CN106067560B - The preparation method of internal short-circuit lithium-ion-power cell - Google Patents
The preparation method of internal short-circuit lithium-ion-power cell Download PDFInfo
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- CN106067560B CN106067560B CN201610630840.5A CN201610630840A CN106067560B CN 106067560 B CN106067560 B CN 106067560B CN 201610630840 A CN201610630840 A CN 201610630840A CN 106067560 B CN106067560 B CN 106067560B
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/3644—Constructional arrangements
- G01R31/3648—Constructional arrangements comprising digital calculation means, e.g. for performing an algorithm
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
- G01R31/3865—Arrangements for measuring battery or accumulator variables related to manufacture, e.g. testing after manufacture
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/44—Methods for charging or discharging
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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
- H01M10/44—Methods for charging or discharging
- H01M10/441—Methods for charging or discharging for several batteries or cells simultaneously or sequentially
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A kind of preparation method of internal short-circuit lithium-ion-power cell, this method induce the internal short-circuit of lithium-ion-power cell, then obtain the discharge curve of the lithium-ion-power cell by carrying out overdischarge to lithium-ion-power cell.The overdischarge curve is further divided into different overdischarge feature stages, selectes more batches of lithium-ion-power cells, overdischarge is carried out to more batches of selected lithium-ion-power cells.The corresponding relationship of multiple internal short-circuit resistance and overdischarge state-of-charge is finally obtained, to obtain the MAP chart of the internal short-circuit of this lithium-ion-power cell.Overdischarge is carried out to selected lithium-ion-power cell according to the MAP chart of the internal short-circuit, to realize that harmless quantitative induces lithium-ion-power cell internal short-circuit.The method proposed by the present invention for inducing internal short-circuit by overdischarge does not need to destroy the mechanical structure of lithium-ion-power cell, and favorable repeatability being capable of harmless quantitative induction lithium-ion-power cell internal short-circuit.
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of preparation method of internal short-circuit lithium-ion-power cell.
Background technique
Under energy shortages and the dual-pressure of environmental pollution, automobile dynamic system motorized has been increasingly becoming future automobile
The main trend of technology development.Lithium-ion-power cell has energy density high, the advantages of having extended cycle life, has become now
One of the main selection in electric powered motor source.With the gradually popularization of electric car, the safety of lithium-ion-power cell
Accident also occurs again and again.Relevant accident threatens the security of the lives and property of the people, also counteracts the big rule of electric car
Mould industrialization.
In lithium-ion-power cell use process, internal short-circuit power battery thermal runaway from generating to ultimately causing need through
Count the time of hour one by one.During a few hours with development occur for internal short-circuit, it is necessary to detect the generation of internal short-circuit simultaneously in time
Judge the degree of internal short-circuit, carry out early warning ahead of time, to ensure the security of the lives and property of passenger.Therefore it just needs reliable effective
Internal short-circuit early detection algorithm, early warning is carried out with the generation for internal short-circuit, guarantees interior personnel safety.Once opening
Internal short-circuit early detection algorithm is issued, actual effect and reliability just need to test.In order to develop in reliable and effective
Short-circuit early detection algorithm needs that the lithium-ion-power cell with internal short-circuit is arranged in battery pack, could effectively
Test the actual effect and reliability of internal short-circuit detection algorithm.However, being not yet completely for the specific origin cause of formation of internal short-circuit at present
It is clear, it is difficult to obtain the lithium-ion-power cell that internal short-circuit has occurred in use.Generally, it only occurs in accident
Afterwards, could speculate whether the accident origin cause of formation is internal short-circuit by accident investigation.
Therefore, the lithium-ion-power cell with internal short-circuit is reached out for, detection internal short-circuit early detection is calculated
The effect of method is necessary.Currently, contrived experiment device includes three classes master to induce lithium-ion-power cell internal short-circuit
The method wanted: 1) battery diaphragm rupture is caused by mechanical presses, puncture or laser convergence and causes internal short-circuit；2) dynamic in lithium ion
Impurity particle is introduced between power battery plus-negative plate, squeezed in corresponding position and causes internal short-circuit；3) in lithium ion power electricity
Built-in controllable material (such as paraffin, memorial alloy) inside pond, it is controllable to activate using specific trigger condition (such as heating up)
Material, controllable material attribute change (such as melted paraffin wax, memorial alloy deform) cause lithium-ion-power cell positive and negative anodes to be shorted,
To induce internal short-circuit.
The method that the above three classes induce internal short-circuit all has certain disadvantages.Method 1) it will cause lithium-ion-power cell knot
The destruction of structure.And under actual conditions, during actual use battery internal short-circuit seldom due to battery structure destroy and occur.Also
Have, method 1) caused by internal short-circuit it is unstable, the thermal runaway of lithium-ion-power cell may be directly contributed, so that morning cannot be induced
Phase internal short-circuit is not used to the verifying of internal short-circuit detection algorithm.In addition, method 1) repeatability be not very good, Bu Nengbao
Card can cause stable quantitative internal short-circuit every time.
Method 2) it equally will cause lithium-ion-power cell deformation, it can not preferably induce interior short under actual conditions
Road.Method 2) caused by lithium-ion-power cell internal short-circuit situation it is also unstable, lithium-ion-power cell may be directly contributed
Thermal runaway.Also, when introducing impurity particle, the microscopic appearance of impurity particle is difficult to control, it cannot be guaranteed that lithium-ion-power cell
The repeatability of internal short-circuit can not obtain accurately different degrees of quantitative internal short-circuit.
Method 3) it not will cause cell deformation, still, built-in controllable material needs certain condition to be triggered, and such as heats up
Melted paraffin, or heating excitation memorial alloy deformation.Temperature-rise period itself changes the normal work of lithium-ion-power cell
Temperature may cause the generation of other side reactions inside lithium-ion-power cell, affect the electrochemistry of lithium-ion-power cell
With heat production characteristic, lithium-ion-power cell has also been damaged to a certain extent.Method 3) introduced controllable material and lithium ion
Microscopic appearance between power battery positive and negative anodes is difficult to determine, still effectively cannot quantitatively control interior short with microcosmic effect relationship
The degree on road, it cannot be guaranteed that the repeatability of internal short-circuit.
Summary of the invention
In view of this, it is necessary to propose that a kind of internal short-circuit lithium-ion-power cell preparation method, this method can be with lossless fixed
What amount induced prepares internal short-circuit lithium-ion-power cell, and internal short-circuit effect stability, favorable repeatability.
A kind of preparation method of internal short-circuit lithium-ion-power cell, comprising the following steps:
S110 selectes a lithium-ion-power cell；
S120 is tested for the property the lithium-ion-power cell, obtains the capacity, interior of the lithium-ion-power cell
Resistance, voltage and positive and negative pole material attribute；
S130 carries out over-discharge electrical testing to the lithium-ion-power cell, and obtains the mistake of the over-discharge Electrical Test Procedure
The ordinate unit of discharge curve, the overdischarge curve is over-discharge piezoelectric voltage, and abscissa unit is state-of-charge；
The overdischarge curve is divided into M overdischarge feature stage according to the over-discharge piezoelectric voltage by S140, and the M is a
Overdischarge feature stage is the 1st overdischarge feature stage, and the 2nd overdischarge feature stage ..., M overdischarge feature stage is each
A corresponding over-discharge electric process of the overdischarge feature stage；Wherein, the M is more than or equal to 3；
S150, takes the M batches of lithium-ion-power cells, and lithium-ion-power cell described in the every batch of in the M batches is uniquely right
An overdischarge feature stage in the M overdischarge feature stage is answered, to each described lithium ion in the M batches
Power battery is overdisharged to corresponding state-of-charge；
S160 carries out internal short-circuit test to lithium-ion-power cell described in each of the M batches, obtains the M batches
Each of described in lithium-ion-power cell internal short-circuit resistance value；
S170 draws the lithium-ion-power cell according to the internal short-circuit resistance value and the overdischarge state of charge
The MAP chart of internal short-circuit, the abscissa of the MAP chart are state-of-charges, and the ordinate of the MAP chart is internal short-circuit resistance；
S180 induces the lithium-ion-power cell according to the MAP chart to a lithium-ion-power cell overdischarge
Internal short-circuit.
The invention proposes a kind of preparation methods of internal short-circuit lithium-ion-power cell.This method by selected lithium from
Sub- power battery carries out overdischarge, and the overdischarge curve of acquisition is divided into M overdischarge feature stage.The selected M batches of lithiums
Ion battery, corresponding M overdischarge feature stage carry out overdischarge.Finally obtain multiple internal short-circuit resistance and state-of-charge
Relationship, the MAP chart of the internal short-circuit of the lithium-ion-power cell can be drawn.It then, can be to one according to the MAP chart
The lithium-ion-power cell overdischarge, to realize that the harmless quantitative of lithium-ion-power cell internal short-circuit induces.The present invention mentions
Internal short-circuit lithium-ion-power cell preparation method out does not need to destroy the mechanical structure of lithium-ion-power cell, repeatability
It is good, it is capable of the internal short-circuit of harmless quantitative induction lithium-ion-power cell, so as to prepare with different internal short-circuit degree
Internal short-circuit lithium-ion-power cell.In the case of quantitatively assessing different degrees of internal short-circuit, the danger of lithium-ion-power cell
Degree.It can also be used to exploitation internal short-circuit detection algorithm, and the validity for internal short-circuit detection algorithm to be quantitatively evaluated.The program
To assessment internal short-circuit early detection algorithm have great importance, it will help improve lithium-ion-power cell safety management can
By property, the generation of security of lithium-ion-power cell accident is reduced.It can be produced by this method with different degrees of internal short-circuit
Lithium-ion-power cell.Utilize the voltage of this method lithium-ion-power cell obtained with internal short-circuit, temperature-responsive
Data can be provided for exploitation internal short-circuit early detection algorithm, for verifying the effective of developed internal short-circuit early detection algorithm
Property and reliability.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the internal short-circuit lithium-ion-power cell in one embodiment of the invention；
Fig. 2 is the series connection situation of battery modules in one embodiment of the invention；
Fig. 3 is the state-of-charge after the battery modules overdischarge in one embodiment of the invention；
Fig. 4 is the overdischarge curve and divided stages situation of lithium-ion-power cell in one embodiment of the invention；
Fig. 5 is the enlarged drawing of described Fig. 4；
Fig. 6 is to use constant current method of testing estimation lithium-ion-power cell internal short-circuit resistance in one embodiment of the invention
Schematic diagram；
Fig. 7 is to use constant pressure method of testing estimation lithium-ion-power cell internal short-circuit resistance in one embodiment of the invention
Schematic diagram；
Fig. 8 is to use the schematic diagram of settled process estimation lithium-ion-power cell internal short-circuit resistance in the embodiment of the present invention；
Fig. 9 is the MAP chart of lithium-ion-power cell in one embodiment of the invention；
The present invention that the following detailed description will be further explained with reference to the above drawings.
Main element symbol description
Lithium-ion-power cell mould group 100
Lithium-ion-power cell 11,12,13,14,15
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings.Below with reference to
The embodiment of attached drawing description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
Referring to Figure 1, the preparation method of a kind of internal short-circuit lithium-ion-power cell proposed by the present invention, including following step
It is rapid:
S110 selectes a lithium-ion-power cell；
S120 is tested for the property the lithium-ion-power cell, obtains the capacity, interior of the lithium-ion-power cell
Resistance, voltage and positive and negative pole material attribute；
S130 carries out over-discharge electrical testing to the lithium-ion-power cell, and obtains the mistake of the over-discharge Electrical Test Procedure
The ordinate unit of discharge curve, the overdischarge curve is over-discharge piezoelectric voltage, and abscissa unit is state-of-charge；
The overdischarge curve is divided into M overdischarge feature stage according to the over-discharge piezoelectric voltage by S140, and the M is a
Overdischarge feature stage is the 1st overdischarge feature stage, and the 2nd overdischarge feature stage ..., M overdischarge feature stage is each
A corresponding over-discharge electric process of the overdischarge feature stage；Wherein, the M is more than or equal to 3；
S150: the corresponding M overdischarge feature stage takes the M batches of lithium-ion-power cells, every in the M batches
It criticizes the lithium-ion-power cell and uniquely corresponds to an overdischarge feature stage in the M overdischarge feature stage,
Overdischarge is carried out to each described lithium-ion-power cell in the M batches and is overdisharged to corresponding state-of-charge；
S160: internal short-circuit test, each corresponding institute are carried out to lithium-ion-power cell described in each of the M batches
Overdischarge feature stage is stated, the internal short-circuit resistance value of lithium-ion-power cell described in each of described M crowd is obtained；
S170: it is drawn according to the internal short-circuit resistance value and the overdischarge state of charge short in lithium-ion-power cell
The MAP chart on road, the abscissa of the MAP chart are state-of-charges, and the ordinate of the MAP chart is internal short-circuit resistance value.
S180: according to the MAP chart to a lithium-ion-power cell overdischarge, the lithium-ion-power cell is induced
Induce internal short-circuit.
In step S110, selected lithium-ion-power cell refers to selects a lithium-ion-power cell according to actual needs.
So-called same money lithium ion battery is parameter having the same, the lithium-ion-power cell of same brand.The lithium ion power
Selection is actually needed in the quantity of battery according to the method for the present invention.But being the need to ensure that all lithium-ion-power cells all is tool
There is identical parameter, that is, with money lithium-ion-power cell.After the completion of to be tested, the harmless quantitative for carrying out internal short-circuit induces
When, also it is corresponding be identical money lithium ion battery.
It is conventional lithium ion power battery to the method that the lithium-ion-power cell is tested for the property in step S120
Traditional test methods, it is therefore an objective to further appreciate that the various performance parameters of the selected lithium-ion-power cell.Specifically,
Including giving the volume test under current condition, battery open circuit voltage test and battery plus-negative plate under current condition are given
The electrochemical properties of material are tested.
The test that the lithium-ion-power cell carries out overdischarge can be can according to need and selected.Implement at one
In example, step S130 need the lithium-ion-power cell mould group that is composed in series of the lithium-ion-power cell described at least three sections come pair
The lithium-ion-power cell carries out over-discharge electrical testing.Specifically, it may comprise steps of:
S131 takes lithium-ion-power cell described at least three sections；
S132 selects a section lithium-ion-power cell as overdischarge from lithium-ion-power cell described at least three sections
Lithium-ion-power cell；
S133, being individually vented the overdischarge lithium-ion-power cell to state-of-charge is 0%；
S134 charges to the remaining lithium-ion-power cell in lithium-ion-power cell described at least three sections
State-of-charge is 100%；
Lithium-ion-power cell series connection described at least three sections is obtained lithium-ion-power cell mould group, used by S135
Overdischarge is carried out for the lithium-ion-power cell mould group with electric current identical in step S120, until the overdischarge lithium ion
Extensive precipitating metal dendrite occurs for power battery, shows voltage and levels off to until 0V.
In step S135, by testing in real time, the overdischarge of the overdischarge lithium-ion-power cell can be obtained
Curve.The abscissa of the overdischarge curve is state-of-charge, and ordinate is battery over-discharge voltage.Therefore, the overdischarge
Curve has reacted the relationship of battery over-discharge voltage and state-of-charge.During overdischarge, abnormal electrochemical potentials distribution
Meeting inducing metal dendrite (such as Li dendrite, iron dendrite, copper dendrite) is grown in abnormal position.The growth of metallic dendrite can be pierced finally
Broken battery diaphragm, leads to the generation of battery internal short-circuit.In one embodiment, the metallic dendrite is copper dendrite.
In one embodiment, in step S140, based on the battery performance test in step S120 as a result, for step
The overdischarge curve obtained in S135 carries out Analysis on Mechanism, and the degree being precipitated using metallic dendrite is partitioning standards, to divide the M
A overdischarge feature stage.It is appreciated that be to the overdischarge curve divided stages in order to obtain stage by stage below it is each not
With the stage, the corresponding internal short-circuit resistance value of different state-of-charges is carried out.The division of the overdischarge feature stage can basis
Actual needs carries out, as long as to the method that the overdischarge curve carries out divided stages, all within that scope of the present invention.
The M overdischarge feature stage is continuously that the state-of-charge of each overdischarge feature stage is in a given range
It is interior.
In step S150, over-discharge electrical testing can be carried out by choosing the M batches of lithium-ion-power cells.In M batches
The quantity of every a batch lithium-ion-power cell be all at least two or more.It is appreciated that described in every a batch
Lithium-ion-power cell quantity is more, then the test data obtained is more.More test data can make according to upper
The figure line for stating test data drafting is more acurrate, and precision is higher.M mistake in the M batches of lithium-ion-power cells and step S140
The discharge characteristic stage is corresponding.That is, how many overdischarge feature stage, it is necessary to select the how many batches of lithiums from
Sub- power battery carries out overdischarge.Since in the M overdischarge feature stage, the state-of-charge in each stage is different
's.Therefore, overdischarge can be carried out according to the different state of charge in each stage.Specifically, the M batches of lithiums are selected
After ion battery, according to the different state of charge in m-th overdischarge feature stage, in the M batches of lithium ion batteries
Each lithium-ion-power cell carry out overdischarge one by one.Each lithium-ion-power cell discharges into different charged shapes
State, and the different state-of-charge is the different state of charge in the corresponding m-th overdischarge feature stage.
In step S160, by short in being carried out to the M after the overdischarge in step S150 batches of lithium-ion-power cells
Drive test examination, it is hereby achieved that the internal short-circuit resistance value of each lithium-ion-power cell.And each lithium-ion-power cell
State-of-charge just had been known in step S150.Therefore, after step S160, multiple internal short-circuit resistance values are just obtained
With multiple state of charge.In step S160, the method for quantitative test internal short-circuit degree includes constant current method of testing, constant pressure test
One of method and settled process are a variety of.
Specifically, the constant current method of testing may include two ways: the first is internal short-circuit not under serious situation, is made
There is with constant current simultaneously for the normal lithium-ion-power cell monomer of a section and a section lithium ion power electricity of internal short-circuit
Pond monomer carries out constant-current charge or electric discharge, is quantified according to the difference value of normal battery and internal short-circuit battery charge or discharge capacity
Assess the degree of internal short-circuit；Second is to use lesser constant current I under internal short-circuit very serious situationConstant currentFor having
The lithium-ion-power cell monomer of internal short-circuit carries out constant-current charge, then the voltage of battery will stabilise at a voltage value VStablize, then
The internal short-circuit resistance that can estimate battery at this time is RISC=VStablize/IConstant current。
Specifically, the constant pressure method of testing, which refers to, carries out constant-voltage charge for the lithium-ion-power cell with internal short-circuit.It will
Lithium-ion-power cell with internal short-circuit is charged to a certain voltage VCVAfterwards, in voltage VCVPlace carries out constant-voltage charge.Constant pressure is filled
In electric process, charging current will be gradually reduced.But since internal short-circuit consumes electric current, charging current is reduced to a certain numerical value ICV
When, charging current will be maintained at ICVWithout changing.At this point it is possible to which it is R that quantitative estimation, which goes out internal short-circuit resistance,ISC=VCV/ICV。
Specifically, the settled process, which refers to, charges to a certain state-of-charge=α for lithium-ion-power cell, by battery standing
And monitor cell voltage.After a period of time Δ t, due to the presence of internal short-circuit, the electricity of the section lithium-ion-power cell will be put
Sky is state-of-charge=0.According to the electricity of discharge time and releasing, it is estimated that being averaged for the section lithium-ion-power cell is put
Electric current is IElectric discharge=α * Q/ Δ t, wherein Q represents the rated capacity of battery, and unit is As.It is assumed that the averaged discharge electricity of battery
Pressure is VIt is average, then it is estimated that the internal short-circuit resistance of battery is about RISC=VIt is average/IElectric discharge。
Step S170, establishes coordinate system, according to the multiple internal short-circuit resistance value that obtains in step S160 and described more
A state of charge can draw the MAP chart of the lithium-ion-power cell.The abscissa of the MAP chart is state-of-charge,
The ordinate of the MAP chart is internal short-circuit resistance value.The method specifically drawn is unlimited, can be various methods.
Step S180 obtains the MAP chart of a lithium-ion-power cell by step S170, as long as selection is the same as described in money
Lithium-ion-power cell, and the state of charge in MAP chart is overdisharged to the selected lithium-ion-power cell.Overdischarge
The internal short-circuit resistance of the later lithium-ion-power cell can directly be read out from the MAP chart.This method obtains
Internal short-circuit lithium-ion-power cell internal short-circuit resistance can in advance select as needed, to realize short in quantitative acquisition
Road lithium-ion-power cell.For with corresponding internal short-circuit resistance RISCLithium-ion-power cell be tested for the property, can obtain
Obtaining internal short-circuit resistance is RISCIn the case of, the electrochemistry and heat production characteristic of lithium-ion-power cell.To be examined for internal short-circuit early stage
The exploitation of method of determining and calculating provides the characteristic of internal short-circuit.Lithium-ion-power cell with corresponding internal short-circuit can also be opened in algorithm
Validity and reliability after the completion of hair, for verification algorithm.
Specific embodiment
In the step S110 of the present embodiment, have chosen a lithium-ion-power cell, this lithium-ion-power cell its
Positive electrode active materials are nickel-cobalt-manganese ternary material, and negative electrode active material is graphite, and diaphragm has PE matrix and carried out single side pottery
Porcelain coating.
In the step S120 of the present embodiment, passage capacity test estimates this lithium-ion-power cell and is being discharged to
When state-of-charge is 0%, inside the precipitation of copper dendrite does not occur.For the precipitation for guaranteeing copper dendrite, battery must overdischarge
To negative voltage.By battery performance test, under the conditions of available use 8.33A (1/3C multiplying power) charge and discharge, this lithium ion
The capacity of power battery is about Q=26.5Ah.
In the step S130 of the present embodiment, as shown in Fig. 2, use described in 5 sections with money lithium-ion-power cell string
Connection constitutes lithium-ion-power cell mould group 100.Before the 100 mould group of lithium-ion-power cell mould group series connection, need
It is 0% that first the electricity of a wherein section lithium-ion-power cell 11, which is individually vented as state-of-charge,；Then again by other four sections lithiums
Ion battery 12,13,14,15 is fully charged, state-of-charge 100%.After completing above-mentioned preparation, then by this 5 section
Lithium-ion-power cell 11,12,13,14,15 is connected in series.Then use with electric current 8.33A identical in step S120 for
The lithium-ion-power cell mould group 100 carries out overdischarge, until the lithium-ion-power cell 11 occurs that copper dendrite is precipitated on a large scale
Until.
In the step S130 of the present embodiment, the lithium-ion-power cell 11 will be by overdischarge, and other lithium ions are dynamic
12,13,14,15, power battery are regular picture.As shown in Fig. 3,11 overdischarge of lithium-ion-power cell starts one section
After time, after starting 1h, state-of-charge will be reduced to -33.3%, and other four sections lithium-ion-power cells 12,13,14,
15 state-of-charge is then reduced to 66.7%.
The overdischarge curve that the step S130 of the present embodiment is obtained is as shown in Fig. 4.With the progress of overdischarge, battery electricity
Drops are negative value, continue overdischarge to about -2.1V or so, it is anti-to correspond to inside battery precipitation copper dendrite for voltage bottom out
The beginning answered.When being overdisharged to -100%SOC, voltage curve levels off to a fixed current potential, illustrates copper dendrite is precipitated complete
It is complete to complete.
In the step S140 of the present embodiment, as shown in Fig. 4, the overdischarge curve of this lithium-ion-power cell is drawn
It is divided into 4 overdischarge feature stages: stage I, stage II, stage III, stage IV.
Stage I corresponds to cell voltage continuous decrease, until cell voltage stops decline.During stage I, this lithium
Lithium ion inside ion battery is embedded in anode, so that cathode voltage declines；Meanwhile lithium ion is deviate from from cathode, so that
Cathode voltage increases.Due to the deintercalation process that lithium ion occurs main during stage I, voltage curve monotonic decreasing.Also, with
The progress of overdischarge, since cathode voltage could possibly be higher than anode, so cell voltage can become negative value.
Stage II initiates from cell voltage and stops decline, and during stage II, cell voltage starts slowly to go up.Battery
The copper foil of negative current collector starts to be dissolved in electrolyte in the form of copper ion since current potential is excessively high.Copper ion to battery just
Pole diffusion is assembled in positive electrode potential lower.When copper ion concentration reaches certain degree, it will be sent out in positive electrode potential lower
The reduction of the pig copper causes the precipitation of copper, that is, analysis copper has occurred.The copper of stage II, precipitation can be in the potential lower of anode
It is grown into, that is, the growth of the copper dendrite in local point range occurs.The growth course of copper dendrite is a chemical balance, according to
Bad over-discharge supplies electricity to the extra electron of anode offer, and the copper ion dissolved in the electrolytic solution is constantly precipitated in positive electrode potential lower, copper
Dendrite is constantly grown.This corresponding chemical balance can see that the rise of cell voltage is relatively more slow from the enlarged drawing of attached drawing 5
Slowly.
The direction of growth of copper dendrite is directed towards battery diaphragm and battery cathode direction, the lasting life of copper dendrite in stage II
Length can be squeezed into the hole of battery diaphragm, and continue to grow to battery cathode direction.Since the hole of battery diaphragm can lead to
To cathode, therefore, copper dendritic growth for a period of time after, will pass through battery diaphragm, cause between anode and battery cathode
Short circuit.Since copper dendrite passes through short circuit caused by diaphragm once occurring, occurs new electric current inside lithium-ion-power cell and return
Road, influence caused by overdischarge are weakened, and cell voltage can go up rapidly.What cell voltage went up rapidly starts to correspond to rank
The section end of II and the starting of stage III.
Since stage III, on the one hand, the short circuit duration inside lithium-ion-power cell works, and cell voltage is lasting
Go up；On the other hand, the analysis copper at anode persistently occurs, and from part, analysis copper is gradually extended to large area analysis copper, short-circuit
Degree also gradually increases therewith.Therefore, in stage III, the voltage of battery gos up rapidly.And the degree for analysing copper is gradually increased, lithium
Inside ion battery when occurrence of large-area internal short-circuit, lithium-ion-power cell gradually becomes a pure short-circuit resistance, battery
Voltage will be approached to a constant negative value.Cell voltage gradually level off to a constant negative value when, the stage, III terminated, the stage
IV starts.
In stage IV, as shown in Fig. 4, occurrence of large-area internal short-circuit inside lithium-ion-power cell, cell voltage is gradually
Go up to a stable numerical value.That is occurrence of large-area short circuit inside the lithium-ion-power cell, so that the lithium ion
Power battery becomes a fixed value resistance, so that cell voltage is at a fixed value.
In the step S150 of the present embodiment, specifically, the over-discharge electrical feature of corresponding aforementioned four lithium-ion-power cell
Stage can select 4 batches of same money lithium-ion-power cells.1st batch of lithium-ion-power cell corresponds to the electric discharge of stage i；
2nd batch of lithium-ion-power cell corresponds to the electric discharge of phase il；3rd batch of lithium-ion-power cell corresponds to the electric discharge in Section III stage；
4th batch of lithium-ion-power cell corresponds to the electric discharge of stage iv.In above-mentioned 4 batches of lithium-ion-power cells, every a batch all has more
A lithium-ion-power cell.
In the step S160 of the present embodiment, carried out to the lithium-ion-power cell after different degrees of overdischarge has been carried out
Performance test.The internal short-circuit degree of lithium-ion-power cell is assessed by testing.Specifically, the 1st batch of lithium ion power
Corresponding battery is stage i, therefore can obtain the state of charge in multiple stage is and corresponding internal short-circuit
Resistance value.Since every a collection of lithium-ion-power cell all has multiple lithium ion batteries, can obtain multiple corresponding interior
Short-circuit resistance value and state of charge are for drawing.Described 2nd, 3,4 batch of lithium-ion-power cell is also such.It illustrates below
It is bright how to carry out the lithium-ion-power cell progress internal short-circuit assessment test different degrees of to overdischarge.
For being overdisharged to the lithium-ion-power cell of state-of-charge=- 100%, which is had occurred greatly
Scale internal short-circuit.Therefore its internal short-circuit degree is assessed using constant current method of testing.As shown in Fig. 6, the lithium from
Under sub- power battery internal short-circuit very serious situation, lesser constant current I is usedConstant current=8.33A is for this with internal short-circuit
Lithium-ion-power cell monomer carries out constant-current charge, and the voltage of the lithium-ion-power cell will stabilise at a voltage value VStablize=
0.386V.The internal short-circuit resistance that can then estimate the lithium-ion-power cell at this time is RISC=VStablize/IConstant current=0.386/8.33=
0.046Ω。
For being overdisharged to the lithium-ion-power cell of state-of-charge=- 14.4%, which is had occurred
Local internal short-circuit.As shown in Fig. 7, using constant pressure method of testing, which is first charged using 8.33A, is charged
To a certain voltage VCVAfter=4.2V, in voltage VCVConstant-voltage charge is carried out at=4.2V.During constant-voltage charge, charging current
It will be gradually reduced.But since internal short-circuit consumes electric current, charging current is reduced to a certain numerical value ICVWhen=1.43A, charging current
It will be maintained at ICVWithout changing.At this point it is possible to which the internal short-circuit resistance that quantitative estimation goes out the lithium-ion-power cell is RISC=
VCV/ICV=2.93 Ω.
For being overdisharged to the lithium-ion-power cell of state-of-charge=- 14.7%, which is had occurred
Local internal short-circuit.As shown in Fig. 8, settled process can be used to estimate the internal short-circuit degree of the lithium-ion-power cell
It calculates.The lithium-ion-power cell is charged into state-of-charge=100%, and the lithium-ion-power cell is stood and monitors battery
Voltage.As shown in Fig. 8, after a period of time Δ t=69174s, due to the presence of internal short-circuit, the section lithium-ion-power cell
Electricity will be vented as state-of-charge=0.According to the electricity of discharge time and releasing, it is estimated that the lithium-ion-power cell
Average discharge current be IElectric discharge=α * Q/ Δ t=1.38A, wherein Q represents the rated capacity of the lithium-ion-power cell, unit
It is As.It is assumed that the average discharge volt of the lithium-ion-power cell is VIt is average=3.8V, the then it is estimated that lithium ion power is electric
The short-circuit resistance in pond is about RISC=VIt is average/IElectric discharge=2.75 Ω.
In the step S170 of the present embodiment, the estimation result of the different degrees of internal short-circuit obtained in combining step S160,
The MAP chart of lithium-ion-power cell internal short-circuit as of fig. 9 shown can be drawn.It can be seen that from described Fig. 9 in stage III
Leading portion, overdischarge state-of-charge are the internal short-circuit resistance R of this lithium-ion-power cell near -15%ISCAbout in 1~10 Ω
The order of magnitude；And once enter stage III back segment, this lithium-ion-power cell internal short-circuit resistance RISC0.01 will be directly entered
~0.1 Ω order of magnitude.
In the step S180 of the present embodiment, for this lithium-ion-power cell, it can be produced with reference to the accompanying drawings 9
Lithium-ion-power cell with quantitative internal short-circuit resistance.Specifically, there is being somebody's turn to do for 1~10 Ω order of magnitude internal short-circuit to produce
Money lithium-ion-power cell should first choose this lithium-ion-power cell, and being overdisharged to state-of-charge is -15% attached
Closely.
In conclusion the invention proposes a kind of preparation methods of internal short-circuit lithium-ion-power cell.This method by pair
Selected lithium-ion-power cell carries out overdischarge, and the overdischarge curve of acquisition is divided into M overdischarge feature stage.It is selected
The M batches of lithium-ion-power cells, corresponding M overdischarge feature stage carry out overdischarge.Finally obtain multiple internal short-circuit resistance
With state-of-charge, the MAP chart of the internal short-circuit of the lithium-ion-power cell can be drawn.It then, can be right according to the MAP chart
One lithium-ion-power cell electric discharge, so that internal short-circuit is quantified to the lithium ion power battery lossless, to prepare
Internal short-circuit lithium-ion-power cell with quantitative internal short-circuit.The method proposed by the present invention that internal short-circuit is induced by overdischarge
The mechanical structure of destruction lithium-ion-power cell is not needed, favorable repeatability being capable of harmless quantitative induction lithium-ion-power cell
Internal short-circuit.In the case of quantitatively assessing different degrees of internal short-circuit, the degree of danger of lithium-ion-power cell also can
It is enough in exploitation internal short-circuit detection algorithm, and the validity for internal short-circuit detection algorithm to be quantitatively evaluated.The program is in assessment
Short-circuit early detection algorithm has great importance, it will help the reliability for improving lithium-ion-power cell safety management subtracts
The generation of few security of lithium-ion-power cell accident.The lithium ion with different degrees of internal short-circuit can be produced by this method
Power battery.It can be open using the voltage of this method lithium-ion-power cell obtained with internal short-circuit, temperature-responsive
Send out internal short-circuit early detection algorithm provide data, for verify developed internal short-circuit early detection algorithm validity and reliably
Property.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of internal short-circuit lithium-ion-power cell, comprising the following steps:
S110 selectes a lithium-ion-power cell；
S120 is tested for the property the lithium-ion-power cell, obtain the capacity of the lithium-ion-power cell, internal resistance,
Voltage and positive and negative pole material attribute；
S130 carries out over-discharge electrical testing to the lithium-ion-power cell, and obtains the overdischarge of the over-discharge Electrical Test Procedure
The ordinate unit of curve, the overdischarge curve is over-discharge piezoelectric voltage, and abscissa unit is state-of-charge；
The overdischarge curve is divided into M overdischarge feature stage according to over-discharge piezoelectric voltage by S140, and the M overdischarge is special
The sign stage is the 1st overdischarge feature stage, the 2nd overdischarge feature stage ..., M overdischarge feature stage, each described mistake
The discharge characteristic stage corresponds to an over-discharge electric process；The M is more than or equal to 3；
S150, takes the M batches of lithium-ion-power cells, and lithium-ion-power cell described in the every batch of in the M batches uniquely corresponds to institute
An overdischarge feature stage in M overdischarge feature stage is stated, to each described lithium ion power in the M batches
Battery over-discharge is to corresponding state-of-charge；
S160 carries out internal short-circuit test to lithium-ion-power cell described in each of the M batches, obtains in the M batches
The internal short-circuit resistance value of each lithium-ion-power cell；
S170 is drawn short in the lithium-ion-power cell according to the internal short-circuit resistance value and the overdischarge state of charge
The MAP chart on road, the abscissa of the MAP chart are state-of-charges, and the ordinate of the MAP chart is internal short-circuit resistance；
S180 induces lithium-ion-power cell induction according to the MAP chart to a lithium-ion-power cell overdischarge
Internal short-circuit.
2. the preparation method of internal short-circuit lithium-ion-power cell as described in claim 1, which is characterized in that in step S120,
Selected lithium-ion-power cell is tested for the property including giving the volume test under current condition, given current condition
Under battery open circuit voltage test and battery plus-negative plate material electrochemical properties test.
3. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 2, which is characterized in that step S130 is specific
The following steps are included:
S131 takes lithium-ion-power cell described at least three sections；
S132, selected from lithium-ion-power cell described at least three sections section lithium-ion-power cell as overdischarge lithium from
Sub- power battery；
S133, being individually vented the overdischarge lithium-ion-power cell to state-of-charge is 0%；
S134 charges to the remaining lithium-ion-power cell in lithium-ion-power cell described at least three sections charged
State is 100%；
S135 lithium-ion-power cell series connection will obtain lithium-ion-power cell mould group described at least three sections, using with step
Identical electric current carries out overdischarge for the lithium-ion-power cell mould group in rapid S120, until the overdischarge lithium ion power
Extensive precipitating metal dendrite occurs for battery, shows voltage and levels off to until 0V, so that it is dynamic to obtain the overdischarge lithium ion
The discharge curve of power battery.
4. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 3, which is characterized in that in step S140,
Based on the performance test results in step S120, the degree being precipitated using metallic dendrite is partitioning standards, to divide the M over-discharge
The electrical feature stage.
5. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 4, which is characterized in that in step S140,
Using copper dendrite be precipitated degree as partitioning standards, the M overdischarge feature stage be respectively stage I, stage II, stage III,
Stage IV；The stage I is continued to decline by cell voltage, until cell voltage stops decline；The stage II is started from
Cell voltage stops decline, until cell voltage Magnification is greater than zero；The stage III starts from cell voltage Magnification and is greater than
Zero, until cell voltage levels off to a constant negative value；The stage IV is to level off to a constant negative value from cell voltage
Stage later.
6. the preparation method of internal short-circuit lithium-ion-power cell as described in claim 1, which is characterized in that in step S150,
Lithium-ion-power cell described in each of the M batches be overdisharged in corresponding state-of-charge described, institute
State the batch corresponding with each described described lithium-ion-power cell of overdischarge stage corresponding to corresponding state-of-charge
It is identical.
7. the preparation method of internal short-circuit lithium-ion-power cell as described in claim 1, which is characterized in that right in S160
The method that the lithium-ion-power cell of each in the M batches carries out internal short-circuit test includes constant current method of testing, constant pressure test
One of method and settled process are a variety of.
8. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 7, which is characterized in that the constant current test
Method are as follows: there is using constant current simultaneously for the normal lithium-ion-power cell of a section and a section lithium ion power of internal short-circuit
Battery carries out constant-current charge or electric discharge, according to normal lithium-ion-power cell with have the charging of internal short-circuit lithium-ion-power cell or
The difference value of discharge capacity is quantitatively evaluated the degree of internal short-circuit.
9. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 7, which is characterized in that the constant pressure test
Method are as follows: the lithium-ion-power cell with internal short-circuit is charged to a certain voltage VCVAfterwards, in voltage VCVPlace carries out constant pressure and fills
Electricity, charging current are reduced to a certain numerical value ICVWhen, if charging current maintains ICVWithout changing, quantitative estimation goes out at this time
Internal short-circuit resistance is RISC=VCV/ICV。
10. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 7, which is characterized in that the settled process
The following steps are included: lithium-ion-power cell is charged to a certain state-of-charge=α, which is stood and supervised
Survey cell voltage；When the electricity of the lithium-ion-power cell be vented to state-of-charge be zero when, according to discharge time Δ t and releasing
Electricity α, estimate the lithium-ion-power cell average discharge current be IElectric discharge=α * Q/ Δ t, wherein Q represents the volume of battery
Constant volume, unit are As, it is assumed that the average discharge volt of the lithium-ion-power cell is VIt is average, then it is dynamic to estimate the lithium ion
The internal short-circuit resistance of power battery is RISC=VIt is average/IElectric discharge。
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| CN106802396B (en) * | 2017-03-28 | 2019-04-05 | 上海理工大学 | A kind of diagnostic method of battery internal short-circuit |
| CN107192914B (en) * | 2017-04-18 | 2019-11-22 | 宁德时代新能源科技股份有限公司 | Lithium-ion-power cell internal short-circuit detection method |
| CN108134126A (en) * | 2017-11-29 | 2018-06-08 | 清华大学 | The triggering method of battery internal short-circuit |
| TWI649573B (en) | 2017-12-04 | 2019-02-01 | 財團法人工業技術研究院 | Method and system for detecting short circuit impedance in battery |
| TWI657639B (en) | 2017-12-04 | 2019-04-21 | Industrial Technology Research Institute | Method and system for determining a discharging flow of a battery |
| CN110687468B (en) * | 2018-06-19 | 2021-01-15 | 华为技术有限公司 | Method and device for estimating state of charge of battery |
| KR20200101754A (en) * | 2019-02-20 | 2020-08-28 | 삼성에스디아이 주식회사 | Battery control appratus and battery control method |
| CN110045290B (en) * | 2019-04-25 | 2021-04-06 | 上海空间电源研究所 | Nondestructive testing method for potential short circuit defects in lithium ion storage battery |
| CN111707909A (en) * | 2020-05-28 | 2020-09-25 | 广州广华智电科技有限公司 | Porcelain insulator detection method and porcelain insulator detection circuit |
| CN112230160B (en) * | 2020-09-22 | 2023-10-20 | 国联汽车动力电池研究院有限责任公司 | Method and device for testing short circuit positioning in battery cell |
| CN112462274A (en) * | 2020-11-23 | 2021-03-09 | 哈尔滨理工大学 | Battery self-discharge effect-based method for diagnosing short-circuit fault in grouped batteries |
| CN112557923A (en) * | 2020-12-01 | 2021-03-26 | 上海电器科学研究所（集团）有限公司 | Battery overdischarge test method |
| CN116500459B (en) * | 2023-06-28 | 2023-08-29 | 中汽研汽车检验中心(常州)有限公司 | Lithium battery safety performance evaluation method and device, storage medium and electronic equipment |
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