CN103487762A - Screening method for lithium ion batteries - Google Patents
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Abstract
The invention discloses a screening method for lithium ion batteries. With the wide application of lithium-ion power / energy storage batteries, some of the lithium ion batteries are degraded untimely in the using process. Therefore, the health status of the lithium ion batteries needs predicting and distinguishing in advance to remove or combine the batteries with different degradation degrees in a graded mode so as to avoid potential safety hazards occurring to a battery system and improve the operation efficiency of the battery system. According to the screening method for the lithium ion batteries, an electrochemical frequency spectrum method is used for judging the degradation degrees of the batteries quickly and providing a reliable method for screening the batteries. Therefore, the screening method for the lithium ion batteries is quite suitable for rapid evaluation and graded screening of a large number of batteries in use and has remarkable practical value and a good effect in respect of gradual utilization of power lithium ion batteries.
Description
Technical field
The present invention relates to a kind of lithium ion battery method for sieving, belong to the energy and technical field.
Background technology
Lithium ion battery is because it has the significant advantages such as specific energy is high, specific power is high, have extended cycle life, operating temperature range is wide, efficiency for charge-discharge is high, not only be widely used as the Power Support of the portable type electronic products such as mobile phone, notebook computer, digital camera, being also the core of the technical field of new energies such as electric automobile, photovoltaic engineering, wind power generation, the peak load stations development of current urgent development, is equally also indispensable vitals in fields such as military affairs, space flight.But after using after a while, huge variation can occur in whole battery system when battery, as the efflorescence of positive and negative pole material, the dilution of electrolytic solution, and the degeneration of SEI film etc., this all will have a strong impact on after the effect of battery use.Especially be applied to the lithium ion battery in the large-scale energy storage systems such as electric automobile, energy-accumulating power station, the performance difference of cell in groups, self to discharge and recharge temperature, self-discharge rate not identical yet, the cell difference that continuous charge and discharge cycles causes is amplified, all will make the capacity of electric battery accelerate decay, premature deterioration even appears in the partial monosomy battery, has greatly affected the normal operation of accumulator system.Therefore, need to predict in advance and to differentiate the health status of battery, in-service battery is carried out to Fast Evaluation and sizing screening, the battery of the different degradations of rejecting or hierarchical composition, avoid the potential safety hazard of battery system and improve operational efficiency.
At present, the method of test battery health status has much both at home and abroad, mainly contain definition method, partial discharge method, voltage curve fitting process etc., major part is based on the external characteristic of battery, parameters such as electric current, voltage, power, capacity, judge the health status of battery with the variation of Life Cycle according to parameter, these class methods are simple, but length consuming time, accuracy requirement is high, be subject to such environmental effects large, and frequently battery carried out to the actual active volume that deep discharge itself also can reduce battery.Due to battery inner electrochemical reaction that series of complex occurs in charge and discharge process, the mechanism of lithium battery capacity decay is very complicated, great many of experiments confirms, lithium battery is after long-term the use, very large variation has occurred in inside, at first be embodied in the obvious increase of both positive and negative polarity impedance, be secondly that the electrolytic solution of inside battery decomposes, positive and negative pole material structural failure and coming off etc.Therefore, using the bulk properties of battery as point of penetration, judge that by internal resistance the research of cell health state is also more and more.IEEE has voted a standardization draft through in April, 1992, the conventionally test method of suggestion accumulator changes admittance or testing impedance into by original float charge voltage test.Impedance spectrum by test battery is the health status of reaction cell to a certain extent.The present invention adopts the electrochemical frequency spectral method to judge fast the degradation of battery, for battery screening provides reliable method.Therefore, the present invention is very suitable for using in a large number Fast Evaluation and the sizing screening of battery, and the echelon utilization of power lithium-ion battery is had to significant practical value and good effect.
Summary of the invention
The present invention seeks to disclose a kind of lithium ion battery method for sieving.It is characterized in that adopting the electrochemical frequency spectral technology, the impedance situation of each component of express-analysis inside battery, by the data fitting analysis, the health status of precognition and judgement battery.Adopt the advantage of measuring the electrochemical impedance spectral method to be, can record the very impedance spectrum of wide frequency ranges and carry out the Electrode system, obtain the information that the method more conventional than other obtains more dynamic information and electrode interface structure, reflect really the variation of battery performance by the variation of electrode structure, thereby reach the purpose of the degradation of accurate judgement battery.
The object of the invention is completed by following technical scheme.
A kind of lithium ion battery method for sieving, it is characterized in that adopting the electrochemical frequency spectral technology, at 2 ~ 20mV, the sinusoidal wave sweep frequency adopted is in 100K ~ 0.1 m Hz scope, adopt the sine wave of different frequency to carry out spectrum scan to battery system, obtain resistance value and the phase angle relation curve to frequency, and then, by each component impedance variation of equivalent electrical circuit sunykatuib analysis inside battery, the standard of the degradation of judgement battery is:
(1) if mean inside battery contact impedance value (Re) initial value of cycle battery (Re0) not relatively, Re is less than 1/10 of Re0, or Re is greater than 10 times of Re0, and battery lost efficacy, can not use;
(2) be greater than 3 times of cycle battery not if flatten the diameter of semicircle in impedance spectrum, can think that battery lost efficacy, can not use;
(3), if a new circular arc occurred at straight-line segment in impedance spectrum, show that battery is in the slump of disastrous proportions stage, the Non-Gradable combination;
(4) if impedance spectrum does not have large variation, show that this battery is in normal operating conditions, can carry out hierarchical composition.
The effect of technical scheme of the present invention is: adopt the electrochemical frequency spectral technology to measure the impedance situation of each component of inside battery, and by the data fitting analysis, the health status of anticipation battery.This electrochemical frequency spectral technology, under certain modulation current potential, adopt the sine wave of different frequency to carry out spectrum scan to battery system, obtain resistance value and the phasing degree relation curve to frequency, and then by each component impedance variation of equivalent electrical circuit sunykatuib analysis inside battery.Analyze the simulating equivalent circuit of impedance in described employing electrochemical frequency spectral technology as depicted in figs. 1 and 2.Wherein, Fig. 1 represents AC impedance model when battery performance is good.Re is ohmic internal resistance, comprises the internal resistance of electrolytic solution internal resistance, barrier film internal resistance, collector and collector and electrode interface etc., and Rct is that electric charge shifts internal resistance, and Q is constant phase angle element, and W is the Warburg impedance of reaction diffusion mass transfer process.AC impedance model when Fig. 2 represents the battery performance slump of disastrous proportions.
The accompanying drawing explanation
Fig. 1 is to analyze the equivalent electrical circuit of impedance when in instructions of the present invention, battery performance is good.
Fig. 2 is to analyze the equivalent electrical circuit of impedance when in instructions of the present invention, battery performance fails.
Fig. 3 is that in the embodiment of the present invention, battery carries out the cycle life curve of charge and discharge cycles under 0.5C, 1C and tri-kinds of different multiplying of 2C.
Fig. 4 is the change curve of the AC impedance of 0.5C multiplying power cycle battery in the embodiment of the present invention with the circulating cycle number.
Fig. 5 is the change curve of the AC impedance of 1C multiplying power cycle battery in the embodiment of the present invention with the circulating cycle number.
Fig. 6 is the change curve of the AC impedance of 2C multiplying power cycle battery in the embodiment of the present invention with the circulating cycle number.
concrete embodiment.
Embodiment
The battery that the present invention uses is No. 5 ferric phosphate lithium cells, and its charging upper limit voltage is 3.65V, and discharge cut-off voltage is 2.0V, and nominal capacity is 550mAh.
The charge and discharge circulation life experiment that adopts the charge-discharge test instrument to carry out battery, the electrochemical AC impedance spectrum test that adopts electric impedance analyzer to carry out battery.
The charge and discharge circulation life experiment that battery is carried out is specific as follows:
Choose 9 well behaved new batteries, be divided into three groups, adopt respectively different multiplying powers to carry out the cycle life experiment to three Battery packs.Charging process all adopts the first constant current pattern of constant voltage again, and discharge process all adopts constant-current discharge.Wherein, the first Battery pack is first with 0.5C(1C=550mA) current charges to 3.65V, then constant-voltage charge, until electric current drops to 0.1C, complete charging process; During electric discharge, adopt identical electric current 0.5C to be discharged to cut-off voltage 2.0V, as one-period, carry out circulation experiment.The charging process of the second Battery pack be current charges with 1C to 3.65V, then constant-voltage charge to electric current drops to 0.1C; Discharge process adopts the 1C current discharge to cut-off voltage 2.0V.The 3rd Battery pack is with the current charges of 2C to 3.65V, then constant-voltage charge to electric current drops to 0.1C, and battery is full of, and then adopts the 2C current discharge to ending 2.0V, battery emptying.
Fig. 3 is for adopting 0.5C, 1C and tri-kinds of different multiplying of 2C to carry out the cycle life curve of the battery of charge and discharge cycles.As can be seen from the figure, the capability retention that battery circulates after 800 weeks under 0.5C and 1C multiplying power is respectively 88.55% and 81.10%, and in whole cyclic process, battery capacity is linear reduction with the increase of circulating cycle number, and decay slowly; And after the circulating battery under the 2C multiplying power 200 weeks, capability retention is only 58.59%, circulate 50 weeks afterwards battery capacity start sharp-decay, after circulation in battery capacity be exponential decay with the increase of circulating cycle number.Explanation thus, adopt the circulating battery of 0.5C and the circulation of 1C multiplying power after 800 weeks, and battery performance still keeps well, in follow-up circulation, can also working; And the circulating battery of 2C multiplying power circulation is after 50 weeks, it is deteriorated that its performance just occurs, deteriorated further serious in follow-up circulation, can not meet the needs of normal operation.
The electrochemical AC impedance test experiments that battery is carried out is specific as follows:
Choose three batteries that carry out the cycle life experiment under different multiplying, when circulating battery proceeds to 0,50,100,200,400,800 cycle, battery when the emptying electricity condition, the AC impedance of test battery.Experiment adopts the ex situ EIS method of testing that constant potential and potential value are open-circuit voltage, and the sinusoidal voltage amplitude is 10 mV, and sweep frequency is in 10K ~ 10m Hz scope, obtains the ac impedance spectroscopy (EIS) of the different circulating cycle numbers of battery.Then set up corresponding equivalent electrical circuit and carry out Fitting Analysis, thereby obtain the variation tendency with the circulating cycle number corresponding to the impedance situation of each component of battery, the current degradation of judgement battery.
Fig. 4 is to be the variation tendency of the AC impedance of 0.5C multiplying power cycle battery with the circulating cycle number.As can be seen from the figure, all EIS mainly characterize by high frequency region the rectilinear(-al) that the circular arc of charge transfer process and slope that low frequency range characterizes diffusion process are 45 °.Along with the carrying out of circulation, the battery ohmic internal resistance changes little, and the high frequency region circular shape does not have significant change, and the radius-of-curvature first increases and then decreases shows that battery system is after circulation in 50 weeks is activated, and charge transfer process is further easy; The straight basic of low frequency range does not change.After this explanation battery circulates 600 weeks under the 0.5C multiplying power, significant change does not occur in each component impedance of battery, and battery performance still keeps well, consistent with the cyclic lifetime test results in Fig. 1.
The AC impedance that Fig. 5 is 1C multiplying power cycle battery is with the variation tendency of circulating cycle number.As can be seen from the figure, all EIS mainly characterize by high frequency region the rectilinear(-al) that the circular arc of charge transfer process and slope that low frequency range characterizes diffusion process are 45 °.In whole cyclic process, the ohmic internal resistance of battery is all in 0.1 Ω left and right.In circulation in first 50 weeks, the radius-of-curvature of high frequency region circular arc die-offs, and from the cyclic process of 100 weeks to 800 weeks, it is stable that the circular arc radius-of-curvature keeps, show battery in circulation early stage in activation stage, charge transfer process carries out more easily and keeps stable afterwards.And circulating battery is while proceeding to 100 weeks, circular arc in the medium and low frequency district departs from more obviously with respect to desirable semicircle, one section small arc-shaped has also indistinctly appearred in the initial rank of straight line herein end than first week, from the cyclic process of 400 weeks to 100 weeks, the small arc-shaped of straight line initiating terminal almost disappears.Battery cycle life curve under the 1C multiplying power in corresponding diagram 1, since 100 weeks, the rate of decay of battery capacity obviously increased, until, after circulation in 400 weeks, the decay of battery capacity tends towards stability.Show thus, when the battery capacity rate of decay changes, in the battery electrochemical impedance spectrum, the straight-line segment that characterizes the electrode interface diffusion process also can be along with changing.It is more obvious that this phenomenon shows in the ac impedance spectroscopy of 2C multiplying power cycle battery.
Fig. 6 is to be the variation tendency of the AC impedance of 2C multiplying power cycle battery with the circulating cycle number.As can be seen from the figure, circulating battery to 50 is during week, and the straight line that characterizes diffusion process variation just occurred in the medium and low frequency district, in follow-up circulation, an obvious capacitive reactance arc has appearred in the straight line initiating terminal, and whole EIS curve is by two sections irregular circular arcs and a rectilinear(-al) that slope is 45 °.Cycle life curve corresponding to battery in Fig. 1 under the 2C multiplying power, battery capacity occurred die-offing after 50 weeks, and was exponential decay in follow-up circulation.Explanation thus, when battery performance occurs seriously when deteriorated, the upper low frequency range straight line of the EIS spectrogram initiating terminal of battery there will be one section new circular arc.
Therefore, the degradation mode of battery performance is mutually corresponding with the ac impedance spectroscopy of battery, can judge by the EIS of test battery the degradation of battery, especially when the actual measurement capacity of some batteries is suitable, if wherein the EIS curve of a joint or two batteries is different from other, in the medium and low frequency district, new circular arc has appearred in the straight line initiating terminal, illustrates that this joint or two batteries performances have entered the serious deteriorated stage, need to reject and change, use to treat him; And other batteries still keep good performance, can continue normal use, also for the sizing screening of battery, carried for scientific basis thus.
Claims (1)
1. a lithium ion battery method for sieving, it is characterized in that adopting the electrochemical frequency spectral technology, at 2 ~ 20mV, the sinusoidal wave sweep frequency adopted is in 100K ~ 0.1 m Hz scope, adopt the sine wave of different frequency to carry out spectrum scan to battery system, obtain resistance value and the phase angle relation curve to frequency, and then, by each component impedance variation of equivalent electrical circuit sunykatuib analysis inside battery, the standard of the degradation of judgement battery is:
If mean inside battery contact impedance value (Re) initial value of cycle battery (Re0) not relatively, Re is less than 1/10 of Re0, or Re is greater than 10 times of Re0, and battery lost efficacy, can not use;
Be greater than 3 times of cycle battery not if flatten the diameter of semicircle in impedance spectrum, can think that battery lost efficacy, can not use;
If a new circular arc occurred at straight-line segment in impedance spectrum, show that battery is in the slump of disastrous proportions stage, the Non-Gradable combination;
If impedance spectrum does not have large variation, show that this battery is in normal operating conditions, can carry out hierarchical composition.
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| CN103884995A (en) * | 2014-03-13 | 2014-06-25 | 清华大学 | Impedance measurement system and method for secondary batteries |
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| CN105576318A (en) * | 2016-02-23 | 2016-05-11 | 上海电力学院 | Multi-parameter comprehensive determination method for determining consistency of electric automobile retired lithium batteries |
| CN105665309A (en) * | 2015-11-20 | 2016-06-15 | 上海展枭新能源科技有限公司 | Screening method for echelon utilization of lithium ion capacitors |
| CN105738830A (en) * | 2016-04-14 | 2016-07-06 | 中山大学 | Cascade utilization analyzing method for lithium-ion power batteries |
| CN106597305A (en) * | 2016-12-09 | 2017-04-26 | 合肥国轩高科动力能源有限公司 | Cycle life prediction method of lithium ion battery |
| CN106772099A (en) * | 2017-01-23 | 2017-05-31 | 合肥国轩高科动力能源有限公司 | A kind of dynamic lithium battery degradation evaluation method |
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| CN109143106A (en) * | 2018-08-09 | 2019-01-04 | 南京卡耐新能源技术发展有限公司 | A method of battery consistency is quickly detected by ac impedance measurement |
| CN110118942A (en) * | 2019-05-22 | 2019-08-13 | 北京科技大学 | A kind of detection method of lithium battery chemical polarization impedance |
| CN110556487A (en) * | 2019-08-30 | 2019-12-10 | 深圳先进储能材料国家工程研究中心有限公司 | Secondary battery and efficient screening method thereof |
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| CN111638257A (en) * | 2020-06-03 | 2020-09-08 | 兰州理工大学 | Test method for voltage resolution in-situ electrochemical alternating-current impedance |
| CN114047444A (en) * | 2021-11-09 | 2022-02-15 | 中国南方电网有限责任公司超高压输电公司广州局 | Storage battery health condition evaluation method and device |
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