy storage device
Described quantity of state is estimated by relaxation function F (t) of best fit approximation according to described,
By being compared with predetermined threshold value the discharge capability judging described electric energy storage device by the quantity of state estimated by described.
The condition detection method of 30. electric energy storage devices as claimed in claim 29, is characterized in that,
Before described state-detection in charging, carry out the charging of the rated capacity 5% of described electric energy storage device.
The condition detection method of 31. electric energy storage devices as claimed in claim 30, is characterized in that,
When terminate charging before described state-detection and the described voltage determination value obtained at first lower than during described stopping during burning voltage, be judged to be that the discharge capability of described electric energy storage device have dropped.
The condition detection method of 32. electric energy storage devices as claimed in claim 31, is characterized in that,
During described stopping, burning voltage uses described relaxation function F (t) by best fit approximation to upgrade.
The condition detection method of 33. electric energy storage devices as claimed in claim 32, is characterized in that,
The relaxation function f of plural each reaction velocity of described relaxation function F (t) by working out in advance accordingly with the reaction velocity of described electric energy storage device inside it the linear combination of () represents, wherein, and i=1 ~ m,
The relaxation function f of described each reaction velocity it voltage variety during described stopping is separated into the component corresponding with described reaction velocity and has carried out optimization by ().
The condition detection method of 34. electric energy storage devices according to any one of claim 29 to 33, is characterized in that,
Described quantity of state is the SOC of described electric energy storage device.
The condition detection method of 35. electric energy storage devices as claimed in claim 33, is characterized in that,
Described quantity of state is the SOH of described electric energy storage device.
The condition detection method of 36. electric energy storage devices as claimed in claim 35, is characterized in that,
At the relaxation function f by the described each reaction velocity under predetermined normal condition it the SOC of (), described electric energy storage device and the described SOH of each reaction velocity is set to f respectively i ref(t), SOC ref, and SOH i ref, by described electric energy storage device be set to G (T) relative to the dependence of temperature T time, best fit approximation is to the relaxation function f of described each reaction velocity in the n-th cycle of described voltage determination i n(t) with in described n-th cycle by the SOC estimated n, described each reaction velocity SOH i nbetween there is relation below represented by formula:
f i n(t)＝f i ref(t)*{SOC n/SOC ref}
*{SOH i n/SOH i ref}*g(T)。
The condition detection method of 37. electric energy storage devices as claimed in claim 36, is characterized in that,
Before carrying out described state-detection before charging, pulsed discharge is carried out to described electric energy storage device and carries out other state-detection.
The condition detection method of 38. electric energy storage devices as claimed in claim 37, is characterized in that,
Before carrying out described state-detection before charging, carry out the impedance measuring of described electric energy storage device, and carry out other state-detection further.
The condition checkout gear of 39. 1 kinds of electric energy storage devices, consist of and the internal charger controlled by control module can be used to charge, the feature of described condition checkout gear is, comprising:
Signal input unit, for input state detecting pattern commencing signal;
Output display unit, for externally exporting predetermined information;
Determination unit, for measuring the voltage of described electric energy storage device; And
State detecting section, described state detecting section has state-detection mode switch, and is connected with described control module, described signal input unit, described output display unit and described determination unit,
Wherein, described state detecting section
When have input described state-detection pattern commencing signal from described signal input unit,
The voltage of the described electric energy storage device of the elapsed time t before described electric energy storage device being carried out to state-detection from described determination unit input after charging,
With voltage determination value described in relaxation function F (t) best fit approximation relative to burning voltage when the discharge and recharge of described electric energy storage device being stopped and reaching stopping when roughly fixing variable quantity described in relaxation function F (t) be the function of the predetermined quantity of state of described electric energy storage device
Described quantity of state is estimated by relaxation function F (t) of best fit approximation according to described,
By being compared with predetermined threshold value the discharge capability judging described electric energy storage device by the quantity of state estimated by described, and
Result of determination is exported to described output display unit.
The condition checkout gear of 40. electric energy storage devices as claimed in claim 39, is characterized in that,
Charging exports predetermined request signal by described state detecting section to described control module before described state-detection, and control described internal charger by described control module and carry out.
The condition checkout gear of 41. electric energy storage devices as claimed in claim 39, is characterized in that,
Before described state-detection, charging is undertaken by connecting external charger on described electric energy storage device.
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