CN104360284A - Novel detection method for self-discharge characteristics of lithium iron phosphate system power lithium ion batteries - Google Patents
Novel detection method for self-discharge characteristics of lithium iron phosphate system power lithium ion batteries Download PDFInfo
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Abstract
The invention discloses a novel detection method for self-discharge characteristics of lithium iron phosphate system power lithium ion batteries. The method comprises the following steps: step 1, charging and discharging batteries, and adjusting SOC (System On Chip) states of the batteries to be 20-40%; step 2, standing for a certain period of time at normal temperature, and measuring open-circuit voltage (OCV)1 of the batteries; step 3, performing high-temperature aging on the batteries; step 4, standing for a certain period of time at normal temperature, and then detecting OCV2 of the batteries; step 5, calculating a voltage drop deltaU of the batteries, wherein deltaU is equal to OCV1-OCV2; and step 6, calculating an average value and standard deviations of the voltage drops of the same group of batteries, determining a self-discharge detection standard of the batteries, and screening. The method for detecting the self-discharge characteristics of the batteries by virtue of voltage differences of the batteries disclosed by the invention can be used for well shielding interference of factors such as equipment, operations and environment temperature existing in a manufacturing process of the batteries in the self-discharge data acquisition accuracy of the batteries, so that the self-discharge characteristic data distortion of a single battery can be avoided, the matching reliability of the batteries can be effectively improved, and the cycle life of a battery pack can be prolonged.
Description
Technical field
The invention belongs to field of lithium ion battery, relate to the characterization processes that ferric phosphate lithium power lithium-ion battery manufactures, specifically, relate to a kind of ferric phosphate lithium power lithium-ion battery self-discharge characteristics new detecting method, be included in after battery partial volume terminates and carry out the characterization processes processes such as SOC state (state-of-charge) adjustment, voltage determination, high temperature ageing, battery screening.
Background technology
Along with the development of global economy, the consumption of human society to the energy increases day by day, fossil resources is day by day exhausted, the problems such as simultaneously environment deteriorations, unusual weather conditions grow in intensity, and developing with lithium ion battery is that the new-energy automobile technology of power becomes one of grand strategy direction that many national future source of energys develop.Lithium ion battery has because of it a kind of energy storage or electrokinetic cell that energy density is high, the life-span is long, self discharge is little, memory-less effect, advantages of environment protection become combination property the best in electrochmical power source.And for the battery pack system that multiple cell forms, output energy, the output power of whole battery pack system and depend on one piece of battery that in battery pack system, performance is the poorest serviceable life, also just mean that the inconsistency of battery is the key factor of the whole battery pack system stability of impact and reliability.And the principal element affecting battery consistency is the voltage of battery, internal resistance, the performance parameter such as capacity and self discharge.First three items data all can comparatively accurately and reliably obtain, and self-discharge of battery detection data are comparatively difficult, detect the traditional method of self-discharge of battery characteristic and be vulnerable to the factors interference such as checkout equipment, operational method and environment temperature, affect the accuracy of self-discharge of battery data, and then affect performance reliability and the cycle life of electric battery.
Lithium ion battery self discharge characteristic is normally evaluated by the change of some performance parameters of ageing process battery.Traditional self-discharge characteristics be by compare battery before ageing after the decay of capacity evaluate self-discharge characteristics level, the method before ageing after all need adopt charging/discharging apparatus discharge and recharge process is carried out to battery, carrying out being subject in battery capacity data gatherer process the many factors impact such as environment temperature of equipment precision, equipment holder contacts situation, mode of operation and charge and discharge process, cause aging before with aging after procurement of reserve capacity condition there is larger deviation, affect data acquisition accuracy.
Summary of the invention
Fundamental purpose of the present invention is by improving the self discharge detection method of ferric phosphate lithium power lithium-ion battery, improves the accuracy that self discharge detects data acquisition, thus promotes battery performance stability and improve the battery cyclic life-span.
For achieving the above object, the invention provides a kind of new detecting method of ferric phosphate lithium power lithium-ion battery self-discharge characteristics, the method comprises following steps:
Step 1, adopts certain electric current to carry out charge-discharge cycles several times to battery, then adopt different electric current several times constant-current discharge the SOC state of battery is adjusted to 0%, then adopt recharge-discharge pattern that the SOC state of battery is adjusted to specified states;
Step 2, battery leaves standstill the regular hour at normal temperatures after step 1 terminates, and measures the open-circuit voltage OCV1 of battery;
Step 3, loads onto aging clamp by battery, puts into high-temperature aging room and carries out high temperature ageing;
Step 4, high temperature ageing terminates, and battery is shelved certain hour at normal temperatures, then detects battery open circuit voltage OCV2;
Step 5, calculates the voltage drop Δ U of battery, Δ U=OCV1-OCV2
Step 6, calculates the mean value of same Battery pack voltage drop
with standard deviation s, wherein,
According to voltage drop mean value and standard deviation data screening spec battery.
Above-mentioned LiFePO4 system power lithium-ion battery self-discharge characteristics new detecting method, wherein, in described step 1, described different electric current substep is repeatedly in constant-current discharge, and each step current value reduces gradually.
Above-mentioned LiFePO4 system power lithium-ion battery self-discharge characteristics new detecting method, wherein, the SOC state that in described step 1, battery is last is 20% ~ 40%.
Above-mentioned LiFePO4 system power lithium-ion battery self-discharge characteristics new detecting method, wherein, the time left standstill under normal temperature in described step 2 is 12 ~ 36h.
Above-mentioned LiFePO4 system power lithium-ion battery self-discharge characteristics new detecting method, wherein, in described step 3, the cell degradation time is 7 ~ 28 days.
Above-mentioned LiFePO4 system power lithium-ion battery self-discharge characteristics new detecting method, wherein, the temperature that in described step 3, battery high-temperature is aging is set to 35 ~ 45 DEG C.
Above-mentioned LiFePO4 system power lithium-ion battery self-discharge characteristics new detecting method, wherein, in described step 6, the screening criteria of battery is: cell voltage fall Δ U meet numerical intervals [
+ (2n-1) * 2s,
+ (2n+1) * 2s) battery of (n ∈-1,0) scope is certified products.
The new detecting method of a kind of ferric phosphate lithium power lithium-ion battery self-discharge characteristics provided by the invention, is included in after battery partial volume terminates and carries out the characterization processes processes such as the adjustment of SOC state, voltage determination, high temperature ageing, battery screening.By adopting different current, multistep constant-current discharge is carried out to LiFePO4 series lithium ion battery, wherein respectively walk current value to reduce gradually, the SOC state of battery is adjusted to 0%, certain electric current is adopted to carry out battery to charge to the SOC state of 20 ~ 40% again, finally adopt certain current discharge certain hour, guarantee that battery SOC is in stable condition.According to LiFePO4 series lithium ion battery OCV and SOC correlativity rule, in the SOC state of 20-40%, battery OCV linearly changes with SOC state, thus is conducive to adopting cell voltage to fall method to evaluate the self-discharge characteristics of battery; And the voltage difference of battery carries out Accurate Measurement by instrumentation, substantially can not be subject to the impact of the factors such as checkout equipment, operational method and environment temperature, be conducive to promoting self discharge the data precision.Adopt the mode of high temperature ageing, inside battery chemical reactivity increases, aggravation self-discharge of battery variation tendency, is also conducive to improving the resolution that self-discharge of battery detects data, promotes detection accuracy.
The beneficial effect that the present invention produces is: adopt ferric phosphate lithium power lithium-ion battery self-discharge characteristics new detecting method of the present invention, be conducive to the accuracy and the reliability that improve self-discharge of battery characteristic garbled data, promote battery performance consistance, have obvious improved action to battery performance reliability and cycle life.
Accompanying drawing explanation
Fig. 1 is the OCV(open-circuit voltage of the ferric phosphate lithium power lithium-ion battery that the present invention relates to) and SOC(state-of-charge) Changing Pattern characteristic curve.
Fig. 2 is the cycle performance curve control schematic diagram of the electric battery that embodiments of the invention and comparative example are prepared by employing self-discharge characteristics detection method.
embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is further described.
The invention provides a kind of new detecting method of ferric phosphate lithium power lithium-ion battery self-discharge characteristics, embodiment is as follows:
1, electrode slice is prepared: make lithium-ion-power cell positive, negative electrode plate, concrete production method is that current the art is known, does not describe at this.
2, battery is assembled into: the rated capacity adopting lamination process that the positive, negative electrode plate of above-mentioned making and barrier film etc. are assembled into some is the battery of 25Ah, and concrete production method is that current the art is known, does not describe at this.
3, fluid injection infiltrates: adopt filling machine to annotate in battery a certain amount of electrolytic solution, and standing infiltrations then carrying out a period of time processes, and concrete production method is that current the art is known, does not describe at this.
4, Battery formation: adopt discharge and recharge detection to carry out preliminary filling to battery and change into process, concrete production method is that current the art is known, does not describe at this.
5, battery partial volume: adopt discharge and recharge to detect and carry out partial volume check processing to battery, concrete production method is that current the art is known, does not describe at this.
6, self-discharge of battery detects: adopt a kind of ferric phosphate lithium power lithium-ion battery self-discharge characteristics detection method provided by the present invention to process:
Step 1, certain electric current is adopted to carry out charge-discharge cycles to battery, then adopt different electric current several times constant-current discharge the SOC state of battery is adjusted to 0%, then adopt recharge-discharge pattern that the SOC state of battery is adjusted to specified states, in some preferred embodiments, SOC specified states is 20% ~ 40%
Step 2, battery leaves standstill the regular hour at normal temperatures after step 1 terminates, and measures the open-circuit voltage OCV1 of battery; In some preferred embodiments, the time left standstill under normal temperature is 12 ~ 36h;
Step 3, loads onto aging clamp by battery, puts into high-temperature aging room and carries out high temperature ageing; In some preferred embodiments, the cell degradation time is 7 ~ 28 days; Aging temperature is set to 35 ~ 45 DEG C;
Step 4, high temperature ageing terminates, and battery is shelved certain hour at normal temperatures, then detects battery open circuit voltage OCV2;
Step 5, calculates the voltage drop Δ U of battery, Δ U=OCV1-OCV2
Step 6, calculates the mean value of same Battery pack voltage drop
with standard deviation s, according to voltage drop mean value and standard deviation data screening spec battery; Wherein, the screening criteria of battery is: cell voltage fall Δ U meet numerical intervals [
+ (2n-1) * 2s,
+ (2n+1) * 2s) battery of (n ∈-1,0) scope is certified products.
Detection method of the present invention is the OCV(open-circuit voltage being based upon ferric phosphate lithium power lithium-ion battery) with SOC(state-of-charge) Changing Pattern feature basis on, as shown in Figure 1.Ferric phosphate lithium cell because of its OCV and SOC relation highly stable, the difference between cell is very little.Whole OCV and SOC curve map mainly can be divided into three sections: (1) platform area: SOC is substantially in two platform area between 40% ~ 100%, even if SOC alters a great deal, but OCV is substantially constant; (2) linear zone: the SOC relation that OCV and SOC is substantially linear between 20% ~ 40%, can be expressed as: Δ OCV=K* Δ SOC, K are certain value (being similar to); (3) abrupt slope district: when SOC is between 0% ~ 10%, when SOC change is less, the change of OCV is but very large.
The present invention is according to the above-mentioned feature of ferric phosphate lithium cell OCV and SOC, and between the linear zone that have chosen OCV and SOC relationship change, namely SOC is between 20% ~ 40%.In this linear zone, OCV and the SOC of battery becomes a positively related linear relationship substantially, so controlled by SOC in this interval, then adopts voltage difference can replace the method evaluation self-discharge of battery characteristic of capacity difference.
Embodiment 1
Ferric phosphate lithium power lithium-ion battery after being terminated by partial volume carries out self discharge check processing: step 1, SOC state adjusts: adopt the current versus cell of 0.5C to carry out charge-discharge cycles 2 times successively, the different electric current of 0.5C, 0.2C, 0.1C, 0.05C is adopted to divide 4 step constant-current discharges again, the SOC state of battery is adjusted to 0%, then the current charges 0.8h of 0.5C is adopted, then adopt the current discharge 0.1 hour of 0.5C, battery SOC state is adjusted to 35%; Step 2, for the first time voltage determination: battery standing 24h, detect cell voltage OCV1 after cell voltage is stable; Step 3, high temperature ageing: adopt unit clamp to clamp on battery, is placed between high temperature ageing, and temperature is 40 ± 3 DEG C, aging 20 days; Step 4, second time voltage determination: take out in battery is between high temperature ageing, places and is not less than 8 ± 2h, detect cell voltage OCV2 under normal temperature condition; Step 5, voltage drop calculates: the voltage drop Δ U calculating battery, Δ U=OCV1-OCV2; Step 6, battery screening: calculate the mean value that cell voltage falls
with standard deviation s:
According to voltage drop mean value and standard deviation data statistics meet numerical intervals [
+ (2n-1) * 2s,
+ (2n+1) * 2s) battery screening of (n ∈-1,0) is certified products.
The mean value that the present embodiment calculates
=16.6mV and standard deviation s=1.6, and thus calculate certified products screening numerical intervals be respectively [7,13), [and 13,20), these group data all concentrate on second interval [13,20) in.Each for the present embodiment group battery is assembled into electric battery and carries out loop test.
The preparation method of embodiment 2-10 is with embodiment 1, and just process conditions change in condition and range.
Comparative example 1-10 adopts traditional self discharge detection method: first battery carries out first time discharge and recharge process, and charging and discharging currents is 0.5C, the battery capacity C1 that the complete discharge process recording final step detects; Then by battery aging 20 days in high temperature environments, then taken out by battery, carry out second time discharge and recharge process, charging and discharging currents is 0.5C, records the battery capacity C2 that first step discharge process detects; Calculate battery capacity attenuation ratio, i.e. Δ C=(C1-C2)/C1*100%.The mean value of calculated capacity decay
=3.4% and standard deviation s=1.10%, and with embodiment press statistical method calculate certified products screening numerical intervals for [-3.22%, 1.19%), [and 1.19%, 5.61%), and there is negative value in first interval, inapplicable, casts out.The each data of comparative example all meet between second screening area.Each for comparative example group battery is assembled into electric battery and carries out loop test.
The concrete outcome of above-described embodiment is as shown in table 1 and Fig. 2.
The self-discharge of battery data of table 1 embodiment and comparative example
In order to eliminate embodiment and comparative example because measuring the different of dimension and numerical value, compared the dispersion degree difference of two groups of data by the coefficient of variation.From theory of probability and statistically, the coefficient of variation, also known as " coefficient of dispersion ", is that a normalization of probability distribution dispersion degree is measured, and it is defined as the ratio of standard deviation and mean value.From the data of table 1, the coefficient of variation of embodiment is C.V=1.6/16.6*100%=9.64%, and the coefficient of variation of comparative example is C.V=1.10%/3.40%*100%=32.35%, and as can be seen here, the dispersion degree of comparative example is obviously greater than embodiment.
Can find out from the result (Fig. 2) of embodiment, adopt the battery of a kind of ferric phosphate lithium power lithium-ion battery self-discharge characteristics new detecting method screening provided by the present invention, the cycle life of the electric battery be assembled into obviously promotes, this is mainly because the self-discharge characteristics of battery is one of key characteristic affecting the battery cyclic life-span, and the self discharge data concentrations adopting embodiment method to screen is higher, illustrate that in electric battery, the consistency of performance of each battery is higher, thus avoid because the increase of individual battery performance difference causes cycle life decay to speed in electric battery.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (8)
1. a new detecting method for LiFePO4 system power lithium-ion battery self-discharge characteristics, it is characterized in that, the method includes the steps of:
Step 1, first carries out charge-discharge cycles several times to battery, then adopts recharge-discharge pattern that the SOC state of battery is adjusted to 20% ~ 40%;
Step 2, battery leaves standstill the regular hour at normal temperatures after step 1 terminates, and measures the open-circuit voltage OCV1 of battery;
Step 3, battery is carried out high temperature ageing, and digestion time is to the stipulated time;
Step 4, high temperature ageing terminates, and battery is shelved certain hour at normal temperatures, then detects battery open circuit voltage OCV2;
Step 5, calculates the voltage drop Δ U of battery, Δ U=OCV1-OCV2
Step 6, calculates the mean value of same Battery pack voltage drop
with standard deviation s, according to voltage drop mean value and standard deviation data screening spec battery.
2. according to the new detecting method of the LiFePO4 system power lithium-ion battery self-discharge characteristics described in claim 1, it is characterized in that: in described step 1, before SOC state is adjusted to specified states, and after charge-discharge cycles several times, also adopt different electric current substep repeatedly constant-current discharge so that the SOC state of battery is adjusted to 0%.
3. according to the new detecting method of the LiFePO4 system power lithium-ion battery self-discharge characteristics described in claim 2, it is characterized in that: described different electric current substep is repeatedly in constant-current discharge, and each step current value reduces gradually.
4. according to the new detecting method of the LiFePO4 system power lithium-ion battery self-discharge characteristics described in claim 1, it is characterized in that: in described step 2, the time left standstill under normal temperature is 12 ~ 36h.
5., according to the new detecting method of the LiFePO4 system power lithium-ion battery self-discharge characteristics described in claim 1, it is characterized in that: in described step 3, the cell degradation time is 7 ~ 28 days.
6., according to the new detecting method of the LiFePO4 system power lithium-ion battery self-discharge characteristics described in claim 5, it is characterized in that: in described step 3, the temperature that battery high-temperature is aging is set to 35 ~ 45 DEG C.
7., according to the new detecting method of the LiFePO4 system power lithium-ion battery self-discharge characteristics described in claim 1, it is characterized in that: in described step 6, the screening criteria of battery is: cell voltage fall Δ U meet numerical intervals [
+ (2n-1) * 2s,
+ (2n+1) * 2s) battery of (n ∈-1,0) scope is certified products.
8., according to the new detecting method of the LiFePO4 system power lithium-ion battery self-discharge characteristics described in claim 7, it is characterized in that: the mean value that cell voltage falls
computing formula be:
；
The computing formula of described standard deviation s is:
。
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