CN102428379A - 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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CN102428379A
CN102428379A CN2010800023268A CN201080002326A CN102428379A CN 102428379 A CN102428379 A CN 102428379A CN 2010800023268 A CN2010800023268 A CN 2010800023268A CN 201080002326 A CN201080002326 A CN 201080002326A CN 102428379 A CN102428379 A CN 102428379A
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storage device
energy storage
electric energy
state
voltage
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CN102428379B (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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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 the condition detection method and the device thereof of electric energy storage device, relate in particular to condition detection method and the device thereof relevant with the discharge capability of electric energy storage device.
Background technology
In recent years, very big to the demand of electric energy storage device, to have installed from accumulator in for example a lot of automobiles and accepted the electric machine that power supply is moved as electric energy storage device, the importance of accumulator uprises day by day.In recent years, line traffic controlization is developed, and being representative with electronic brake system (EPB) also carries out Electronic Control to the parts of security system.In addition, along with the restriction of energy-conservation and emission of carbon-dioxide, the idling hold function that requires to have in the intersection etc. when locating temporarily to stop to be reset ability with it.
Electric energy storage device for example in order to promote the utilization of natural energies such as solar electrical energy generation or wind-power electricity generation, is also used in field beyond automobile, can and store dump energy to be used for balanced generating.Standby power supplies such as the stabilized power source that in addition, when have a power failure waiting, is used for supplying power to electric machine, accessory power supply also use electric energy storage device.The electric energy storage device that such electric energy storage device adopts secondary cell or capacitor etc. to move with electrolytic solution.
Usually, stop to discharge and recharge under the highly stable condition in back, have shown in the label 81 of Figure 35 such between its open-circuit voltage (OCV) and the residual capacity (SOC:State of charge) by 1: 1 corresponding relationship at electric energy storage device.But this 1: 1 relation is under condition stable as the laboratory, to obtain.Electric energy storage device after discharging and recharging is to contain under the situation of accumulator of electrolytic solution at it for example, can receive generation and the annihilation reaction of the ion that on polar board surface, is caused by electrochemical reaction respectively and the influence of moving of the ion that caused by electrolytic solution diffusion or convection current etc.
In the electric energy storage device that the ion as lithium ion battery or lead accumulator moves, will inevitably produce above-mentioned influence in electrolytic solution.In addition, even if capacitor and so on is using under the situation of electrolytic solution as the electric power storage medium,, therefore also can receive the influence of ions diffusion etc. because the concentration of this medium changes.Even use under the situation of solid electrolyte as medium replacing electrolytic solution, the ion in this electrolyte also can squint under the electric power storage effect.Therefore, reaching steady state (SS) according to medium or medium needs certain hour, obtain stable OCV, need with the corresponding convergence time of the characteristic of various electric energy storage devices (for example, pregnant solution type lead acid accumulator needs about 20 hours).
As stated; When the ion concentration transient changing in electrolyte or the electrolytic solution; Need the long period just can reach ion concentration state very uniformly, therefore according to the result who in limited minute, measures cell voltage, 1: 1 relation is false between OCV and SOC.Figure 36, Figure 37 are the figure of a SOC and temperature example of the transient changing of OCV fixedly time that accumulator is shown.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 the (impairment grade at SOH; State of health) variation of the OCV in the asynchronous accumulator ( label 83,84,85); Even wherein show SOC also is being set under the identical situation to the same terms and with the nearest condition that discharges and recharges with adjustment,, just can converging to identical OCV as long as SOH is different.
So, in order to obtain SOC accurately, need to use the SOC of the SOH that has reflected electric energy storage device rightly based on OCV.In addition, discharge and recharge transient changing after stopping comprise as the generation of ion and eliminate reaction time the reaction short, change fast variation and as like this reaction time length, the slow variation of variation such as the diffusion of electrolytic solution or convection current.Different transient changing of such reaction time is also respectively according to SOC or SOH and difference.
Electric energy storage device is stable can be used if will make, and need carry out its state-detection accurately, so that possibly take place to detect this situation in advance tackling under the situation of discharge capability deficiency etc.In using the system of electric energy storage device, in order to make regular event such as intrasystem electric machine, electric energy storage device set in charge and discharge process, also required the lower voltage limit (critical point of discharge capability) kept.Therefore, in the state-detection of electric energy storage device,, judge accurately importantly whether the voltage of electric energy storage device is higher than above-mentioned lower voltage limit as the judgement of its discharge capability (COD:Capability of Discharge).
Whether the COD of electric energy storage device always judges and can more keep the voltage of electric energy storage device in the highland than lower voltage limit for any load.An example of the change in voltage of electric energy storage device when Figure 38 shows discharge.Show on accumulator when connecting load and discharging cell voltage 33 over time Figure 38 model utility.Cell voltage 33 during discharge descends with the passing of time and gradually, but if drop to system requirements lower voltage limit, be the critical point of discharge capability, just can't appropriate electric energy be provided to the electric machine of system etc.
Can be from the falling quantity of voltages that initial cell voltage 31 is started at like following formulate.
Falling quantity of voltages=reaction resistance (increase) * electric current+built-in potential (decline)
Here, the voltage decline (arrow D) that is caused by reaction resistance is to descend with the voltage that causes the energy that electrochemical reaction is required, and its deterioration according to electric energy storage device (SOH) changes.In addition, built-in potential descend (arrow C) be by causing along with the variation of the active substance that causes of electrochemical reaction etc., its residual capacity according to electric energy storage device (SOC) changes.Can know from Figure 38, even if built-in potential 34 than drop-out voltage 35 height, if the slippage that is caused by exoelectrical reaction resistance is big, also can drop to the critical point of discharge capability.So; In electric energy storage device with electrochemical reaction; Lower voltage limit 35 decisions of stipulating in built-in potential C, exoelectrical reaction resistance D and the system definition of discharge capability COD by accumulator; Therefore if will judge discharge capability accurately, need differentiation exoelectrical reaction resistance D (deterioration) and built-in potential C (residual capacity) to judge.
As the method for the discharge capability of judging electric energy storage device, can consider system to be stopped so that discharge equipment discharges fully, come the direct method of measuring residual capacity and judging through carrying out full charging once more then.But in the method, in order to measure residual capacity, electric energy storage device becomes disabled state.Especially there is the danger can not realize original function in electric energy storage device in as subsequent use system.In addition, when bleeding off all told and carry out practical measurement, discharge time and duration of charging the two all need the suitable time, thereby reduced the operational efficiency of system significantly.
As the method for the deterioration state of judging electric energy storage device, known have through impedance method infer internal state and infer the method for discharge capability based on its information.But, though this method can be applied to electric energy storage device under full charging or state, be used near full charging in, when can't be applied to electric energy storage device and under partial charging state (PSOC:Partial State of charge), be used.In recent years, electric energy storage device is used in the purposes of balanced natural energy, but in such purposes, to compare use electric energy storage device under the residual capacity partial charging state mutually far short of what is expected with full charging.
Application mode when using Figure 39 to explain electric energy storage device used with full charging when using different with PSOC.Figure 39 (a) shows the state-detection in the existing application method, and Figure 39 (b) shows the state-detection in the application process of PSOC.In the existing application method, require to detect the reduction 42a of the deterioration allowance 42 that causes by deterioration, to judge remaining deterioration allowance 42b.Relative therewith; In the application process of PSOC, need carry out following control: detect the charging zone 44 and deterioration allowance 45 reduction 44a, 45a separately that cause by deterioration; And, come to be provided with again charging zone 44 and deterioration allowance 45 through the scope that changes deployment area 43 in order to guarantee necessary charging capacity and discharge capacity.
In the application process of the existing electric energy storage device that always is used, can think that the impedance of electric energy storage device only receives the influence of deterioration and changes with the state of basic full charging.Therefore, through measuring impedance, can know the impairment grade (SOH) of electric energy storage device.Relative therewith, in the application based on PSOC, impedance receives the two the influence of deterioration and residual capacity, therefore can't obtain impairment grade based on impedance.
Different transient changing of reaction time after in electric energy storage device, discharging and recharging has been described in front, but in order to reflect the difference in this reaction time, for example in patent documentation 1, has been put down in writing transient changing is divided into the method that the component of three time constants is estimated.In patent documentation 1, transient response changed according to the time of discharging and recharging, and in addition, had also mentioned transient response and resistive component, relevant with the rate of propagation of the corresponding polarization components of internal-response of battery and electrolytic solution.
Technical literature formerly
[patent documentation 1] Japanese patent application open communique JP2005-106615 number (japanese kokai publication hei 2005-106615).
Brief summary of the invention
Invent technical matters to be solved
But, do not carry out accurately still so far that system using discharge and recharge the time the method for state-detection of electric energy storage device.As the means of supplementing out economy that are used for the residual capacity that decision-making system using, known electric current aggregate-value when having based on the discharging and recharging of electric energy storage device is inferred the current residual capacity and is used this residual capacity to judge the method for discharge capability.But; Only the aggregate-value through charging current and discharge current is the decline of the efficiency for charge-discharge that can't reflect that the change by the internal state amounts such as deterioration of electric energy storage device causes; There are differences between the residual capacity of the residual capacity of the electric energy storage device of calculating based on the electric current aggregate-value and actual available electric energy storage device, thereby can't correctly calculate discharge capability.In addition, only keep watch on residual capacity and can't judge discharge capability, promptly can't judge and more to keep the voltage of electric energy storage device in the highland than the voltage of system requirements.
Below, use identical but the example that voltage electric energy storage device is different of Figure 40 plain telegram stream aggregate-value.This Figure 40 is the follow-up periodicity of transverse axis, shows the voltage when repeating the following charging end of the electric current aggregate-value is identical in charging and discharge charge status.Make the charging cumulative amount in the one-period be 5% (Δ SOC=5%), and the cumulative amount that discharges and recharges in each cycle is 0 with the discharge cumulative amount.In addition, to show the residual capacity (SOC) that discharges and recharges when beginning of electric energy storage device be the situation of 90% (label 51～53), 80% (label 54), 70% (label 55～60), 60% (label 61) to Figure 40.
Can know that from Figure 40 increase along with discharging and recharging periodicity, the voltage when charging finishes also rises.The inner quantity of state of this expression electric energy storage device changes along with the repetition in the cycle of discharging and recharging.In addition, even the variable quantity of electric current aggregate-value is 0, variation has also taken place in the quantity of state of electric energy storage device.The experimental data that the pregnant solution type lead acid accumulator (JIS standard 55D23) that data shown in Figure 40 are to use the Furukawa battery to make carries out.
On the other hand, because therefore the transient changing of the asynchronism(-nization) that in the state-detection that discharges and recharges after stopping, yet can reacting in the inside of electric energy storage device does not still infer influence that is brought by these transient changing and the method for carrying out state-detection so far rightly.Even if as the condition detection method of being put down in writing in the patent documentation 1, will discharge and recharge the component that transient changing after stopping is divided into the different time constant and carry out under the situation of state-detection; If the SOC of electric energy storage device or SOH change; Then also need correspondingly regulate each time constant; Therefore there is following problem: be difficult to obtain accurately, thereby be difficult to carry out accurately the state-detection of accumulator to different SOC or the time constant of SOH.In view of above-mentioned technical matters, the objective of the invention is to, provide no matter be in discharge and recharge in the middle of or stopped discharging and recharging condition detection method and the device thereof whether decidables is all keeping the electric energy storage device of appropriate discharge capability.
The technical scheme that the technical solution problem adopts
The condition detection method of the electric energy storage device that first aspect present invention is related is to be used for corresponding predetermined cycle judgement to discharge and recharge condition detection method central and that discharge and recharge the electric energy storage device of the discharge capability in the middle of stopping; The voltage determination value of the said electric energy storage device of after last discharging and recharging stops, and then measuring is as discharging and recharging when stopping voltage V_end and being stored in the predetermined storage part; Read in the said voltage V_end when stopping that discharging and recharging from said storage part; Through from the said voltage determination value V_now that deducts current (being made as periodicity is n) when stopping the voltage V_end that discharges and recharges; And calculate as forehead voltage variety Δ Va_n; Impairment grade SOH and said voltage variety Δ Va_n based on said electric energy storage device also 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 said electric energy storage device; Through following formula, calculate the current discharge capability COD_now of said electric energy storage device
COD_now＝V_now-COD_SOH_n
And as said discharge capability COD_now during greater than predetermined threshold COD_Th, the discharge capability that is judged to be said electric energy storage device is kept.
In the condition detection method of the related electric energy storage device of others of the present invention; Said impairment grade SOH is that the periodicity in the middle of stopping from current nearest discharging and recharging is that (the impairment grade SOH_n1 that calculates during n1≤n), said discharge capability correction COD_SOH_n is through reading in the said discharge capability correction function F (SOH_n1, x) (x be variable) corresponding with said impairment grade SOH_n1 and with calculating the said variable x of said voltage variety Δ Va_n substitution from said storage part for n1.
In the condition detection method of the related electric energy storage device of others of the present invention; Said discharge capability correction function F (SOH, Δ Va) through with the relaxation function fi of each reaction velocity of more than two of establishment (being made as m) (the incompatible expression of linear junction of i=1～m) in advance accordingly of the speed of the inner transient changing of said electric energy storage device; In the middle of discharging and recharging of said electric energy storage device stops, said voltage determination value is kept in the said storage part, and the relaxation function fi of said each reaction velocity is according to discharging and recharging the elapsed time that stops to start at and use the said voltage determination value that is kept at the said storage part to be optimised from said.
In the condition detection method of the related electric energy storage device of others of the present invention; Stop central and from discharging and recharging the elapsed time that stops to start at when having surpassed the scheduled time (being made as for first slack time) when said electric energy storage device is in to discharge and recharge; The relaxation function fi that use is kept at said voltage determination value pair in the said storage part said each reaction speed corresponding with transient changing fast carries out optimization; Use the relaxation function fi of each reaction speed after the said optimization to calculate and depend on the impairment grade SOH_fast_n of transient changing fast; That calculates when being based on periodicity in the middle of current nearest discharging and recharging stops and being n2(n2≤n) depends on the impairment grade SOH_slow_n2 and the said impairment grade SOH_fast_n of transient changing slowly; And utilize predefined function G; Calculate current impairment grade SOH_n by following formula
SOH_n＝G(SOH_fast_n，SOH_slow_n2)
And said discharge capability correction COD_SOH_n is through reading in the said discharge capability correction function F (SOH_n, x) corresponding with said impairment grade SOH_n and with calculating the said variable x of said voltage variety Δ Va_n substitution from said storage part.
In the condition detection method of the related electric energy storage device of others of the present invention; Stop central and from discharging and recharging the elapsed time that stops to start at when having surpassed when said electric energy storage device is in to discharge and recharge than long predetermined second slack time said first slack time; The relaxation function fi of said each reaction velocity of transient changing carries out optimization to depending on slowly further to use the said voltage determination value that is kept in the said storage part; Use the relaxation function fi of each reaction velocity after the said optimization to calculate and depend on the impairment grade SOH_slow_n of transient changing slowly; Based on the said impairment grade SOH_fast_n and the said impairment grade SOH_slow_n of transient changing slowly that depends on of transient changing fast of depending on that calculates; And utilize said function G, calculate current impairment grade SOH_n through following formula
SOH_n＝G(SOH_fast_n，SOH_slow_n)。
In the condition detection method of the related electric energy storage device of others of the present invention; And then said electric energy storage device is carried out the charging (before the state-detection charging) of predetermined volumes after stopping discharging and recharging, and will before said state-detection, charge finish after and then the said voltage determination value of mensuration discharge and recharge when stopping voltage V_end and be saved in the said storage part as said.
The first aspect of the present invention, the electric energy storage device state detection means is means for determining a predetermined period corresponding to charging and discharging and charging and discharging is stopped among which discharge capacity of the electric energy storage device state detection device, characterized by comprising: a storage part of the electric energy storage device for storing a voltage measurement value; state detection unit, corresponding to the period for reading stored in the storage unit of the data to determine the discharge capacity of the electric energy storage device;, and status output unit, the state detection unit for input from the determination result to the external output; wherein said storage unit stores the last charging and discharging is stopped immediately after measurement of the electric energy storage device of the measured voltage value, as discharge stop voltage V_end; said state detecting unit reads from the storage unit when the voltage of the charging and discharging is stopped V_end, by discharging from said charge voltage V_end stop subtracting the current (set number of cycles n) The measured voltage value to calculate the current V_now voltage change amount ΔVa_n, based on the degree of degradation of the power storage device and said voltage change amount SOH ΔVa_n prepared in advance using the discharge capacity correction function F (SOH, ΔVa_n) calculates the accumulator Electric discharge capacity correction device COD_SOH_n, by the following equation to calculate the electric energy storage device of the present discharge capacity COD_now,
COD_ow＝V_ow-COD_SOH_n
And as said discharge capability COD_now during greater than predetermined threshold COD_Th, the discharge capability that is judged to be said electric energy storage device is kept.
In the condition detection method of the related electric energy storage device of others of the present invention; The condition detection method of electric energy storage device; Said electric energy storage device is stopped to discharge and recharge and the voltage of said electric energy storage device when reaching the state that satisfies predetermined stable condition burning voltage when stopping; Will be after said electric energy storage device stops to discharge and recharge through variable quantity voltage variety when stopping of the burning voltage during of the voltage during time t with respect to said stopping; At this moment; The relaxation function F (t) of voltage variety works out as the function of the predetermined quantity of state of said electric energy storage device in advance in the time of will being used to calculate said stopping; Voltage when measuring will the stopping charging before charging and finish of said electric energy storage device, or will stop to discharge before discharge voltage when finishing; Voltage after said charging or the said discharge of measuring said electric energy storage device stops; The said relaxation function F of voltage variety and optimization (t) when calculating said stopping according to said voltage determination value infers said quantity of state according to the said relaxation function F (t) that is optimised, and voltage and said quantity of state of being inferred were judged the discharge capability (COD) of said electric energy storage device when voltage or said charging finished when utilizing said discharge to finish.
In the condition detection method of the related electric energy storage device of others of the present invention, said relaxation function F (t) through with the inner reaction velocity of the said electric energy storage device relaxation function f of each reaction velocity of more than two of establishment (being made as m) in advance accordingly i(t) (the relaxation function f of said each reaction velocity is represented in the linear combination of i=1～m) i(t) (voltage variety is separated into the component corresponding with said reaction velocity and has carried out optimization during said stopping that i=1～m) will calculate according to said voltage determination value.
In the condition detection method of the related electric energy storage device of others of the present invention; Thereby to discharge and recharge caused electric current small or when being limited in the predetermined scope for the influence that inner transient changing is brought of said electric energy storage device for fixed value when said, judges that said electric energy storage device has stopped discharging and recharging.
In the condition detection method of the related electric energy storage device of others of the present invention; Establishment in advance is used to revise the voltage correction of the change in voltage that is caused by said electric current; Be utilized in the voltage that adds the above voltage correction gained on the said voltage determination value, the said relaxation function F of optimization (t).
In the condition detection method of the related electric energy storage device of others of the present invention; Will discharge and recharge electric current aggregate-value that the electric current in the discharging and recharging before stopping to obtain according to accumulative total and calculate the residual capacity increase and decrease amount (Δ SOC) that discharges and recharges when stopping; On the last residual capacity that once discharges and recharges when stopping, adding the above residual capacity increase and decrease amount and calculate current discharging and recharging the residual capacity when stopping, voltage when voltage or said charging finish when finishing based on said discharge, the quantity of state and the said SOC that infer from said relaxation function F (t) judge said COD.
In the condition detection method of the related electric energy storage device of others of the present invention; Voltage was as the charge efficiency calculating formula of variable when establishment in advance finished predetermined quantity of state with charging; The said SOC that discharges and recharges when stopping to utilize charge efficiency correction said residual capacity increase and decrease amount and calculates, and the said charge efficiency calculating formula of voltage substitution was calculated when said charge efficiency finished the said quantity of state that utilizes said relaxation function F (t) to calculate and said charging.
In the condition detection method of the related electric energy storage device of others of the present invention, said quantity of state is the residual capacity of said electric energy storage device.
In the condition detection method of the related electric energy storage device of others of the present invention, said quantity of state is the impairment grade (SOH) of said electric energy storage device.
In the condition detection method of the related electric energy storage device of others of the present invention, said relaxation function F (t) has the fast component f of relaxation velocity Fast(t) and the slow component f of relaxation velocity Slow(t), work out said f in advance Fast(t), said f Slow(t) and both ratio f Fast(t)/f Slow(t) separately reference value is utilized the said f that calculates according to the said F that is optimised (t) Fast(t), said f Slow(t) and said f Fast(t)/f Slow, and said reference value separately judge said COD.
In the condition detection method of the related electric energy storage device of others of the present invention, said quantity of state is the impairment grade SOH of said electric energy storage device, utilizes said f Fast(t), said f Slow(t) and said f Fast(t)/f Slow, and said reference value separately calculate said impairment grade.
In the condition detection method of the related electric energy storage device of others of the present invention; Voltage changed the correction calculating formula as the High-speed transient of variable when establishment in advance finished residual capacity with charging, and the said High-speed transient of voltage substitution changed the correction calculating formula and calculates with respect to said f when said residual capacity and the said charging that discharges and recharges when stopping to be finished Fast(t) correction, and utilize said f with said correction correction Fast(t) calculate said impairment grade.
In the condition detection method of the related electric energy storage device of others of the present invention, work out change in concentration amount calculating formula in advance, said change in concentration amount calculating formula is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f Slow, the change in concentration amount of the electrolytic solution of said electric energy storage device, utilize the said relaxation function F (t) that is optimised and calculate the change in concentration amount of said electrolytic solution and be used for said quantity of state according to said change in concentration amount calculating formula.
In the condition detection method of the related electric energy storage device of others of the present invention, establishment in advance is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f SlowThe stratification variable quantity calculating formula of stratification variable quantity; In said stratification variable quantity calculating formula; CONCENTRATION DISTRIBUTION bias (stratification) variable quantity of the electrolytic solution of said electric energy storage device as said stratification variable quantity, is utilized the said said relaxation function F (t) that is optimised and calculates said stratification variable quantity and be used for said quantity of state according to said stratification variable quantity calculating formula.
In the condition detection method of the related electric energy storage device of others of the present invention, establishment in advance is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f SlowThe horizontal stratification variable quantity calculating formula of horizontal stratification variable quantity; In said horizontal stratification variable quantity calculating formula; Will be to the variable quantity of the liquid level CONCENTRATION DISTRIBUTION bias (laterally stratification) in the horizontal of the electrolytic solution of said electric energy storage device as said horizontal stratification variable quantity, utilize the said said relaxation function F (t) that is optimised and calculate said horizontal stratification variable quantity and be used for said quantity of state according to said horizontal stratification variable quantity calculating formula.
In the condition detection method of the related electric energy storage device of others of the present invention, establishment in advance is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f SlowThe portraitlandscape stratification variable quantity calculating formula of portraitlandscape stratification variable quantity; In said portraitlandscape stratification variable quantity calculating formula; Will be to the variable quantity of the liquid level of the electrolytic solution of the said electric energy storage device CONCENTRATION DISTRIBUTION bias (laterally stratification, vertically stratification) on horizontal and vertical as said portraitlandscape stratification variable quantity, utilize the said said relaxation function F (t) that is optimised and calculate said horizontal stratification variable quantity with vertical stratification variable quantity and be used for said quantity of state according to said portraitlandscape stratification variable quantity calculating formula.
In the condition detection method of the related electric energy storage device of others of the present invention; Said relaxation function F (t) further as the function of the temperature of said electric energy storage device by establishment in advance, measure the temperature of said electric energy storage device and be used for the calculating of said relaxation function F (t).
In the condition detection method of the related electric energy storage device of others of the present invention; Burning voltage is OCV when stablizing during said stopping; The OCV calculating formula is calculated when said voltage determination value deducts according to establishment in advance stable when said stable, and OCV calculates said OCV variable quantity, the voltage variety during as said stopping with said OCV variable quantity.
In the condition detection method of the related electric energy storage device of others of the present invention, according to the relaxation function f of said each reaction velocity i(t) infer the quantity of state of corresponding each said reaction velocity, and the quantity of state that amounts to each said reaction velocity calculates said quantity of state.
In the condition detection method of the related electric energy storage device of others of the present invention, at relaxation function f with said each reaction velocity under the predetermined state i(t), the said SOH of said SOC and each reaction velocity is made as fi respectively Ref(t), SOC Ref, and SOHi Ref, when the dependence with respect to temperature T of said electric energy storage device is made as G (T), the n time the relaxation function fi that discharges and recharges said each reaction velocity after the end n(t) be expressed as:
fi n(t)＝fi ref(t)*{SOC n/SOC ref}
*{SOHi n/SOHi ref}*g(T)
(SOHi here, nThe SOH of said each reaction velocity of expression).
In the condition detection method of the related electric energy storage device of others of the present invention; Measure the voltage and current of said electric energy storage device; Be judged to be said electric energy storage device when having stopped discharging and recharging when discharge and recharge stop signal according to said electric current or predetermined; According to said voltage determination value calculate with from said elapsed time of stopping to start at voltage variety during corresponding said stopping that discharging and recharging; Voltage variety when utilizing said stopping is to comparing the relaxation function f of short pairing said each reaction velocity of said reaction velocity of time constant with the said elapsed time i(t) carry out optimization, compare the relaxation function f of long pairing said each reaction velocity of said reaction velocity of time constant with the said elapsed time i(t) use its previous relaxation function, and according to the relaxation function f of said its previous relaxation function, said said each reaction velocity that is optimised iVoltage was inferred said quantity of state when voltage and said charging finished when (t), said discharge finished.
In the condition detection method of the related electric energy storage device of others of the present invention, burning voltage is that the voltage after discharging and recharging of said electric energy storage device stops is that per 1 hour variation becomes the said voltage of 5mv when following during said stopping.
In the condition detection method of the related electric energy storage device of others of the present invention; The condition detection method of electric energy storage device; The said electric energy storage device that has stopped discharging and recharging is carried out charge before the state-detection of predetermined volumes; Measure after charging finishes before the said state-detection through the voltage of the said electric energy storage device during time t with predetermined period; With the said voltage determination value of relaxation function F (t) best fit approximation with respect to discharging and recharging of said electric energy storage device being stopped and the variable quantity (voltage variety when stopping) of burning voltage during stopping when being reached for almost fixed; Said relaxation function F (t) is the function of the predetermined quantity of state of said electric energy storage device; Infer said quantity of state according to said relaxation function F (t), through said quantity of state of being inferred and predetermined threshold value relatively being judged the discharge capability of said electric energy storage device by best fit approximation.
In the condition detection method of the related electric energy storage device of others of the present invention, before said state-detection, in the charging, carry out the charging of the rated capacity 5% of said electric energy storage device.
In the condition detection method of the related electric energy storage device of others of the present invention; During burning voltage, the discharge capability that is judged to be said electric energy storage device had descended when charging and the said voltage determination value that obtains at first were lower than said stopping before finishing said state-detection.
In the condition detection method of the related electric energy storage device of others of the present invention, burning voltage uses said relaxation function F (t) by best fit approximation to upgrade during said stopping.
In the condition detection method of the related electric energy storage device of others of the present invention, said relaxation function F (t) through with the inner reaction velocity of the said electric energy storage device relaxation function f of each reaction velocity of more than two of establishment (being made as m) in advance accordingly i(t) (the relaxation function f of said each reaction velocity is represented in the linear combination of i=1～m) i(t) (voltage variety is separated into the component corresponding with said reaction velocity and has carried out optimization during i=1～m) with said stopping.
In the condition detection method of the related electric energy storage device of others of the present invention, said quantity of state is the residual capacity (SOC) of said electric energy storage device.
In the condition detection method of the related electric energy storage device of others of the present invention, said quantity of state is the impairment grade (SOH) of said electric energy storage device.
In the condition detection method of the related electric energy storage device of others of the present invention, at relaxation function f with said each reaction velocity under the predetermined normal condition i(t), the said impairment grade of said residual capacity and each reaction velocity is made as f respectively i Ref(t), SOC Ref, and SOH i Ref, when the dependence with respect to temperature T of said electric energy storage device is made as G (T), the relaxation function f of said each reaction velocity in n cycle of best fit approximation to said voltage determination i n(t) with the said residual capacity SOC that is inferred in said n the cycle n, said each reaction velocity impairment grade SOH i nBetween have a represented relation of following 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 related electric energy storage device of others of the present invention, before carrying out said state-detection, before the charging, said electric energy storage device is carried out pulsed discharge its state-detection of Xingqi of going forward side by side.
In the condition detection method of the related electric energy storage device of others of the present invention, before carrying out said state-detection, before the charging, carry out the impedance measuring of said electric energy storage device, its state-detection of stepping Xingqi of going forward side by side.
In the condition checkout gear of the related electric energy storage device of others of the present invention; It constitutes the internal charger that can use by control module control and charges; Said condition checkout gear is characterised in that, comprising: signal input unit is used for input state detecting pattern commencing signal; The output display unit is used for to the predetermined information of outside output; Determination unit is used to measure the voltage of said electric energy storage device; And state-detection portion; Said state-detection portion has the state-detection mode switch; And be connected with said control module, said signal input unit, said output display unit and said determination unit; Wherein, Said state-detection portion is when having imported said state-detection pattern commencing signal from said signal input unit; Said electric energy storage device is carried out the voltage of the said electric energy storage device of the elapsed time t after the charging before the state-detection from the input of said determination unit; With respect to discharging and recharging of said electric energy storage device being stopped and the variable quantity (voltage variety when stopping) of burning voltage during stopping when reaching almost fixed, said relaxation function F (t) is the function of the predetermined quantity of state of said electric energy storage device, infers said quantity of state according to said relaxation function F (t) by best fit approximation with the said voltage determination value of relaxation function F (t) best fit approximation; Through said quantity of state of being inferred and predetermined threshold value relatively being judged the discharge capability of said electric energy storage device, and result of determination is exported to said output display unit.
In the condition checkout gear of the related electric energy storage device of others of the present invention; Before the said state-detection charging be by said state-detection portion to the predetermined request signal of said control module output, and control said internal charger by said control module and carry out.
In the condition checkout gear of the related electric energy storage device of others of the present invention, charging is carried out through external charging device on said electric energy storage device before the said state-detection.
The invention effect
According to the present invention, can provide no matter be in discharge and recharge in the middle of or stopped discharging and recharging condition detection method and the device thereof whether decidables is all keeping the electric energy storage device of appropriate discharge capability.
Description of drawings
Fig. 1 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of first embodiment of the invention;
Fig. 2 is the block diagram of structure that the electric energy storage device of first embodiment is shown;
Fig. 3 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of second embodiment of the invention;
Fig. 4 is the curve map of the relation of voltage and SOH when the discharge of the electrical storage device when stablizing is shown;
Fig. 5 illustrates the curve map of transient changing that stops the OCV after first discharge;
Fig. 6 is the curve map of the timeliness of the falling quantity of voltages when being illustrated in the first elapsed time different time point place of discharge after stopping and having carried out second discharge;
Fig. 7 is OCV and the OCV variable quantity curve map over time that illustrates after charging stops;
Fig. 8 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of third embodiment of the invention;
Fig. 9 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of fourth embodiment of the invention;
Figure 10 is the process flow diagram of the condition detection method of explanation first reference example;
Figure 11 is the block diagram of summary structure that the condition checkout gear of the condition detection method that has used first reference example is shown;
Figure 12 is the process flow diagram that the timing of carrying out the required data determination of state-detection (timing, sequential) is judged;
Figure 13 is used to explain that judgement discharges and recharges the process flow diagram of the method that stops;
Figure 14 is used to explain OCV 20hrThe process flow diagram of system of selection;
Figure 15 is used for the optimized process flow diagram that F (t) is carried out in explanation;
Figure 16 is used for the optimized process flow diagram that F (t) is carried out in explanation;
Figure 17 is the process flow diagram that is used to explain the method for computing mode amount SOH, SOC;
Figure 18 is the curve map of an example that the relaxation function of relaxation function and each reaction velocity is shown;
Figure 19 is the curve map of an example that relaxation function and the ratio thereof of each reaction velocity are shown;
Figure 20 illustrates to stablize the curve map that OCV infers an example of formula;
Figure 21 is the process flow diagram of the condition detection method of explanation second reference example;
Figure 22 is the curve map that the example of charge efficiency η 1, η 2 is shown;
Figure 23 is the process flow diagram of the condition detection method of explanation the 3rd reference example;
Figure 24 is the curve map of an example of variation that the relaxation function of each reaction velocity is shown;
Figure 25 is the curve map of SOH with respect to an example of fast reaction velocity variation;
Figure 26 illustrates the curve map of correction factor with respect to the example of SOH;
Figure 27 is the process flow diagram of decision method that is used for explaining the quantity of state of the 3rd reference example;
Figure 28 is the mode chart that is used to explain the stratification of electric energy storage device;
Figure 29 is the process flow diagram that is used to explain according to the summary of the condition detection method of the electric energy storage device of the 4th reference example;
Figure 30 is the block diagram according to the condition checkout gear of the electric energy storage device of the 4th reference example;
Figure 31 be illustrate by in the middle of the operation discharge and recharge with state-detection before the curve map of variation of the electric current that causes of charging, voltage;
Figure 32 is the process flow diagram that is used to explain the processing till being played charging before the state-detection by request and finish from the state-detection pattern;
Figure 33 is the process flow diagram of the processing when being used for the establishment of description status detecting pattern;
Figure 34 is the process flow diagram that is used to explain the summary of the condition detection method of the electrical storage device of other embodiment according to the present invention;
Figure 35 is the curve map that the relation of stablizing open-circuit voltage and SOC is shown;
Figure 36 is the curve map that the variation of the OCV of SOC fixedly the time is shown;
Figure 37 is the curve map that the variation of the asynchronous OCV of SOH is shown;
Figure 38 is illustrated in cell voltage mode chart over time when the connection load is discharged on the accumulator;
Figure 39 is the different key diagram that is used to explain when electric energy storage device used with full charging the application mode when using with PSOC;
Figure 40 illustrates the curve map that discharges and recharges the voltage when finishing that repeats under identical charging of electric current aggregate-value and the discharge scenario.
Embodiment
With reference to accompanying drawing, the condition detection method and the device thereof of the electric energy storage device in the preferred embodiment of the present invention described.For the identical label of each component part mark, with simplicity of illustration and explanation with identical function.Below, with carrying accumulators such as pregnant solution type lead acid accumulator on vehicle, the condition detection method and the condition checkout gear of electric energy storage device of the present invention described as an example of electric energy storage device.But the content of explanation is not limited to Vehicular accumulator cell below, can be applicable to the electric energy storage device that is used for solar electrical energy generation or wind-power electricity generation etc. too or be used for the electric energy storage device of standby power supplies such as stabilized power source, accessory power supply.
The condition detection method of electric energy storage device of the present invention and device thereof be no matter electric energy storage device is in still to discharge and recharge in the middle of discharging and recharging to be stopped, all the discharge capability of decidable electric energy storage device.At first, be object with the situation that discharges and recharges state-detection when lax of transient changing after stopping (below be called the state-detection when lax), the base conditioning content related to the condition detection method of electric energy storage device of the present invention describes.Below; Electric energy storage device is stopped to discharge and recharge and voltage when reaching the state that satisfies predetermined stable condition is made as burning voltage when stopping, will be after electric energy storage device stops to discharge and recharge through the variable quantity of burning voltage when stopping of the voltage determination value during time t be made as voltage variety when stopping.
Establishment in advance depend on electric energy storage device predetermined quantity of state relaxation function F (t) and with the function of its voltage variety when calculating above-mentioned stopping.In addition, use based on the voltage determination value obtain stop the time voltage variety relaxation function F (t) is carried out optimization, the relaxation function F (t) after the optimization infers predetermined quantity of state and carries out state-detection.In the condition detection method of electric energy storage device of the present invention; Use above-mentioned relaxation function F (t) to infer discharge capability (COD), and compare the discharge capability of judging electric energy storage device through COD that this is inferred and pre-set threshold and whether kept rightly.
In the present invention, use relaxation function F (t) to infer the cell voltage of electric energy storage device when stablizing, as the COD that is used to judge discharge capability.In addition, threshold value adopts and to be set to such magnitude of voltage: even if also make cell voltage not drop to the system below the desired lower voltage limit when the COD that infers discharges and recharges from this state during greater than threshold value.This threshold value is set according to the variation in voltage amount that is caused by common discharging and recharging at least, so that cell voltage does not drop to below the lower voltage limit of system requirements.In addition, as the quantity of state that can infer based on relaxation function F (t), SOH (State of health) or residual capacity as the impairment grade index of electric energy storage device etc. are for example arranged.
The transient changing that discharges and recharges the electric energy storage device after stopping to comprise from as the generation of ion and eliminate reaction velocity the reaction fast be changed to the slow variation of reaction velocity as electrolytic solution mobile etc., these variable effects the variation that discharges and recharges the above-mentioned quantity of state after stopping.Therefore, in the condition detection method of electric energy storage device of the present invention, use relaxation function F (t) infers the variation of the quantity of state of each reaction velocity, and comprehensively these change the judgement of carrying out quantity of state.
Burning voltage during as above-mentioned stopping can to use after stopping to discharge and recharge through the open-circuit voltage of the electric energy storage device during time enough when stablizing (below be called OCV).Thereby the voltage between terminals of discharge when stopping of being opened a way that open-circuit voltage OCV is the terminal of electric energy storage device.In the condition detection method of electric energy storage device of the present invention, use stop the time burning voltage be not limited to stablize OCV, under to the limited situation of the transient effect of electric energy storage device, also can use burning voltage at that time.As an example; From electric energy storage device to load stop power supply during; Sometimes to control device of load etc. Weak current (dark current) is provided; Under the situation that such dark current etc. is provided, also can with after stopping load through the burning voltage when stopping of the voltage during time enough.
In addition, be always under the situation of fixed value, can think that also the transient effect of bringing to electric energy storage device is very little at the electric weight that charges and discharge of electric energy storage device, therefore can with after stopping load through the burning voltage when stopping of the voltage during time enough.So; Thereby it is small or when being limited in the predetermined scope for the electric energy storage device influence that inner transient changing is brought for fixed value when discharging and recharging caused electric current; Can when the power supply that has stopped to load, be judged to be the discharge that has stopped from electric energy storage device, and will stop the back and passed through the voltage burning voltage when stopping when long-time discharging and recharging with the state of keeping Weak current or fixed current.Preferably confirm to be used to revise the voltage correction of the change in voltage that is caused by Weak current or fixed current this moment in advance, and use this voltage correction to revise the voltage determination value.
Below, an example of burning voltage when stopping to use that OCV describes when stablizing.When using when stablizing OCV, applicable relation shown in Figure 35 such as following formulate quantity of state SOC.
SOC＝FS(OCV S’(SOC’，SOH，T)) (1)
OCV s(SOC，SOH，T)＝Lim(V mes(t)) (2)
Here, OCV sExpression is calculated specifically OCV when stable, OCV during last calculate stable of OCV ' expression, t represent elapsed time of stopping to start at from discharging and recharging, the last residual capacity of calculating of SOC ' expression, V Mes(t) the voltage determination value at expression elapsed time t place, T representes the temperature of electric energy storage device.The Lim of formula (2) representes and will be made as infinity from discharging and recharging the elapsed time that stops to start at, and the voltage determination value V of the elapsed time t electric energy storage device when infinitely great after stopping to be represented to discharge and recharge in the right of formula (2) Mes(t).When using when stablize stopping beyond the OCV during burning voltage, also can be in advance and SOC between work out above-mentioned same relational expression and use.
SOC has been shown in the following formula has depended on the OCV that the last time calculates S' and be determined while OCV SAlso depend on SOC, but also depend on as the temperature T of the SOH of other quantity of state and electric energy storage device and change.In addition, because OCV SDepend on quantity of state SOH, so quantity of state SOC also depends on SOH, thereby need carry out renewal separately with appropriate timing.
Shown in formula (2), OCV sBe from discharging and recharging the elapsed time t that stops the to start at V when infinitely great MesBut in practical application, can be set at V (t), Mes(t) variation 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 at the every variable quantity of OCV and be below the 5mV at a distance from one hour, perhaps from discharging and recharging the V when having stopped passing through 20 hours Mes(t).Below, with accumulator from discharging and recharging the V when having stopped passing through 20 hours Mes(t) be made as the OCV of following formula 20hr, and use it for OCV s
OCV 20hr＝V mes(t＝20hr)
OCV s(SOC，SOH，T)≒OCV 20hr (3)
As the voltage determination value V that will discharge and recharge after stopping Mes(t) when stablizing the variable quantity of OCV, when OCV variable quantity (voltage variety when stopping) being made as Δ V (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 regarded as and comprises all transient changing in existing galvanochemistry definition.But Δ V (t) is by until the change in voltage that produces near the relaxation till stablizing OCV, therefore receives the influence of the following change in voltage factor of enumerating.
As the factor of change in voltage, have polar plate status, pole plate vicinity ion concentration, they solid phase reaction, solid-liquid reaction and move by the ion that deposition, convection current or the diffusion of electrolytic solution causes etc.OCV variation delta V (t) can be considered to caused by the different relaxation combination of these reaction velocitys.So; The transient changing that discharges and recharges after stopping of electric energy storage device comprises the course of reaction that speed is different; Therefore preferably adopt the method that the state variation of each reaction velocity is estimated to carry out state-detection by the discharge capability that discharges and recharges the electric energy storage device after stopping in order to judge accurately.
According to the difference of reaction velocity, use the function F (t) that constitutes by m polynomial expression as following formula, to represent OCV variation delta V (t).
ΔV(t)＝F(t)
＝f 1(t)+f 2(t)+…f m(t)＝∑f i(t) (5)
In above-mentioned relaxation function F (t), each item f i(t) each relaxation that the reaction velocity of expression electric energy storage device is different below is made as the relaxation function f of each reaction velocity to the contribution amount of change in voltage i(t).Each item f i(t) be the function that depends on as impairment grade SOH, residual capacity SOC and the temperature T of the quantity of state of electric energy storage device.The relaxation function f of each reaction velocity of formula (5) i(t) can use based on the voltage determination value V that discharges and recharges after stopping Mes(t) the OCV variation delta V (t) that calculates confirms, so that it is optimised to this OCV variation delta V (t).
In the condition checkout gear that has used condition detection method of the present invention, detect SOC, SOH, OCV before for initial state 20hrInitial value SOC separately 0, SOH i 0, OCV 20hr 0, can use the reference value SOC separately that is kept in advance in the condition checkout gear 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 discharging and recharging of the n time (n is the integer more than 1) after the state-detection that is begun electric energy storage device by condition checkout gear stops, as the relaxation function F (t) of the formula (5) that will represent OCV variation delta V (t) and the relaxation function f of each reaction velocity i(t) be made as F respectively n(t), f i n(t) time, the relaxation function fi of each reaction velocity n(t) (be made as SOC respectively based on SOC and with i the corresponding SOH of reaction velocity n, SOH i n) can be like following formulate.
f in(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 RefBe the f under the predefined original state (for example unused state) i(t), SOC, SOH i, g (T) is the temperature dependent function of expression.
In formula (6), when supposition temperature T and SOC and time have nothing to do and fixedly the time, SOH i nCan calculate through following formula.
SOH i n＝{f i n(t)/f i ref(t)}*SOH i ref (7)
Thus, can be with the f of formula (5) i n(t) optimum turns to based on voltage determination value V Mes(t) the Δ V (t) that calculates, and use this Δ V (t) to calculate SOH through formula (7) i n
At the SOH that calculates the different various transient responses of reaction velocity through formula (7) i nThe time, these are integrated whole SOH of calculating nCan use predetermined function G to represent as follows.
SOH n＝G(SOH 1 n、SOH 2 n、…、SOH m n) (8)
For example, when with m SOH iCoefficient separately when being made as 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.Can use the SOH that as above calculates nCarry out the detection of the deterioration state of electric energy storage device.Likewise, the relaxation function F (t) after the use optimization also can calculate the SOC as other quantity of state n
Use the SOH that calculates through formula (7) i nAnd through following formula renewal f i nAnd the f after will upgrading (t), i n(t) be used 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 20hrCan calculate through following formula.
OCV 20hr＝V mes(t)-∑[f i ref(t)*{SOC n-1/SOC ref}
*{SOH i n/SOH i ref}]*g(T) (9)
Through with this OCV 20hrIn the substitution formula (1), can calculate SOC nThereby, can be used in the state-detection of SOC.
As stated, can be based on m the reference value f corresponding with m kind reaction velocity i Ref(t) (the reference value SOH of i=1～m), a m impairment grade i Ref(i=1～m) and the reference value SOC of 1 residual capacity Ref, calculate the relaxation function f of the m that discharges and recharges for the n time after stopping each reaction velocity i n(t) (i=1～m).And obtain OCV, SOC and the SOH that has reflected with the different corresponding impairment grades of reaction velocity based on this, can carry out high-precision state-detection.
In above-mentioned; State-detection is an object when discharging and recharging lax after stopping; The basic processing content that condition detection method is related has been described; But the condition detection method of electric energy storage device of the present invention is not defined to state-detection when relaxing, and in charge and discharge process, can carry out the state-detection of electric energy storage device yet.Below, be in the middle of the operation system and the state-detection of electric energy storage device when just discharging and recharging is made as state-detection when discharging and recharging.In above-mentioned explanation; Because only state-detection is an object when lax; Therefore the periodicity n of state-detection is made as and discharges and recharges the number of times that stops; But in the state-detection that comprises state-detection when discharging and recharging, preferably periodicity n is made as the periodicity when for example carrying out state-detection with preset time gap periods ground.
In addition; Because state-detection is limited to OCV along with the state-detection the relaxation of the OCV convergence when stablize (OCV variation delta V (t) is to 0 convergence) from discharging and recharging the elapsed time t that stops to start at when lax, so can relaxation function only be expressed as the function F (t) of elapsed time t.But; The discharge capability COD of the electric energy storage device in the charge and discharge process receives to influence from the very big of voltage variety that the voltage that discharges and recharges when stopping to be started in the elapsed time that stops to start at from nearest discharging and recharging in short-term; And, influenced by the very big of impairment grade SOH along with the elapsed time is elongated.
Therefore, the function F that will when discharging and recharging lax after stopping, be used as relaxation function in the state-detection following as discharge capability correction function F, with the function that uses in the state-detection when discharging and recharging as state-detection when lax.In addition, for the OCV variation delta V (t) with formula (4) differentiates, will be made as Δ Va (t) from the voltage variety that the voltage that discharges and recharges when stopping to be started at.At this moment, discharge capability correction function F can be expressed as F (SOH, Δ Va), as the function of voltage variety Δ Va (t) and impairment grade SOH.Here, the dependence to elapsed time t is comprised in the time dependence of voltage variety Δ Va (t).
Voltage when nearest discharging and recharging stopped, from state-detection time point (current), carried out discharging and recharging voltage when stopping at last and be made as and discharge and recharge voltage when stopping, and it has been expressed as V_end.In addition, the elapsed time till will stopping from last discharging and recharging playing state-detection time point (current) is made as t, when current voltage is made as V_now, and voltage variety Δ Va (t) can calculate through following formula.
ΔVa(t)＝V_end-V_now (10)
Here, discharge and recharge that voltage V_end is made as V_cha_end when stopping when charging stops, when discharge, being made as V_dis_end.
Describe down in the face of the relation that discharges and recharges OCV variation delta V (t) and above-mentioned voltage variety Δ Va (t) in stopping.The V of formula (4) Mes(t) be V_now here, so the computing formula of the OCV variation delta V (t) shown in the formula (4) can be rewritten as following formula.
ΔV(t)＝V_now-OCV 20hr (4-1)
＝F(SOH，ΔVa)
Can know to have the relation shown in the following formula between voltage variety Δ Va (t) and the OCV variation delta V (t) from formula (10) and formula (4-1).
ΔVa(t)+ΔV(t)＝V_end-OCV 20hr (11)
Discharge and recharge OCV, the OCV of discharge capability (being made as COD_now) when equaling to stablize in stopping 20hr, therefore can provide by following formula through formula (4-1).
COD_now＝OCV 20hr＝V_now-ΔV(t)
＝V_now-F(SOH，ΔVa) (12)
That is, discharge capability COD_now be from current voltage V_now deduct the discharge capability correction, be discharge capability correction function F (SOH, Δ Va) value and value.
With identical during above-mentioned discharging and recharging stops, the discharge capability COD_now in the charge and discharge process also can use formula (12) to calculate.When will be as discharge capability correction function F (SOH; When the discharge capability correction table of value Δ Va) is shown COD_SOH; In the condition detection method of electric energy storage device of the present invention, when discharging and recharging state-detection and when lax the discharge capability COD_now of the electric energy storage device in the state-detection all can calculate through following formula.
ΔVa(t)＝V_end-V_now
COD_SOH＝F(SOH，ΔVa)
COD_now＝V_now-COD_SOH
Keep discharge capability when the discharge capability COD_now that will in following formula, calculate is judged to be during greater than threshold value COD_Th, when being less than or equal to threshold value COD_Th, be judged to be the discharge capability deficiency.
(first embodiment)
Use Fig. 1, Fig. 2, the condition detection method and the device thereof of the electric energy storage device that first embodiment of the invention is related to describe.Fig. 1 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of present embodiment, and Fig. 2 is the block diagram of structure of condition checkout gear that the electric energy storage device of present embodiment is shown.
The condition checkout gear 100 of present embodiment shown in Figure 2 is used for the electric energy storage device (accumulator) 10 on the vehicle 1 that is installed in objective system is carried out state-detection.Vehicle 1 comprises: the control module 12 of the charging that charhing unit (alternator, alternator) 11 that is used in the middle of engine operation, accumulator 10 being charged and control are carried out through charhing unit 11 etc.In addition, the load 2 of various electronic devices and components is installed on the vehicle 1, can accepts power supply thereby these loads 2 are connected on the accumulator 10.In accumulator 10, be provided with voltage measuring unit for measuring 20, amperometric determination unit 21 and temperature measurement unit 22, the measured value of each in condition checkout gear 100 these determination units of input is also carried out state-detection.
Condition checkout gear 100 comprises: state-detection portion 110, storage part 120 and state output unit 130.State-detection portion 110 imports voltage determination value, amperometric determination value and the temperature measuring value of accumulator 10 respectively from voltage measuring unit for measuring 20, amperometric determination unit 21 and temperature measurement unit 22, and carries out carrying out based on the processing of the condition detection method of present embodiment the state-detection of accumulator 10.Various reference datas that the processing that storage part 120 preservation states detect is required and determination data etc.In addition, state output unit 130 is the unit to driver's untill further notice state-detection result etc.
The condition detection method of the electric energy storage device of present embodiment no matter accumulator 10 whether be in discharge and recharge in the middle of, after condition checkout gear 100 starting all in state-detection portion 110 with the preset time gap periods be performed.In Fig. 1, in step S1, begun the n time state-detection after, working voltage determination unit 20 obtains the voltage determination value of accumulator 10 in step S2, and with this voltage determination value as current voltage V_now.
In step S3; Judgement accumulator 10 is to be in to discharge and recharge central (result of determination is " being "), still is in to discharge and recharge to stop central (result of determination is " denying "), and when result of determination is " being "; Get into step S8, when result of determination is " denying ", get into step S4.Judge about this, can use amperometric determination unit 21 to obtain the amperometric determination value of accumulator 10, and this value be judged to be in 0 o'clock discharge and recharge stop in the middle of, when be value beyond 0 be judged to be discharge and recharge in the middle of.Perhaps, be judged to be when also can the absolute value of amperometric determination value be less than or equal to the predetermined current threshold value discharge and recharge stop in the middle of, with time beyond it be judged to be discharge and recharge in the middle of.
When in step S3, be judged to be discharge and recharge stop in the middle of when (result of determination for " deny "), then in step S4, judge accumulator 10 whether be in just stopped discharging and recharging after, when result of determination gets into step S5, entering step S7 when being " denying " during for " being ".About this judgement, when in the state-detection of preceding once (the n-1 time), be judged to be discharge and recharge in the middle of the time can be judged to be in just stop to discharge and recharge after.When in step S4, be judged to be in just stop to discharge and recharge after when (result of determination for " being "); In step S5, current voltage V_now being set at the voltage V_end that discharges and recharges when stopping (is V_cha_end when charging stops; Discharge is V_dis_end when stopping); And be stored in the storage part 120, charge to step S7 then.
In step S7, read the voltage V_end when stopping that discharging and recharging that is stored in the storage part 120.This voltage V_end that discharges and recharges when stopping to be stored in the storage part 120 through step S5 when current nearest discharging and recharging stops.Discharge and recharge voltage V_end and current voltage V_now when stopping based on this, and through following formula calculating voltage variation delta Va_n.
ΔVa_n＝V_end-V_now
In step S8, read in the impairment grade SOH_n1 that is stored in the storage part 120.Here, (n1≤n), impairment grade SOH_n1 is the previous SOH of final updating to the periodicity when n1 representes SOH by final updating.The characteristic value of the accumulator 10 during with new product data in advance as a reference is kept in the storage part 120, and from this reference data, reads in the initial value SOH_0 that SOH is used as SOH_n.Perhaps, with the characteristic value of general electric energy storage device as a reference data in advance be kept in the storage part 120, and with the SOH of this reference data as SOH_0.This SOH_0 is rewritten by SOH_1, and SOH_1 is the value of calculating when carrying out state-detection first behind the installation accumulator 10.In step S9, from storage part 120, read in the discharge capability correction function F (SOH_n1, x) corresponding with the impairment grade SOH_n1 that in step S8, reads in.
In step S10, among the variable x of the Δ Va_n substitution discharge capability correction function F (SOH_n1, x) that will in step S7, calculate, calculate discharge capability correction COD_SOH_n.
COD_soh_n＝F(SOH_n1，ΔVa_n)
In step S11,, calculate current discharge capability COD_now through following formula based on current voltage V_now and the discharge capability correction COD_SOH_n that in step S10, calculates.
COD_now＝V_now-COD_SOH_n
In step S12; The current discharge capability COD_now that will in step S11, calculate and the threshold value COD_Th of discharge capability compare; During greater than threshold value COD_Th, be judged to be the discharge capability (step S13) of keeping accumulator 10, on the other hand at current discharge capability COD_now; When current discharge capability 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 can wait to the driver and notify through suitably exporting to suitable state output unit 130.
As stated, according to the condition detection method and the condition checkout gear of the electric energy storage device of present embodiment, no matter be in discharge and recharge in the middle of or be in discharge and recharge stop in the middle of, all whether the decidable discharge capability is kept rightly.In the present embodiment; As calculating the required impairment grade SOH of discharge capability correction; Used the SOH_n1 that is stored in the storage part from current nearest last time; But because the variation of SOH is very little at short notice, even if therefore use SOH_n1 also can infer current discharge capability COD_now accurately.
(second embodiment)
Use Fig. 3, the condition detection method of the electric energy storage device that second embodiment of the invention is related to describes.Fig. 3 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of present embodiment.Present embodiment can reflect the judgement of the discharge capability of the transient changing in the short time that discharges and recharges after stopping in the state-detection that discharges and recharges when stopping.
Below, at first the COD to electric energy storage device describes from the suffered influence of transient changing that discharges and recharges after stopping.SOH when Fig. 4 shows discharge and the relation of discharge capability COD.In Fig. 4, will be after discharge stops through the voltage determination value (D1) that reaching when stablizing of 20 hours electric energy storage devices be illustrated on the longitudinal axis as discharge capability COD, will be illustrated on the transverse axis with the SOH that the condition of this moment is calculated.In addition, show the dotted line L1 of approximate voltage measured value in the lump, shown in dotted line L1, can know to have basic 1 to 1 relation between SOH and the COD.Based on this, the SOH during through calculation stability accurately can obtain COD accurately.
On the other hand, below, the influence of the transient changing the when electric energy storage device after the research charging stops not to be stablized.Fig. 5 shows the transient changing of the OCV after charging stops.The variation of OCV when (a) of Fig. 5 shows time shaft with transverse axis and illustrate with logarithmic scale, the variation of the OCV of Fig. 5 (a) when showing time shaft with transverse axis Fig. 5 (b) model utility and illustrating with linear graduation.As shown in Figure 5, after stopping charging, the caused transient changing of charging is slowly lax, and OCV is gradually to stablizing the OCV convergence.
But the elapsed time after charging stops is short more, and the influence of the caused transient changing of charging is just big more, if therefore discharge at this time point, and very big influence of charging before will receiving.Falling quantity of voltages when therefore, different a plurality of time points of elapsed time after charging stops being shown in Fig. 6 having carried out discharge over time.Here show from the elapsed time that charging stops to start at be the time point of 30 seconds (label t1), 100 seconds (label t2), 300 seconds (label t3), 3600 seconds (label t4), 36000 seconds (label t5) and 72000 seconds (label t6) falling quantity of voltages when having carried out discharge over time.Here, as discharge, the discharge sustain of 100 [A] has been carried out 30 seconds.
Can know that from Fig. 6 the elapsed time after charging stops is short more, falling quantity of voltages is just big more.Especially after charging stops through the falling quantity of voltages of 30 seconds the time point falling quantity of voltages (label t1) when having carried out discharge during greater than elapsed time of having prolonged more till charging stops to play the discharge beginning.If more than will prolonging to a certain degree from the elapsed time that charging stops to start at, falling quantity of voltages not almost be seen any difference.Because the missionary society of such falling quantity of voltages Δ va influence COD, therefore when the time point judgement COD that lacks in the elapsed time that stops to start at from charging, preferably carry out 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 by along with the variation of the caused impairment grade SOH_fast of transient changing fast causes; Thereby calculate SOH_fast based on formula (7); And the function G shown in the formula (8) in the storage part 120 is worked out and is stored in use in advance, and (SOH_fast SOH_slow) calculates SOH.Here, the SOH_slow impairment grade that causes by transient changing slowly that is illustrated in that nearest discharging and recharging calculate when stopping.In order to calculate the impairment grade SOH_fast that is caused by transient changing fast accurately, the working voltage measured value is to the relaxation function f of each reaction velocity of discharge capability correction function F (SOH, Δ Va) i(t) the fast relaxation function f of reaction velocity in i(t) carry out optimization.This optimization can be carried out stop to have passed through the schedule time (being made as for first slack time) from discharging and recharging after.
With respect to this, when long time point was judged COD in the elapsed time that stops to start at from discharge, the influence that falling quantity of voltages Δ va is brought was little, and the influence of the precision of the SOH that use Fig. 4 describes is very big.In addition, in above-mentioned Fig. 4～Fig. 6, the influence of the transient changing after charging stopped to be illustrated, but the influence of the transient changing of discharge after stopping too.
In the condition detection method of the electric energy storage device of present embodiment; When from discharging and recharging elapsed time of stopping to start in short-term; Calculate accurately and poor corresponding SOH_fast, and use this SOH_fast to infer discharge capability COD along with the voltage variety Δ va that transient changing produced fast.Here, below, use Fig. 7 to being used to distinguish describing of transient changing fast from discharging and recharging the elapsed time that stops to start at.The first above-mentioned slack time can be as the elapsed time of distinguishing above-mentioned transient changing fast.The time that Fig. 7 (a) shows OCV (label 71) and the OCV variation delta V (label 72) of pregnant solution type lead acid accumulator (battery capacity is 48 [Ah]) after charging stops to change, and Fig. 7 (b) shows the OCV (label 73) of small-sized sealed lead-acid battery (battery capacity I 5.5 [Ah]) after charging stops and the time of OCV variable quantity (label 74) changes.
In the pregnant solution type accumulator shown in Fig. 7 (a), electrolytic solution reaches that to stablize the required time long from its structure, reaches stable if the absolute value of OCV variation delta V is not less than 0.2V then can not be called.Therefore, in Fig. 7 (a), when the absolute value of OCV variation delta V is dropped to 0.2V roughly from discharge and recharge the elapsed time t_fast that stops to start at as with corresponding elapsed time of transient changing fast.On the other hand; In the sealed type battery shown in Fig. 7 (b); Electrolytic solution reaches that to stablize required time short from its structure, when the absolute value of OCV variation delta V is dropped to 0.3V from discharge and recharge the elapsed time t_fast that stops to start at as with corresponding elapsed time of transient changing fast.Below, elapsed time t_fast that will be corresponding with transient changing fast is as first slack time.
Below, use process flow diagram shown in Figure 3, the condition detection method of the electric energy storage device of present embodiment is described.Play till whether being in of step S3 discharge and recharge the judgement in the middle of stopping since the n time state-detection, carry out the identical processing of step S1～S3 shown in the process flow diagram with Fig. 1.In addition, discharge and recharge when central, carry out identical processing with step S7～S10 of Fig. 1 (with above as processing module A), step S11 and step S12～S14 (with above as processing module B) when in step S3, being judged to be to be in.
On the other hand; When in step S3, be judged to be not in discharge and recharge in the middle of when (be in discharge and recharge stop in the middle of); After carrying out the processing identical, in step S20, judge from whether discharging and recharging elapsed time of stopping to start at greater than first slack time with step S4, the S5 of Fig. 1.Then, identical with first embodiment when the elapsed time was less than or equal to for first slack time, carry out the processing of processing module A, step S11 and processing module B.Relative therewith, when in step S20, being judged to be, carry out the processing of following steps S21～S27 in the present embodiment from discharging and recharging elapsed time of stopping to start at during greater than first slack time.
In step S21, with the step S7 identical calculations voltage variety Δ Va_n of processing module A.In following step S22, use formula (7) to calculate the impairment grade SOH_fast_n that causes by transient changing fast.In step S23, read in the impairment grade SOH_slow_n that causes by transient changing slowly that is stored in the storage part 120, in step S24, from storage part 120, read in SOH calculating formula G (SOH_fast, SOH_slow).In step S25,, calculate current SOH_n through with the SOH_fast and the SOH_slow of the above-mentioned SOH_fast_n that calculates with the SOH_slow_n difference substitution SOH calculating formula G (SOH_fast, SOH_slow) that reads in.
In step S26, S9 is identical with step, from storage part 120, reads in the discharge capability correction function F (SOH_n, x) corresponding with the impairment grade SOH_n that in step S25, calculates.Then, in step S27, among the variable x through the Δ Va_n substitution discharge capability correction function F (SOH_n, x) that will in step S21, calculate, calculate discharge capability correction COD_SOH_n.
COD_soh_n＝F(SOH_n1，ΔVa_n)
Afterwards, in step S11, calculate current discharge capability COD_now based on current voltage V_now and the discharge capability correction COD_SOH_n that in step S27, calculates.And use current discharge capability COD_now to carry out the processing of processing module B.
According to the condition detection method of the electric energy storage device of present embodiment and the condition checkout gear of electric energy storage device that used the present embodiment of this condition detection method; Except no matter be in discharge and recharge in the middle of or be in and discharge and recharge all whether the decidable discharge capability is kept rightly in the middle of stopping; Also calculate impairment grade SOH based on fast transient response in short-term discharging and recharging stand-by time, thereby can infer current discharge capability COD_now more accurately than the occasion of the SOH_n1 that uses first embodiment.
(the 3rd embodiment)
Use Fig. 8, the condition detection method of the electric energy storage device that third embodiment of the invention is related to describes.Fig. 8 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of present embodiment.Present embodiment makes and can calculate and reflected the discharge capability that discharges and recharges the transient changing after stopping as discharging and recharging state-detection when stopping.Promptly; In the middle of discharging and recharging of electric energy storage device stops; Not only calculate the impairment grade SOH_fast that causes by transient changing fast and also calculate the impairment grade SOH_slow that causes by transient changing slowly and come to obtain accurately impairment grade SOH, and use this impairment grade SOH to come to infer accurately and judge the discharge capability of electric energy storage device.Below, elapsed time that will be corresponding with transient changing slowly is as second slack time.
In process flow diagram shown in Figure 8,, carry out the identical processing of condition detection method of second embodiment shown in the process flow diagram with Fig. 3 since elapsed time that the n time state-detection plays step S20 whether till the judgement greater than first slack time.In addition, when in step S20, being judged to be the elapsed time when being less than or equal to for first slack time, carry out the processing of processing module A, step S11 and the processing module B of Fig. 3.On the other hand, identical when in step S20, being judged to be the elapsed time during with second embodiment greater than first slack time, in rapid 21, calculate voltage variety Δ Va_n, the processing that gets into step S30 then.
In step S30, judge from whether discharging and recharging elapsed time of stopping to start at greater than second slack time.Its result, identical with second embodiment when the elapsed time was less than or equal to for second slack time, carry out the processing of step S22～S27 (as processing module C).Relative therewith, when in step S30, being judged to be, carry out the processing of following steps S31～S34 in the present embodiment from discharging and recharging elapsed time of stopping to start at during greater than second slack time.
In step S31, calculate OCV variation delta V_n based on formula (4), and use this OCV variation delta V_n relation according to formula (5) in step S32 that discharge capability correction function F (SOH, Δ Va) is carried out optimization.In step S33, use formula (7) and formula (8) to calculate current impairment grade SOH_n.And in step S34, the discharge capability correction function F (SOH, Δ Va) through after Δ Va_n that will in step S21, calculate and the SOH_n substitution optimization of in step S33, calculating calculates discharge capability correction COD_SOH_n.
Afterwards, in step S11, calculate current discharge capability COD_now based on current voltage V_now and the discharge capability correction COD_SOH_n that in step S27, calculates.And, use current discharge capability COD_now to carry out the processing of processing module B.
According to the condition detection method of the electric energy storage device of present embodiment and the condition checkout gear of electric energy storage device that used the present embodiment of this condition detection method; Except no matter be in discharge and recharge in the middle of or be in and discharge and recharge all whether the decidable discharge capability is kept rightly in the middle of stopping; Also through discharge and recharge when stopping through with stop after elapsed time irrespectively calculate impairment grade SOH accurately, thereby can infer current discharge capability COD_now more accurately.
(the 4th embodiment)
Use Fig. 9, the condition detection method of the electric energy storage device that fourth embodiment of the invention is related to describes.Fig. 9 is the process flow diagram of treatment scheme of condition detection method that is used to explain the electric energy storage device of present embodiment.
When discharging and recharging when carrying out the state-detection of electric energy storage device after stopping, because of before this discharge and recharge differences such as history, there is very big-difference in transient changing.For example, be installed in the accumulator on the automobile owing in the middle of vehicle ', carry out various discharging and recharging, the migration that therefore in the electrolytic solution of accumulator, produces, deposition, convection current, diffusion etc. are also various because of the difference of vehicle operating condition.Therefore, the transient changing that discharges and recharges the accumulator after stopping to be because of the difference of before this vehicle operating condition is different, can't produce identical or can think trend identical have a reproducible halted state.
Present embodiment is made in order to address these problems, and is used to provide the influence that discharges and recharges that reduces before electric energy storage device stops to carry out the condition detection method and the device thereof of the electric energy storage device of state-detection.In the present embodiment; When discharging and recharging when carrying out state-detection after stopping; Discharge and recharge the charging that just stops the back and accumulator 10 carried out predetermined volumes (below be called state-detection before charging), and before state-detection, carrying out the state-detection of electric energy storage device after the charging end.As charging before the state-detection, preference is as carrying out the charging of rated capacity 5%.
Process flow diagram shown in Figure 9 is except that the processing that discharges and recharges after just stopping; The identical treatment scheme of condition detection method with the 3rd embodiment shown in Figure 8; In the present embodiment; Can irrespectively calculate impairment grade SOH accurately with the elapsed time after stopping, thereby can infer current discharge capability COD_now accurately.And, in the present embodiment, when in step S4, determine be discharge and recharge just stop after, then in step S40, carry out charging before the state-detection.Charge before such state-detection through carrying out, electric energy storage device is transferred to the state with reproducible transient changing.Thus, can be identical or can think that identical the having of trend carry out state-detection under the reproducible halted state, thus can carry out the state-detection of electric energy storage device more accurately.
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 that is installed on engine-driven vehicle, the reserve battery of working during applicable to electric automobile, portable phone, power failure, with the cooperation of electric system in be used for the electrical storage device of electric power that natural the subject of knowledge and the object of knowledge that equilibrium utilizes sun power or wind-force sends and the system that they have been made up.The 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 install any device that electric energy storage device also need be kept watch on or state is judged.As electric energy storage device, accumulator or capacitor etc. are arranged, being about to make via moving of electronics or ion the energy increase of device interior or reducing also to be object with the device that its internal energy is obtained by the outside with the electric power mode.Lithium (Li) ion battery, nickel (Ni) hydrogen battery, sodium-sulphur battery, lead-acid battery, capacitor etc. are for example arranged, can also be applied to the accumulating system that they have been made up.The example of above-mentioned electric energy storage device is a part just, is not limited to above-mentioned accumulator or capacitor.
According to the condition detection method and the device thereof of electric energy storage device of the present invention, though system not necessarily be in stop in the middle of the also discharge capability of decidable electric energy storage device, therefore can be owing to the mistake of discharge capability is judged the misoperation that cause the electric energy storage device installation system.In addition, receive the very big condition that influences of electric energy storage device external factor and the algorithm that the condition beyond it is calculated, therefore can use respectively according to state because the discharge capability decision method of electric energy storage device has made up differentiation.Its result broadens based on the range of choice of the control method of result of determination, can realize system employs more flexibly.
(the 5th embodiment)
The condition detection method of the electric energy storage device that fifth embodiment of the invention is related to describes.
In the condition detection method of the electric energy storage device of present embodiment, the variation through the voltage that can measure from electric energy storage device detects the transient changing that discharges and recharges the electric energy storage device after stopping.Promptly; Electric energy storage device is stopped to discharge and recharge and voltage when reaching the state that satisfies predetermined stable condition burning voltage when stopping, and utilization discharges and recharges voltage determination value variable quantity of burning voltage when stopping after stopping and carries out the state-detection under the transient behaviour of electric energy storage device.Below, will be after electric energy storage device stops to discharge and recharge through variable quantity voltage variety when stopping of the burning voltage when stopping of the voltage determination value during time t.
In the condition detection method and device thereof of the electric energy storage device of present embodiment, establishment in advance depends on the relaxation function F (t) of the predetermined state amount of electric energy storage device, and with the function of its voltage variety when calculating above-mentioned stopping.And, use by the voltage determination value obtain stop the time voltage variety relaxation function F (t) is carried out optimization, the relaxation function F (t) after optimization infers predetermined quantity of state and has carried out state-detection.In the condition detection method of present embodiment; Voltage status before detection discharges and recharges and just stops; And use above-mentioned relaxation function F (t) to infer predetermined quantity of state, and compare the discharge capability (COD) of judging electric energy storage device through said quantity of state of inferring and predefined each determinating reference and whether kept rightly.As predetermined quantity of state, for example can use as the SOH (State of health) of the index of the impairment grade of electric energy storage device or the SOC of expression residual capacity etc.
The transient changing that discharges and recharges the electric energy storage device after stopping to comprise from as the generation of ion and eliminate reaction velocity the reaction fast be changed to the slow variation of reaction velocity as electrolytic solution mobile etc., these variable effects the variation that discharges and recharges the above-mentioned quantity of state after stopping.Therefore, in the condition detection method of the electric energy storage device of present embodiment, use relaxation function F (t) to infer the variation of the quantity of state of each reaction velocity, and comprehensively these change the judgement of carrying out quantity of state.For example, the quantity of state at the time point place that elapsed time of discharging and recharging after the end is short is judged in the influence of also considering slow reaction velocity.
Burning voltage during as above-mentioned stopping, known have after stopping to discharge and recharge through the open-circuit voltage OCV of the electric energy storage device during time enough when stablizing (below be called OCV).Thereby the voltage between terminals of discharge when stopping of being opened a way that OCV is the terminal of electric energy storage device.In the condition detection method of the electric energy storage device of present embodiment, use stop the time burning voltage be not limited to OCV, under situation about defining, also can use burning voltage at that time to the transient effect of electric energy storage device.As an example; From electric energy storage device to load stop power supply during; Sometimes to control device of load etc. Weak current (dark current) is provided; Under the situation that such dark current etc. is provided, also can with after stopping load through the burning voltage when stopping of the voltage during time enough.
In addition,, can think that also the transient effect of bringing to electric energy storage device is very little even be always under the situation of fixed value at the electric weight that charges and discharge of electric energy storage device, therefore can with after stopping load through the burning voltage when stopping of the voltage during time enough.So; Small or when being limited in the predetermined scope for the electric energy storage device influence that inner transient changing is brought when discharging and recharging caused electric current for fixed value; Can when the power supply that has stopped to load, be judged to be the discharge that has stopped from electric energy storage device, and will stop the back and passed through the voltage burning voltage when stopping when long-time discharging and recharging with the state of keeping Weak current or fixed current.Preferably confirm to be used to revise the voltage correction of the change in voltage that is caused by Weak current or fixed current this moment in advance, and use this voltage correction to revise the voltage determination value.
Below, an example of burning voltage when stopping to use that OCV describes when stablizing.When using when stablizing OCV, applicable relation shown in Figure 35 such as following formulate quantity of state SOC.
SOC＝FS(OCV S’(SOC’，SOH，T)) (1-1)
OCV s(SOC，SOH，T)＝Lim(V mes(t)) (1-2)
Here, OCV sExpression is calculated specifically OCV when stable, OCV during last calculate stable of OCV ' expression, the last residual capacity of calculating of SOC ' expression, T representes the temperature of electric energy storage device.And the Lim of following formula representes and will be made as infinity from discharging and recharging the elapsed time that stops to start at, and the voltage determination value V of the elapsed time electric energy storage device when infinitely great after stopping to be represented to discharge and recharge in the right of formula (1-2) Mes(t).Likewise, when using when stablize stopping beyond the OCV during burning voltage, also can and SOC between work out above-mentioned same relational expression in advance.
SOC has been shown in the following formula has depended on the OCV that the last time calculates S' and be determined while OCV SAlso depend on SOC, but also depend on as the temperature T of the SOH of other quantity of state and electric energy storage device and change.In addition, because OCV SDepend on other quantity of state SOH, quantity of state SOC also depends on SOH, thereby need carry out renewal separately with appropriate timing.
Shown in formula (1-2), OCV sBe from discharging and recharging the elapsed time t that stops the to start at V when infinitely great MesBut in practical application, also can be set at V (t), Mes(t) variation is considered to the V at the time point place of very little elapsed time t Mes(t).In addition, be under the situation of pregnant solution type lead acid accumulator at electric energy storage device, OCV sCan be set at the every variable quantity of OCV and be below the 5mV at a distance from one hour, perhaps from discharging and recharging the V when having stopped passing through 20 hours Mes(t).Below, with electric energy storage device be the occasion of 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, with accumulator from discharge and recharge Vmes (t) when having stopped passing through 20 hours be made as 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)
As the voltage determination value V that will discharge and recharge after stopping Mes(t) when stablizing the variable quantity of OCV, when OCV variable quantity (voltage variety when stopping) being made as Δ V (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 regarded as and comprises all transient changing in existing galvanochemistry definition.But Δ V (t) is by until the change in voltage that produces near the relaxation till stablizing OCV, therefore receives the influence of the following change in voltage factor of enumerating.As the factor of change in voltage, have polar plate status, pole plate vicinity ion concentration, they solid phase reaction, solid-liquid reaction and move by the ion that deposition, convection current or the diffusion of electrolytic solution causes etc.Δ V (t) can be considered to caused by the different relaxation combination of these reaction velocitys.So; The transient changing that discharges and recharges after stopping of electric energy storage device 11 comprises the course of reaction that speed is different; Therefore preferably adopt the method that the state variation of every kind of reaction velocity is estimated to carry out state-detection by the discharge capability that discharges and recharges the electric energy storage device 11 after stopping in order to judge accurately.
According to the difference of reaction velocity, use the function F (t) that constitutes by m polynomial expression like following formulate Δ V (t).
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), each item f i(t) relaxation that the reaction velocity of expression electric energy storage device is different below is made as the relaxation function f of each reaction velocity to the contribution amount of change in voltage i(t).Each item f i(t) be the function that depends on impairment grade SOH, residual capacity SOC (ion concentration) and temperature T as the quantity of state of accumulator.The relaxation function f of each reaction velocity of formula (1-5) i(t) can use according to discharging and recharging the voltage determination value V after stopping Mes(t) the Δ V (t) that calculates confirms, so that it is optimised to this Δ V (t).
In the condition detecting system of the condition detection method of present embodiment, SOC, SOH, OCV before beginning for state-detection 20hrInitial value SOC separately 0, SOH i 0, OCV 20hr 0, can use the reference value SOC separately that is kept in advance in the condition detecting system 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)It is respectively the value of in other battery, obtaining.
After stopping, as the relaxation function F (t) of the formula (1-5) that will represent OCV variation delta V (t) and the relaxation function f of each reaction velocity by discharging and recharging of the n time (n being the integer more than 1) after the detection of condition detecting system initial state i(t) be made as F respectively n(t), f i n(t) time, the relaxation function f of each reaction velocity i n(t) based on (being made as SOC respectively with i corresponding SOC and the SOH of reaction velocity n, SOH i n) can be like following formulate.
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 RefBe the f under the predefined original state (for example unused state) i(t), SOC, SOH i, g (T) is the temperature dependent function of expression.
In formula (1-6), irrelevant and fixedly the time when temperature T and SOC and time, SOH i nCan calculate through following formula.
SOH i n＝{f i n(t)/f i ref(t)}*SOH i ref (1-7)
Thus, can be with the f of formula (1-5) i n(t) optimum turns to based on voltage determination value V Mes(t) the Δ V (t) that calculates, and use this Δ V (t) to calculate SOH through formula (1-7) i n
At the SOH that calculates each different transient response of reaction velocity through 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)
For example, when with m SOH iEach coefficient when being made as 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.Can use the SOH that as above calculates nCarry out the detection of the deterioration state of accumulator.Likewise, the relaxation function F (t) after the use optimization also can calculate the SOC as other quantity of state n
Relaxation function F (t) shown in the formula (1-5) is because the relaxation function f with each different reaction velocity of reaction velocity i(t), thus after the n time discharge and recharge stops, if the elapsed time is short, then can't be through f that will be corresponding with slow reaction velocity i n(t) optimization is obtained.Its result can't use relaxation function F (t) to upgrade SOC n, SOH i nTherefore, at the f corresponding with slow reaction velocity i n(t) but before the optimization that becomes, replace SOC n, SOH i nAnd use the last time to discharge and recharge the value SOC when stopping N-1, SOH i N-1, and be following formula with 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 n(t) can use under the situation of formula (1-6-1), can from discharge and recharge stop after through the time point of short time carry out state-detection.Especially, when only carrying out discharging and recharging below the predetermined threshold, can be with having utilized the last SOC that discharges and recharges after the end N- 1, SOH i N-1Relaxation function F n(t) be used in state-detection.
On the other hand; Residual capacity SOC about accumulator; Can be to discharging and recharging of (the n-1 time) stops to play interior discharging and recharging during discharging and recharging of current (the n time) stop from finishing the last time; The charging and discharging currents interior during this period through accumulative total calculates residual capacity variation delta SOC, and through revising last residual capacity SOC with this residual capacity variation delta SOC N-1Calculate SOC nPromptly set like following formula.
SOC n-1’＝SOC n-1+ΔSOC
Use this SOC N-1' replacement SOC n, can be following formula with 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 that calculates through formula (1-7) i nAnd through following formula renewal f i nAnd the f after will upgrading (t), i n(t) be used 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 20hrCan calculate through following formula.
OCV 20hr＝V mes(t)-∑[f i ref(t)*{SOC n-1/SOC ref}
*{SOH i n/SOH i ref}]*g(T) (1-9)
Through with this OCV 20hrIn the substitution formula (1-1), can calculate SOC nThereby, can be used in the state-detection of SOC.
As stated, can be based on m the reference value f corresponding with m kind reaction velocity i Ref(t) (the reference value SOH of i=1～m), a m impairment grade i Ref(i=1～m) and the reference value SOC of 1 residual capacity Ref, calculate the relaxation function f of the m that discharges and recharges for the n time after stopping each reaction velocity i n(t) (i=1～m).And obtain based on this and to have reflected and OCV, SOC and the SOH of the corresponding impairment grade of different reaction velocitys, can carry out high-precision state-detection.
Below, use Figure 10, Figure 11 that the condition detection method of the electric energy storage device of fifth embodiment of the invention is described.Figure 10 is the process flow diagram that is used to explain the treatment scheme that the condition detection method through present embodiment carries out.In addition, Figure 11 is the block diagram of summary structure that the condition checkout gear of the condition detection method that has used present embodiment is shown.Condition checkout gear 210 shown in Figure 11 is installed in the state-detection of the accumulator 1 on the vehicle as an example.Be connected with charhing unit 202 and load 203 on the accumulator 201, thereby can charge and discharge through charhing unit 202 to load 203.In addition, be provided with temperature measurement unit 201a, voltage measuring unit for measuring 201b and amperometric determination unit 201c in the accumulator 201, these unit can be via input block 204 to condition checkout gear 210 inputs measured value separately.And be provided with the control device 205 that discharging and recharging of accumulator 201 controlled.Also can be from control device 205 via input media 204 to condition checkout gear 210 input control informations.
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 temperature measuring value, voltage determination value and the amperometric determination value of input block 204 input accumulators 201, and these measured values are saved in the temporary storage cell 213.In addition, preserve the relaxation function f of each reaction velocity in the static memory cell 212 i(t), the initial value of various quantity of states or reference value.Arithmetic unit 211 uses and is kept at initial value or the reference value in the static memory cell 212 and is kept at voltage determination value in the temporary storage cell 213 etc.; And, then the result is inputed to state output unit 215 to carry out the state-detection of accumulator 201 through the preset time cycle of timer 2 14 countings.The output information of state output unit 215 also can be provided for supplying the information of the controlled variable that control device 205 uses.
Below, use process flow diagram shown in Figure 10, the condition detection method of present embodiment is described.At first, in step S201, use the voltage determination value and the amperometric determination value of input block 204 input accumulators.In following step S202, judge to discharge and recharge to stop whether to begin based on the amperometric determination value of being imported.Discharge and recharge when stopping to begin when being judged to be, in step S203 will before voltage determination value voltage V when finishing as discharge DEOr the voltage V when finishing that charges CEBe saved in the temporary storage cell 213.Then, in step S204, voltage V when finishing will discharge DEOr the voltage V when finishing that charges CEWith the V that is kept at the reference value in the static memory cell 212 RefCompare, and be higher than reference value V RefIn time, get among the following step S205.On the other hand, voltage V when discharge finishes DEOr the voltage V when finishing that charges CEBe lower than reference value V RefThe time, be judged to be discharge capability COD deficiency, get among the step S213 to state output unit 215 output COD deficiencies, end then.
Here, V RefBe the value in other battery, measured in advance (for example, 12.8V).
Voltage V when in step S204, being judged to be the discharge end DEOr the voltage V when finishing that charges CEMore than or equal to V RefThe time, in step S205, judgement be in discharge and recharge stop in the middle of or restarted to discharge and recharge.When being judged to be when having restarted to discharge and recharge, done state detects.On the other hand, when discharging and recharging when stopping to continue, in step S206, the voltage determination value is set at V MesAnd it is saved in the temporary storage cell 213.In following step S207, the OCV of burning voltage when selecting conduct to stop 20hr, and use this OCV 20hrWith voltage determination value V MesIn step S208, calculate Δ V (t).
In step S209, use the Δ V (t) that in step S208, calculates that relaxation function F (t) is carried out optimization.About approximating method, can consider the various computing method of utilizing regression Calculation of least square method etc., but in this match because Δ V (20hr)=0, if therefore use exponential function simply with carry out regression Calculation, it is big that error will become.Therefore, preferred introduce with Δ V (20hr)=0 near the function that inclination offsets and Δ V (20hr)＞0 always sets up (for example, after the formula (1-10-4) stated) of tangent line, and to its residual quantity carry out based on exponential function and match.
In step S210, use relaxation function F (t) after the optimization to infer predetermined quantity of state (following represent) with S.In step S211, with the quantity of state S that infers be kept at the reference value S in the static memory cell 212 RefRelatively, and when having satisfied predetermined condition, quantity of state S gets into step S212 being judged to be, to the guaranteed thing of state output unit 215 output COD.On the other hand, when not satisfying predetermined condition, quantity of state S gets among the step S213, to the not enough thing of state output unit 215 output COD when in the judgement of step S211, being judged to be.
In the condition detection method of the accumulator of present embodiment, with the SOC calculating formula of formula (1-1) and with SOC, SOH, OCV 20hrInitial value corresponding reference value SOC Ref (0), SOH i Ref (0), OCV 20hr Ref (0)Be kept in advance in the static memory cell 212, and use them that initial value separately is set at SOC 0=SOC Ref (0), SOH i 0=SOH i Ref (0), OCV 20hr 0=OCV 20hr Ref (0)
Figure 12 shows the processing details of step S201.In Figure 12; Regularly confirm the timer count value in predetermined affirmation; And for the mensuration of stipulating regularly, measure timing value (step S201-2) if timer count value (t_count) has surpassed it, then import voltage, the electric current (step S201-4) of accumulators 201 from input block 214.
Figure 13 shows an example that discharges and recharges the method that stops of in step S202, judging accumulator 1.When the amperometric determination value of in step S202-2, measuring is less than or equal to the predetermined threshold that is kept in the static memory cell 212, be judged to be to discharge and recharge and stopped (step S202-4); But; For example be in and stop or during temporary parking when control device 205 is judged as automobile; When the information that perhaps has been connected with accumulator 201 when expression condition checkout gear 210 is imported in the arithmetic unit 211 (step S202-1), also can use these information to judge and discharge and recharge to have stopped (step S202-3).
The OCV of step S207 is shown at the process flow diagram of Figure 14 20hrSystem of selection.Begin to calculate OCV for the n time 20hrThe time SOC n, SOH nUse last calculated value SOC N-1, SOH N-1(step S207-1).The Current Temperatures T of accumulator 201 uses from the measured value (step S207-2) of input block 204 inputs.If the OCV that will select thus 20hrBe made as OCV 20hr Temp, then use the relational expression of under the h kind condition that value and temperature combinations with a plurality of SOC, SOH form, in advance working out:
H (SOC_j, SOH_k, T_l)=OCV 20hr Ref (h)(k, l are natural number for h, j) (step S207-4) sets OCV through following formula 20hr Temp(step S207-5).
OCV 20hr temp＝OCV 20hr ref(h)
Below, in order to simplify, postulation formula (1-5) constitutes 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, for example formula (1-10) is expressed as following formula:
Fast lax function of speed 1:f Fast1(t)=A*exp (B*t^C) (1-10-1)
Fast lax function of speed 2:f 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)
Work out the optimized function of Δ V (t) easily thus.But memory span and the desired precision conditions of determination sensor etc. that also can use arithmetic speed, static memory cell 212 and temporary storage cell 213 according to arithmetic unit 211 with this function complicated or simplify after function.
Use Figure 15 and Figure 16, to obtaining F based on Δ V (t) based on the elapsed time of timer counting n(t) method describes (step S209).Function shown in formula (1-10-1)～formula (1-10-4) has been confirmed each coefficient so that become the mode of ascendancy separately through match in the interval of being divided by 4 reference times (10 seconds, 1000 seconds, 36000 seconds, 72000 seconds).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, and the driving conditions in the vehicle that can use according to reality or pause condition, the desired precision of sensor wait the above-mentioned time as benchmark that changes.
Use Figure 15 to explain discharging and recharging elapsed time after stopping and obtain F based on Δ V (t) during less than 20 hours n(t) method.When determining time t (step S209-1), discharge and recharge the calculated value F after stopping based on the last time less than first reference time (10 seconds) N-1(t) calculate F through following formula 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, likewise as time t during more than or equal to first reference time and less than second reference time (1000 seconds) (step S209-3), discharge and recharge the F after the end based on the last time N-1(t) and up-to-date data calculate F through following formula 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 determining time t (step S209-5), discharge and recharge the F after the end based on the last time more than or equal to second reference time and less than the 3rd reference time (36000 seconds) N-1(t) and up-to-date data calculate F through following formula 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 determining time t (step S209-7), discharge and recharge the F after the end based on the last time more than or equal to the 3rd reference time and less than the 4th reference time (72000 seconds) N-1(t) and up-to-date data calculate F through following formula 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)
With the F of substitution in t=20 hour based on above-mentioned formula (1-11)～(1-14) obtain n(t), can obtain following formula (step S209-11).
OCV 20hr n＝F n(20hr)
When determining time t (step S209-7) more than or equal to the 4th reference time (for example, 20 hours), shown in figure 16, based on based on up-to-date V MesThe OCV that (20hr) obtains 20hr TempThe Δ V (t) of record is (as Δ V (t) up to now Temp), as following formula, calculate Δ V n(t) (step S209-13).
ΔV n(t)＝ΔV(t) temp+OCV 20hr temp-OCV 20hr n (1-15)
And, calculate F through following formula 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 shows use and calculates and be saved in the f in the temporary storage cell 213 through the processing of Figure 15 and Figure 16 i(t) and in advance be kept at the reference value f in the static memory cell 212 i Ref(t), SOH i RefCalculate SOH i n, SOC the treatment scheme of step S210.Read the above-mentioned OCV that draws 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) is through being kept at the function I (OCV in the static memory cell 212 with value importing separately 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 the variation of each item when Figure 18 shows and representes as formula (1-10) as the optimized example of relaxation function F (t) in the condition detection method of the accumulator of this reference example and with relaxation function F (t).Figure 18 illustrates the curve map that transverse axis is made as the variation of the Δ V (t) (=F (t)) when discharging and recharging the elapsed time that finishes to start at, and label 251～254 shows the (f of each item of formula (1-10) respectively Fast1(t), f Fast2(t), f Slow1(t), f Slow2(t)) variation.In addition, label 250 shows true value, and label 255 shows the value of the F (t) that calculates from formula (1-10).The F (t) that the figure shows through using this reference example can predict Δ V (t) accurately.
Below, the stratification degree (diffusion of electrolytic solution etc.) of long response time speed is made as the SOH of formula (1-7) 1And suppose the SOH after discharging and recharging for the n time (i=1), 1 nCalculate through following formula.
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, with the f of formula (1-7) i n(t), f i Ref(t) further being assumed to can be based on two sum { f Slow1 n(t)+f Slow2 n(t) }, { f Slow1 Ref(t)+f Slow2 Ref(t) } calculate.
As an example; The size model of using Furukawa battery formula to make: the pregnant solution type lead acid accumulator of 55D23 is at 25 ℃ of environment temperatures, DOD (Depth of discharge; Depth of discharge) under 10% the condition, will implement in the cycle of discharging and recharging 20 times, 50 times and 100 times from unused state.Based on the determination data after back and the discharging and recharging of 100 cycles that discharges and recharges that discharges and recharges back, 50 cycles in 20 cycles, and according to 20 cycles the time OCV variable quantity f that benchmark has stopped passing through 5 hours from discharging and recharging when (t=5 hour) i n(5hr) can as following formula, calculate SOH 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 that calculates based on determination data Slow n(t)/f Slow 20(t).Label 261,262,263 shows f respectively Slow 20(t), f Slow 50(t), f Slow 100(t), label 264,265 shows f respectively Slow 50(t)/f Slow 20(t), f Slow 100(t)/f Slow 20(t).Can know that from Figure 19 for example the time point in t=18000 second can draw:
{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，
Likewise, can draw:
f slow 100(5hr)/f slow 20(5hr)
＝1.63。
So, can grasp and discharge and recharge the variation of periodicity corresponding battery state from the variable quantity F (t) of OCV.
In addition, as an example, discharge and recharge after the end through the OCV 20 hours the time with respect to discharging and recharging periodicity 20,50,100 be:
OCV 20hr 20＝12.896[V]
OCV 20hr 50＝13.032[V]
OCV 20hr 100＝13.036[V]，
Above-mentioned f has been shown in Figure 20 Slow n(t)/f Slow 20(t) and OCV 20hr 20Relation.Can result shown in Figure 20 be used in the OCV that infers similar accumulator 20hrStable OCV infer in the formula.
As stated, according to the present invention, can provide the deterioration that causes through the course of reaction of estimating by friction speed to carry out the condition detection method of the accumulator of state-detection.Through detecting the impairment grade SOH of battery, can detect residual capacity SOC accurately.
(the 6th embodiment)
Below use the condition detection method of the electric energy storage device that Figure 21 relates to the 6th embodiment to describe.Figure 21 is the process flow diagram that the treatment scheme that the condition detection method through present embodiment carries out is shown.Voltage V when present embodiment finishes based on discharge in the step S204 of the 5th embodiment DEOr the voltage V when finishing that charges CEJudge COD, in step S221, use to discharge and recharge the residual capacity SOC when stopping then Stop nJudge COD.That is, in step 221, with residual capacity SOC Stop nWith the SOC that is kept at the reference value in the static memory cell 212 Stop RefCompare, as residual capacity SOC Stop nMore than or equal to reference value SOC Stop RefThe time, get into following step S205 and later step thereof, when less than reference value SOC Stop RefThe time, be judged to be the COD deficiency, get among the step S213.Thus, can judge the discharge capability of accumulator 201 more accurately.
Residual capacity SOC when using Figure 22 to stop to discharging and recharging Stop nComputing method describe.Through to the above-mentioned SOC that calculates when stopping that discharging and recharging Stop N-1Use after this from restart discharge and recharge up to discharge and recharge specifically stop during in the increase and decrease SOC (this is increased decrement SOC as residual capacity) revise, can calculate the residual capacity SOC that discharges and recharges specifically when stopping Stop nResidual capacity increase decrement SOC can through accumulative total from the last time discharge and recharge restart up to discharge and recharge specifically stop during in the charging and discharging currents of accumulator 1 calculate.
In this reference example,, can calculate residual capacity increase and decrease amount more accurately through the Δ SOC that as above calculates further being scheduled to correction.In the condition detection method of this reference example, calculate the residual capacity SOC that discharges and recharges when stopping through following formula Stop n
SOC stop n＝SOC stop n-1+ΔSOC*η 1 n-1*η 2 n-1 (1-20)
Here, shown in Figure 22 (a), η 1 N-1It is the function f that depends on slow relaxation velocity Slow(the 10hr) (f of formula (1-10-3) Slow1Or the f of formula (1-10-4) Slow2) and definite correction factor, shown in Figure 22 (b), η 2 N-1Be voltage V when depending on the charging end CE nAnd the correction factor of confirming.These correction factors are used to revise the charge efficiency of accumulator 201.
(the 7th embodiment)
Below, use Figure 23 describes the condition detection method of the electric energy storage device that the seventh embodiment of the present invention relates to.Figure 23 is the process flow diagram of treatment scheme that the condition detection method of present embodiment is shown.In this reference example, change the disposal route of step S210 in the processing of the 6th embodiment shown in Figure 23, S211 and as step S230.In the step S210 of the 6th embodiment, S211 (among the 5th embodiment too), through calculate predetermined quantity of state S and with its be kept at the reference value S in the static memory cell 212 RefCompare, judged whether quantity of state S satisfies the condition that discharge capability is being kept in expression.Relative therewith, in the step S230 of this reference example,, and judge whether satisfy the condition that discharge capability is being kept in expression according to every kind of reaction velocity to every kind of reaction velocity evaluation amount S.In addition, also carry out judgement based on the ratio of slow reaction velocity and fast reaction velocity.
Below, with the example of impairment grade SOH, describe to the decision method that carries out according to each reaction velocity and based on the decision method of the ratio of slow reaction velocity and fast reaction velocity as quantity of state S.The impairment grade SOH of each reaction velocity Fast n, SOH Slow nCan pass through the following calculating of 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)
And, combine the impairment grade SOH of each reaction velocity Fast n, SOH Slow nTotal SOH nExpression as formula (1-8) for example can be passed through formula (1-8-1) and calculate.
The impairment grade SOH that calculates based on the ratio of slow reaction velocity and fast reaction velocity Fast/slow nAlso same as described above through following formula calculating.
SOH fast/slow n＝{f fast/slow n(t)/f fast/slow ref_n(t)}
*SOH fast/slow _ref (1-23)
An example that kind shown in figure 24, the impairment grade SOH that calculates based on the ratio of slow reaction velocity and fast reaction velocity Fast/slow nThrough using the ratio of slow reaction velocity and fast reaction velocity, can estimate the variation that changes the impairment grade that a big phenomenon causes in the transient phenomenon by the transient phenomenon of fast reaction velocity or slow reaction velocity.
For to the above-mentioned SOH that calculates through formula (1-21) Fast n', revise by as the residual capacity SOC that discharges and recharges the quantity of state when stopping Stop nAnd the voltage V when finishing that charges CE nThe influence that brings is calculated revised impairment grade SOH through following formula Fast nThis correction is used to revise SOH Fast nDemonstrate the variation of that kind shown in Figure 25 with respect 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 nWith respect to residual capacity SOC Stop nAnd the voltage V when finishing that charges CE nThe for example variation of that kind shown in Figure 26 (a), Figure 26 (b) is shown.Therefore, through the variation shown in predefined function (High-speed transient changes the correction calculating formula) expression Figure 26 (a), Figure 26 (b), can be based on residual capacity SOC Stop nAnd the voltage V when finishing that charges CE nCalculate corrected parameter α 1 n, α 2 n
More than to SOH Fast nCorrection be illustrated, but about SOH Slow n, also can work out in advance and for example calculate corrected parameter β 1 n, β 2 nFormula and use this formula likewise to revise.
Through using the SOH that as above calculates Fast n, SOH Slow n, and SOH Fast/slow nAnd that kind shown in figure 27 compares with separately reference value, can judge the COD of accumulator 1.In Figure 27, use S FastDeng having represented quantity of state, but when SOH is estimated, use SOH Fast nDeng replacement S FastDeng being used as quantity of state.In step S231, use formula (1-22) to calculate SOH Slow n, and in step S232 with reference value SOH Slow Ref_nCompare.Its result works as SOH Slow nLess than SOH Slow Ref_nThe time, be judged to be the COD deficiency, and get among the step S213, and in the next entering following step of all the other situation S233.
Likewise, in step S233, S234, judge SOH Fast n, in step S235, S236 and judge SOH Fast/slow nAnd,, then get among the step S212 and be judged to be COD and kept if all satisfy predetermined condition.In this reference example,, can carry out the state-detection of accumulator 1 accurately through carrying out the processing of Figure 23 and that kind shown in Figure 27.
In above-mentioned, to obtain SOC, SOH is illustrated as the quantity of state of electric energy storage device and the reference example of using these quantity of states to carry out state-detection.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 with the discharge capability of electric energy storage device.Except that SOC, the SOH,, also has the change in concentration amount of the electrolytic solution in the electric energy storage device as the quantity of state that can in the judgement of the discharge capability of electric energy storage device, use.The concentration of electrolytic solution changes along with discharging and recharging, and needs the time from discharging and recharging to reach after stopping till stable.
Therefore, for the concentration of electrolyte variable quantity is used for state-detection, establishment in advance is used for calculating each item f with respect to relaxation function F (t) Fast(t), f Slow(t) and f Fast(t)/f SlowThe change in concentration amount calculating formula of concentration of electrolyte variable quantity (t), and this calculating formula is kept in the static memory cell 212.And, can use the relaxation function F (t) after the optimization and calculate the concentration of electrolyte variable quantity through change in concentration amount calculating formula, and through judging that whether this concentration of electrolyte variable quantity satisfies predetermined condition, carries out state-detection.Through in the condition detection method of electric energy storage device, also using the concentration of electrolyte variable quantity, can carry out high-precision state-detection.
Another quantity of state as can in the judgement of the discharge capability of electric energy storage device, using has the variation of the CONCENTRATION DISTRIBUTION bias (stratification) of electrolytic solution.Figure 28 shows the example of CONCENTRATION DISTRIBUTION of the electrolytic solution of electric energy storage device.The CONCENTRATION DISTRIBUTION that Figure 28 shows electrolytic solution 293 is the mode chart that the center has changed and formed the state of stratification 294 with positive pole 291 with negative pole 292.In electric energy storage device, the CONCENTRATION DISTRIBUTION of electrolytic solution changes and forms stratification shown in figure 28 294 along with discharging and recharging.This stratification comprises horizontal stratification and vertically stratification, and horizontal stratification is the CONCENTRATION DISTRIBUTION bias of liquid level on horizontal (arrow 295) to electrolytic solution, and vertically stratification is the CONCENTRATION DISTRIBUTION bias of liquid level on vertical (arrow 296) to electrolytic solution.The variation of this stratification is along with being taken place by the variation that discharges and recharges the concentration of electrolyte that causes, and the same with the variation of concentration of electrolyte, needs the time from discharging and recharging to reach after stopping till stable.
Therefore, for the stratification variable quantity is used for state-detection, establishment in advance is used for calculating each item f with respect to relaxation function F (t) Fast(t), f Slow(t) and f Fast(t)/f SlowThe stratification variable quantity calculating formula of stratification variable quantity (t), and this calculating formula is kept in the static memory cell 212.And, can use the relaxation function F (t) after the optimization and calculate the stratification variable quantity through stratification variable quantity calculating formula, and through judging that whether this stratification variable quantity satisfies predetermined condition, carries out state-detection.Through in the condition detection method of electric energy storage device, also using the stratification variable quantity, can carry out high-precision state-detection.
As the another quantity of state that can in the judgement of the discharge capability of electric energy storage device, use, the variation to (the laterally stratification) of the liquid level CONCENTRATION DISTRIBUTION bias in the horizontal of electrolytic solution is arranged.The variation of this horizontal stratification is along with being taken place by the variation that discharges and recharges the concentration of electrolyte that causes, and the same with the variation of concentration of electrolyte, needs the time from discharging and recharging to reach after stopping till stable.
Therefore, for horizontal stratification variable quantity is used for state-detection, establishment in advance is used for calculating each item f with respect to relaxation function F (t) Fast(t), f Slow(t) and f Fast(t)/f SlowThe horizontal stratification variable quantity calculating formula of horizontal stratification variable quantity (t), and this calculating formula is kept in the static memory cell 212.And, can use the relaxation function F (t) after the optimization and calculate horizontal stratification variable quantity through horizontal stratification variable quantity calculating formula, and through judging whether this horizontal stratification variable quantity satisfies predetermined condition, carries out state-detection.Through in the condition detection method of electric energy storage device, also using horizontal stratification variable quantity, can carry out high-precision state-detection.
As another quantity of state that can in the judgement of the discharge capability of electric energy storage device, use, have to the liquid level of electrolytic solution laterally and the variation of the CONCENTRATION DISTRIBUTION bias vertically (laterally stratification, vertically stratification).When with it during as portraitlandscape stratification variable quantity, portraitlandscape stratification variable quantity is along with being produced by the variation that discharges and recharges the concentration of electrolyte that causes, and the same with the variation of concentration of electrolyte, needs the time from discharging and recharging to reach after stopping till stable.
Therefore, for portraitlandscape stratification variable quantity is used for state-detection, establishment in advance is used for calculating each item f with respect to relaxation function F (t) Fast(t), f Slow(t) and f Fast(t)/f SlowThe portraitlandscape stratification variable quantity calculating formula of portraitlandscape stratification variable quantity (t), and this calculating formula is kept in the static memory cell 12.And, can use the relaxation function F (t) after the optimization and calculate portraitlandscape stratification variable quantity through portraitlandscape stratification variable quantity calculating formula, and through judging that whether this portraitlandscape stratification variable quantity satisfies predetermined condition, carries out state-detection.Through in the condition detection method of electric energy storage device, also using portraitlandscape stratification variable quantity, can carry out high-precision state-detection.
(the 8th embodiment)
Another condition detection method to discharging and recharging after stopping is described in more details.
When discharging and recharging when carrying out the state-detection of electric energy storage device after stopping, according to before this discharge and recharge history etc., there is very big-difference in transient changing, therefore exists because the very big problem that is difficult to judge accurately discharge capability etc. that influences that is discharged and recharged history.
For example, be installed in the accumulator on the automobile owing in the middle of vehicle ', carry out various discharging and recharging repeatedly, the migration that therefore in the electrolytic solution of accumulator, produces, deposition, convection current, diffusion etc. are also various because of the difference of vehicle operating condition.Therefore, the transient changing that discharges and recharges the accumulator after stopping to be according to the vehicle operating condition before this and difference, can't produce identical or can think trend identical have a reproducible halted state.Even carry out under the situation of state-detection as the condition detection method of record in the patent documentation 1, will discharging and recharging the component that transient changing after stopping is divided into the different time constant; If it is widely different to discharge and recharge the transient changing of the accumulator after stopping; Also be difficult to obtain accurately each time constant component, be difficult to high-precision problem of carrying out the state-detection of accumulator thereby still exist.
Therefore, in order to address these problems, provide the influence that discharges and recharges that reduces before electric energy storage device stops to carry out the 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 keep the discharge capability of electric energy storage device rightly, be provided with the state-detection state-detection pattern that is used for suitably carrying out electric energy storage device.In possessing the system of electric energy storage device, thus for example out of service stopped the time point that discharges and recharges of electric energy storage device or discharging and recharging stop after through the reasonable time time point etc., by user or maintainer's executing state detecting pattern.When to electric energy storage device solicited status detecting pattern, can carry out the state-detection of this electric energy storage device accurately.
Below, with being installed in battery on the vehicle, the condition detection method and the condition checkout gear of the electric energy storage device of this reference example described as an example of electric energy storage device.But below the content of explanation is not limited to on-vehicle battery, can be applicable to the electric energy storage device that is used for solar electrical energy generation or wind-power electricity generation etc., the electric energy storage device that is used for standby power supplies such as stabilized power source, accessory power supply too.
Below, use Figure 29, Figure 30 that the condition detection method and the device thereof of the electric energy storage device of this reference example are described.Figure 29 is the process flow diagram of summary of condition detection method that is used to explain the electric energy storage device of this reference example, and Figure 30 is the block diagram of condition checkout gear that the electric energy storage device of this reference example is shown.
The condition checkout gear 400 of this reference example is installed on the vehicle 310 and is used to carry out the state-detection of electric energy storage device (accumulator) 311, and it comprises: signal input unit 401, output display unit 402, determination unit 403 and state-detection portion 410.Electric energy storage device 311 is connected with onboard electrical machine even load 312, and is connected with vehicle-mounted chargers 314 such as alternators.Signal input unit 401 is used to import the signal that is used for user's solicited status detecting patterns such as driver (below be called state-detection pattern commencing signal), and output display unit 402 is used for having carried out to user notification the result etc. of state-detection.Signal input unit 401 and output display unit 402 be owing to all be to supply the driver to use, and therefore preferably is arranged near driver's seat or its.
State-detection portion 410 goes forward side by side to exercise with these measured values and carries out the processing of the state-detection of electric energy storage device 311 accurately from measured values such as the voltage of determination unit 403 input electric energy storage devices 311, electric currents.In addition; State-detection portion 410 has state-detection mode switch 411; Thereby replace from signal input unit 401 input state detecting pattern commencing signals, through opening detecting pattern switch 411, state-detection pattern commencing signal is exported to state-detection portion 410.State-detection mode switch 411 is in order to be provided with when the state-detection that makes maintainer etc. carry out electric energy storage device 311 fast when safeguarding such as making regular check on.
State-detection portion 410 carries out the charging (below be called state-detection before charging) of predetermined volumes to electric energy storage device 311 before carrying out state-detection.That is, when before 410 pairs of control modules 313 of state-detection portion have been asked the state-detection of electric energy storage device 311, charging, control module 313 is controlled, and makes to make onboard charger 314 actions by engine start, thus electric energy storage device 311 is carried out the charging of predetermined volumes.Perhaps, charge before also can waiting the state-detection carry out above-mentioned electric energy storage device 311 by maintainer.At this moment, before state-detection, wait external charger 320 is connected on the electric energy storage device 311 by maintainer and charge.State-detection portion 410 after the charging, carries out the state-detection of electric energy storage device 311 before having carried out through the state-detection of onboard charger 314 or external charger 320.In addition; As the communication unit between state-detection portion 410 and signal input unit 401, output display unit 402, determination unit 403 and the control module 313; Can use LIN (Local Interconnect Network; Local internet) or CAN communication buss such as (Controller Area Network, controller local area networks).
Then, use process flow diagram shown in Figure 29, the summary of the condition detection method of this reference example is described.When the condition checkout gear 400 that uses this reference example carries out the state-detection of electric energy storage device 311, at first to state-detection portion 410 input state detecting pattern commencing signals (step S301).Thus, judge in state-detection portion 410 whether predetermined state-detection enabled condition sets up (step S302).As this state-detection enabled condition, comprise electric energy storage device 311 at least and stopped discharging and recharging.
When in step S302, being judged to be the establishment of state-detection enabled condition, in step S303, the state-detection pattern is set to unlatching (ON), in following step S304, electric energy storage device 311 is carried out charging before the state-detection.In case charging finishes before the state-detection, just in state-detection portion 410, carry out the state-detection (step S305) of electric energy storage device 311.State-detection can be carried out as follows: for example infer the residual capacity SOC of electric energy storage device 311, and judge the discharge capability of electric energy storage device 311 based on this.After judging the discharge capability of electric energy storage device 311 through the processing of state-detection, its result is exported to output display unit 402, and is given user or maintainer etc. by notice.(step S306).On the other hand, when in step S302, being judged to be state-detection enabled condition when being false, under the situation of the processing of not carrying out step S303～S306, finish.
Below, the condition detection method of the electric energy storage device 311 in state-detection portion 410, carried out is described.The transient changing that discharges and recharges after stopping of battery 311 comprises the course of reaction that speed is different; Therefore in order to judge the discharge capability that discharges and recharges the battery 311 after stopping accurately, preferred use can be carried out state-detection to the method that the state variation of each reaction velocity is estimated.For example, can use the function that constitutes by M polynomial expression according to the difference of reaction velocity (below be called relaxation function) F (t), the change in voltage Δ V (t) that discharges and recharges the battery after stopping to be represented as 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) the expression voltage determination value V when charging finishes to have passed through time t before state-detection Mes(t) when stopping burning voltage (below be called OCV 20hr) poor, wherein, when stopping burning voltage be discharge and recharge stop after through the enough time (for example, 20 hours) thereby voltage becomes the voltage during basic fixed (below be called OCV 20hr).
ΔV(t)＝V mes(t)-OCV 20hr (2-2)
In this reference example, use following formula to carry out state-detection.
In above-mentioned relaxation function F (t), each item f i(t) relaxation that the reaction velocity of expression battery 311 is different below is made as the relaxation function f of each reaction velocity to the contribution amount of change in voltage i(t).Each item f i(t) be the function that depends on impairment grade SOH, residual capacity SOC (ion concentration) and temperature T as the quantity of state of battery 311.Through from voltage determination value V Mes(t) calculate Δ V (t), and use from voltage determination value V Mes(t) the Δ V (t) that calculates carries out optimization to formula (2-1), can confirm the relaxation function f of each reaction velocity i(t).
The condition detection method of this reference example charges before state-detection and finishes the voltage determination value of back with predetermined cycle input electric energy storage device 311, and when the input voltage measured value, carries out the optimization of relaxation function F (t) and upgrade.The relaxation function of each reaction velocity when using the voltage determination value of measuring for the n time to carry out optimization is made as f i n(t) time, f i n(t) can as following formula, represent.
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 RefThe impairment grade SOH that representes relaxation function, residual capacity SOC and each reaction velocity of each reaction velocity under the predetermined normal condition respectively, G (T) expression is to the dependence of the temperature T of electric energy storage device.From formula (2-3), the residual capacity SOC that sends as an envoy at last and infer with the n time voltage determination value nAnd the impairment grade SOH of each reaction velocity i nFrom SOC nCan judge the discharge capability of electric energy storage device 311.In addition, based on add up the impairment grade SOH of each reaction velocity to all reaction velocitys i nAnd impairment grade SOH, can judge the impairment grade of electric energy storage device 311.
In order to carry out the optimization of the relaxation function F (t) shown in the formula (2-1) accurately, carry out the transient changing of time point of state-detection preferred always identical or can think trend identical have a reproducible state.Therefore, in the condition detection method of the electric energy storage device 311 of this reference example, before carrying out state-detection, its charging and discharging state is transferred to as far as possible and had reproducible state, carry out state-detection then.For being transferred to as far as possible, the charging and discharging state of state-detection before beginning have reproducible state; This reference example is carried out the charging (state-detection before charging) of predetermined volumes in the step S304 of Figure 29, carry out the mensuration of change in voltage etc. then and carry out state-detection.
Be used for that electric energy storage device 311 is transferred to and have the capacity that the capacity that charges before the appropriate state-detection of reproducible state is preferably set to the influence of the electrophoresis that takes place with discharge in the electrophoresis that is enough to eliminate the electrolytic solution that takes place along with discharging and recharging of vehicle operating.Thus, charging reduces the influence that is caused by the discharge in the vehicle operating before the state-detection, when carrying out state-detection, can measure the change in voltage that takes place with the charging polarization.Below, be object with the accumulator of automobile, to as charging before the state-detection and appropriate capacity describes.
In the automobile actual travel, charge/discharge capacity changes arbitrarily and continually, therefore can consider to measure and accumulative total in going charge/discharge capacity and confirm the method for charging capacity before the state-detection based on this.But, in the method for the charge/discharge capacity in accumulative total is gone, not necessarily can access high-precision charge/discharge capacity, the charging capacity when being difficult to confirm to be suitable for transferring to the state-detection pattern.In addition, when after as repeating that idling is stopping etc., having carried out the high capacity discharge, transferring to the state-detection pattern, the needed capacity of charging may become greatly before the state-detection, has the elongated problem of required time of charging this moment.
Therefore; In the condition detection method of this reference example; Not to confirm the capacity that charges before the state-detection, but the transient changing when each object electric energy storage device investigated charging in advance, and come the capacity that charges before definite in advance state-detection based on this through accumulative total discharging and recharging in going.As an example, under the situation of the vehicle that the accumulator 55B24 (36 [Ah]) that the Furukawa battery makes has been installed, when cruising about 1～2 hour the time, the size (absolute value) of the charging and discharging of accumulator capacity in going (Δ SOC) is below 0.5%.
Therefore, the fully big capacity of electric weight that charges and discharge that can be when the capacity that charges before the state-detection being set at than above-mentioned going fully reduces the influence of transferring to before the state-detection pattern that discharges and recharges.Its result, in the condition detection method of this reference example, the battery condition when carrying out state-detection receives the domination by the transient changing that causes of charging before the state-detection, therefore we can say to have become to have reproducible transient behaviour.Use transient changing that Figure 31 explains the accumulator after the charging before state-detection how according to before the size of charge/discharge capacity when going change.Figure 31 be illustrate the accumulator when after stopping, carrying out state-detection from running status electric current and voltage variation and model utility illustrate according to the magnitude relationship of charging capacity before operating charge/discharge capacity and the state-detection and the curve map how transient changing changes.Here, charging capacity before the state-detection is made as 5% of rated capacity.
Figure 31 (a) shows the variation of the preceding charging capacity of state-detection greater than the electric current under the situation of operating charge/discharge capacity, voltage; Figure 31 (b) shows the electric current under the situation that charging capacity before operating charge/discharge capacity and the state-detection is in same degree, the variation of voltage, Figure 31 (c) show operating charge/discharge capacity greater than state-detection before electric current, the variation of voltage under the situation of charging capacity.As the bigger situation of charging capacity before the state-detection shown in Figure 31 (a), operating charge/discharge capacity is made as below 1%.In the case, the operating influence that discharges and recharges is charged before through state-detection and is lowered, and reduces and demonstrates to burning voltage convergent trend thereby the change in voltage after the charging is dull before the state-detection.
In addition, be in the situation of same degree, be made as more than 1% operating charge/discharge capacity and below 5% as charging capacity before the operating charge/discharge capacity shown in Figure 31 (b) and the state-detection.In the case, also can reduce the operating influence that discharges and recharges through charging before the state-detection, the likewise dull minimizing of the change in voltage before the state-detection after the charging and Figure 31 (a) also demonstrates to burning voltage convergent trend.In addition, before the operating charge/discharge capacity shown in Figure 31 (c) is greater than state-detection, under the situation of charging capacity,, demonstrate and the diverse trend of Figure 31 (a) and (b) even if voltage also had the dull trend that increases after charging finished before state-detection.
Charge/discharge capacity during vehicle ' when charging capacity is made as 5% before with state-detection, discharges and recharges the electropolarized influence that charges and discharge that causes in the time of can fully reducing usually by vehicle ' usually below about 1%.Its result, in the state-detection before carrying out state-detection after the charging, such transient changing shown in the Figure 31 (a) that will cause, Figure 31 (b) and detect discharge capability based on charging by 5% capacity.Through using the functional form to be suitable for the approximate transient changing that causes by the charging of 5% capacity most relaxation function F (t), can utilize the state-detection of relaxation function F (t) accurately as formula (2-1).
Relative therewith; Before operating charge/discharge capacity such shown in Figure 31 (c) is greater than state-detection under the situation of charging capacity; Because tested the making of voltage than stable electrical is forced down therefore through detecting this voltage, can descend to user's untill further notice discharge capability.The situation that has repeated to stop after idling stops operation at short notice is that operating discharge capacity becomes a big example.The voltage determination value except that the king-sized situation of operating discharge capacity, also has the deterioration of accumulator 11 to increase the weight of or by long-time situation of placing etc. than the situation of burning voltage step-down.Under these circumstances, also can come detection capacity decline (off-capacity) or deterioration to increase the weight of through the condition detection method of this reference example.
The capacity of charging can be set different values as object according to which kind of that general vehicle is gone the mode of going before the state-detection, and size, characteristic that preferred consideration is installed to the accumulator on the vehicle wait to confirm.For example, in the time will coming set condition to detect the capacity of preceding charging as object through the discharge that idling stop to take place, the charging capacity of the capacity that is discharged when preferred settings stops more than or equal to idling.Carry out the charging bigger through making, shown in Figure 31 (a), Figure 31 (b), can carry out state-detection under the dull transient behaviour that reduces of voltage when state-detection than operating discharge capacity.
Below, use Figure 32, Figure 33, the condition detection method that uses Figure 29 to carry out this reference example of summary description is described in more details.Figure 32 is used to explain the process flow diagram of being asked the processing till the charging end before state-detection from the state-detection pattern.Figure 32 (a) shows by driver and waits the treatment scheme when signal input unit 401 has been imported state-detection pattern commencing signal, and Figure 32 (b) shows by maintainer and waits the treatment scheme when having opened state-detection mode switch 411.
When from signal input unit 401 input state detecting pattern commencing signals, perhaps when opening detecting pattern switch 411, all exist because maloperation and the possibility of generation signals input.Therefore, the treatment scheme in Figure 32 (a) when constituting with the mode that can prevent maloperation describes, and the treatment scheme in Figure 32 (b) when not considering the preventing of maloperation describes.But, in Figure 32 (b), also can likewise constitute with Figure 32 (a) with the mode that can prevent maloperation, and, in Figure 32 (a), also can omit the processing that prevents maloperation.
In Figure 32 (a), when having imported state-detection pattern commencing signal from signal input unit 401 (step S311), this signal is exported to state-detection portion 410.State-detection portion 410 shows the affirmation message (step S312) that is used to confirm to ask state-detection on output display part 402 behind input state detecting pattern commencing signal.Based on acknowledge message,, judge next then whether predetermined state-detection enabled condition sets up (step S314) for example if imported confirmation signal (step S313) from signal input unit 401.
As above-mentioned state-detection enabled condition, require accumulator 311 not discharge and recharge at least.As the method for judging that accumulator 311 does not does not discharge and recharge, for example confirm that vehicle 310 is in halted state (key switch is in closed condition).In addition; Can confirm that also state-detection portion 410 could communicate by letter with peripheral device, whether value in the normal range is shown, whether can make onboard charger 314 regular events or the like by starting engine from the measured value of determination unit 403; And, think that all state-detection enabled condition is false no matter under which unusual situation.
The result who in step S314, judges when state-detection enabled condition is set up, is unlatching with the state-detection mode initialization in step S315.At this moment, output display unit 402 show state detecting patterns are unlocked.In step S316, use 314 pairs of accumulators 311 of onboard charger to begin to carry out to charge before the state-detection.Used before the state-detection of onboard charger 314 charging through by state-detection portion 410 to the charging of control module 313 request predetermined volumes and by control module 313 starting engines so that onboard charger 314 actions carry out.
On the other hand, when state-detection enabled condition is false in the judgement of step S314, under the situation of the processing of not carrying out step S315, S316, finish.Which condition that at this moment, output display unit 402 show states are detected in the enabled condition is false.
Then, use Figure 32 (b) that the treatment scheme of opening the detection of state-detection mode switch 411 initial states is described.When maintainer etc. has opened state-detection mode switch 411 (step S321), state-detection pattern commencing signal is exported to state-detection portion 410.State-detection portion 410 judges then behind input state detecting pattern commencing signal whether predetermined state-detection enabled condition sets up (step S322).State-detection enabled condition can be identical with the situation of Figure 32 (a).
The result who in step S322, judges, when state-detection enabled condition is set up, in step S323 with the state-detection mode initialization for opening, in step S324, use 320 pairs of accumulators 311 of external charger to begin to carry out charging before the state-detection.Charging through external charger 320 is carried out is undertaken by maintainer etc.Therefore, can in step S324, on output display unit 402, show the message of request charging beginning, and by charging after this message of affirmations such as maintainer.In addition, after the charging of predetermined volumes finishes, can wait mode of operation detecting pattern switch 411, perhaps also can be used for notify status and detect the signal that preceding charging is through with from signal input unit 401 inputs by the maintainer.
On the other hand, when state-detection enabled condition is false in the judgement of step S322, under the situation of the processing of not carrying out step S323, S324, finish.Which condition that at this moment, output display unit 402 show states are detected in the enabled condition is false.
Treatment scheme when then, using Figure 33 that the state-detection pattern is set up describes.Processing shown in Figure 33 was carried out with the predetermined cycle.At first, in step S331, whether the decision state detecting pattern starts.Its result gets among the step S332 when the state-detection pattern has started, when the state-detection pattern is closed, under the situation of not carrying out subsequent treatment, finishes.In following step S332, judge whether above-mentioned state-detection enabled condition is set up.The affirmation of state-detection enabled condition is carried out in supposing during the state-detection pattern often.Its result when state-detection enabled condition is set up, gets among the following step S333, when state-detection enabled condition is false, gets among the step S339 on the other hand.Which condition that at this moment, output display unit 402 show states are detected in the enabled condition is false.
In step S333, whether charging finished before decision state detected.When using onboard charger 314 to carry out charging before the state-detection, can be through control module 313 be confirmed whether charging has finished to judge.Perhaps also can use from the elapsed time that charging begins to start at and judge.In addition, when using external charger 320 to carry out charging before the state-detection, judge according to imported the signal that charging finishes from state-detection mode switch 411 or signal input unit 401.The result who in step S333, judges when charging before the state-detection has finished, gets among the following step S334.On the other hand, when charging does not finish before being judged to be state-detection, end process under the situation of not carrying out subsequent treatment.
In step S334, use determination unit 403 to import the voltage determination value V of current point in time Mes(t), in step S335, use the voltage determination value V of input so far Mes(t) relaxation function F (t) is carried out optimization.In following step S336, the F (t) after the use optimization infers the discharge capability of accumulator 311.As discharge capability, for example can use through formula (2-1), burning voltage OCV when (2-2) upgrades and stop 20hrPresumed value and based on the OCV of this presumed value and that kind shown in Figure 35 20hrThe SOC that obtains with the relation of SOC.In step S337, the SOC that so infers is saved in the predetermined storage part temporarily.
In step S338, judge that detecting the elapsed time t that starts at from initial state has not reached the schedule time, when elapsed time t has reached the schedule time, gets among the step S339.On the other hand, when elapsed time t does not reach the schedule time, under the situation of not carrying out subsequent treatment, finish.In step S339, read out among the step S337 the interim discharge capability of preserving, it is normal this discharge capability to be judged to be discharge capability more than or equal to predetermined threshold the time, and to be judged to be discharge capability less than predetermined threshold the time unusual when this discharge capability.In step S340, the result who has judged discharge capability is exported to output display unit 402.Then, in step S341, closed condition detecting pattern and end process.
(the 9th embodiment)
Below, use 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 carrying out the state-detection of accumulator 311 through the state-detection pattern, carry out based on pulsed discharge state-detection (step S351) and based on the state-detection (step S352) of impedance measuring.Based on the state-detection of pulsed discharge is the method for measuring electric current when making accumulator 311 pulsed discharges, voltage and detecting the discharge capability or the deterioration state of accumulator 311 based on these electric currents, voltage.In addition, be to infer the internal driving of accumulator 311 and detect the method for the deterioration state of accumulator 311 based on internal driving based on the state-detection of impedance measuring from the measured value of electric current, voltage.
This reference example based on the condition detection method of state-detection pattern both can be as the 4th reference example independent carrying out, perhaps also can be as this reference example, and carry out based on the state-detection of pulsed discharge and based on the state-detection combination of impedance measuring.In addition; Be not must be with both combine based on the state-detection of pulsed discharge and based on the state-detection of impedance measuring, also can be with carrying out with state-detection combination based on the state-detection pattern based on the state-detection of pulsed discharge and based on one in the state-detection of impedance measuring.
In above-mentioned, explained stopping to carry out the situation of state-detection at once after the discharging and recharging of accumulator 311, but be not limited thereto, for example stopped also can carrying out state-detection under the long situation discharging and recharging of accumulator 311.For example, through with month frequency executing state detecting pattern about once, can confirm the discharge capability of accumulator 311.Meanwhile, through charging before the state-detection based on the state-detection pattern, even if also can be safely when long-time the parking and implement the recovery charging (5% charging) of accumulator 311 efficiently.
In this reference example; As the method for carrying out charging before the state-detection, make control module 313 according to request from state-detection portion 410, starting engine is so that onboard charger 314 actions; Thus accumulator 311 is charged; But, replace this method, also can make the driver will finish to go and shutting engine down before input state detecting pattern commencing signal.At this moment, even if for example close key switch, engine is stopped but charging before utilizing the state-detection of onboard charger 314 at once, and after charging finishes, engine is stopped automatically.
In addition, in above-mentioned reference example, to as the state-detection of electric energy storage device and detect the situation whether discharge capability be guaranteed and be illustrated, but be not limited thereto, also can further easily judge the deterioration of SOH etc.Relaxation function F (t) therefore, can derive the formula that is used to calculate SOH from relaxation function F (t) owing to also SOH is had dependence.Through using such formula, can infer SOH and judge the deterioration state of electric energy storage device.
As stated, according to the condition detection method and the condition checkout gear of the electric energy storage device of this reference example, through before carrying out state-detection, carrying out the charging of predetermined volumes, electric energy storage device is transferred to the state with reproducible transient changing.Thus, can be identical or can think that identical the having of trend carry out state-detection under the reproducible transient behaviour, thus can carry out the state-detection of electric energy storage device more accurately.Its result can detect undercharge or fault of electric energy storage device etc. in advance, can improve the subsequent use reliability of conduct of vehicle operating and auxiliary engine.And, through charging before the state-detection, can prevent the capacity wretched insufficiency and reduce the deterioration of electric energy storage device, go back the stable utilization of feasible system, and can prolong the life-span of electric energy storage device.
Record in the embodiment is used to the example according to the condition detection method of electric energy storage device of the present invention is shown, and the present invention is not limited thereto.The structure of the detailed part of the condition detection method of the electric energy storage device in the embodiment and moving in detail etc. can be carried out appropriate change in the scope that does not break away from purport of the present invention.
Description of reference numerals
1: vehicle
2: load
10: accumulator
11: charhing unit
12: control module
20: voltage measuring unit for measuring
21: the amperometric determination unit
22: temperature measurement unit
100: condition checkout gear
110: state-detection portion
120: storage part
130: the state output unit

Claims (41)

1. the condition detection method of an electric energy storage device is used for the corresponding predetermined cycle and judges and discharge and recharge central and discharge and recharge the discharge capability in the middle of stopping, it is characterized in that,
The voltage determination value of the said electric energy storage device of will be after last discharging and recharging stops and then to measure is as discharging and recharging when stopping voltage V_end and be stored in the predetermined storage part,
Read in the said voltage V_end when stopping that discharging and recharging from said storage part,
Deduct current voltage determination value V_now from said discharging and recharging when stopping the voltage V_end, and calculate the voltage variety Δ Va_n of current (being made as periodicity n),
Impairment grade SOH and said voltage variety Δ Va_n based on said electric energy storage device also use the prior discharge capability correction function F (SOH, Δ Va_n) that works out to calculate the discharge capability correction COD_SOH_n of said electric energy storage device,
Through following formula, calculate the current discharge capability COD_now of said electric energy storage device,
COD_now＝V_now-COD_SOH_n
And as said discharge capability COD_now during greater than predetermined threshold COD_Th, the discharge capability that is judged to be said electric energy storage device is kept.
2. the condition detection method of electric energy storage device as claimed in claim 1 is characterized in that,
Said impairment grade SOH be the impairment grade SOH_n1 that calculates during for n1 of periodicity in the middle of stopping from current nearest discharging and recharging (n1≤n),
Said discharge capability correction COD_SOH_n is through reading in the said discharge capability correction function F (SOH_n1, x) (x be variable) corresponding with said impairment grade SOH_n1 and with calculating the said variable x of said voltage variety Δ Va_n substitution from said storage part.
3. according to claim 1 or claim 2 the condition detection method of electric energy storage device is characterized in that,
Said discharge capability correction function F (SOH, Δ Va) through with the speed of the inner transient changing of said electric energy storage device accordingly in advance the relaxation function fi of each reaction velocity of more than two of establishment (being made as m) (the incompatible expression of linear junction of i=1～m),
In the middle of discharging and recharging of said electric energy storage device stops, said voltage determination value is kept in the said storage part,
The relaxation function fi of said each reaction velocity also uses the said voltage determination value that is kept at the said storage part to be optimised according to said from discharging and recharging the elapsed time that stops to start at.
4. the condition detection method of electric energy storage device as claimed in claim 3 is characterized in that,
Stop central and surpassed the schedule time (being made as for first slack time) when said electric energy storage device is in to discharge and recharge from discharging and recharging the elapsed time that stops to start at,
The relaxation function fi that use is kept at said voltage determination value pair in the said storage part said each reaction velocity corresponding with transient changing fast carries out optimization,
Use the relaxation function fi of each reaction velocity after the said optimization to calculate and depend on the impairment grade SOH_fast_n of transient changing fast,
(that calculates during n2≤n) depends on the impairment grade SOH_slow_n2 and the said impairment grade SOH_fast_n of transient changing slowly to be based on periodicity in the middle of current nearest discharging and recharging stops and to be n2; And utilize predefined function G; Through following formula, calculate current impairment grade SOH_n
SOH_n＝G(SOH_fast_n，SOH_slow_n2)
And said discharge capability correction COD_SOH_n is through reading in the said discharge capability correction function F (SOH_n, x) corresponding with said impairment grade SOH_n and with calculating the said variable x of said voltage variety Δ Va_n substitution from said storage part.
5. the condition detection method of electric energy storage device as claimed in claim 4 is characterized in that,
Stop central and from discharging and recharging the elapsed time that stops to start at when having surpassed when said electric energy storage device is in to discharge and recharge than long predetermined second slack time said first slack time,
The relaxation function fi of said each reaction velocity of transient changing carries out optimization to depending on slowly further to use the said voltage determination value that is kept in the said storage part,
Use the relaxation function fi of each reaction velocity after the said optimization to calculate and depend on the impairment grade SOH_slow_n of transient changing slowly,
Based on the said impairment grade SOH_fast_n that depends on transient changing fast that calculates with saidly depend on the impairment grade SOH_slow_n of transient changing slowly, and utilize said predefined function G,, calculate current impairment grade SOH_n through following formula,
SOH_n＝G(SOH_fast_n，SOH_slow_n)。
6. like the condition detection method of each described electric energy storage device in the claim 1 to 5, it is characterized in that,
And then said electric energy storage device is carried out the charging (before the state-detection charging) of predetermined volumes after stopping discharging and recharging, and will before said state-detection, charge finish after and then the said voltage determination value of mensuration discharge and recharge when stopping voltage V_end and be saved in the said storage part as said.
7. the condition checkout gear of an electric energy storage device is used for the corresponding predetermined cycle and judges and discharge and recharge central and discharge and recharge the discharge capability in the middle of stopping, and it is characterized in that, comprising:
Storage part, the voltage determination value that is used to preserve said electric energy storage device;
State-detection portion is used for corresponding each said cycle to read in data that are kept at said storage part and the discharge capability of judging said electric energy storage device; And
The state output unit is used for the input result of determination from said state-detection portion, and to outside output,
Wherein, the said voltage determination value of the said electric energy storage device that and then said storage part is kept at last discharging and recharging measures after stopping, as discharging and recharging voltage V_end when stopping,
The said voltage V_end when stopping that discharging and recharging is read in from said storage part in said state-detection portion; By from the said voltage determination value V_now that deducts current (being made as periodicity n) when stopping the voltage V_end that discharges and recharges; Calculate current voltage variety Δ Va_n; And based on the impairment grade SOH of said electric energy storage device and said voltage variety Δ Va_n and use discharge capability correction function F(SOH, the Δ Va_n of establishment in advance) calculate the discharge capability correction COD_SOH_n of said electric energy storage device
The current discharge capability COD_now of said electric energy storage device calculates through following formula in said state-detection portion,
COD_ow＝V_ow-COD_SOH_n
And as said discharge capability COD_now during greater than predetermined threshold COD_Th, the discharge capability that is judged to be said electric energy storage device is kept.
8. the condition detection method of an electric energy storage device is characterized in that,
Said electric energy storage device is stopped to discharge and recharge and the voltage of said electric energy storage device when reaching the state that satisfies predetermined stable condition burning voltage when stopping; Will be after said electric energy storage device stops to discharge and recharge through variable quantity voltage variety when stopping of the burning voltage during of the voltage during time t with respect to said stopping; At this moment
The relaxation function F (t) of voltage variety works out as the function of the predetermined quantity of state of said electric energy storage device in advance in the time of will being used to calculate said stopping,
Voltage when measuring will the stopping charging before charging and finish of said electric energy storage device, or will stop to discharge before discharge voltage when finishing,
Voltage after said charging or the said discharge of measuring said electric energy storage device stops,
The said relaxation function F of voltage variety and optimization (t) when calculating said stopping according to said voltage determination value,
Infer said quantity of state according to the said relaxation function F (t) that is optimised,
Voltage and said quantity of state of being inferred were judged the discharge capability (COD) of said electric energy storage device when voltage or said charging finished when utilizing said discharge to finish.
9. the condition detection method of electric energy storage device as claimed in claim 8 is characterized in that,
Said relaxation function F (t) through with the inner reaction velocity of the said electric energy storage device relaxation function f of each reaction velocity of more than two of establishment (being made as m) in advance accordingly i(t) (linear combination of i=1～m) representes,
The relaxation function f of said each reaction velocity i(t) (voltage variety is separated into the component corresponding with said reaction velocity and has carried out optimization during said stopping that i=1～m) will calculate according to said voltage determination value.
10. like the condition detection method of claim 8 or 9 described electric energy storage devices, it is characterized in that,
Thereby to discharge and recharge caused electric current small or when being limited in the predetermined scope for the influence that inner transient changing is brought of said electric energy storage device for fixed value when said, judges that said electric energy storage device has stopped discharging and recharging.
11. the condition detection method of electric energy storage device as claimed in claim 10 is characterized in that,
Establishment in advance is used to revise the voltage correction of the change in voltage that is caused by said electric current,
Be utilized in the voltage that adds the above voltage correction gained on the said voltage determination value, the said relaxation function F of optimization (t).
12. the condition detection method like each described electric energy storage device in the claim 8 to 11 is characterized in that,
Will discharge and recharge electric current aggregate-value that the electric current in the discharging and recharging before stopping to obtain according to accumulative total and calculate the residual capacity increase and decrease amount (Δ SOC) that discharges and recharges when stopping; On the last residual capacity that once discharges and recharges when stopping, adding the above residual capacity increase and decrease amount and calculate current discharging and recharging the residual capacity when stopping
Voltage when voltage or said charging finish when finishing based on said discharge, the quantity of state and the said SOC that infer from said relaxation function F (t) judge said COD.
13. the condition detection method of electric energy storage device as claimed in claim 12 is characterized in that,
Voltage was as the charge efficiency calculating formula of variable when establishment in advance finished predetermined quantity of state with charging,
The said SOC that discharges and recharges when stopping to utilize charge efficiency correction said residual capacity increase and decrease amount and calculates, and the said charge efficiency calculating formula of voltage substitution was calculated when said charge efficiency finished the said quantity of state that utilizes said relaxation function F (t) to calculate and said charging.
14. the condition detection method like each described electric energy storage device in the claim 8 to 13 is characterized in that,
Said quantity of state is the residual capacity of said electric energy storage device.
15. the condition detection method like each described electric energy storage device in the claim 8 to 13 is characterized in that,
Said quantity of state is the impairment grade (SOH) of said electric energy storage device.
16. the condition detection method like each described electric energy storage device in the claim 8 to 15 is characterized in that,
Said relaxation function F (t) has the fast component f of relaxation velocity Fast(t) and the slow component f of relaxation velocity Slow(t),
Work out said f in advance Fast(t), said f Slow(t) and both ratio f Fast(t)/f Slow(t) separately reference value,
The said f that utilization is calculated according to the said F that is optimised (t) Fast(t), said f Slow(t) and said f Fast(t)/f Slow, and said reference value separately judge said COD.
17. the condition detection method of electric energy storage device as claimed in claim 16 is characterized in that,
Said quantity of state is the impairment grade SOH of said electric energy storage device,
Utilize said f Fast(t), said f Slow(t) and said f Fast(t)/f Slow, and said reference value separately calculate said impairment grade.
18. the condition detection method of electric energy storage device as claimed in claim 17 is characterized in that,
Voltage changed the correction calculating formula as the High-speed transient of variable when establishment in advance finished residual capacity with charging,
The said High-speed transient of voltage substitution changed the correction calculating formula and calculates with respect to said f when said residual capacity and the said charging that discharges and recharges when stopping to be finished Fast(t) correction, and utilize said f with said correction correction Fast(t) calculate said impairment grade.
19. the condition detection method of electric energy storage device as claimed in claim 16 is characterized in that,
Work out change in concentration amount calculating formula in advance, said change in concentration amount calculating formula is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f Slow, the change in concentration amount of the electrolytic solution of said electric energy storage device,
Utilize the said relaxation function F (t) that is optimised and calculate the change in concentration amount of said electrolytic solution and be used for said quantity of state according to said change in concentration amount calculating formula.
20. the condition detection method of electric energy storage device as claimed in claim 16 is characterized in that,
Establishment in advance is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f SlowThe stratification variable quantity calculating formula of stratification variable quantity, in said stratification variable quantity calculating formula, with CONCENTRATION DISTRIBUTION bias (stratification) variable quantity of the electrolytic solution of said electric energy storage device as said stratification variable quantity,
Utilize the said said relaxation function F (t) that is optimised and calculate said stratification variable quantity and be used for said quantity of state according to said stratification variable quantity calculating formula.
21. the condition detection method of electric energy storage device as claimed in claim 16 is characterized in that,
Establishment in advance is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f SlowThe horizontal stratification variable quantity calculating formula of horizontal stratification variable quantity; In said horizontal stratification variable quantity calculating formula; Will be to the variable quantity of the liquid level CONCENTRATION DISTRIBUTION bias (laterally stratification) in the horizontal of the electrolytic solution of said electric energy storage device as said horizontal stratification variable quantity
Utilize the said said relaxation function F (t) that is optimised and calculate said horizontal stratification variable quantity and be used for said quantity of state according to said horizontal stratification variable quantity calculating formula.
22. the condition detection method of electric energy storage device as claimed in claim 16 is characterized in that,
Establishment in advance is used for calculating the said f with respect to said relaxation function F (t) Fast(t), said f Slow(t) and said f Fast(t)/f SlowThe portraitlandscape stratification variable quantity calculating formula of portraitlandscape stratification variable quantity; In said portraitlandscape stratification variable quantity calculating formula; Will be to the variable quantity of the liquid level of the electrolytic solution of the said electric energy storage device CONCENTRATION DISTRIBUTION bias (laterally stratification, vertically stratification) on horizontal and vertical as said portraitlandscape stratification variable quantity
Utilize the said said relaxation function F (t) that is optimised and calculate said horizontal stratification variable quantity with vertical stratification variable quantity and be used for said quantity of state according to said portraitlandscape stratification variable quantity calculating formula.
23. the condition detection method like each described electric energy storage device in the claim 8 to 22 is characterized in that,
Said relaxation function F (t) is further worked out as the temperature funtion of said electric energy storage device in advance,
Measure the temperature of said electric energy storage device and be used for the calculating of said relaxation function F (t).
24. the condition detection method like each described electric energy storage device in the claim 8 to 23 is characterized in that,
Burning voltage is OCV when stablizing during said stopping, and the OCV calculating formula is calculated when said voltage determination value deducts according to establishment in advance stable when said stable, and OCV calculates said OCV variable quantity,
The voltage variety during as said stopping with said OCV variable quantity.
25. the condition detection method like each described electric energy storage device in the claim 8 to 24 is characterized in that,
Relaxation function f according to said each reaction velocity i(t) infer the quantity of state of corresponding each said reaction velocity, and the quantity of state that amounts to each said reaction velocity calculates said quantity of state.
26. the condition detection method like each described electric energy storage device in the claim 8 to 25 is characterized in that,
At relaxation function f with said each reaction velocity under the predetermined state i(t), the said SOH of said SOC and each reaction velocity is made as fi respectively Ref(t), SOC Ref, and SOHi Ref, when the dependence with respect to temperature T of said electric energy storage device is made as G (T), the n time the relaxation function fi that discharges and recharges said each reaction velocity after the end n(t) be expressed as:
fi n(t)＝fi ref(t)*{SOC n/SOC ref}
*{SOHi n/SOHi ref}*g(T)
(SOHi here, nThe SOH of said each reaction velocity of expression).
27. the condition detection method of electric energy storage device as claimed in claim 9 is characterized in that,
Measure the voltage and current of said electric energy storage device,
Be judged to be said electric energy storage device when having stopped discharging and recharging when discharge and recharge stop signal according to said electric current or predetermined,
According to said voltage determination value calculate with from said elapsed time of stopping to start at voltage variety during corresponding said stopping that discharging and recharging,
Voltage variety when utilizing said stopping is to comparing the relaxation function f of short pairing said each reaction velocity of said reaction velocity of time constant with the said elapsed time i(t) carry out optimization,
The relaxation function fi (t) that compares long pairing said each reaction velocity of said reaction velocity of time constant with the said elapsed time uses its previous relaxation function, and according to the relaxation function f of said its previous relaxation function, said said each reaction velocity that is optimised iVoltage was inferred said quantity of state when voltage and said charging finished when (t), said discharge finished.
28. the condition detection method like each described electric energy storage device in the claim 8 to 27 is characterized in that,
Burning voltage is that the voltage after discharging and recharging of said electric energy storage device stops is that per 1 hour variation becomes the said voltage of 5mv when following during said stopping.
29. the condition detection method of an electric energy storage device is characterized in that,
The said electric energy storage device that has stopped discharging and recharging is carried out charge before the state-detection of predetermined volumes,
Measure after charging finishes before the said state-detection through the voltage of the said electric energy storage device during time t with predetermined period,
With the said voltage determination value of relaxation function F (t) best fit approximation with respect to discharging and recharging of said electric energy storage device being stopped and the variable quantity (voltage variety when stopping) of burning voltage during stopping when being reached for almost fixed; Said relaxation function F (t) is the function of the predetermined quantity of state of said electric energy storage device
Infer said quantity of state according to said relaxation function F (t) by best fit approximation,
Through said quantity of state of being inferred and predetermined threshold value relatively being judged the discharge capability of said electric energy storage device.
30. the condition detection method of electric energy storage device as claimed in claim 29 is characterized in that,
Before said state-detection, in the charging, carry out the charging of the rated capacity 5% of said electric energy storage device.
31. the condition detection method like claim 29 or 30 described electric energy storage devices is characterized in that,
During burning voltage, the discharge capability that is judged to be said electric energy storage device had descended when charging and the said voltage determination value that obtains at first were lower than said stopping before finishing said state-detection.
32. the condition detection method like each described electric energy storage device in the claim 29 to 31 is characterized in that,
Burning voltage uses said relaxation function F (t) by best fit approximation to upgrade during said stopping.
33. the condition detection method like each described electric energy storage device in the claim 29 to 32 is characterized in that,
Said relaxation function F (t) through with the inner reaction velocity of the said electric energy storage device relaxation function f of each reaction velocity of more than two of establishment (being made as m) in advance accordingly i(t) (linear combination of i=1～m) representes,
The relaxation function f of said each reaction velocity i(t) (voltage variety is separated into the component corresponding with said reaction velocity and has carried out optimization during i=1～m) with said stopping.
34. the condition detection method like each described electric energy storage device in the claim 29 to 33 is characterized in that,
Said quantity of state is the residual capacity (SOC) of said electric energy storage device.
35. the condition detection method like each described electric energy storage device in the claim 29 to 33 is characterized in that,
Said quantity of state is the impairment grade (SOH) of said electric energy storage device.
36. the condition detection method like each described electric energy storage device in the claim 29 to 35 is characterized in that,
At relaxation function f with said each reaction velocity under the predetermined normal condition i(t), the said impairment grade of said residual capacity and each reaction velocity is made as f respectively i Ref(t), SOC Ref, and SOH i Ref, when the dependence with respect to temperature T of said electric energy storage device is made as G (T), the relaxation function f of said each reaction velocity in n cycle of best fit approximation to said voltage determination i n(t) with the said residual capacity SOC that is inferred in said n the cycle n, said each reaction velocity impairment grade SOH i nBetween have a represented relation of following formula:
f i n(t)＝f i ref(t)*{SOC n/SOC ref}
*{SOH i n/SOH i ref}*g(T)。
37. the condition detection method like each described electric energy storage device in the claim 29 to 36 is characterized in that,
Before carrying out said state-detection, before the charging, said electric energy storage device is carried out pulsed discharge its state-detection of Xingqi of going forward side by side.
38. the condition detection method like each described electric energy storage device in the claim 29 to 37 is characterized in that,
Before carrying out said state-detection, before the charging, carry out the impedance measuring of said electric energy storage device, its state-detection of stepping Xingqi of going forward side by side.
39. the condition checkout gear of an electric energy storage device, it constitutes the internal charger that can use by control module control and charges, and said condition checkout gear is characterised in that, comprising:
Signal input unit is used for input state detecting pattern commencing signal;
The output display unit is used for to the predetermined information of outside output;
Determination unit is used to measure the voltage of said electric energy storage device; And
State-detection portion, said state-detection portion has the state-detection mode switch, and is connected with said control module, said signal input unit, said output display unit and said determination unit,
Wherein, said state-detection portion
When having imported said state-detection pattern commencing signal from said signal input unit,
Said electric energy storage device is carried out the voltage of the said electric energy storage device of the elapsed time t after the charging before the state-detection from the input of said determination unit,
With the said voltage determination value of relaxation function F (t) best fit approximation with respect to discharging and recharging of said electric energy storage device being stopped and the variable quantity (voltage variety when stopping) of burning voltage during stopping when reaching almost fixed; Said relaxation function F (t) is the function of the predetermined quantity of state of said electric energy storage device
Infer said quantity of state according to said relaxation function F (t) by best fit approximation,
Through said quantity of state of being inferred and predetermined threshold value relatively being judged the discharge capability of said electric energy storage device, and
Result of determination is exported to said output display unit.
40. the condition checkout gear of electric energy storage device as claimed in claim 39 is characterized in that,
Before the said state-detection charging be by said state-detection portion to the predetermined request signal of said control module output, and control said internal charger by said control module and carry out.
41. the condition checkout gear of electric energy storage device as claimed in claim 39 is characterized in that,
Charging is carried out through external charging device on said electric energy storage device before the said state-detection.
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CN111896877B (en) * 2020-07-31 2023-07-14 Oppo广东移动通信有限公司 Battery detection method, device, electronic equipment and storage medium
CN112946507A (en) * 2021-02-01 2021-06-11 中国电力科学研究院有限公司 Method, system, equipment and storage medium for online detection of health state of energy storage battery
CN112946507B (en) * 2021-02-01 2023-10-27 中国电力科学研究院有限公司 Method, system, equipment and storage medium for on-line detection of energy storage battery health status

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