CN101657947A - The charging method of double electric layer electrochemical capacitors - Google Patents
The charging method of double electric layer electrochemical capacitors Download PDFInfo
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- CN101657947A CN101657947A CN 200780050527 CN200780050527A CN101657947A CN 101657947 A CN101657947 A CN 101657947A CN 200780050527 CN200780050527 CN 200780050527 CN 200780050527 A CN200780050527 A CN 200780050527A CN 101657947 A CN101657947 A CN 101657947A
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Abstract
The present invention relates to method to the automatic charging of electrochemistry electric energy energy storage device.Charging can be carried out, till the voltage increment value that the terminal of striding energy storage device is measured reaches the value of preassignment.Cycle charging and rest period be can adopt, voltage measurement and definite voltage increment after by the electric energy of institute's assignment amount, carried out.Not how are the value of the initial state of charge of the design feature of the energy storage device in the tube module (as capacitor) and quantity, energy storage device and/or temperature or charging current and/or time unsteadiness, all finish charging process automatically.
Description
Background of invention
The present invention relates to design the charging of the electrochemical capacitor of store electrical energy.More specifically, the present invention is devoted to provide effective electrochemical capacitor charging method when charge power changes at any time, in case and be devoted to reach the optimal charge state and guarantee that charging process in time finishes.
Heterogeneous electrochemical ultracapacitor (HES) energy storage device (for example is used for electrical power storage gradually, referring to authorizing United States Patent (USP) 6 A.Nourai etc., that be entitled as " System And Method Of FormingCapacitor-Based Electrical Energy Storage Modules ", 518,734).Traditionally, the electrical power storage of rechargable power supplies is dominant by storage battery.Yet each feature of HES device more is better than battery when making it be used for electrical power storage.For example, when the HES device is compared when battery is in a disadvantageous position at the value aspect of its concrete weight and stored energy capacitance, the HES device aspect the scope of life cycle, the charging current value of allowing and quick charge capability significantly better than battery.Like this, the HES device can be suitable for use as (but non-being limited to) well: the energy-intensive power supply of industry, telecommunication system, utility company, electric automobile and hybrid vehicle; The energy storage device of the electric energy that fixing or portable (transportation or on-the-spot) wind-force and water power device produce; And from the portable power supplies of muscle-powered generator charging etc.
For effectively using the electric energy energy storage device of any sealing, must control its charging process.The parameter list of monitoring during charging process depends on parameter, its specific design, and the field of employment of energy storage device of electro-chemical systems to a great extent.
There are a variety of known methods to can be used for controlling the charging process of battery.For example, there are various charging techniques, wherein determine charged state and charge control by the variation of controlling the major parameter of battery through the controlled change of charge mode at any time.In such method, during charging-discharge cycle, carry out the measurement of electric current and voltage, and measured parameter compares with the value of giving in advance, described value of giving in advance can be by experiment or mathematical modeling determine.Afterwards, based on the described controlled change that relatively carries out charge mode.In another such method, first or second time-derivative of measuring voltage, the variations in temperature during the control charging process, and the curtage in the different step in the control charging process changes.In another such method, charging voltage or electric current are controlled by the parameter that changes output charging current pulse or pulse train.
Yet, between battery and electrochemical capacitor energy storage device, important difference being arranged, these difference stop or teaching can not be used same charging process controlling schemes.Mainly be, different with battery, in electrochemical capacitor, the energy value that the magnitude of voltage that capacitor is charged to is determined thereby stored.Therefore, specify charging voltage value to obtain desirable stored energy value by capacitor is charged to, wherein charging voltage value is selected from the operating voltage range of capacitor.When selecting this to specify charging voltage value, must consider the Current Temperatures condition of capacitor, temperature changes during high current charges process usually fast.
Therefore, developed other known capacitor charging methods.For example, known capacitor can be charged by constant current, constant voltage or firm power technology.Under constant current, be charged to given voltage and may be the charging method of normal use.
As mentioned above, the value of given voltage depends on the value of working temperature and charging current, and is main the setting with the experience for this concrete capacitor design.For example, in patent application PCT/RU03/00109, WO03/081618 applications such as I.Varakin, that be entitled as " Method Of Charge And Discharge Of Capacitor WithDouble Electric Layer ", under electrolytical given mensuration temperature, the voltage the when leakage current of capacitor and power level are best is assumed that the maximum working voltage of charging.
When reaching the given voltage value, the charging of capacitor can constant voltage continue.Along with charged state increases, the value of charging current reduces.For example, when fixed time expiration or charging current dropped to designated value, the charging of carrying out with constant voltage can be considered end.
A kind of interested constant current charge method is being authorized description in the United States Patent (USP) 5,640,080 Mikitaka Tamai, that be entitled as " Secondary Battery Charge " (' 080 patent).Wherein the charging process of Miao Shuing is undertaken by adopting alternately charging and rest period.During each charging interval, the electric weight Δ Q by battery is limited to and will cause the value of any deterioration of battery parameter because of overcharging.This electric weight is defined as the part (for example, be not higher than rated capacity 5%) of all told of battery.When striding voltage that battery terminal records when being equal to or higher than scheduled voltage during rest period, charging is considered as finishing.
The battery of ' 080 patent (has initial duration T by replacing charge cycle
Cha) and rest period (have constant duration T
Re) charge.Thereafter, measured voltage V
ChDuring charge cycle with scheduled voltage V
ChaRelatively.When striding the voltage V that terminal records
ChEqual or exceed scheduled voltage V
ChaThe time, battery is regarded as abundant charging.Whenever measured voltage V
ChReach predetermined value V
ChaThe time, the electric weight that provides in each charge cycle (being rest period thereafter) subsequently reduces.Charging process finishes when the electric weight that charging is provided reaches null value.
In the variation of charging process, ' 080 patent teaching whenever measured voltage V
ChReach predetermined value V
ChaThe time, preassigned charge capacity can remain unchanged, and the duration of rest period subsequently increases.In other words, consider the variations in temperature of battery.Influenced by battery temperature, value V
ChaCan reduce.
When HES is recharged, stride the voltage U of its terminal
ChThe parameter and the charging process situation that depend on HES:
U
ch＝U
0+IR+ΔU (1)
U wherein
0Corresponding to the quiescent voltage of setting in the capacitor that is being full of after finishing charging and process of depolarization, IR is switched on corresponding to charging current or the voltge surge when disconnecting, and reaching Δ U will more elaborate below.
Quiescent voltage U
0Value determine by the charge volume Q of capacitor and capacitor C.In addition, the electric capacity of known capacitor is the electromotive force of polarizable electrode
The function of its charged state and temperature T thereof (
).
Voltge surge IR is the performance in the pressure drop at Ohmic resistance place.It is the function of the charging current amplitude I (t) that changes at any time, and the temperature of the electromotive force of internal resistance and charged state, polarizable electrode and capacitor is relevant (promptly
).
The variation of voltage that Δ U strides the terminal of HES during to charging process has contribute significantly.One of component in value Δ U is determined by the polarization process of HES.Its depend on Q,
T, t also depend on the type of the electro-chemical systems that is adopted and the specific design feature of HES.For example, these design features can comprise: the space structure of conductivity, polarizable and non-polarizable electrode and thickness, electrolytical conductivity, and the thickness of dividing plate.
Second important component among the value Δ U determined by the process that takes place during the gas circulation of HES, and it is adopting moisture non-organic acid solution to occur in as electrolytical system.When the potential value of electrode surpassed equilibrium valve, this second component was relevant with the liberation of hydrogen process of analysing in oxygen process and the negative pole in the positive pole.As HES during near maximum state of charge, the electric weight that charging is worked reduces, and electrolyte is decomposed the electric weight that works increases.Afterwards, the voltage of striding the terminal of HES reaches maximum.
These processes also cause the hydrogen reduction of separating out in the negative pole and form water, this make negative pole the electromotive force depolarising thereby make the voltage of HES reduce.The exothermic reaction that is associated with hydrogen reduction follows the HES temperature to increase.Thus, overpotential for oxygen evolution and overpotential of hydrogen evolution anodal and negative pole are minimized respectively, and the voltage of striding the terminal of HES begins reduction.When charging current was further passed through, the gassing that the oxygen amount that also can occur separating out in the positive pole increases and the HES housing is interior increased.
Therefore, in the process of charging HES device, maximum voltage value is generally the parameter of variation.Maximum voltage depends on concrete electrochemistry and design feature and charged state, Current Temperatures condition and the charge rate of HES.Charge capacity value when these actual conditionses are issued to maximum voltage is corresponding to optimal charge state and coulomb and the energy loss level of HES.
Those skilled in the art can find out obviously that from the description of front depolarising that takes place and electrochemical process make that its Coulomb capacity reduces, the energy efficiency of its charging-discharge cycle reduces and internal resistance increases during the gas circulation of HES.In addition, when carrying out uncontrolled charging, also may partly reduce the life cycle of HES.
In practice, make and when wide region changes, also to finish effective charging in the value of charge power, how regardless of the heat condition of initial state of charge and HES even must guarantee to be applied to the charging algorithm of HES device.Occur when for example, sizable variation of the heat condition of HES is can be in the charge rate of HES high.Because HES fully can be by the current charges of different value, the duration of charging process can change between a few minutes arrive several hours.The ability that the control charge rate changes makes best power and the price parameter that may select charger on the one hand, on the other hand the versatility of charging method is forced some requirement.
For floating charge (promptly with constant-potential charge), the charging process algorithm is set severe requirement.For example, occur when the stand-by power supply at the electric energy energy storage device for compensation or in capacity and energy loss that this device occurs during the maximum full state long term storage with it, must carry out other charging.When the electric energy energy storage device was battery, this other charging was carried out by the whole bag of tricks.For example, charging in addition can constant voltage be carried out, be carried out or carried out by the periodic switch of floating charge by little value (near the value of leakage current) electric current.These methods all require accurately to be provided with floating voltage value, maximum charging current value the limit, and keep the stable temperature condition.When violating the static heat pattern, high " heat is quickened " risk is arranged, during " heat is quickened ", gas recycle process can be accelerated, and temperature rises, and charging current increases in mode spontaneous and that be exceedingly fast.
At present, be subjected to the influence of aforementioned parameter, the charging and the Dynamic Modeling of discharge process make may (with high probability) predict capacitor with different designs energy feature (for example, referring to D.Dunn, J.Newman, " Prediction Of Specific Energies And SpecificPowers Of Double-Layer Capacitors Using A Simplified Model, " J.Electrochem.Soc., 147,820 (2000); S.Kazaryan, S.Razumov, S.Litvinenko, G.Kharisov, and V.Kogan, " Mathematical Model OfHeterogeneous Electrochemical Capacitors And Calculation Of TheirParameters, " J.Electrochem.Soc., (2006), in press).Yet the actual task of the charging process of control HES is still unresolved.
Summary of the invention
The present invention is devoted to the controlled and optimal charge of electrochemical capacitor.For example, charging process of the present invention should provide: the energy storage value of the best or preassignment; Charging process is regularly interrupted to get rid of any overcharging; No matter how fully initial state of charge charging; Optimal charge in the whole operating temperature range of capacitor; Prevent too overheated and possible gassing through safety valve; And compensation condenser operates to during the stand-by power supply or because the energy loss that self discharge causes, so that capacitor device is in maximum state of charge for a long time.
Charging method of the present invention based on the special design feature of HES device and operation principle (referring to authorizing United States Patent (USP) 6 R.S.Razumov etc., that be entitled as " Asymmetric ElectrochemicalCapacitor And Method Of Making ", 222,723).In this HES, use two types electrode: polarizable electrode and non-polarizable electrode.Preferably, its electrochemical properties is used as non-polarizable electrode by definite cell type (just) electrode of faraday's method.Polarizable electrode (negative pole) adopts electric double layer Charge Storage method.Usually be used as the active material of this polarizable (bearing) electrode based on the different synthetics of the material with carbon element that activates.
In order to realize effective operation of this HES device, the electricity of non-polarizable electrode (coulomb) capability value preferably is chosen as than high several times of the capacitance value of polarizable electrode.In addition, the maximum discharge energy of HES in its operating voltage window determined corresponding to whole discharges of polarizable electrode and by its stored energy.Because the electric capacity of non-polarizable electrode is much higher, non-polarizable electrode is discharged into the degree of lacking than polarizable electrode during the HES periodic duty.Like this, when HES fully discharged, its non-polarizable electrode was discharged into the degree of lacking than the positive pole of the complete interdischarge interval battery of battery and negative pole.Therefore, the life cycle of HES is much larger than the life cycle of battery, because when the capacity of HES device and energy parameter were determined by the parameter of polarizable electrode, its life cycle characteristic depended primarily on the parameter of non-polarizable electrode.
In of the present invention one exemplary charging method, the charging of HES is carried out with constant current, does not need tentatively to give specific charging voltage value.According to this embodiment, the control of charging process can be finished as described below: (1) sets the positive increment size of charging voltage, and when reaching this value, charging process is interrupted; (2) by after specifying the electric weight part, determine voltage increment; Reach (3) when voltage increment is reduced to designated value, charging process stops.
The designated positive value of voltage increment is determined the charged state that HES is relevant with its optimal charge level.Optimal charge state under existing charge rate of HES and temperature conditions is corresponding to the voltage zero increment.If charging continues till the negative increment that reaches voltage, then temperature raises fast, and the Coulomb capacity of charging-discharge cycle and energy efficiency reduce, and the risk that exists the capacitor casing internal gas pressure to increase.
In this embodiment, after the electric weight of predetermined value passes through, measure charging voltage and determine voltage increment, the time discrete of electric weight predetermined value setting measurement.The predetermined value of electric weight will depend on each feature and design and measurement parameter and the employed charge control system of HES usually.
In this embodiment, charging process regularly interrupts causing electric energy stored among the HES to reach desired horizontal.Like this, do not need accurately to determine the maximum voltage value when charging process finishes or do not need the temperature of each battery of continuous measurement HES.
In another exemplary embodiment of the present invention, the charging of HES exists in constant charge current under the instable situation to be carried out.Under truth, such unsteadiness can provide in the initial parameter of power supply, can be caused by the magnetic pick-up of constant-current source or the significant change of ambient temperature, maybe can be derived from the variation of charge power according to unexpected rule.In this case, the voltage of striding the terminal of HES during charging process can reach several local maximums, and it will not correspond to the optimal charge state.Voltage increment also can change in wide region, changes near its symbol these local maximums.
By using cycle charging and rest period to charge, this embodiment of the present invention allows that phenomenon is as the circulation change of not having the pulse of control charging current, constant charge current amplitude, the change at random that reaches charge power.According to this embodiment, when circuit disconnected after charging current is interrupted, because the depolarising of electrode and the self discharge of capacitor, the voltage of striding the terminal of HES descended gradually.In the starting stage, voltage drop is determined by the depolarising of electrode.Subsequently, self discharge process becomes the principal element that voltage reduces.Therefore, process of depolarization and self discharge process follow the voltage of HES to reduce and energy consumption.Afterwards, the HES that carries out according to this embodiment charges till the voltage increment of measuring when each rest period finishes reaches predetermined value.
Subsequently, on by the basis of specifying electric weight part Δ q, carry out cycle charging.In rest period interrupt charging current thereafter.The duration t of each rest period
rShould be enough to measuring voltage, it interrupts having similar value to all chargings and influenced especially by the design of HES selects.The magnitude of voltage U that when each rest period finishes, records
rThe magnitude of voltage that records with rest period in front compares, and definite voltage increment Δ U
rAs long as voltage increment is reduced to designated value, the charging of HES stops.
Charging technique according to this embodiment of the invention enables to use the charge power of change at random at any time.This makes and may use cheap power supply, does not wherein have the special technique means to be used for the constant charge electric current.
Charging technique is devoted to compensate energy loss and is increased the electric energy that stores among the HES according to another embodiment of the present invention.According to this technology, charging is charged and rest period to produce by regular interruption.As long as be required the electric weight part Δ q by appointment, charge cycle continues.The duration t of all rest period
R1The specific design that depends on HES reaches by the temporal characteristics of electrode depolarization process definite.The magnitude of voltage U that when rest period finishes, measures
R1Compare with the magnitude of voltage of measuring in last rest period, determine voltage increment Δ U subsequently
R1
In case voltage increment is reduced to designated value Δ U
R, set1, with the upper limit charging voltage U that when a last charge cycle finishes, reaches
ChmaxCharge.Thereafter, in case when charge cycle finishes voltage reach U
Chmax, then make to disconnect in short-term.Voltage U
R2During rest period, measure, and compare with rest period magnitude of voltage that last rest period is measured.Determine voltage increment Δ U thereafter,
R2When voltage increment is reduced to designated value Δ U
R, set2The time, or when the duration of charge cycle reduced specified factor, charging was considered as finishing.
According to the charging technique of this embodiment of the invention, do not need to specify the predetermined upper limit of charging voltage, and do not need to control the temperature of HES.In addition, compensated owing to the loss of electrode depolarization, and finished the optimal charge of HES automatically.
The charging technique of this embodiment of the invention energy loss that compensation caused because of the self discharge of HES between the long-term charged storage life of HES that also can be used for circulating.For this reason, after HES finishes charging, continue the voltage that the terminal of HES is striden in control.Like this, in case the voltage that records reaches designated value, can carry out the recharge of HES.
Therefore, be appreciated that according to the present invention that charging has several variations to HES from top description.Generally speaking, and according to first embodiment, HES can be connected to constant-current source and charge, and just specifies the electric weight part to control by HES between charge period, measuring voltage, and measured voltage and its predetermined (preassignment) value compare, and charging is finished.In this changed, the electric weight part was determined based on the capacitance of HES and the threshold sensitivity of register system.By after specifying the electric weight part, measure the voltage of the terminal of striding energy storage device and determine voltage increment.When voltage increment reached (dropping to) designated value, charging process was considered as finishing.No matter how are the charged state initial value of HES and working temperature, all can adopt such charging process.
In alternative charging scheme of the present invention, HES can use constant-current source to charge as mentioned above.Yet in this embodiment, charging also circulation is ended to produce rest period after specifying the electric weight part.All rest period all have the constant duration of setting.Voltage when measuring each charge cycle and each rest period and finishing, thereby and the voltage that records when finishing of the voltage that when given rest period finishes, records with last rest period compare definite voltage increment.When the voltage increment during the rest period reached designated value, charging process was considered as finishing.No matter how are the charged state initial value of HES and working temperature, all can use this charging method.The duration of rest period can be set at equal effect that the rapid depolarization process reduces voltage reduce specified factor during, perhaps the duration of rest period can be set at and equal rest period during voltage reduce the needed time of specified factor.Certainly, also can set other rest period duration.
In another charging scheme of the present invention, the charging of HES can be used by regularly closing as mentioned above or disconnecting the current source be connected with HES and finish so that rest period to be provided, but also randomly changing at any time of its current value.Current value can be caught and can change in the scope that HES can be recharged, and in this case, when the voltage increment in the rest period reached a certain designated value, charging process was considered as.By this method, in case when the voltage increment in the rest period reaches designated value, also may continue charging with the voltage limit in the charge cycle, and magnitude of voltage is set at the magnitude of voltage when equaling last charge cycle and finishing.In this case, when the duration of part of the electric weight in the charge cycle or charge cycle reduces specified factor, or when voltage increment reached designated value, charging process was considered as finishing.
Especially about the method for this back, reach when wherein HES is by the standby power mode operation, the circulation recharge can carry out or carry out after reaching the maximum voltage value of appointment the fixed time at interval, is derived from the energy loss of the self discharge of HES with compensation.
Description of drawings
Except above mentioned feature, others of the present invention can find out that wherein the like reference numerals in institute's drawings attached refers to identical or equivalent features easily from the description of following accompanying drawing and exemplary embodiment, and wherein:
Fig. 1 illustrates the change in voltage and the variations in temperature of striding terminal in the process of constant current charge and discharge based on the capacitor module of HES.
Fig. 2 illustrates with different electric currents based on change in voltage between the capacitor module charge period of HES and the module variations in temperature that causes.
Fig. 3 illustrates changed based on the voltage increment of the terminal of the capacitor module of HES by electric weight part charge period span that the normalization charged state influences.
Fig. 4 is the block diagram of an exemplary embodiment of charger of the present invention.
The job order of charger between charge period of Fig. 5 graphic representation Fig. 4.
Fig. 6 is the block diagram of another exemplary embodiment of charger of the present invention.
The job order of the charger of Fig. 7 graphic representation Fig. 6.
Fig. 8 illustrates the change in voltage of striding based on the terminal of the capacitor module of HES after charging process is interrupted.
Fig. 9 illustrates under variable power the charge period span based on the change in voltage of the terminal of the capacitor module of HES.
Figure 10 is the job order of another charge operation embodiment.
Figure 11 illustrates during charge cycle and carries out the change in voltage of charge period span based on the terminal of the capacitor module of HES with voltage limit.
Figure 12 illustrates the change in voltage of striding based on the terminal of the capacitor module of HES when charging cycle is opened energy loss with compensation HES.
Embodiment
Several concrete but detailed description of exemplary embodiment of the present invention will provide below.
Example 1
By seven P that are connected in series
bO
2| H
2SO
4| the capacitor module that the HES of C system forms is recharged.In the voltage window of 2.4-0.8V, at room temperature the parameter of observed single HES is during with the 50A constant current charge:
Electric capacity 180kF
Coulomb capacity 62Ah
The energy 110Wh of transmission
Impedance (in the 50Hz frequency) 1.2mOhm
Self discharge electric current 50mA
Fig. 1 shows in the room temperature environment air voltage and the variations in temperature with this capacitor module in the process of 50A constant current charge and discharge.As shown in the figure, charged state increases, and reaches maximum U up to charging voltage
MaxTill=the 16.8V, begin to reduce along with continuing charging thereafter.
As shown in Figure 2, when capacitor module with the constant current of different value and when under the varying environment air themperature, charging, the voltage of capacitor module changes in a similar manner.Relevant in this voltage condition feature during the charging process and the HES device by " gas circulation ".The maximum U that is issued in these temperature conditions and a certain constant charge rate
MaxCorresponding to maximum charge amount Q
Opt
Fig. 3 illustrates voltage increment Δ U
MaxWith the optimum capacity value Q that is rated for module
OptCharging capacity between correlation.Experiment shows, all has this correlation for the charging current value of all permissions and the working temperature of module.Fig. 3 also shows the Coulomb capacity η under difference charging and discharge cycles pattern
QWith energy efficiency η
EVariation.Use these correlations to make and HES may be charged to the given charged state relevant with optimum value, and its desirable capacity of setting and energy loss level.
Fig. 4 illustrates an exemplary embodiment of charging device 2 of the present invention, and it can be used for HES is charged.HES module 1 is connected to charging device 2.As shown in the figure, charging device 2 comprises power supply 3, current sensitive element 4, quantity of electricity controller 5, voltage controller 6 and telegraph key 7.
This device 2 charges by the order shown in Fig. 5.With reference to figure 5, as can be seen, when charging device 2 is connected (S1), signal is sent to voltage controller 6 to measure initial voltage U
Ch0(S2).Voltage controller 6 is measured the voltage of the terminal of striding energy storage device and it is kept in the memory.Finish on the basis of these operations, the telegraph key 7 of charging circuit is switched on, and begins to count electric weight Q (S3).If surpassing, electric weight do not specify electric weight part Δ q
Set, then charging continues (S4).When reaching Δ q
SetThe time, quantity of electricity controller 5 provides signal and the value of electric weight is reset to zero to voltage controller 6.Voltage controller 6 is measured the voltage U of the terminal of striding HES module 1
Ch1(S5) and with it be kept in the memory.Afterwards, measured magnitude of voltage U
Ch1With the measuring voltage value U in the memory that is kept at controller
Ch0Compare and definite voltage increment U
Ch1-U
Ch0(S6).If U
Ch1-U
Ch0Difference surpass the value Δ U of preassignment
Set, then charging process continues, and the new value U that measures
Ch1Be kept in the memory of voltage controller 6.Thereafter, S3-S7 is repeated in the operation of this appointment, up to U
Ch1-U
Ch0Difference be lower than designated value Δ U
SetTill, at this moment voltage controller 6 is opened telegraph key 7, and charging process stops (S8).
In this specific examples, the value range delta q of recommendation
SetTest result based on dissimilar multiple electrochemical capacitors.The long-time running under circulation pattern of foreign peoples's capacitor shows that the optimum operation pattern is corresponding to the Coulomb capacity value between about 0.93-0.98.This means that stable circulation is moved needed capacitor and overcharged at specified (technical data sheet) Coulomb capacity Q of benchmark energy storage device
sAbout 0.02-0.08 between.Afterwards, for suitable control accuracy being provided and keeping desirable Coulomb capacity level, minimum and maximum electric weight partly is chosen as and overcharges than the best that low at least to be no less than 3 times (be Δ q to rate
Min≈ 0.007Q
sWith Δ q
Max≈ 0.03Q
s).
The accuracy rating of the measuring equipment that is associated with the charging process control system is also forced some requirement to Δ q value selection course.For example, be 3 the factor because the voltage increment of the terminal of striding the HES module that calculated should surpass that the absolute error Δ U of voltage measurement be no less than, then:
Δq
min≥3C?ΔU＝3κCU
max/100
Wherein C is corresponding to the electric capacity of HES module, and k represents the accuracy rating of measuring equipment, supposes U
MaxThe upper limit near the device measuring scope.
Therefore, specify the electric weight part by after stride the HES module terminal carry out voltage measurement, and it preferably is chosen as in below the scope:
min{0.007?Q
s；3κCU
max/100}＜Δq
set＜0.03Q
s(2)
In this example, based on expression formula (2), the value Δ q of electric weight part
SetBe set at 1000C.
Charge with the constant current of its value in the value scope that allows.When reaching the voltage increment value of appointment, charging process is finished.
For example, the advantage of this exemplary charging method can be demonstrated together with charging current is increased to 80A by the HES module being charged to preassignment voltage 16.8V.In this case, the voltage of striding the terminal of HES does not reach designated value.In addition, when charging continues, the temperature that voltage reduces and cause because of overcharging occurs and roll up.
Example 2
The HES module that its design proposes in the description of example 1 is charged.Fig. 6 is the block diagram that is used to carry out the charger 9 of described charging.HES module 8 is connected to charging device 9 once more.As shown in the figure, charging device 9 comprises power supply 10, current sensitive element 11, quantity of electricity controller 12, voltage controller 13, telegraph key 14 and abort timer 15.
This specific charging process is pressed the order shown in Fig. 7 and is carried out.Charge power change at random during charging process.In this specific examples, the charge power variation diagram is corresponding to the variation of the power output of wind-driven generator during the windy day of Russian center.
When connecting, charger 9 is given signal to abort timer 15, itself so that give signal to measure initial voltage U to voltage controller 13
R0(S9).Voltage controller 13 is measured the voltage of the terminal of striding the HES module and it is kept in the memory.Finish on the basis of these operations, signal is sent to timer 15 from voltage controller 13, and it provides the signal of connecting telegraph key 14 (S10) and starting quantity of electricity controller 12 (S11) then.If surpassing, electric weight do not specify electric weight part Δ q
Set, then charging continues (S12).Specify charge value Δ q when reaching
SetThe time, quantity of electricity controller 12 is reset to zero with charge value and also gives timer 15 signals, the duration t that it disconnects telegraph key 14 (S13) and begins rest period
rCounting (S14).If the duration of rest period does not reach designated value, then time counting continues.Reach designated value t when the duration of rest period
RsetThe time, timer 15 is given voltage controller 13 signals (S15).Afterwards, voltage controller 13 is measured the voltage U of the terminal of striding the HES module
R1(S16), determine voltage increment Δ U=U
R1-U
R0(S17), the value Δ U that preserves in the memory and with measured voltage increment value Δ U and controller
SetCompare.If voltage increment value Δ U surpasses designated value Δ U
Set, the new value U that measures
R1Be kept in the memory of controller 13, and controller 13 sends the signal (S18) that continues charging process to timer 15.Timer 15 is connected telegraph key 14 (S10) and quantity of electricity controller 12 (S11) once more, and repeats the step of S12-S17 appointment.Perhaps, if voltage increment value Δ U is lower than Δ U
Set, voltage controller 13 is opened timer 15 and charging process stops (S19).
In this certain exemplary embodiments, select the duration t of rest period based on the measurement of electrode depolarization rate
RsetFig. 8 shows the change in voltage in the single capacitor, and it initially is charged to voltage 2.4V charging current disconnection then with constant current.The empirical curve that the change in voltage of capacitor terminal is striden in expression approaches with following second order exponential function:
U＝U
0+2.9·10
-2·e
-t/tr1+4·10
-4·e
-t/tr2 (3)
T wherein
R1And t
R2Constant for process of depolarization.
U
0The value of=2.07V is determined the quiescent voltage based on the process of depolarization end setup that is full of capacitor.Value t
R1And t
R2In the same value scope that influenced by the capacitor charged state, change.Measurement shows, when different capacitor temperature, charge rate and charged state, is worth t
R1Be no more than 25 and t
R2Be no more than 200 seconds.During rest period, stride the time t of the terminal measuring voltage of capacitor
rFrom interval t
R1＜t
R, set＜t
R2Select.In this specific examples, the value t between the capacitor charge period
R, setBe set at 25 seconds.This means that the effect that the rapid depolarization process reduces voltage during rest period reduces e doubly, after this time expiration, the change in voltage in the capacitor is mainly determined by slow depolarising.
Electric current that charges under variable power in response to the HES module and change in voltage are as shown in Figure 9.As ise apparent from FIG. 9, reach several local maximum voltage value when under variable power the HES module being charged, these local maximums do not correspond to the optimal charge state.Near these local maximums, the value and the symbol of voltage increment all change.
In this specific examples, passing through to specify electric weight Δ q
SetInterrupt charging after the=1000C.If designated value Δ U
Set=0, be issued to the optimal charge state at this temperature conditions of module.As the voltage increment Δ U in rest period
rReach the value Δ U of preassignment
R, setThe time, the charging of HES module is finished.
Example 3
Capacitor energy storage device based on three modules that are connected in parallel is recharged.Each module is based on 100 N that are connected in series
iThe HES of OOH|KOH|C system.In the voltage window of 1.7-0.8V, at room temperature the single capacitor parameters with constant current charge is:
The electric capacity 100kF of capacitor
Internal resistance 0.5mOhm
The charging device that uses in this specific examples is as reaching aforesaid charging device 9 shown in Fig. 6.Power supply 10 comprises: the no more than 100kW of its power that consumes when specified charging current is provided from the transformer of 380V industrial electrical network to its 3 phase power that provide; Rectifier assembly; And pulse-phase control device.The relative error of current stabilization is ± 3%.The maximum of constant current is 450A.Maximum constant voltage is output as 220V.
Digital indicator in the Data Entry Panel is pressed the control panel arrangement.The parameter value of preassignment is from the keyboard input of control panel.The parameter of these preassignment comprises charging current value, electric weight part Δ q
Set, Δ U
Rset1With rest period t
R1, t
R2The value of duration.
The timer 15 of charging device 9 provides the signal of control telegraph key 14 and voltage controller 13 to keep the duration of needed charging and Abored Cycle.Telegraph key 14 is in response to the signal interruption charging process of coming self- controller 12,13 and timer 15.The charging of capacitor is pressed the order shown in Figure 10 and is carried out.The change in voltage of cross-module terminal as shown in Figure 11.
When connecting, charging device 9 provides signal to timer 15, itself so that provide signal to measure initial voltage U to voltage controller 13
R0Afterwards, voltage controller 13 is measured the voltage of cross-module terminal and it is kept at (S20) in the memory.Finish on the basis of these operations, be sent to timer 15 from the signal of voltage controller, it is used to connect telegraph key (S21) then and starts quantity of electricity controller 12 (S22).If surpassing, electric weight do not specify electric weight part Δ q
Set, then charging continues (S23).Specify electric weight Δ q when reaching
SetThe time, quantity of electricity controller 12 is reset to zero with charge value and also gives timer 15 signals, its starting resistor controller 13.If electric current can be used in the charging circuit, the voltage U of the terminal of controller 13 measurements cross-module 8
Ch1And it is kept at (S24) in the memory, disconnect telegraph key 14 (S25) thereafter and begin to count rest period t
R1(S26).If the duration of rest period does not reach designated value, rest period continues (S27).Reach the assignment t of institute when the duration of rest period
Rset1The time, timer 15 signals to voltage controller 13.Afterwards, the voltage U of the terminal of voltage controller 13 measurements cross-module 8
R1(S28), determine voltage increment Δ U=Δ U
R1-U
R0(S29), the value Δ U that preserves in the memory and with measured value and controller 13
R, set1Compare.If the value of Δ U surpasses designated value Δ U
R, set1, the new value U that measures
R1Be kept in the memory of controller 13, and controller gives the signal (S30) that timer 15 continues charging process.Under the situation that continues charging process, timer is connected telegraph key 14 (S21) once more and is started quantity of electricity controller 12 (S22), repeats the step of S23-S29 appointment thereafter.
Perhaps, if difference U
R1-U
R0(being voltage increment Δ U) is lower than Δ U
Set1, then timer 15 signals to voltage controller 13, and timer 15 is increased to t with duration (S31) of rest period
Rset2(S32-S33).When rest period finishes, the voltage U in voltage controller 13 measurements and the memory energy storage device 8
R0(S34).Thereafter, telegraph key 14 is switched on (S35), begins to measure electric weight (S36), and voltage controller 13 is switched to the continuous voltage measurement pattern.During charging process, the voltage of the terminal when cross-module 8 reaches value U
Ch1The time, voltage controller 13 signals to timer 15 and disconnects telegraph key 14 (S38), and also to quantity of electricity controller 12 signallings (S39).
If the electric weight Q that records between ending is lower than 0.1 Δ q
Set, then stop charging (S45).As Q＞0.1 Δ q
SetThe time, timer 15 countings are ended up to duration t
Rset2(S40-S41).Ending t
Rset2During end, timer 15 is to voltage controller 13.Afterwards, the voltage U of the terminal of voltage controller 13 measurements cross-module 8
R1(S42) and will measured value and be kept at value U in the memory of controller 13
R0Compare (S43).
If difference U
R1-U
R0Surpass designated value Δ U
Set2, the then new value U that measures
R0=U
R1Be kept in the memory of controller 13, and controller 13 signals (S44) to continue charging process to timer 15.Timer 15 is connected telegraph key 14 (S35) and quantity of electricity controller 12 (S36), as mentioned above.Perhaps, if difference U
R1-U
R0＜Δ U
Set2, then stop charging process (S45).
Before carrying out charging according to this exemplary embodiment, following data are transfused in the display of microcontroller:
Charging current 360A
Electric weight part Δ q during the charge cycle
Set3600C
Voltage increment value Δ U
Rset1+ 200mV
Between charge period be up to reaching the given voltage increment
The rest period duration t that ends
Rset11 second
Between with the voltage limit charge period in the charge cycle
Rest period duration t
Rset25 seconds
Electric weight in the condition charge cycle that charging is finished
Part reduces by 10 times
Afterwards, to being in the capacitor module charging of different initial state of charge.To fully charge duration (according to aforementioned algorithm) of needed charging process of module be 924 seconds.The value of rechargeable energy is 13.1kWh.With the 90A electric current to the module charge period between, the value of discharge energy is about 9.3kWh.
The duration of the charging process of the module of partial discharge is 186 seconds, and the value of rechargeable energy is about 2.3kWh.When with the 90A constant current module being discharged, the value of discharge energy is about 9.6kWh.The heating of capacitor when 18 ℃ of ambient temperatures is no more than 10 ℃.
Therefore, carry out with different initial state of charge levels even it will be appreciated by those skilled in the art that charging, last charging process enables to finish automatically charging process, and need not the end point voltage of initial setting up charging.
Example 4
The capacitor energy storage device is as stand-by power supply.Energy storage device comprises the capacitor module with ten HES that are connected in series.Described in the design of the single capacitor of this module and parameter such as the top example 3.In time course, the voltage of cross-module terminal reduces gradually.For compensating these energy losses, circulation is carried out other charging to module, begins to recharge when the preassignment value of the minimum voltage that reaches permission.
The block diagram that is used to carry out the described charging device that recharges 9 as shown in Figure 6.The voltage of the voltage controller 13 continuous measurement modules of charging device 9.When voltage was reduced to designated value, voltage controller signaled to timer 15 and connects charging device 9.By order Fig. 7 shown in charge thereafter.
Before charging, following data are transfused to relevant microcontroller:
Minimum voltage U
Min, when reaching this minimum voltage, to module
Automatically carry out other charging 17V
Electric weight part Δ q during the charge cycle
Set1000C
Voltage increment value Δ U
Rset0mV
Rest week between charge period till reaching the given voltage increment
1 second duration phase
When the voltage increment during rest period reached the value of preassignment, the charging of module was finished.The once duration of charging in addition is about 4-7 minute.
Figure 12 shows the change in voltage of terminal cross-module during recharging with the power supply with charge-variable power.
This example shows by means of other cycle charging and keeps capacitor device to be in the possibility of full state.No matter initial state of charge how, all can be carried out other charging, need not the temperature conditions of control capacitance apparatus, and use unsettled constant current source charging.
When some embodiments of the present invention were described in detail in the above, scope of the present invention should not be considered as being limited to these disclosures, can make amendment under the situation of the spirit of the present invention that does not deviate from the claims demonstration.
Claims (25)
1, the method for rechargeable electrochemical electric energy energy storage device comprises:
Described electrochemistry electric energy energy storage device is connected to the constant current electric energy;
Use electric energy that described electrochemistry electric energy energy storage device is charged from described constant current electric energy;
Measure the voltage of described electrochemistry electric energy energy storage device;
Measured voltage and scheduled voltage are compared; And
Based on the comparison of measuring voltage, or described electrochemistry electric energy energy storage device further charged, or stop described charging process;
Wherein to controlling by the specified portions of described rechargeable electrical energy by described electrochemistry electric energy energy storage device between charge period.
2, according to the process of claim 1 wherein that described electrochemistry electric energy energy storage device is an electrochemical capacitor.
3, according to the method for claim 2, wherein said electrochemical capacitor is foreign peoples's electric chemical super capacitor.
4, according to the process of claim 1 wherein that the specified portions of the rechargeable electrical energy that passed through by described electrochemistry electric energy energy storage device determines based on the capacitance of described electrochemistry electric energy energy storage device and the threshold sensitivity of register system.
5,, after the specified portions of described electrochemistry electric energy energy storage device, measure the voltage of the terminal of striding described electrochemistry electric energy energy storage device and determine voltage increment by described rechargeable electrical energy according to the process of claim 1 wherein.
6, according to the process of claim 1 wherein that described charging process is considered as finishing when voltage increment reaches scheduled voltage.
7, how all to carry out described charging process according to the process of claim 1 wherein regardless of the charged state of described electrochemistry electric energy energy storage device and/or the initial value of working temperature.
8, according to the method for claim 1, also comprise:
After the specified portions of rechargeable electrical energy was passed through by described electrochemistry electric energy energy storage device, circulation disconnected described constant current electric energy to produce interrupted charging and rest period, and each cycle has the duration;
When finishing, each rest period measures the voltage of described electrochemistry electric energy energy storage device;
The voltage that to measure when each rest period finishes compares with the measuring voltage that obtains in last rest period;
Use relatively more definite voltage increment of described voltage measurement; And
When reaching predetermined value, described voltage increment stops described charging process.
9, the method for rechargeable electrochemical electric energy energy storage device comprises:
Described electrochemistry electric energy energy storage device is connected to electric energy;
Use electric energy that described electrochemistry electric energy energy storage device is charged from described electric energy;
After the specified portions of rechargeable electrical energy was passed through by described electrochemistry electric energy energy storage device, circulation disconnected described electric energy to produce interrupted charging and rest period, and each cycle has the duration;
When finishing, each rest period measures the voltage of described electrochemistry electric energy energy storage device;
The voltage that to measure when each rest period finishes compares with the measuring voltage that obtains in last rest period;
Use relatively more definite voltage increment of described voltage measurement; And
Value based on described voltage increment stops described charging process;
Wherein to controlling by the specified portions of described rechargeable electrical energy by described electrochemistry electric energy energy storage device between charge period.
10, according to the method for claim 9, wherein said electric energy is the constant current electric energy.
11, according to the method for claim 9, wherein all described rest period are set to the constant duration.
12,, also be included in the voltage of measuring described electrochemistry electric energy energy storage device when each charge cycle finishes according to the method for claim 9.
13, according to the method for claim 9, the duration of wherein said rest period is set equal to the rapid depolarization process reduces role reduction specified factor to the voltage of described electrochemistry electric energy energy storage device time.
14, according to the method for claim 9, the voltage that the duration of wherein said rest period is set equal to described electrochemistry electric energy energy storage device during rest period reduces the needed time of specified factor.
15, according to the method for claim 9, the current value of wherein said electric energy is change at random in the current value range that allows.
16, according to the method for claim 9, wherein in a single day described voltage increment reaches predetermined value, continues charging with the voltage limit during the charge cycle, the magnitude of voltage that described voltage limit equals last charge cycle when finishing.
17, according to the method for claim 9, wherein how all to carry out charging process regardless of the charged state of described electrochemistry electric energy energy storage device and/or the initial value of working temperature.
18, according to the method for claim 9, also comprising circulated to described electrochemistry electric energy energy storage device at interval with the fixed time recharges to compensate the self discharge energy loss of described electrochemistry electric energy energy storage device.
19, according to the method for claim 9, wherein when reaching predetermined value, described voltage increment stops described charging process.
20, the method for rechargeable electrochemical electric energy energy storage device comprises:
Described electrochemistry electric energy energy storage device is connected to the electric energy of current value with change at random;
Use electric energy that described electrochemistry electric energy energy storage device is charged from described electric energy;
After the specified portions of rechargeable electrical energy had been passed through by described electrochemistry electric energy energy storage device, circulation disconnected described electric energy and has the interrupted rest period of duration with generation;
When finishing, each rest period measures the voltage of described electrochemistry electric energy energy storage device;
The voltage that to measure when each rest period finishes compares with the measuring voltage that obtains in last rest period;
Use relatively more definite voltage increment of described voltage measurement; And
Value based on described voltage increment stops described charging process;
Wherein to controlling by the specified portions of described rechargeable electrical energy by described electrochemistry electric energy energy storage device between charge period.
21, according to the method for claim 20, wherein all described rest period are set to the constant duration.
22, according to the method for claim 20, wherein in a single day described rest period voltage increment reaches predetermined value, continues charging with the voltage limit during the charge cycle, the magnitude of voltage that described voltage limit equals last charge cycle when finishing.
23, according to the method for claim 22, wherein when reducing specified factor, the amount of the electric energy that offers described electrochemistry electric energy energy storage device during the described charge cycle stops charging process.
24, according to the method for claim 22, wherein when reducing specified factor, stops the duration of described charge cycle described charging process.
25, according to the method for claim 20, also comprising circulated to described electrochemistry electric energy energy storage device at interval with the fixed time recharges to compensate the self discharge energy loss of described electrochemistry electric energy energy storage device.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86727106P | 2006-11-27 | 2006-11-27 | |
| US60/867,271 | 2006-11-27 | ||
| US11/945,827 | 2007-11-27 |
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| Publication Number | Publication Date |
|---|---|
| CN101657947A true CN101657947A (en) | 2010-02-24 |
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ID=41711157
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200780050527 Pending CN101657947A (en) | 2006-11-27 | 2007-11-27 | The charging method of double electric layer electrochemical capacitors |
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| CN (1) | CN101657947A (en) |
| UA (1) | UA100848C2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114156957A (en) * | 2020-09-07 | 2022-03-08 | 北京小米移动软件有限公司 | Battery charging method, device and storage medium |
| CN115178501A (en) * | 2022-07-12 | 2022-10-14 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Screening method of high-reliability solid electrolyte tantalum capacitor |
-
2007
- 2007-11-27 CN CN 200780050527 patent/CN101657947A/en active Pending
- 2007-11-27 UA UAA200906750A patent/UA100848C2/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114156957A (en) * | 2020-09-07 | 2022-03-08 | 北京小米移动软件有限公司 | Battery charging method, device and storage medium |
| CN115178501A (en) * | 2022-07-12 | 2022-10-14 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Screening method of high-reliability solid electrolyte tantalum capacitor |
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| Publication number | Publication date |
|---|---|
| UA100848C2 (en) | 2013-02-11 |
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Application publication date: 20100224 |