CN109358290A - A kind of lossless detection method of lithium ion battery analysis lithium - Google Patents
A kind of lossless detection method of lithium ion battery analysis lithium Download PDFInfo
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- CN109358290A CN109358290A CN201811037776.5A CN201811037776A CN109358290A CN 109358290 A CN109358290 A CN 109358290A CN 201811037776 A CN201811037776 A CN 201811037776A CN 109358290 A CN109358290 A CN 109358290A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 143
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 114
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000001514 detection method Methods 0.000 title claims abstract description 63
- 238000004458 analytical method Methods 0.000 title claims abstract description 59
- 230000005518 electrochemistry Effects 0.000 claims abstract description 88
- 230000005284 excitation Effects 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000007600 charging Methods 0.000 claims abstract description 29
- 230000007704 transition Effects 0.000 claims abstract description 5
- 238000005259 measurement Methods 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 abstract description 16
- 238000005457 optimization Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- 210000004027 cell Anatomy 0.000 description 9
- 238000013507 mapping Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009659 non-destructive testing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4285—Testing apparatus
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of lossless detection methods of lithium ion battery analysis lithium.The characteristics of present invention is precipitated for lithium metal detects the lithium metal precipitation in charging process, so that the selection and control for charging strategy provide a kind of lossless and effective method.The specific steps are carry out constant-current charge to mesuring battary, then intermittent electrochemistry excitation is carried out to battery, analyze the relationship of cell voltage variation and time, if electrochemistry excitation front and back, transition phenomenon occurs for the change rate of the difference of lithium ion battery voltage to be measured, then illustrates that analysis lithium process occurs in the lithium ion battery.The lossless detection method of lithium ion battery analysis lithium in the present invention, operation is simple, does not need complicated calculating process, the lithium ion battery suitable for different model, the lithium metal precipitation detection that can be used for during power battery charging, moreover it is possible to provide for battery core design optimization with reference to basis.
Description
Technical field
The invention belongs to lithium ion battery testing fields, and in particular to a kind of non-destructive testing side of lithium ion battery analysis lithium
Method.
Background technique
The year two thousand twenty, country propose lithium-ion battery monomer specific energy >=300Wh/kg, this is also for meeting user to continuous
The most direct solution of anxiety of boat mileage can reduce the quantity of single battery in battery pack by the increase of specific energy
And weight, to accomplish cost declining and promote the purpose of overall performance.At present in industry the realization of the target mainly using
Nickelic anode/cathode containing Si, on the basis of high qualification rate and high reliability, cathode adds still based on graphite cathode at present
Enter a small amount of Si, promote the capacity of cathode, to promote the specific energy of entire battery core.In energy density lifting process, terminal is used
Family propose battery must satisfy a degree of rapid charge characteristic because rapid charge characteristic can largely save user time at
This, during being at war with fuel vehicle, enhances the competitiveness of pure electric automobile, in addition to energy density is high, charge rate
It fastly, is also a difficult point there are also the decline for being exactly cost.
High-energy density, quick charge characteristic and low cost require to correspond in battery cathode, it is meant that high compacted density,
The application of high Si content, quick charge characteristic and inexpensive graphite, these all bring great test to the application of graphite.In electricity
In the charging process of pond, the current potential and lithium metal current potential of cathode are substantially close to easily causing the precipitation of Li dendrite, thus to battery
Safety and cycle performance bring bad influence.
Aiming at the problem that lithium ion battery Li dendrite is precipitated, developer wants to timely and accurately judge lithium ion battery
Analysis lithium situation during the charging process, and then suitable charge parameter is selected for lithium ion battery.Developer is to lithium battery at present
Analysis lithium done a large amount of research, and propose corresponding analysis lithium detection method, including dismantling method and lossless detection method.Dismantling
It is owned by France that subsequent analysis test can not be carried out in destructive detection method, after disassembling to battery, it is often more important that
During the dismantling of battery, there are serious security risk, it is easy that safe thing occurs because misoperation or production environment are bad
Therefore lead to property loss, or even endanger the personal safety of staff.
Dismantling method is just gradually substituted by non-destructive testing at present, and non-destructive testing is not required to carry out irreversible dismantling just to battery
The case where battery analysis lithium can be obtained.Application No. is in 201711141760.4 entitled " detection methods of lithium ion battery analysis lithium "
State's patent of invention, which disclose a kind of detection methods of lithium ion battery analysis lithium: after lithium ion battery to be measured is melted into advance
It carries out shelving sealing, specially once shelve；High current constant-current charge；It is secondary to shelve；Low current constant-current constant-voltage charging.If small
There is voltage and continuously declines in a certain stage during electric current constant-current constant-voltage charging, then determines that lithium ion battery to be measured has analysis lithium existing
As.This method principle is relatively simple, but it is longer to shelve sealing time, and detection process needs to spend longer time, detection effect
Rate is lower.Application No. is the Chinese invention patents of 201810194583.4 entitled " analysis lithium detection method and device ", disclose one
Kind analysis lithium detection method obtains the discharge curve of battery by collecting the voltage signal in battery discharge procedure；Then by putting
Whether electric curve obtains the voltage fluctuation curve of battery, occurred to analyse lithium according to voltage fluctuation curve detection battery.The detection method
Accuracy with higher, but the calculating process and mathematical model that are related in detection process are complex.Application No. is
The Chinese invention of 201610255360.5 entitled " detection method, battery management system and the battery systems of rechargeable battery analysis lithium " is special
Benefit discloses a kind of detection method of rechargeable battery analysis lithium, carries out pulse charge to mesuring battary, obtains battery in the lotus of setting
Polarization potential is compared by the polarization potential under electricity condition with preset polarization potential threshold value, if polarization potential is greater than in advance
If polarization potential threshold value, then determine rechargeable battery occur during pulse charge analyse lithium.Above-mentioned detection method is not being disassembled
In the case where lithium battery, by obtaining suitable electrical parameter, then electrical parameter is analyzed, can then obtain lithium electricity
The analysis lithium situation in pond.In lithium battery test process, simpler lossless detection method is found, it is accurate to determine that battery analyses lithium feelings
Condition expands the applicability of detection method, and in lithium ion battery testing field, there is also very big progress spaces.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides a kind of non-destructive testing sides of lithium ion battery analysis lithium
Method.The characteristics of present invention is precipitated for lithium metal detects the lithium metal precipitation in charging process, to be charging strategy
Selection and control a kind of lossless and effective method is provided.The specific steps are to mesuring battary carry out constant-current charge, it is then right
Battery carries out intermittent electrochemistry excitation, the relationship of analysis cell voltage variation and time, if electrochemistry excitation front and back, to be measured
Transition phenomenon occurs for the change rate of the difference of lithium ion battery voltage, then illustrates that analysis lithium process occurs in the lithium ion battery.This
The lossless detection method of lithium ion battery analysis lithium in invention, operation is simple, does not need complicated calculating process, is suitable for not
With the lithium ion battery of model, the lithium metal precipitation detection that can be used for during power battery charging, moreover it is possible to be designed for battery core excellent
Change and basis is provided.
Present invention technical effect to be achieved is realized by following scheme:
The present invention provides a kind of lossless detection methods of lithium ion battery analysis lithium, include the following steps:
S01, by lithium ion battery constant-current charge to be measured to setting voltage；
S02 after the constant-current charge, carries out intermittent electrochemistry excitation to the lithium ion battery to be measured, described in measurement
The voltage swing of the lithium ion battery to be measured during intermittent electrochemistry excitation；
S03, during analyzing the intermittent electrochemistry excitation, the voltage of the electrochemistry excitation front and back lithium ion battery to be measured
The relationship of variation and time, if electrochemistry excitation front and back, the change rate of the difference of the lithium ion battery voltage to be measured occur
Transition phenomenon then illustrates that analysis lithium occurs in the lithium ion battery to be measured.
The lossless detection method of lithium ion battery analysis lithium in the present invention, to the lithium ion battery for charging to certain voltage state
Intermittent electrochemistry excitation is carried out, the voltage change of lithium ion battery, passes through the change of voltage during monitoring electrochemistry excitation
Law come judge inside lithium ion cell whether occur analyse lithium process.Specific method is analysis before and after electrochemistry excitation, lithium
The change rate of the difference of ion battery voltage is said if transition phenomenon occurs for the change rate of the difference of lithium ion battery voltage
There is analysis lithium process in bright inside lithium ion cell.The lossless detection method of lithium ion battery analysis lithium, easy to operate easy in the present invention
Row, the analysis lithium situation of inside lithium ion cell can accurately be learnt by not needing complicated calculating process.
In lithium battery charging process, the precipitation phenomenon of lithium metal was occurred in the latter stage of constant-current charge；In constant voltage process,
With polarized elimination, cathode potential rises, and the lithium metal for causing negative terminal surface to be precipitated is embedded in battery cathode again, thus unfavorable
In detection and analysis, therefore constant current charging method is selected in the present invention, by lithium battery constant-current charge to setting voltage after without perseverance
Pressure charging excludes influence due to lithium metal is caused to be embedded in battery cathode again for constant-voltage charge to testing result.
Further, the lithium ion battery to be measured is the lithium ion battery for meeting factory and requiring.Lithium ion in the present invention
The lossless detection method that battery analyses lithium is applied widely, has good applicability to different model, various sizes of battery.To
Surveying lithium ion battery can be cylinder type lithium battery, quadrate lithium battery, flexible-packed battery, aluminum-shell battery etc..In order to guarantee to survey
The accuracy of test result avoids the difference because of lithium battery itself from having an impact experiment, and lithium ion battery to be tested will meet out
Factory requires, i.e., lithium ion battery to be measured requires to be the battery in cell production process after forming and capacity dividing process, keeps battery
State is normal, and capacity performance index, internal resistance index all meet the factory requirement of battery production enterprise, and battery consistency is good, detection knot
Fruit is more accurate, and the truth of lithium whether can be more analysed inside reaction cell.
Further, the voltage when setting voltage is full no more than the lithium ion battery to be measured electric.It is first in the present invention
The voltage that battery is first charged to setting does not need to be defined the voltage value of setting, by battery as a test condition
It charges to a certain voltage and is used to detect analysis lithium situation.Different types of lithium battery has different size of operating voltage, this
Invention is not required to be defined the voltage of lithium battery after charging, illustrates that detection method of the invention has different types of lithium battery
There is good applicability.Certainly, the voltage of lithium battery cannot avoid out beyond the voltage under mesuring battary full power state after charging
Existing overcharge conditions, influence the service life and cycle performance of lithium ion battery, avoid causing danger because of over-charging of battery.
Further, during the constant-current charge, the temperature of the lithium ion battery to be measured is -40 ~ 60 DEG C, temperature
Control errors are within ± 2 DEG C.During the intermittence electrochemistry excitation, the temperature of the lithium ion battery to be measured is -40 ~
60 DEG C, the control errors of temperature are within ± 2 DEG C.Charging process and electrochemistry excitation process battery temperature be lithium battery just
The normal range of operation that normal operating temperature range, i.e. detection method in the present invention are suitable for lithium battery, in the normal of lithium battery
In working range, method of the invention can obtain accurate detection result.Process battery is motivated to charging process and electrochemistry
The error range of temperature makes certain restriction, guarantees the stability of temperature, can be improved the accuracy of testing result.
Further, during the constant-current charge, the control errors of charging current 0.2C-1.5C, charging current are
Within ± 0.3%.Charging current is too small during lithium battery constant-current charge, can extend the charging time, reduces detection efficiency；Charging
Electric current is excessive, easily leads to the reinforcement of inside battery polarization, accelerates the formation of Li dendrite, influence the service performance of battery.Charging
Current error controls within ± 0.3%, it is ensured that the stabilization of charging current in charging process guarantees inside battery electrochemical reaction
Stabilization, avoid inside battery cause because of being widely varied for charging current electrochemistry reaction speed and the extent of reaction hair
Raw acute variation.Under the premise of lithium battery works normally, the accuracy of testing result is improved.
Further, after the constant-current charge, the voltage of the lithium ion battery to be measured and the setting voltage
Control errors are within ± 0.3%.Although not needing to carry out the voltage value of setting in the present invention tight as a test condition
The restriction of lattice, but in specific detection process, for different battery and detection process, it is determined that setting voltage value it
Afterwards, after constant-current charge, the voltage of lithium ion battery to be measured and the control errors for setting voltage is within ± 0.3%.Afterwards
Continuous electrochemistry excitation process need to monitor the size of lithium battery voltage, to the error of lithium battery virtual voltage size after constant-current charge into
Row limits, and is conducive to monitoring of the subsequent electrochemical excitation to voltage, improves the accuracy of detection.
Further, the intermittent electrochemistry is actuated to intermittent constant-current pulse electrochemistry excitation.Preferably, in constant current
Pulse electrochemical excitation front and back, the change rate of lithium ion battery voltage difference are similar to the variation of lithium ion battery direct-current internal resistance
Rate, therefore electrochemistry excitation front and back cell voltage situation of change is compactly described in order to more clear, it can be used in the present invention
Analysis DC internal resistance changes with time rule to judge the case where inside lithium ion cell analyses lithium.The calculation of DC internal resistance
For DCR=(U1-U2)/I, in formula: DCR is the DC internal resistance of lithium ion battery to be measured；U1Lithium ion to be measured before being motivated for electrochemistry
The voltage of battery；U2For the voltage of lithium ion battery to be measured after electrochemistry excitation；I is size of current when electrochemistry motivates.
Further, during the intermittent electrochemistry excitation, the interval time per the excitation of electrochemistry twice is 1-
5min.During the intermittence electrochemistry excitation, the electric current of each electrochemistry excitation is 1C-5C；Each electrochemistry excitation
Time is 5-15s.Suitable electrochemistry excitation interval time, electrochemistry exciting current size and electrochemistry are selected in the present invention
Actuation duration is premised on the accuracy for guaranteeing testing result.It is too short per the time interval between the excitation of electrochemistry twice, swash
It encourages excessively frequently, amplification electrochemistry excitation cannot really reflect the working condition of lithium battery interior to the contribution margin of testing result；
It is too long per the time interval between the excitation of electrochemistry twice, then it is very few to will lead to detection data sample, so that testing result is accurate
Property reduce.Suitable interval time is selected in the present invention, not only can control detection process the time it takes, but also can guarantee detection knot
Fruit meets the actual conditions of lithium battery, improves detection accuracy.Equally, the electric current of electrochemistry excitation is excessive or too small, each
The electrochemistry actuation duration is too long or the too short stability and accuracy that can all influence testing result.As important in the present invention
Experiment parameter, determine compatible with lithium ion battery to be measured electrochemistry motivate interval time, electrochemistry exciting current size,
The length of electrochemistry actuation duration can obtain the enough data samples of quantity within the limited time, improve testing result
Stability and accuracy.
The invention has the following advantages that
1. detection method does not need to disassemble battery in the present invention, to the normal use of subsequent detection and lithium battery without shadow
It rings, avoids dismantling battery bring security risk.
2. selecting suitable electrochemistry excitation interval time, electrochemistry exciting current size, electrochemistry excitation in the present invention
The length of time, can control detection process the time it takes, obtain the enough data samples of quantity within the limited time,
Improve the stability and accuracy of testing result.
3. detection method is simple and easy in the present invention, it is not required to the lithium ion by complicated calculating, suitable for different model
Battery can really reflect the actual conditions of lithium battery interior work.
Detailed description of the invention
Fig. 1 is three electrode curve of lithium ion battery constant-current constant-voltage charging process to be measured in the present invention.
Fig. 2 is the constant-current pulse curve of electrochemistry excitation in the present invention.
Fig. 3 is the voltage's distribiuting that electrochemistry motivates constant-current pulse in the present invention.
Fig. 4 is the dismantling situation of lithium battery to be measured in the present invention.
Fig. 5 is the dismantling situation of lithium battery to be measured in the present invention.
Fig. 6 is the relationship of lithium battery voltage and electric current and time in detection process in the present invention.
Fig. 7 is the relationship of lithium battery DC internal resistance and time to be measured in the present invention.
Specific embodiment
The present invention will be described in detail with reference to the accompanying drawings and examples.
It is used using the 2.6Ah-18650 battery of our company's production as research object in the embodiment of the present invention
2.6Ah-18650 battery passes through forming and capacity dividing process, and battery status is normal, and battery capacity index, internal resistance index reach this public affairs
The factory requirement of department.
Embodiment 1
The test of three electrode constant-current constant-voltage chargings is carried out to the lithium ion battery to be measured in the present embodiment, resulting three electrode charge is bent
Line is as shown in Fig. 1.By attached drawing 1 it is found that during the charging process, the precipitation phenomenon of lithium metal was sent out in the latter stage of constant-current charge
It is raw；In constant voltage process, with polarized elimination, cathode potential rises, and the lithium metal for causing negative terminal surface to be precipitated is embedded in electricity again
Pond cathode, to be unfavorable for testing and analyzing.During constant current, the boundary multiplying power for being precipitated with a precipitation of lithium metal, when filling
When electric multiplying power is greater than the boundary multiplying power, lithium battery precipitating metal lithium；When rate of charge is less than the boundary multiplying power, lithium battery is not analysed
Lithium metal out.Therefore the present invention in select constant current charging method, by lithium battery constant-current charge to setting voltage after without constant pressure
Charging excludes influence due to lithium metal is caused to be embedded in battery cathode again for constant-voltage charge to testing result.
The detection method of lithium battery analysis lithium in the present embodiment are as follows:
Lithium ion battery constant-current charge to be measured to voltage is at 5 DEG C 4.0V with the electric current of 0.6C by S01；
Lithium ion battery to be measured after constant-current charge, is carried out intermittent electrochemistry excitation, measurement interval by S02 at 10 DEG C
Property electrochemistry excitation during the lithium ion battery to be measured voltage swing；Intermittent electrochemistry motivational techniques be at interval of
3min carries out a constant-current pulse electrochemistry excitation to lithium ion battery to be measured, and constant-current pulse size of current is 1.0C, permanent every time
The stream pulse electrochemical actuation duration is 10s.The constant-current pulse curve that electrochemistry motivates in the present embodiment is as shown in Fig. 2.
S03, during the excitation of above-mentioned constant-current pulse electrochemistry, the voltage U of lithium battery before record motivates1With lithium after excitation
The voltage U of battery2, pass through DCR=(U1-U2)/I calculates DC internal resistance DCR, and electric current I is 1.0C in formula, then to internal resistance DCR and
Time mapping, obtains lithium battery DC internal resistance and the relationship of time (such as attached drawing 7) to be measured.The DC internal resistance DCR is by ohm
Hinder Ri, transmitting internal resistance Rct, diffusion internal resistance RdIt forms (such as attached drawing 3), with (U1-U2)/I, which calculates DC internal resistance, can simplify internal resistance
Analytic process, and it is able to reflect the situation of change of the internal resistance of cell, simplify the calculation method of internal resistance in the present invention, improves detection effect
Rate.
In the present embodiment test process, lithium battery voltage and electric current and the relationship of time are as shown in Fig. 6, and with reference to the accompanying drawings 6
The data of middle record select voltage, current data needed for constant-current pulse electrochemistry excitation process, in the direct current of lithium battery
Resistance is calculated.
Do not occur lithium metal precipitation in 3.85V by lithium ion battery to be measured known to the test result in attached drawing 7, and 3.85V
Appear above lithium metal precipitation.Battery is disassembled when 3.85V, dismantling situation is as shown in Fig. 4；Battery is carried out when 3.9V
Dismantling, dismantling situation is as shown in Fig. 5, and it is obvious to find out that surface occurs after comparing attached drawing 4 and attached drawing 5 it is found that disassembling in attached drawing 5
Shinny metal, the metal of the precipitation is lithium metal, is then precipitated without lithium metal in attached drawing 4.Illustrate that lithium ion battery to be measured exists
Do not occur analysis lithium when 3.85V, analysis lithium occurs in when 3.9V, i.e., the testing result of detection method and lithium ion battery to be measured in the present invention
Practical analysis lithium situation be consistent.
Embodiment 2
The detection method of lithium battery analysis lithium in the present embodiment are as follows:
Lithium ion battery constant-current charge to be measured to voltage is 4.0V with the electric current of 1.0C at 20 DEG C by S01；
Lithium ion battery to be measured after constant-current charge, is carried out intermittent electrochemistry excitation, measurement interval by S02 at 20 DEG C
Property electrochemistry excitation during the lithium ion battery to be measured voltage swing；Intermittent electrochemistry motivational techniques be at interval of
3min carries out a constant-current pulse electrochemistry excitation to lithium ion battery to be measured, and constant-current pulse size of current is 2.0C, permanent every time
The stream pulse electrochemical actuation duration is 10s.
S03, during the excitation of above-mentioned constant-current pulse electrochemistry, the voltage U of lithium battery before record motivates1With lithium after excitation
The voltage U of battery2, pass through DCR=(U1-U2)/I calculates DC internal resistance DCR, and electric current I is 2.0C in formula, then to internal resistance DCR and
Time mapping, obtains the relationship of lithium battery DC internal resistance and time to be measured.
Lithium ion battery to be measured does not occur lithium metal precipitation in 3.78V in the present embodiment, and 3.78V appears above metal
Lithium is precipitated.
Embodiment 3
The detection method of lithium battery analysis lithium in the present embodiment are as follows:
Lithium ion battery constant-current charge to be measured to voltage is 4.0V with the electric current of 1.5C at 20 DEG C by S01；
Lithium ion battery to be measured after constant-current charge, is carried out intermittent electrochemistry excitation, measurement interval by S02 at 20 DEG C
Property electrochemistry excitation during the lithium ion battery to be measured voltage swing；Intermittent electrochemistry motivational techniques be at interval of
3min carries out a constant-current pulse electrochemistry excitation to lithium ion battery to be measured, and constant-current pulse size of current is 3.0C, permanent every time
The stream pulse electrochemical actuation duration is 10s.
S03, during the excitation of above-mentioned constant-current pulse electrochemistry, the voltage U of lithium battery before record motivates1With lithium after excitation
The voltage U of battery2, pass through DCR=(U1-U2)/I calculates DC internal resistance DCR, and electric current I is 3.0C in formula, then to internal resistance DCR and
Time mapping, obtains the relationship of lithium battery DC internal resistance and time to be measured.
Lithium ion battery to be measured does not occur lithium metal precipitation in 3.75V in the present embodiment, and 3.75V appears above metal
Lithium is precipitated.
Embodiment 4
The detection method of lithium battery analysis lithium in the present embodiment are as follows:
Lithium ion battery constant-current charge to be measured to voltage is 4.0V with the electric current of 1.2C at 30 DEG C by S01；
Lithium ion battery to be measured after constant-current charge, is carried out intermittent electrochemistry excitation, measurement interval by S02 at 30 DEG C
Property electrochemistry excitation during the lithium ion battery to be measured voltage swing；Intermittent electrochemistry motivational techniques be at interval of
3min carries out a constant-current pulse electrochemistry excitation to lithium ion battery to be measured, and constant-current pulse size of current is 4.0C, permanent every time
The stream pulse electrochemical actuation duration is 10s.
S03, during the excitation of above-mentioned constant-current pulse electrochemistry, the voltage U of lithium battery before record motivates1With lithium after excitation
The voltage U of battery2, pass through DCR=(U1-U2)/I calculates DC internal resistance DCR, and electric current I is 4.0C in formula, then to internal resistance DCR and
Time mapping, obtains the relationship of lithium battery DC internal resistance and time to be measured.
Lithium ion battery to be measured does not occur lithium metal precipitation in 3.72V in the present embodiment, and 3.72V appears above metal
Lithium is precipitated.
Embodiment 5
The detection method of lithium battery analysis lithium in the present embodiment are as follows:
Lithium ion battery constant-current charge to be measured to voltage is 4.0V with the electric current of 1.5C at 30 DEG C by S01；
Lithium ion battery to be measured after constant-current charge, is carried out intermittent electrochemistry excitation, measurement interval by S02 at 30 DEG C
Property electrochemistry excitation during the lithium ion battery to be measured voltage swing；Intermittent electrochemistry motivational techniques be at interval of
2min carries out a constant-current pulse electrochemistry excitation to lithium ion battery to be measured, and constant-current pulse size of current is 4.0C, permanent every time
The stream pulse electrochemical actuation duration is 10s.
S03, during the excitation of above-mentioned constant-current pulse electrochemistry, the voltage U of lithium battery before record motivates1With lithium after excitation
The voltage U of battery2, pass through DCR=(U1-U2)/I calculates DC internal resistance DCR, and electric current I is 4.0C in formula, then to internal resistance DCR and
Time mapping, obtains the relationship of lithium battery DC internal resistance and time to be measured.
Lithium ion battery to be measured does not occur lithium metal precipitation in 3.7V in the present embodiment, and 3.7V appears above lithium metal
It is precipitated.
Embodiment 6
The detection method of lithium battery analysis lithium in the present embodiment are as follows:
Lithium ion battery constant-current charge to be measured to voltage is 4.0V with the electric current of 1.5C at 30 DEG C by S01；
Lithium ion battery to be measured after constant-current charge, is carried out intermittent electrochemistry excitation, measurement interval by S02 at 30 DEG C
Property electrochemistry excitation during the lithium ion battery to be measured voltage swing；Intermittent electrochemistry motivational techniques be at interval of
5min carries out a constant-current pulse electrochemistry excitation to lithium ion battery to be measured, and constant-current pulse size of current is 4.0C, permanent every time
The stream pulse electrochemical actuation duration is 10s.
S03, during the excitation of above-mentioned constant-current pulse electrochemistry, the voltage U of lithium battery before record motivates1With lithium after excitation
The voltage U of battery2, pass through DCR=(U1-U2)/I calculates DC internal resistance DCR, and electric current I is 4.0C in formula, then to internal resistance DCR and
Time mapping, obtains the relationship of lithium battery DC internal resistance and time to be measured.
Lithium ion battery to be measured does not occur lithium metal precipitation in 3.8V in the present embodiment, and 3.8V appears above lithium metal
It is precipitated.
Finally, it should be noted that above embodiments be only to illustrate the technical solution of the embodiment of the present invention rather than to its into
Row limitation, although the embodiment of the present invention is described in detail referring to preferred embodiment, those skilled in the art
It should be understood that the technical solution of the embodiment of the present invention can be still modified or replaced equivalently, and these are modified or wait
The range of modified technical solution disengaging technical solution of the embodiment of the present invention cannot also be made with replacement.
Claims (10)
1. a kind of lossless detection method of lithium ion battery analysis lithium, which comprises the steps of:
S01, by lithium ion battery constant-current charge to be measured to setting voltage；
S02 after the constant-current charge, carries out intermittent electrochemistry excitation to the lithium ion battery to be measured, described in measurement
The voltage swing of the lithium ion battery to be measured during intermittent electrochemistry excitation；
S03, during analyzing the intermittent electrochemistry excitation, the voltage of the electrochemistry excitation front and back lithium ion battery to be measured
The relationship of variation and time, if electrochemistry excitation front and back, the change rate of the difference of the lithium ion battery voltage to be measured occur
Transition phenomenon then illustrates that analysis lithium occurs in the lithium ion battery to be measured.
2. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the lithium-ion electric to be measured
Pond is the lithium ion battery for meeting factory and requiring.
3. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the setting voltage does not surpass
The voltage that the lithium ion battery to be measured is crossed when expiring electricity.
4. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the constant-current charge process
In, the temperature of the lithium ion battery to be measured is -40 ~ 60 DEG C, and the control errors of temperature are within ± 2 DEG C.
5. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the intermittence electrochemistry
During excitation, the temperature of the lithium ion battery to be measured is -40 ~ 60 DEG C, and the control errors of temperature are within ± 2 DEG C.
6. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the constant-current charge process
In, charging current 0.2C-1.5C, the control errors of charging current are within ± 0.3%.
7. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the constant-current charge terminates
Afterwards, the voltage of the lithium ion battery to be measured and the control errors for setting voltage is within ± 0.3%.
8. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the intermittence electrochemistry
It is actuated to intermittent constant-current pulse electrochemistry excitation.
9. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the intermittence electrochemistry
During excitation, the interval time per the excitation of electrochemistry twice is 1-5min.
10. the lossless detection method of lithium ion battery analysis lithium as described in claim 1, it is characterised in that: the intermittent electrification
During learning excitation, the electric current of each electrochemistry excitation is 1C-5C；Each electrochemistry actuation duration is 5-15s.
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