CN103801521A - Sorting method of secondary batteries - Google Patents
Sorting method of secondary batteries Download PDFInfo
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- CN103801521A CN103801521A CN201410041257.1A CN201410041257A CN103801521A CN 103801521 A CN103801521 A CN 103801521A CN 201410041257 A CN201410041257 A CN 201410041257A CN 103801521 A CN103801521 A CN 103801521A
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Abstract
The invention relates to a sorting method of secondary batteries. The sorting method comprises the following steps: selecting featured charge states corresponding to to-be-sorted batteries, acquiring electrochemical alternating-current impedance spectroscopy of the to-be-sorted batteries, extracting two-dimensional feature parameters of the to-be-sorted batteries, and then determining battery monomers combined to form a battery pack. According to the internal features of the parts, from a charging platform to a charging cut-off voltage, of the secondary batteries, the consistency of the essentially sorted batteries is better than that of batteries sorted by a conventional method, the integral performance of the battery pack is improved, and the service life is prolonged.
Description
Technical field:
The present invention relates to a kind of battery sorting method, more specifically relate to a kind of method for separating of secondary cell.
Background technology:
Secondary cell is for energy storage technology, is limited to the reasons such as capacity, voltage, the energy/power of battery cell be limited, must, by after connection in series-parallel in groups, just can reach the electric pressure of stored energy application, the requirement of energy/power grade.The quantity of stack battery is directly related with the specific requirement of the specification of monomer, stored energy application, and the overall performance of battery after be in groups not equal to simply adding of cell performance and, because causing battery, the uniformity difference between battery cell there is afterwards in groups " wooden barrel effect ", the overall performance of battery after is in groups limited by the poorest battery cell of performance, especially be starkly lower than especially the service life of battery cell in service life, this situation is had a greatly reduced quality the stored energy application effect of secondary cell, both limit the performance of battery performance, improved again use cost.
For this situation, there is the sorting technology of secondary cell, secondary cell in groups before, from numerous batteries, filter out the approaching battery cell of uniformity by technological means, get rid of the battery cell differing greatly, reduce the harmful effect of " wooden barrel effect ", screen battery by sorting technology and carry out again integrated in groups, improve the overall performance of battery pack, and increase the service life.
But, current traditional sorting technology is the capacity with battery cell mostly, voltage, the external characteristics parameters such as internal resistance are that index is screened, be characterized in that screening time is short, efficiency is high, can complete rapidly sorting, its shortcoming is the uniformity that the battery cell that goes out take these external characteristics parameters as index screening can only guarantee these indexs often, cannot reflect the uniformity of inside battery feature, and along with battery manufacturers quality management, the raising of technical merit, these external characteristics parameters are substantially just very approaching in the stage of dispatching from the factory, conventional method for separating is difficult to effectively distinguish the fine difference between battery cell in " resolution ratio ", this conventional sorting technology has just lost meaning in such cases.
The uniformity of battery cell in groups, its external presentation is capacity, voltage, these external characteristics parameters of internal resistance, its inherence is the uniformity of inside battery at all.Battery in groups after, " wooden barrel effect " is mainly reflected in batteries charging latter stage, first indivedual battery cells reach charge cutoff voltage, and other battery cell voltages are lower, long this circulates down, cause indivedual batteries to overcharge for a long time, other batteries are the phenomenon for being full of for a long time, the further like this difference of having accelerated between the interior monomer of battery pack.
In batteries charging latter stage, the voltage of secondary cell can rise rapidly from charging voltage platform, then reach charge cutoff voltage, there is obvious concentration polarization phenomenon in inside battery in this process, carrier increases at the diffusional resistance of inside battery, because of the existence of battery pole piece surface electric double layer effect, also can show certain capacity effect simultaneously.The application be exactly in the battery by secondary cell charge voltage is risen to this one-phase of charge cutoff voltage from charging platform the uniformity of carrier dispersal behavior and Capacitance Dispersion effect carry out the sorting of secondary cell.
Summary of the invention:
The object of this invention is to provide a kind of method for separating of secondary cell, the method improves the overall performance of battery pack, and increases the service life.
For achieving the above object, the present invention is by the following technical solutions: a kind of method for separating of secondary cell, said method comprising the steps of:
(1) choose and treat sorting battery characteristic of correspondence state-of-charge;
(2) electrochemical AC impedance for the treatment of sorting battery described in collection is composed;
(3) treat the two dimensional character parameter of sorting battery described in extracting;
(4) be identified for being combined into the battery cell of a battery pack.
The method for separating of a kind of secondary cell provided by the invention, in described step (1) by treating that maximum curvature in the charging curve of sorting battery is worth corresponding point and determines feature state-of-charge.
The method for separating of a kind of secondary cell provided by the invention, if described maximum curvature value is more than two, selects to approach most the maximum curvature value of the corresponding point of blanking voltage in described charging curve.
The method for separating of another preferred a kind of secondary cell provided by the invention, described charging curve is below charge-discharge magnification 1 multiplying power, treats that to described the monomer of sorting battery carries out the last charging curve of three complete charge and discharge cycles.
The method for separating of a preferred a kind of secondary cell more provided by the invention, determines the curvature function of described last charging curve by numerical analysis; Described curve is considered as to the functional relation of independent variable time and dependent variable voltage.
The method for separating of another preferred a kind of secondary cell provided by the invention, described functional relation carries out Nonlinear Numerical matching by described last charging curve to be determined, thereby determines its curvature function.
The method for separating of another preferred a kind of secondary cell provided by the invention, is characterized in that: described curvature function through type (1) is determined:
K(t)=|d
2V(t)/dt
2|/(1+(dV(t)/dt)
2)
3/2 （1）
In formula, V, t are respectively voltage and the time in described last charging curve;
Described last charging curve is carried out to secondary differentiate; Determine first derivative (t, dV (t)/dt) front, first by carrying out smoothing processing and removing assorted point and the abnormal discrete point in its data described last charging curve, described first derivative (t, dV (t)/dt) curve is carried out smoothing processing and removes the new assorted point producing in a differentiate process obtaining dV (the t)/dt in formula (1) with abnormal discrete point; To described formula (1) dV (t)/dt again a differentiate obtain second dervative (t, d
2v (t)/dt
2), to described second dervative (t, d
2v (t)/dt
2) curve carries out smoothing processing again and remove in secondary differentiate process the new assorted point producing and abnormal discrete point obtains the d in formula (1)
2v (t)/dt
2.
The method for separating of another preferred a kind of secondary cell provided by the invention, in described step (2) by the battery for the treatment of sorting in feature state-of-charge, shelve 6-12 hours; Carry out again the suffered electrochemical AC impedance test for the treatment of sorting battery.
The method for separating of another preferred a kind of secondary cell provided by the invention, described ac impedance spectroscopy frequency range is at 0.01Hz-0.1Hz, the collection in 5mV-10mV of its amplitude.
The method for separating of another preferred a kind of secondary cell provided by the invention, in described step (3), choose the impedance spectrum of described ac impedance spectroscopy frequency range in 0.01Hz-0.1Hz, carry out linear fit by least square method, obtain the functional relation formula (2) of described linear segment:
Z
Im＝k·Z
Re+b （2）
Wherein, Z
refor the real part of impedance Z, Z
imfor the imaginary part of impedance Z, b is the intercept of linear segment real axis in ac impedance spectroscopy for this reason, Ohmic resistance, electrochemical reaction resistance and diffusion resistance information that its value comprises secondary cell; Slope k value has reflected the information of secondary cell electric capacity dispersion effect.
The method for separating of another preferred a kind of secondary cell provided by the invention, treats that by extracting the two dimensional character parameter k of sorting battery and b are identified for being combined into the battery cell of a battery pack described in n in described step (4).
The method for separating of another preferred a kind of secondary cell provided by the invention, described two dimensional character parameter is reflected in two-dimensional space, according to the battery cell number m treating in groups, from two-dimensional space, solve m immediate point, this m the corresponding battery cell separately of point be the battery cell that can be used for being combined into a battery pack sub-electing.
With immediate prior art ratio, the invention provides technical scheme and there is following excellent effect
1, technical scheme of the present invention is according to secondary cell this part of inside battery feature from charging platform to charge cutoff voltage, and the battery consistency of selecting than conventional method for separating from the battery sub-electing is in essence better;
2, technical scheme of the present invention is to carry out the sorting of battery with the difference of the behavior of inside battery carrier diffusion and capacity effect, from " resolution ratio ", can distinguish more significantly the difference degree between battery population sample;
3, technical scheme of the present invention is utilized electrochemical AC impedance spectral technology, extract two dimensional character parameter by solving of low frequency linear segment, avoid design and the matching of equivalent circuit, both shortened the time, avoided again equivalent circuit to resolve the uncertain problem causing;
4, the consistency problem that technical scheme of the present invention faces battery sorting is converted into two-dimensional space closest approach to Solve problems, makes the sorting of battery more rationally, intuitively;
5, method of the present invention improves the overall performance of battery pack, and increases the service life.
Accompanying drawing explanation
Fig. 1 is the flow chart of the inventive method;
Fig. 2 is the ferric phosphate lithium cell 0.3C charging curve schematic diagram of battery sorting of the present invention;
Fig. 3 is the lithium titanate battery 0.5C charging curve schematic diagram of battery sorting of the present invention;
Fig. 4 is two dimensional character parameter extraction schematic diagram in the present invention;
Fig. 5 be in the present invention the discrete point in two-dimensional space to schematic diagram;
Fig. 6 be in the present invention two-dimensional space closest approach to solving schematic diagram.
The specific embodiment
Below in conjunction with embodiment, the invention will be described in further detail.
Embodiment 1:
As shown in Fig. 1-6, the method for separating of a kind of secondary cell of invention of this example, said method comprising the steps of:
(1) treat choosing of sorting battery characteristic of correspondence state-of-charge;
The secondary cell monomer for the treatment of sorting carries out complete charge and discharge cycles three times, selects to boost the charging curve of this section of curve in charging curve, and charge-discharge magnification is below 1 multiplying power; The described secondary cell monomer for the treatment of sorting comprises ferric phosphate lithium cell and lithium titanate battery.
Described last charging curve is considered as to the functional relation V (t) of independent variable time t and dependent variable voltage V, by numerical analysis, solves the curvature function K (t) of V (t);
Described numerical analysis comprises following process: the one, described last charging curve is carried out to Nonlinear Numerical matching, obtain the functional relation V(t of obvious parameter value and functional form), then this function is asked to curvature K (t);
The 2nd, described last charging curve is carried out to smoothing processing, remove test initial data (t, V) (t is the time for the assorted point in and abnormal discrete point, V is voltage), then directly the charging curve after level and smooth is carried out to a differentiate, obtain first derivative (t, dV (t)/dt), again to described first derivative (t, dV (t)/dt) curve carries out smoothing processing, removes the new assorted point producing and abnormal discrete point in a differentiate process and obtains dV (t)/dt, then described dV (t)/dt carried out to a differentiate again, obtain second dervative (t, d
2v (t)/dt
2), to described second dervative (t, d
2v (t)/dt
2) curve carries out smoothing processing again, remove the new assorted point producing and abnormal discrete point in secondary differentiate process and obtain d
2v (t)/dt
2, then according to the computing formula of curvature (1), calculate curvature K (t).
K(t)=|d
2V(t)/dt
2|/(1+(dV(t)/dt)
2)
3/2 （1）
In formula, d
2v (t)/dt
2for described second dervative (t, d
2v (t)/dt
2) curve carries out smoothing processing again, remove the assorted point of new generation in secondary differentiate process and the result that abnormal discrete point obtains, dV (t)/dt is described first derivative (t, dV (t)/dt) curve carries out smoothing processing, removes the result that in a differentiate process, the new assorted point producing and abnormal discrete point obtain.
Get the maximum of curvature function K (t) near described last charging curve blanking voltage, the state-of-charge of the corresponding battery of time point t that this curvature maximum occurs, is exactly sorting battery characteristic of correspondence state-of-charge point, as shown in Figures 2 and 3.
(2) the electrochemical AC impedance spectrum for the treatment of sorting battery described in gathers;
Adjustment treats that the battery of sorting, in feature state-of-charge, shelves 6---12 hours, treat the electrochemical AC impedance test of sorting battery, and at frequency 0.01Hz---0.1Hz, amplitude 5mV---in 10mV, gather ac impedance spectroscopy.
(3) described in, treat the two dimensional character parameter extraction of sorting battery;
Choose the impedance spectrum linear segment in the above frequency range of 10mHz, carry out linear fit by least square method, obtain the functional relation of this linear segment:
Z
Im＝k·Z
Re+b （1）
Wherein, Z
refor the real part of impedance Z, Z
imfor the imaginary part of impedance Z, b value is the intercept of linear segment real axis in ac impedance spectroscopy for this reason, the information such as Ohmic resistance, electrochemical reaction resistance and diffusion resistance that its value has comprised secondary cell; Slope k value, has reflected the information of secondary cell electric capacity dispersion effect, as shown in Figure 4.
(4) be identified for being combined into the battery cell of a battery pack;
By above three steps, extract two dimensional character parameter b and the k of n battery sample treating sorting, these 2-D datas are reflected in two-dimensional space, show as the discrete point pair being distributed in two-dimensional space, as shown in Figure 5;
According to the battery cell number m treating in groups, from two-dimensional space, solve m right to immediate point, this m to correspondence battery cell separately, is the battery cell that can be used for being combined into a battery pack sub-electing to point; This solution procedure is the process that adopts substep to calculate, and makes successively the histogram of two dimensional character parameter point on k axle and b direction of principal axis, selects first three the most concentrated region of distribution number strong point, as shown in Figure 6, k axle is 1,2,3 districts, b axle is 4,5th, 6 district, wherein in the part of k axle and b axle area coincidence, distribution maximum region of counting is the region that will select, and the data point in region to being that point the most approaching, the most concentrated distribution is right each other in this at this lot sample.Complete thus right the solving in two-dimensional space closest approach.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit, although the present invention is had been described in detail with reference to above-described embodiment, those of ordinary skill in the field are to be understood that: still can modify or be equal to replacement the specific embodiment of the present invention, and do not depart from any modification of spirit and scope of the invention or be equal to replacement, it all should be encompassed in the middle of this claim scope.
Claims (12)
1. a method for separating for secondary cell, is characterized in that: said method comprising the steps of:
(1) choose and treat sorting battery characteristic of correspondence state-of-charge;
(2) electrochemical AC impedance for the treatment of sorting battery described in collection is composed;
(3) treat the two dimensional character parameter of sorting battery described in extracting;
(4) be identified for being combined into the battery cell of a battery pack.
2. the method for separating of a kind of secondary cell as claimed in claim 1, is characterized in that: in described step (1) by treating that maximum curvature in the charging curve of sorting battery is worth corresponding point and determines feature state-of-charge.
3. the method for separating of a kind of secondary cell as claimed in claim 2, is characterized in that: if described maximum curvature value is more than two, select to approach most the maximum curvature value of the corresponding point of blanking voltage in described charging curve.
4. the method for separating of a kind of secondary cell as claimed in claim 3, is characterized in that: described charging curve, for below charge-discharge magnification 1 multiplying power, treats that to described the monomer of sorting battery carries out the last charging curve of three complete charge and discharge cycles.
5. the method for separating of a kind of secondary cell as claimed in claim 4, is characterized in that: the curvature function of determining described last charging curve by numerical analysis; Described curve is considered as to the functional relation of independent variable time and dependent variable voltage.
6. the method for separating of a kind of secondary cell as claimed in claim 5, is characterized in that: described functional relation carries out Nonlinear Numerical matching by described last charging curve to be determined, thereby determines its curvature function.
7. the method for separating of a kind of secondary cell as claimed in claim 5, is characterized in that: described curvature function through type (1) is determined:
K(t)=|d
2V(t)/dt
2|/(1+(dV(t)/dt)
2)
3/2 （1）
In formula, V, t are respectively voltage and the time in described last charging curve;
Described last charging curve is carried out to secondary differentiate; Determine first derivative (t, dV (t)/dt) front, first by carrying out smoothing processing and removing assorted point and the abnormal discrete point in its data described last charging curve, described first derivative (t, dV (t)/dt) curve is carried out smoothing processing and removes the new assorted point producing in a differentiate process obtaining dV (the t)/dt in formula (1) with abnormal discrete point; To dV (the t)/dt in described formula (1) again a differentiate obtain second dervative (t, d
2v (t)/dt
2), to described second dervative (t, d
2v (t)/dt
2) curve carries out smoothing processing again and remove in secondary differentiate process the new assorted point producing and abnormal discrete point obtains the d in formula (1)
2v (t)/dt
2.
8. the method for separating of a kind of secondary cell as claimed in claim 1, is characterized in that: in described step (2) by the battery for the treatment of sorting in feature state-of-charge, shelve 6-12 hours; Carry out again the suffered electrochemical AC impedance test for the treatment of sorting battery.
9. the method for separating of a kind of secondary cell as claimed in claim 8, is characterized in that: described ac impedance spectroscopy frequency range is at 0.01Hz-0.1Hz, the collection in 5mV-10mV of its amplitude.
10. the method for separating of a kind of secondary cell as claimed in claim 9, it is characterized in that: in described step (3), choose the impedance spectrum of described ac impedance spectroscopy frequency range in 0.01Hz-0.1Hz, carry out linear fit by least square method, obtain the functional relation formula (2) of described linear segment:
Z
Im＝k·Z
Re+b （2）
Wherein, Z
refor the real part of impedance Z, Z
imfor the imaginary part of impedance Z, b is the intercept of linear segment real axis in ac impedance spectroscopy for this reason, Ohmic resistance, electrochemical reaction resistance and diffusion resistance information that its value comprises secondary cell; Slope k value has reflected the information of secondary cell electric capacity dispersion effect.
The method for separating of 11. a kind of secondary cells as claimed in claim 1, is characterized in that: in described step (4), treat that by extracting the two dimensional character parameter k of sorting battery and b are identified for being combined into the battery cell of a battery pack described in n.
The method for separating of 12. a kind of secondary cells as claimed in claim 11, it is characterized in that: described two dimensional character parameter is reflected in two-dimensional space, according to the battery cell number m treating in groups, from two-dimensional space, solve m immediate point, this m the corresponding battery cell separately of point be the battery cell that can be used for being combined into a battery pack sub-electing.
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Cited By (12)
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| CN104866872A (en) * | 2015-06-03 | 2015-08-26 | 哈尔滨工业大学 | Multi-feature parameter battery equivalent grouping method |
| CN105583170A (en) * | 2016-01-28 | 2016-05-18 | 珠海光宇电池有限公司 | Method for screening lithium ion batteries |
| CN106289566A (en) * | 2016-07-19 | 2017-01-04 | 清华大学 | A kind of method secondary cell internal temperature estimated based on electrochemical impedance |
| CN106311634A (en) * | 2016-08-30 | 2017-01-11 | 北京华特时代电动汽车技术有限公司 | Battery module screening method and power battery pack screening method |
| CN106483464A (en) * | 2015-08-31 | 2017-03-08 | 丰田自动车株式会社 | The method for separating of recycling nonaqueous electrolytic solution secondary battery |
| CN108535650A (en) * | 2017-03-01 | 2018-09-14 | 苏州协鑫集成科技工业应用研究院有限公司 | Li-ion batteries piles consistency discrimination method and system |
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| CN109731808A (en) * | 2018-11-30 | 2019-05-10 | 天合光能股份有限公司 | The detection method for separating that a kind of pair of lithium battery echelon utilizes |
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| CN104866872B (en) * | 2015-06-03 | 2018-06-05 | 哈尔滨工业大学 | The battery equivalent group technology of more characteristic parameters |
| CN104866872A (en) * | 2015-06-03 | 2015-08-26 | 哈尔滨工业大学 | Multi-feature parameter battery equivalent grouping method |
| CN106483464B (en) * | 2015-08-31 | 2019-06-21 | 丰田自动车株式会社 | The method for separating of recycling nonaqueous electrolytic solution secondary battery |
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| CN105583170B (en) * | 2016-01-28 | 2017-12-26 | 珠海光宇电池有限公司 | A kind of screening technique of lithium ion battery |
| CN106289566B (en) * | 2016-07-19 | 2018-12-11 | 清华大学 | A method of secondary cell internal temperature is estimated based on electrochemical impedance |
| CN106289566A (en) * | 2016-07-19 | 2017-01-04 | 清华大学 | A kind of method secondary cell internal temperature estimated based on electrochemical impedance |
| CN106311634A (en) * | 2016-08-30 | 2017-01-11 | 北京华特时代电动汽车技术有限公司 | Battery module screening method and power battery pack screening method |
| CN108535650A (en) * | 2017-03-01 | 2018-09-14 | 苏州协鑫集成科技工业应用研究院有限公司 | Li-ion batteries piles consistency discrimination method and system |
| CN108957323B (en) * | 2017-05-18 | 2021-02-02 | 中信国安盟固利动力科技有限公司 | Method and device for judging health state of battery |
| CN108957323A (en) * | 2017-05-18 | 2018-12-07 | 中信国安盟固利动力科技有限公司 | A kind of judgment method and device of cell health state |
| CN108828453B (en) * | 2018-06-29 | 2020-11-03 | 深圳市科列技术股份有限公司 | Method and device for acquiring charging data of power battery |
| CN108828453A (en) * | 2018-06-29 | 2018-11-16 | 深圳市科列技术股份有限公司 | A kind of acquisition methods and device for power battery charging data |
| CN109731808A (en) * | 2018-11-30 | 2019-05-10 | 天合光能股份有限公司 | The detection method for separating that a kind of pair of lithium battery echelon utilizes |
| CN110280500A (en) * | 2019-06-21 | 2019-09-27 | 深圳博磊达新能源科技有限公司 | A kind of screening technique of lithium ion battery |
| CN110826023A (en) * | 2019-11-13 | 2020-02-21 | 国网电力科学研究院有限公司 | Method for improving resolution of running data of battery system |
| CN110826023B (en) * | 2019-11-13 | 2023-08-25 | 国网电力科学研究院有限公司 | Method for improving resolution of battery system operation data |
| CN111679215A (en) * | 2020-06-19 | 2020-09-18 | 中国电力科学研究院有限公司 | Lithium battery real-time sorting method, device, equipment and storage medium |
| CN111679215B (en) * | 2020-06-19 | 2022-07-26 | 中国电力科学研究院有限公司 | Lithium battery real-time sorting method, device, equipment and storage medium |
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