CN103163478A - Method for detecting capacity of attenuated lithium ion secondary battery - Google Patents
Method for detecting capacity of attenuated lithium ion secondary battery Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 9
- 229910001416 lithium ion Inorganic materials 0.000 title description 9
- 230000002238 attenuated effect Effects 0.000 title 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 44
- 229910052744 lithium Inorganic materials 0.000 claims description 44
- 238000005259 measurement Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 230000005059 dormancy Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 5
- 230000004087 circulation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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Abstract
The invention relates to a method for detecting the capacity of an attenuated lithium ion secondary battery. The method comprises the following steps of: acquiring alternating-current internal resistance and discharge capacity of a lithium ion secondary battery for multiple times at selected temperature in the selected charge state; performing data processing on the acquired alternating-current internal resistance and discharge capacity data to obtain an alternating-current internal resistance-discharge capacity fitted curve of the alternating-current internal resistance and discharge capacity; when the capacity of the attenuated lithium ion secondary battery is needed to be measured, only measuring alternating-current internal resistance which is measured in the same charge state at the same temperature in the same frequency as those of the acquisition of the alternating-current internal resistance; and comparing the measured alternating-current internal resistance with the alternating-current internal resistance-discharge capacity fitted curve to obtain the capacity of the attenuated lithium ion secondary battery. The method has the advantages that the capacity is estimated according to the linear relation of the alternating-current internal resistance and the battery capacity, so that the waste of time, energy and funds due to multi-time charging and discharging is avoided, and the detection speed and high detection accuracy are high.
Description
Technical field
The invention belongs to the lithium ion secondary battery capacity detection technique, relate in particular to the capacity check method of a kind of lithium rechargeable battery after overdamping.
Background technology
Lithium rechargeable battery has the advantages such as voltage is high, specific energy is high, recycle often, storage time is long, not only be used widely as mobile phone, Digital Video and laptop computer on portable electric appts, and be widely used in the big-and-middle-sized electrical equipment such as electric automobile, electric bicycle, electric tool and the aspects such as power station and emergency standby power.Therefore more and more higher to the performance requirement of lithium rechargeable battery.
Particularly with lithium rechargeable battery as emergency standby power the time, more important to the assurance of battery capacity attenuation situation after the some time uses.But when using as emergency power pack, take to be discharged to 100%DOD(Depth of Discharge depth of discharge) assay method will make power supply lose emergent effectiveness within a period of time and lose time, the energy and funds.Discharge the fully method of (namely being discharged to 100%DOD) of battery is measured battery capacity, namely with battery discharge to the sparking voltage of manufacturer's regulation or the minimum of electric current.If after battery discharges fully, just outage, emergency power pack can't be powered, and also just can't play emergent effectiveness.Number of patent application: 201010265668.0 disclose a kind of method and system of estimating remaining available capacity of lithium ion power battery pack.The method is by recording current value in charging process and charging time used, the total active volume when adopting the ampere-hour integral method to calculate lithium rechargeable battery to begin to discharge, thus obtain the value A of the total active volume of lithium rechargeable battery; Record open-circuit voltage and voltage drop Δ V in discharge process, select to calculate residue active volume percent curvilinear function used by voltage drop Δ V, obtain the percent a of lithium rechargeable battery residue active volume; Utilize the relation between temperature and the available SOC of residue, obtain the service efficiency of remaining battery active volume SOC under Current Temperatures; The A*a* addition of all batteries is the residue active volume of lithium ion secondary batteries.The system that realizes the method is voltage, electric current and the temperature monitoring module that comprises for the monitoring battery pack information, and this monitoring module feeds back to MCU with the information that monitors, the remaining available capacity of lithium ion power battery pack output that MCU obtains estimation.This patent shortcoming 1. comes the total volume of estimating battery inaccurate with A, has ignored the problem of efficiency for charge-discharge.Namely be charged into the electric weight of battery and be not equal to the electric weight that battery can be emitted.2. the residual capacity of cell voltage V and battery is nonlinear relation; And in the battery use procedure, the voltage of battery-discharge capacity curve can change, therefore come estimated capacity and out of true with magnitude of voltage V.
Application number: 201210488606.5 disclose a kind of battery capacity method for quick of lithium rechargeable battery, comprise step: the first step: choose arbitrary number in all batteries as the sample electric battery, then measure the actual discharge capacity of each battery in the sample electric battery; Second step: the open-circuit voltage of measuring each battery in the sample electric battery; The 3rd step: according to actual discharge capacity and the open-circuit voltage of each battery in the sample electric battery, obtain the corresponding relation between actual discharge capacity and open-circuit voltage; The 4th step: measure respectively open-circuit voltage for each battery remaining except the sample electric battery; The 5th step: according to the actual discharge capacity of each battery and the corresponding relation between open-circuit voltage, obtain the actual discharge capacity of remaining each battery.This invention can be carried out efficiently a plurality of lithium rechargeable batteries actual discharge capacity under different condition, detect quickly.This patent shortcoming 1. is certain to there are differences between different samples because the consistance of making can't guarantee.And it is inevitable inaccurate to remove to demarcate undeterminate measuring object with the sample of measuring in discrepant situation.2. the residual capacity of cell voltage V and battery is nonlinear relation; And in the battery use procedure, the voltage of battery-discharge capacity curve can change, therefore come estimated capacity and out of true with magnitude of voltage V.3. the method needs sample is discharged to demarcate discharge capacity fully, is unfavorable for Emergency use.And the waste of produce power, funds.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned technology, the capacity check method of a kind of lithium rechargeable battery after overdamping is provided, by the residual capacity of measurement lithium rechargeable battery and the AC internal Resistance at certain temperature, according to AC internal Resistance-discharge capacity matched curve, draw battery capacity attenuation degree at that time, the estimating battery capacity.Need not to adopt the conventional method of battery discharge 0% to 100%DOD, can estimating battery capacity attenuation degree.
The present invention for achieving the above object, by the following technical solutions: the capacity check method of a kind of lithium rechargeable battery after overdamping, comprise the following steps,
1) under selected state-of-charge and selected temperature conditions, gather the discharge capacity data of its AC internal Resistance data and depth of discharge from 0% to 100% for lithium rechargeable battery several times to be measured;
2) with in the AC internal Resistance and discharge capacity data typing computer that collect, process by data, obtain the AC internal Resistance of AC internal Resistance and discharge capacity-discharge capacity matched curve;
3) survey lithium rechargeable battery in use procedure in the future, when needing to measure its capacity after decay after a while, when only needing to measure state-of-charge identical when gathering AC internal Resistance before, uniform temp, with the AC internal Resistance of same frequency measurement;
4) with the AC internal Resistance before the AC internal Resistance contrast that records-discharge capacity matched curve, can obtain the capacity of battery after decay.
The a-c cycle that uses during described measurement lithium rechargeable battery AC internal Resistance is defined in 700 to 1300Hz.
Described lithium rechargeable battery is the linear matched curve of capacity after fixation measuring frequency, fixed temperature and the AC internal Resistance fixedly measured under the state-of-charge condition and decay.
The number of times at least twice of the AC internal Resistance of described collection lithium rechargeable battery and discharge capacity data.
Beneficial effect: compared with prior art, the AC internal Resistance under the residual capacity by measuring lithium rechargeable battery and certain temperature conditions is processed the linear matched curve that obtains internal resistance and capacity by data; In the lithium rechargeable battery use procedure, when needs are measured the capacity of lithium rechargeable battery after decay after a while, only need to measure under the SOC state identical with gathering before lithium rechargeable battery, temperature and the condition with same frequency, the AC internal Resistance that collects and AC internal Resistance before-discharge capacity matched curve compare, and can obtain the capacity of battery after decay.According to the linear relationship of AC internal Resistance and battery capacity, capacity is estimated, avoided can obtaining higher detection speed and precision simultaneously by the waste that repeatedly discharges and recharges time of causing, the energy and funds aspects.Especially be applicable to polymkeric substance and square lithium ion secondary battery, avoided repeatedly discharging and recharging the waste on time that detection brings, funds, the energy, can obtain higher detection speed and precision.
Description of drawings
Fig. 1 is that lithium rechargeable battery normally discharges and recharges schematic diagram;
Fig. 2 is the view of lithium rechargeable battery after decay after a while;
Fig. 3 is the AC internal Resistance-discharge capacity curve map of embodiment 1;
Fig. 4 is the AC internal Resistance-discharge capacity curve map of embodiment 2;
Fig. 5 is the AC internal Resistance-discharge capacity curve map of embodiment 3.
Embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with preferred embodiment.
The invention provides the capacity check method of a kind of lithium rechargeable battery after overdamping, comprise the following steps,
1) under selected state-of-charge and selected temperature conditions, gather the discharge capacity data of its AC internal Resistance data and depth of discharge from 0% to 100% at least for lithium rechargeable battery several times to be measured (twice);
2) with in the AC internal Resistance and discharge capacity data typing computer that collect, process by data, obtain the AC internal Resistance of AC internal Resistance and discharge capacity-discharge capacity matched curve;
3) survey lithium rechargeable battery in use procedure in the future, when needing to measure its capacity after decay after a while, when only needing to measure state-of-charge identical when gathering AC internal Resistance before, uniform temp, with the AC internal Resistance of same frequency measurement;
4) with the AC internal Resistance before the AC internal Resistance contrast that records-discharge capacity matched curve, can obtain the capacity of battery after decay.
The a-c cycle that uses during described measurement lithium rechargeable battery AC internal Resistance is defined in 700 to 1300Hz.
Described lithium rechargeable battery is the linear matched curve of capacity after fixation measuring frequency, fixed temperature and the AC internal Resistance fixedly measured under the state-of-charge condition and decay.
Theoretical analysis
As shown in Figure 1, normally discharge and recharge schematic diagram for lithium rechargeable battery.As shown in the figure, N is negative pole, and P is that lithium ion, G are barrier film for anodal, X.
As shown in Figure 2, repeating to discharge and recharge use or after storage after a while, containing the film M of Li and form the battery performance decay because generate in negative terminal surface.If the capacitance loss that causes thus is Q.If the thickness of film M is t, in film, the density of Li is that d(is considered as film M the uniform material of material herein), S is the cross-sectional area after cutting off along the Y-Y line.Formula is arranged 1.
Q=d×t×S ……①
The lithium rechargeable battery AC impedance R that records
ACCan be for thinking the impedance R of the film that generated by negative terminal surface
FilmWith other impedances R
0Common formation.2. represent with formula
Ｒ
AC＝Ｒ
film＋Ｒ
0 ……②
R herein
ACFor battery is applied in the alternating voltage of certain frequency and the measured AC impedance of alternating current.At this moment, R
0Can be considered and be constant.
The film of anticathode Surface Creation carries out following setting, and the resistivity that contains the film M of Li is ρ (film M being considered as the uniform material of material herein), and the thickness of film is t, and its cross-sectional area is S, R
FilmCan 3. be represented by formula
Ｒ
film＝ρ·t／Ｓ ……③
By formula 1. 2. 3.,
R
AC＝R
film+R
0
(bringing formula 3 into)
(bringing formula 1 into)
Be R
AC=A * Q+B(A, B are constant)
The AC impedance R of secondary cell as can be known
ACCan be expressed as formula 4. with the relation of capacitance loss Q
Ｒ
AC＝Ａ×Ｑ＋Ｂ ……④
A wherein, B is all constant.The AC impedance and the capacitance loss that namely record are linear.
If the battery initial capacity is Q
0, the capacity after decay is Q
Rest, have
Q
rest=Q
0-Q ……⑤
And Q
0Also a constant, so the residual capacity Q after cell decay
RestWith AC impedance R
ACAlso linear.
The parameter ρ in formula on business, S, d, R
0, the frequency that applies during all with temperature, SOC state, measurement battery AC internal Resistance is relevant, so when measuring, the temperature in the time of guaranteeing to measure battery, SOC state and a-c cycle used are consistent as far as possible.So just can make the capability value of deriving according to the AC internal Resistance of measuring more accurate.
The present invention does not have specific (special) requirements to tested battery selected temperature and SOC state.Only need when measuring, guarantee with before in advance the temperature of measurement, the SOC state is identical gets final product.
When making matched curve, the measurement of data is also nonessentially carried out when the finished product that lithium rechargeable battery has just been made, and also can use or the measurement midway of storage, get point, drawing.
Embodiment 1
Selecting nominal capacity is the lithium rechargeable battery (being 1C=16.5A) of 16.5Ah.Under 25 ℃ of conditions, use 1C electric current constant-current charge to 3.65V, then constant-voltage charge to electric current to be reduced to 1C/20(be 0.825A) time charging cut-off.The charged state of this moment is defined as 100%SOC, i.e. 0% depth of discharge (Depth of discharge abridge DOD).When using the 1C current discharge to 2.0V, the discharge cut-off, the state of this moment is defined as 100%DOD, i.e. 0%SOC.It is the process of " to 100%DOD, dormancy 2min recharges afterwards to 100%SOC, dormancy 2min with battery discharge " with the 1C circular in definition.
The battery of the present embodiment in the loop test process midway, respectively after the 0th time (namely before the circulation), 21 times, 49 times, 98 times circulations, under 25 ℃ of conditions, frequency of utilization is that the AC internal Resistance of battery has at that time been measured and recorded to the measuring equipment of 1000Hz, getting X-axis is the AC internal Resistance value, Y-axis is the capability value after decaying, and does scatter diagram and simulates linearity curve by data processing software (adopting Excel and MiniTab in this experiment).
The AC internal Resistance of measured value and loose point-discharge capacity curve map as shown in Figure 3, (internal resistance VS capacity after circulation)
Wherein " calculated capacity " is the AC internal Resistance-discharge capacity straight line according to match, different AC internal Resistance value R
ACThe capability value of correspondence on fitting a straight line." actual capacity " is discharged to the discharge capacity of 100%DOD for the last time by 0%DOD before measuring the internal resistance of cell." deviation " is the ratio of difference and actual capacity both.
By above-mentioned chart as can be known, minimum according to the capability value that AC internal Resistance-the discharge capacity curve estimation goes out and the deviation between the actual capability value that records of match after measuring AC internal Resistance, can be used for the estimation to normal temperature circulation, 100%SOC state battery capacity.
Battery experimental procedure in the present embodiment is as follows:
1. under 25 ℃ of conditions, first use the 1C electric current with battery discharge to 2.0V, dormancy 2min, then with the current charges 38min of 1C/2, dormancy 2min adjusts to the 30%SOC state with battery;
2. measure and record the AC internal Resistance of battery, after internal resistance measurement is completed, under 25 ℃ of conditions, with battery with 1C electric current constant-current charge to 3.65V, then constant-voltage charge is reduced to 1C/20 to electric current, dormancy 2min; The 1C constant-current discharge records this discharge capacity to 2.0V, dormancy 2min; With the current charges 38min of 1C/2, dormancy 2min readjusts the 30%SOC state with battery again.
3. battery is placed under 25 ℃ of conditions and stores a period of time, measure the AC internal Resistance of battery.
Certain interval of time repeating step 2 and step 3, repeatedly record battery under the 30%SOC state later on, the AC internal Resistance of different times and corresponding capacity thereof.
As shown in Figure 4, the AC internal Resistance of measured value and scatter diagram-discharge capacity curve map (normal temperature storage 30%SOC internal resistance VS capacity)
| AC internal Resistance/m Ω | Actual capacity/Ah | Calculated capacity/Ah | Deviation |
| 4.171 | 16.561 | 16.544 | 0.108% |
| 4.183 | 16.411 | 16.437 | 0.161% |
| 4.207 | 16.234 | 16.225 | 0.056% |
By above-mentioned chart as can be known, minimum according to the capability value that AC internal Resistance-the discharge capacity curve estimation goes out and the deviation between the actual capability value that records of match after measuring AC internal Resistance, can be used for the estimation to normal temperature storage, 30%SOC state battery capacity.
Embodiment 3
Battery experimental procedure in the present embodiment is as follows:
1. under 25 ℃ of conditions, use 1C electric current constant-current charge to 3.65V, then the charging cut-off when being reduced to 1C/20 of constant-voltage charge to electric current.Dormancy 2min.When re-using the 1C current discharge to 2.0V, dormancy 2min.Record this discharge capacity.
2. use 1C electric current constant-current charge to 3.65V, then the charging cut-off when being reduced to 1C/20 of constant-voltage charge to electric current.Dormancy 2min.Battery is adjusted to the 100%SOC state.Measure and record the battery AC internal Resistance of this moment.
3. battery is put into 60 ℃ of incubator a period of times (at least 10 hours, consistent with environment temperature to guarantee internal temperature of battery, thus the purpose of the storage that reaches a high temperature).
4. battery is taken out cooling in standing 6 hours under 25 ℃ of environment from incubator.
5. capacity and the AC internal Resistance of battery repeatedly measured and recorded to repeating step 1 to the process of step 4.
As shown in Figure 5, the AC internal Resistance of measured value and scatter diagram-discharge capacity curve map (high temperature storage 100%SOC internal resistance VS capacity)
| AC internal Resistance/m Ω | Actual capacity/Ah | Calculated capacity/Ah | Deviation |
| 4.50 | 15.458 | 15.492 | 0.217% |
| 4.85 | 13.368 | 13.292 | 0.570% |
| 5.13 | 11.490 | 11.532 | 0.365% |
By above-mentioned chart as can be known, minimum according to the capability value that AC internal Resistance-the discharge capacity curve estimation goes out and the deviation between the actual capability value that records of match after measuring AC internal Resistance, can be used for the estimation to high temperature storage, 100%SOC state battery capacity.
SOC(state of charge) refer to state-of-charge.Claim again residual capacity, the ratio of the capacity of the residual capacity charged state complete with it after lithium rechargeable battery uses a period of time or lies idle for a long time, percentage commonly used represents.SOC=1 namely is expressed as the battery full state.Must consider its state-of-charge when controlling the lithium rechargeable battery operation.
Equally, this detection method also can be applicable to polymer lithium ion secondary battery, and its concrete testing process and above-mentioned square lithium ion secondary battery are similar, do not repeat them here.
The above is only preferred embodiment of the present invention, is not structure of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment does.
Claims (4)
1. the capacity check method of a lithium rechargeable battery after overdamping is characterized in that: comprise the following steps,
1) under selected state-of-charge and selected temperature conditions, gather the discharge capacity data of its AC internal Resistance data and depth of discharge from 0% to 100% for lithium rechargeable battery several times to be measured;
2) with in the AC internal Resistance and discharge capacity data typing computer that collect, process by data, obtain the AC internal Resistance of AC internal Resistance and discharge capacity-discharge capacity matched curve;
3) survey lithium rechargeable battery in use procedure in the future, when needing to measure its capacity after decay after a while, when only needing to measure state-of-charge identical when gathering AC internal Resistance before, uniform temp, with the AC internal Resistance of same frequency measurement;
4) with the AC internal Resistance before the AC internal Resistance contrast that records-discharge capacity matched curve, can obtain the capacity of battery after decay.
2. the capacity check method of lithium rechargeable battery according to claim 1 after overdamping, it is characterized in that: the a-c cycle that uses during described measurement lithium rechargeable battery AC internal Resistance is defined in 700 to 1300Hz.
3. the capacity check method of lithium rechargeable battery according to claim 1 and 2 after overdamping is characterized in that: described lithium rechargeable battery is the linear matched curve of capacity after fixation measuring frequency, fixed temperature and the AC internal Resistance fixedly measured under the state-of-charge condition and decay.
4. the capacity check method of lithium rechargeable battery according to claim 3 after overdamping, is characterized in that: the number of times twice of the AC internal Resistance of described collection lithium rechargeable battery and discharge capacity data at least.
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