CN106067560A - 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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- CN106067560A CN106067560A CN201610630840.5A CN201610630840A CN106067560A CN 106067560 A CN106067560 A CN 106067560A CN 201610630840 A CN201610630840 A CN 201610630840A CN 106067560 A CN106067560 A CN 106067560A
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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
The preparation method of a kind of internal short-circuit lithium-ion-power cell, the method, by lithium-ion-power cell carries out overdischarge, induces the internal short-circuit of lithium-ion-power cell, then obtains the discharge curve of described lithium-ion-power cell.Further this overdischarge curve is divided into different overdischarge feature stage, selected many batches of lithium-ion-power cells, many batches of selected lithium-ion-power cells are carried out overdischarge.Finally obtain multiple internal short-circuit resistance and the corresponding relation of overdischarge state-of-charge, thus obtain the MAP of the internal short-circuit of this lithium-ion-power cell.MAP according to this internal short-circuit carries out overdischarge to selected lithium-ion-power cell, thus realizes harmless quantitative induction lithium-ion-power cell internal short-circuit.The method by overdischarge induction internal short-circuit that the present invention proposes need not destroy the frame for movement of lithium-ion-power cell, favorable repeatability, it is possible to harmless quantitative induction lithium-ion-power cell internal short-circuit.
Description
Technical field
The invention belongs to cell art, be specifically related to the preparation method of a kind of internal short-circuit lithium-ion-power cell.
Background technology
Under the energy scarcity dual-pressure with environmental pollution, automobile dynamic system motorized has been increasingly becoming future automobile
The major trend of technology development.It is high that lithium-ion-power cell has energy density, and the advantage having extended cycle life has become as now
One of the main selection in electric powered motor source.Along with the gradually popularization of electric automobile, the safety of lithium-ion-power cell
Accident occurs the most again and again.Relevant accident threatens the security of the lives and property of the people, also counteracts that the big rule of electric automobile
Mould industrialization.
Lithium-ion-power cell use during, internal short-circuit from produce to ultimately cause electrokinetic cell thermal runaway need through
The time counted one by one hour.During a few hours that internal short-circuit occurs and develops, it is necessary to the generation of internal short-circuit detected in time also
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 is accomplished by reliable effective
Internal short-circuit in early days detection algorithm, to carry out early warning for internal short-circuit, it is ensured that the personal security in car.Once open
Sending internal short-circuit detection algorithm in early days, its actual effect and reliability are accomplished by testing.Reliable and effective interior in order to develop
Short circuit detection algorithm in early days, needs to arrange a lithium-ion-power cell with internal short-circuit in set of cells, could effectively
The actual effect of test internal short-circuit detection algorithm and reliability.But, the concrete origin cause of formation for internal short-circuit is not already completely at present
Clear, very difficult acquisition in use there occurs the lithium-ion-power cell of internal short-circuit.Usually, only there is it in accident
After, could pass through whether the accident investigation supposition accident origin cause of formation is internal short-circuit.
Therefore, reach out for a lithium-ion-power cell with internal short-circuit, the detection in early days of detection internal short-circuit is calculated
The effect of method is necessary.At present, contrived experiment device includes three class masters with induction lithium-ion-power cell internal short-circuit
The method wanted: 1) rupture cause internal short-circuit by mechanical presses, puncture or laser convergence initiation battery diaphragm；2) move at lithium ion
Introduce impurity particle between power battery plus-negative plate, carry out extruding at correspondence position and cause internal short-circuit；3) at lithium ion power electricity
The internal built-in controllable material (such as paraffin, memorial alloy etc.) in pond, uses specific trigger condition (such as intensification etc.) to activate controlled
Material, controllable material attribute change (such as melted paraffin wax, memorial alloy deformation etc.) causes lithium-ion-power cell both positive and negative polarity short circuit,
Thus induce internal short-circuit.
The method of above three class induction internal short-circuits all has certain disadvantages.Method 1) lithium-ion-power cell can be caused to tie
The destruction of structure.And under practical situation, actually used during battery internal short-circuit seldom due to battery structure destroy and occur.Also
Having, method 1) internal short-circuit that causes is unstable, and may directly contribute the thermal runaway of lithium-ion-power cell, thus can not induce early
Phase internal short-circuit, it is impossible to for the checking of internal short-circuit detection algorithm.It addition, method 1) repeatability be not fine, it is impossible to protect
Card can cause stable quantitative internal short-circuit every time.
Method 2) lithium-ion-power cell can be caused equally to deform, can not preferably induce under practical situation is interior short
Road.Method 2) the lithium-ion-power cell internal short-circuit situation that causes is the most unstable, may directly contribute lithium-ion-power cell
Thermal runaway.Further, when introducing impurity particle, the microscopic appearance of impurity particle is difficult to control to, it is impossible to ensure lithium-ion-power cell
The repeatability of internal short-circuit, can not obtain quantitative internal short-circuit the most in various degree.
Method 3) do not result in cell deformation, but, built-in controllable material needs certain condition to be triggered, as heated up
Melted paraffin, or heat up excite memorial alloy to deform.Temperature-rise period itself changes the normal work of lithium-ion-power cell
Temperature, is likely to result in the generation of lithium-ion-power cell other side reactions internal, have impact on the electrochemistry of lithium-ion-power cell
With heat production characteristic, damage lithium-ion-power cell the most to a certain extent.Method 3) introduced controllable material and lithium ion
Microscopic appearance between electrokinetic cell both positive and negative polarity is difficult to determine with microcosmic effect relation, still can not be effectively short in fixing quantity
The degree on road, it is impossible to ensure the repeatability of internal short-circuit.
Summary of the invention
In view of this, it is necessary to proposing a kind of internal short-circuit lithium-ion-power cell preparation method, the 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.
The preparation method of a kind of internal short-circuit lithium-ion-power cell, comprises the following steps:
S110, selected a lithium-ion-power cell；
S120, carries out performance test to described lithium-ion-power cell, it is thus achieved that the capacity of described lithium-ion-power cell, interior
Resistance, voltage and positive and negative pole material attribute；
S130, carries out overdischarge test, and obtains the mistake of described overdischarge test process described lithium-ion-power cell
Discharge curve, the vertical coordinate unit of described overdischarge curve is overdischarge voltage, and abscissa unit is state-of-charge；
S140, is divided into M overdischarge feature stage according to described overdischarge voltage by described overdischarge curve, described M
Overdischarge feature stage is the 1st overdischarge feature stage, the 2nd overdischarge feature stage ..., M overdischarge feature stage, each
The corresponding overdischarge process of individual described overdischarge feature stage；Wherein, described M is more than or equal to 3；
S150, takes M and criticizes described lithium-ion-power cell, and every batch of described lithium-ion-power cell during described M criticizes is the most right
Answer a described overdischarge feature stage in described M overdischarge feature stage, each described lithium ion during described M is criticized
Electrokinetic cell is overdisharged to corresponding state-of-charge；
S160, each the described lithium-ion-power cell in criticizing described M carries out internal short-circuit test, it is thus achieved that described M criticizes
In the internal short-circuit resistance value of each described lithium-ion-power cell；
S170, draws described lithium-ion-power cell according to described internal short-circuit resistance value with described overdischarge SOC
The MAP of internal short-circuit, the abscissa of described MAP is state-of-charge, and the vertical coordinate of described MAP is internal short-circuit resistance；
S180, according to described MAP to a described lithium-ion-power cell overdischarge, induces this lithium-ion-power cell
Internal short-circuit.
The present invention proposes the preparation method of a kind of internal short-circuit lithium-ion-power cell.The method by selected lithium from
Sub-electrokinetic cell carries out overdischarge, and the overdischarge curve of acquisition is divided into M overdischarge feature stage.Selected M criticizes described lithium
Ion battery, corresponding M overdischarge feature stage carries out overdischarge.Finally obtain multiple internal short-circuit resistance and state-of-charge
Relation, the MAP of the internal short-circuit of described lithium-ion-power cell can be drawn.Then, can be to one according to described MAP
Described lithium-ion-power cell overdischarge, thus realize the harmless quantitative induction of lithium-ion-power cell internal short-circuit.The present invention carries
The internal short-circuit lithium-ion-power cell preparation method gone out need not destroy the frame for movement of lithium-ion-power cell, repeatable
Good, it is possible to the internal short-circuit of harmless quantitative induction lithium-ion-power cell, such that it is able to prepare, there is different internal short-circuit degree
Internal short-circuit lithium-ion-power cell.For assessing in various degree in the case of internal short-circuit quantitatively, the danger of lithium-ion-power cell
Degree.Can also be used to develop internal short-circuit detection algorithm, and for the effectiveness of qualitative assessment internal short-circuit detection algorithm.The program
Assessment internal short-circuit in early days detection algorithm is had great importance, it will help that improves lithium-ion-power cell safety management can
By property, reduce the generation of security of lithium-ion-power cell accident.Can be produced by the method and there is internal short-circuit in various degree
Lithium-ion-power cell.Utilize the voltage of the lithium-ion-power cell with internal short-circuit, temperature-responsive that the method obtained
Can be that exploitation internal short-circuit detection algorithm in early days provides data, for verifying the effective of the internal short-circuit developed detection algorithm in early days
Property and reliability.
Accompanying drawing explanation
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 in one embodiment of the invention, battery modules be connected in series situation；
Fig. 3 is in one embodiment of the invention, the state-of-charge after described battery modules overdischarge；
Fig. 4 is in one embodiment of the invention, the overdischarge curve of lithium-ion-power cell and divided stages situation；
Fig. 5 is the enlarged drawing of described Fig. 4；
Fig. 6 is in one embodiment of the invention, uses constant current method of testing estimation lithium-ion-power cell internal short-circuit resistance
Schematic diagram；
Fig. 7 is in one embodiment of the invention, uses constant voltage method of testing estimation lithium-ion-power cell internal short-circuit resistance
Schematic diagram；
Fig. 8 is in the embodiment of the present invention, uses the schematic diagram of settled process estimation lithium-ion-power cell internal short-circuit resistance；
Fig. 9 is in one embodiment of the invention, the MAP of lithium-ion-power cell；
Following detailed description of the invention will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Main element symbol description
Lithium-ion-power cell module 100
Lithium-ion-power cell 11,12,13,14,15
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings.Below with reference to
The embodiment that accompanying drawing describes is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
Referring to Fig. 1, the preparation method of a kind of internal short-circuit lithium-ion-power cell that the present invention proposes, including following step
Rapid:
S110, selected a lithium-ion-power cell；
S120, carries out performance test to described lithium-ion-power cell, it is thus achieved that the capacity of described lithium-ion-power cell, interior
Resistance, voltage and positive and negative pole material attribute；
S130, carries out overdischarge test, and obtains the mistake of described overdischarge test process described lithium-ion-power cell
Discharge curve, the vertical coordinate unit of described overdischarge curve is overdischarge voltage, and abscissa unit is state-of-charge；
S140, is divided into M overdischarge feature stage according to described overdischarge voltage by described overdischarge curve, described M
Overdischarge feature stage is the 1st overdischarge feature stage, the 2nd overdischarge feature stage ..., M overdischarge feature stage, each
The corresponding overdischarge process of individual described overdischarge feature stage；Wherein, described M is more than or equal to 3；
S150: corresponding described M overdischarge feature stage, takes M and criticizes described lithium-ion-power cell, described M criticize in every
Criticize a described overdischarge feature stage in the most corresponding described M the overdischarge feature stage of described lithium-ion-power cell,
In criticizing described M, each described lithium-ion-power cell carries out overdischarge and is overdisharged to corresponding state-of-charge；
S160: each described lithium-ion-power cell in criticizing described M carries out internal short-circuit test, each institute corresponding
State overdischarge feature stage, it is thus achieved that described M criticize in the internal short-circuit resistance value of each described lithium-ion-power cell；
S170: short in drawing lithium-ion-power cell according to described internal short-circuit resistance value with described overdischarge SOC
The MAP on road, the abscissa of described MAP is state-of-charge, and the vertical coordinate of described MAP is internal short-circuit resistance value.
S180: according to described MAP to a described lithium-ion-power cell overdischarge, induce this lithium-ion-power cell
Induction internal short-circuit.
In step S110, selected lithium-ion-power cell refers to select a lithium-ion-power cell according to actual needs.
So-called is to have identical parameter with money lithium ion battery, the lithium-ion-power cell of same brand.Described lithium ion power
Quantity the method according to the invention of battery is actually needed selection.However it is necessary that all of lithium-ion-power cell of guarantee is all tool
There is identical parameter, namely with money lithium-ion-power cell.To be tested complete after, carry out internal short-circuit harmless quantitative induction
Time, also corresponding is the lithium ion battery of identical money.
In step S120, the method that described lithium-ion-power cell carries out performance test is conventional lithium ion electrokinetic cell
Traditional test methods, it is therefore an objective to further appreciate that the various performance parameters of selected described lithium-ion-power cell.Specifically,
Including the volume test under given current condition, the battery open circuit voltage test under given current condition, and battery plus-negative plate
The electrochemical properties test of material.
The test that described lithium-ion-power cell carries out overdischarge can select as required.An enforcement
In example, it is right that step S130 needs the lithium-ion-power cell module being composed in series by least three described lithium-ion-power cells of joint
Described lithium-ion-power cell carries out overdischarge test.Specifically, may comprise steps of:
S131, takes at least three described lithium-ion-power cells of joint；
S132, saves described lithium-ion-power cell from described at least three and selects a joint lithium-ion-power cell as overdischarge
Lithium-ion-power cell；
S133, described overdischarge lithium-ion-power cell is individually vented to state-of-charge be 0%；
S134, saves described at least three remaining described lithium-ion-power cell in described lithium-ion-power cell and charges to
State-of-charge is 100%；
S135, saves described at least three the series connection of described lithium-ion-power cell and obtains lithium-ion-power cell module, use
The electric current identical with step S120 carries out overdischarge for this lithium-ion-power cell module, until described overdischarge lithium ion
There is extensive precipitating metal dendrite in electrokinetic cell, shows voltage and level off to till 0V.
In step S135, by real-time test, it is possible to obtain the overdischarge of described overdischarge lithium-ion-power cell
Curve.The abscissa of described overdischarge curve is state-of-charge, and vertical coordinate is battery over-discharge voltage.Therefore, described overdischarge
Curve has reacted the relation of battery over-discharge voltage and state-of-charge.During overdischarge, abnormal electrochemical potentials distribution
Can grow at abnormal position by inducing metal dendrite (such as Li dendrite, ferrum dendrite, copper dendrite etc.).The growth of metallic dendrite can finally be stung
Broken battery diaphragm, causes the generation of battery internal short-circuit.In one embodiment, described metallic dendrite is copper dendrite.
In one embodiment, in step S140, based on the battery performance test result in step S120, for step
The overdischarge curve obtained in S3 carries out Analysis on Mechanism, and the degree separated out with metallic dendrite, as partitioning standards, divides described M
Overdischarge feature stage.It is appreciated that to described overdischarge curve divided stages it is different in order to obtain each the most stage by stage
The internal short-circuit resistance value that stage different state-of-charge is corresponding is carried out.The division of described overdischarge feature stage can be according to reality
Border needs to carry out, as long as the method that described overdischarge curve is carried out divided stages, all within scope.Institute
Stating M overdischarge feature stage is continuous print, and the state-of-charge of each overdischarge feature stage is all in a given scope.
In step S150, described lithium-ion-power cell can be criticized carry out overdischarge test by choosing M.During M criticizes
The quantity of every a collection of described lithium-ion-power cell be all at least two or more.Be appreciated that the most a collection of in described
Lithium-ion-power cell quantity is the most, then the test data of acquisition are the most.More test data are so that according to upper
The figure line stating test data drafting is more accurate, and precision is higher.Described M criticizes lithium-ion-power cell and M mistake in step S140
The discharge characteristic stage is corresponding.It is to say, there are how many overdischarge feature stage, it is necessary to select how many batches of described lithiums from
Sub-electrokinetic cell carries out overdischarge.Owing to, in described M overdischarge feature stage, the state-of-charge in each stage is different
's.Therefore, it can carry out overdischarge according to the different SOC in each stage.Specifically, selected M criticizes described lithium
After ion battery, according to the different SOC in m-th overdischarge feature stage, described M is criticized in lithium ion battery
Each lithium-ion-power cell carry out overdischarge one by one.Described each lithium-ion-power cell all discharges into different charged shapes
State, and described different state-of-charge is the different SOC in corresponding described m-th overdischarge feature stage.
In step S160, carry out interior short by the described M after the overdischarge in step S150 is criticized lithium-ion-power cell
Drive test tries, 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 have been known in step S150.Therefore, after step S160, just obtain multiple internal short-circuit resistance value
With multiple SOC.In step S160, the method for quantitative test internal short-circuit degree includes constant current method of testing, and constant voltage is tested
One or more in method, and settled process.
Specifically, described constant current method of testing can include two ways: the first be internal short-circuit serious in the case of, make
There is simultaneously for a normal lithium-ion-power cell monomer of joint and a joint lithium ion power electricity of internal short-circuit with constant current
Pond monomer carries out constant-current charge or electric discharge, comes quantitatively according to the difference value of normal battery with internal short-circuit battery charge or discharge capacity
The degree of assessment internal short-circuit；The second is in the case of internal short-circuit is very serious, uses less constant current IConstant 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 magnitude of voltage VStable, then
The internal short-circuit resistance that now can estimate battery is RISC=VStable/IConstant current。
Specifically, described constant voltage method of testing refers to the lithium-ion-power cell with internal short-circuit is carried out constant-voltage charge.Will
The lithium-ion-power cell with internal short-circuit is charged to a certain voltage VCVAfter, at this voltage VCVPlace carries out constant-voltage charge.Constant voltage is filled
In electric process, charging current will be gradually reduced.But, owing to internal short-circuit consumes electric current, charging current is reduced to a certain numerical value ICV
Time, charging current will be maintained at ICVAnd do not change.At this point it is possible to it is R that quantitative estimation goes out internal short-circuit resistanceISC=VCV/ICV。
Specifically, described settled process refers to lithium-ion-power cell charge to a certain state-of-charge=α, by battery standing
And monitor cell voltage.After a period of time Δ t, due to the existence of internal short-circuit, the electricity of this joint lithium-ion-power cell will be put
Sky is state-of-charge=0.According to discharge time and the electricity of releasing, it is estimated that averagely the putting of this joint lithium-ion-power cell
Electricity electric current is IElectric discharge=α * Q/ Δ t, wherein Q represents the rated capacity of battery, and unit is A s.Assuming that the averaged discharge electricity of battery
Pressure is VAveragely, then it is estimated that the internal short-circuit resistance of battery is about RISC=VAveragely/IElectric discharge。
Step S170, sets up coordinate system, according to the plurality of internal short-circuit resistance value obtained in step S160 with described many
Individual SOC just can draw the MAP of described lithium-ion-power cell.The abscissa of described MAP is state-of-charge,
The vertical coordinate of described MAP is internal short-circuit resistance value.The concrete method drawn does not limits, and can be various method.
Step S180, obtains the MAP of a lithium-ion-power cell by step S170, as long as selecting with described in money
Lithium-ion-power cell, and the SOC that selected described lithium-ion-power cell is overdisharged in MAP.Overdischarge
The internal short-circuit resistance of later described lithium-ion-power cell just can directly read out from described MAP.The method obtains
The internal short-circuit resistance of internal short-circuit lithium-ion-power cell can shift to an earlier date and select as required, it is achieved thereby that short in quantitatively obtaining
Road lithium-ion-power cell.For having corresponding internal short-circuit resistance RISCLithium-ion-power cell carry out performance test, can obtain
Obtaining internal short-circuit resistance is RISCIn the case of, the electrochemistry of lithium-ion-power cell and heat production characteristic.Thus be internal short-circuit inspection in early days
The exploitation of method of determining and calculating provides the characteristic of internal short-circuit.The lithium-ion-power cell with corresponding internal short-circuit can also be opened at algorithm
After distributing into, for the validity and reliability of verification algorithm.
Specific embodiment
In step S110 of the present embodiment, have chosen a lithium-ion-power cell, this lithium-ion-power cell its
Positive electrode active materials is nickel-cobalt-manganese ternary material, and negative active core-shell material is graphite, and barrier film has PE substrate and carried out one side pottery
Porcelain is coated with.
In step S120 of the present embodiment, by performance test, estimate this lithium-ion-power cell and be discharged to
When state-of-charge is 0%, inside it, there is not the precipitation of copper dendrite.For ensureing the precipitation of copper dendrite, battery must overdischarge
To negative voltage.By battery performance test, under the conditions of can obtaining using 8.33A (1/3C multiplying power) discharge and recharge, this lithium ion
The capacity of electrokinetic cell is about Q=26.5Ah.
In step S130 of the present embodiment, as shown in Figure 2, have employed the 5 described same money lithium-ion-power cell strings of joint
Connection constitutes lithium-ion-power cell module 100.Before this lithium-ion-power cell module 100 module is connected in series, need
First individually being vented the electricity of wherein one joint lithium-ion-power cell 11 for state-of-charge is 0%；The most again by other four joints lithiums
Ion battery 12,13,14,15 is fully charged, and state-of-charge is 100%.After completing above-mentioned preparation, then by this 5 joint
Lithium-ion-power cell 11,12,13,14,15 is connected in series.Then use with identical electric current 8.33A in step S120 for
This lithium-ion-power cell module 100 carries out overdischarge, until this lithium-ion-power cell 11 occurs to separate out copper dendrite on a large scale
Till.
In step S130 of the present embodiment, described lithium-ion-power cell 11 will by overdischarge, and other lithium ions move
12,13,14,15, power battery is regular picture.As shown in Figure 3, the overdischarge of described lithium-ion-power cell 11 starts one section
After time, as started after 1h, its state-of-charge will be reduced to-33.3%, and other four save lithium-ion-power cell 12,13,14,
The state-of-charge of 15 is then reduced to 66.7%.
The overdischarge curve that step S130 of the present embodiment obtains is as shown in Figure 4.Along with the carrying out of overdischarge, battery electricity
Negative value is reduced in pressure, and lasting overdischarge, to about about-2.1V, voltage bottom out, correspond to inside battery precipitation copper dendrite anti-
The beginning answered.When being overdisharged to-100%SOC, voltage curve levels off to a fixed potential, illustrates to separate out copper dendrite the completeest
Entirely complete.
In step S140 of the present embodiment, as shown in Figure 4, the overdischarge curve of this lithium-ion-power cell is drawn
It is divided into 4 overdischarge feature stage: stage I, stage II, stage III, stage IV.
Stage I correspond to cell voltage continuous decrease, stopping declining to cell voltage.During stage I, this lithium
Lithium-ion embeding positive pole within ion battery so that cathode voltage declines；Meanwhile, lithium ion is deviate from from negative pole so that
Cathode voltage raises.Due to the deintercalation process that lithium ion occurs main during stage I, voltage curve monotonic decreasing.Further, with
The carrying out of overdischarge, owing to cathode voltage could possibly be higher than positive pole, so cell voltage can become negative value.
Stage II initiates from cell voltage to be stopped declining, and during stage II, cell voltage starts slowly to go up.Battery
The Copper Foil of negative current collector is too high due to current potential, starts to be dissolved in electrolyte with the form of copper ion.Copper ion is to battery just
Pole is spread, and assembles in positive electrode potential lower.When copper ion concentration reaches certain degree, will send out in positive electrode potential lower
The reduction of the pig copper, causes the precipitation of copper, i.e. there occurs analysis copper.At stage II, the copper of precipitation can be in the electromotive force lower of anode
It is grown into, the growth of copper dendrite in the range of partial points i.e. occurs.The growth course of copper dendrite is a chemical equilibrium, depends on
Rely the extra electron that overdischarge provides to positive pole, dissolve copper ion in the electrolytic solution and constantly separate out in positive electrode potential lower, copper
Dendrite constantly grows.This chemical equilibrium corresponding, can see that from the enlarged drawing of accompanying drawing 5 rise of cell voltage is more slow
Slowly.
In stage II, the direction of growth of copper dendrite is directed towards battery diaphragm and battery cathode direction, the lasting life of copper dendrite
Length can be squeezed in the hole of battery diaphragm, and continues to grow to battery cathode direction.Owing to the hole of battery diaphragm can lead to
To negative pole, therefore, after copper dendritic growth a period of time, battery diaphragm will be passed, cause between anode and battery cathode
Short circuit.The short circuit caused through barrier film due to copper dendrite once occurs, and lithium-ion-power cell is internal occurs that new electric current returns
Road, the impact that overdischarge causes is weakened, and cell voltage can go up rapidly.What cell voltage went up rapidly starts i.e. to correspond to rank
The end of section II, and stage III's is initial.
From the beginning of stage III, on the one hand, the short circuit duration within lithium-ion-power cell works, and cell voltage is lasting
Go up；On the other hand, the analysis copper at anode persistently occurs, and is gradually extended to large area analysis copper from local analysis copper, short circuit
Degree the most gradually strengthens.Therefore, in stage III, the voltage of battery gos up rapidly.And the degree analysing copper is gradually increased, lithium
During the internal occurrence of large-area internal short-circuit of ion battery, lithium-ion-power cell gradually becomes a pure short-circuit resistance, battery
Voltage is by the negative value convergence constant to.Cell voltage gradually level off to a constant negative value time, the stage, III terminated, the stage
IV starts.
At stage IV, as shown in Figure 4, the internal occurrence of large-area internal short-circuit of lithium-ion-power cell, cell voltage is gradually
Go up to a stable numerical value.That is this lithium-ion-power cell internal occurrence of large-area short circuit so that this lithium ion
Electrokinetic cell becomes a fixed value resistance, thus cell voltage has become a fixed value.
In step S150 of the present embodiment, specifically, the overdischarge feature of corresponding aforementioned four lithium-ion-power cell
In the stage, 4 batches of described same money lithium-ion-power cells can be selected.The electric discharge of the 1st batch of lithium-ion-power cell correspondence stage i；
The electric discharge of the 2nd batch of lithium-ion-power cell correspondence phase il；The electric discharge of the 3rd batch of lithium-ion-power cell correspondence ii I-stage；
The electric discharge of the 4th batch of lithium-ion-power cell correspondence stage iv.In above-mentioned 4 batches of lithium-ion-power cells, the most a collection of all have many
Individual lithium-ion-power cell.
In step S160 of the present embodiment, the lithium-ion-power cell after having carried out overdischarge in various degree is carried out
Performance test.The internal short-circuit degree of lithium-ion-power cell is assessed by test.Specifically, described 1st batch of lithium ion power
What battery was corresponding is stage i, the most just can obtain the SOC in multiple stage i, and the internal short-circuit of correspondence
Resistance value.Owing to every a collection of lithium-ion-power cell all has multiple lithium ion battery, the interior of multiple correspondence therefore can be obtained
Short-circuit resistance value and SOC are used for drawing.Described 2nd, 3,4 batches of lithium-ion-power cells are also such.Hereinafter illustrate
Bright how carrying out carries out internal short-circuit assessment test to overdischarge lithium-ion-power cell in various degree.
For being overdisharged to the lithium-ion-power cell of state-of-charge=-100%, this lithium-ion-power cell there occurs greatly
Scale internal short-circuit.Therefore constant current method of testing is used to be assessed for its internal short-circuit degree.As shown in Figure 6, this lithium from
In the case of sub-electrokinetic cell internal short-circuit is very serious, use less constant current IConstant current=8.33A has internal short-circuit for this
Lithium-ion-power cell monomer carries out constant-current charge, and the voltage of this lithium-ion-power cell will stabilise at a magnitude of voltage VStable=
0.386V.The internal short-circuit resistance that the most now can estimate this lithium-ion-power cell is RISC=VStable/IConstant current=0.386/8.33=
0.046Ω。
For being overdisharged to the lithium-ion-power cell of state-of-charge=-14.4%, this lithium-ion-power cell there occurs
Locally internal short-circuit.As shown in Figure 7, use constant voltage method of testing, first use 8.33A to charge this lithium-ion-power cell, charging
To a certain voltage VCVAfter=4.2V, at this voltage VCVConstant-voltage charge is carried out at=4.2V.During constant-voltage charge, charging current
To be gradually reduced.But, owing to internal short-circuit consumes electric current, charging current is reduced to a certain numerical value ICVDuring=1.43A, charging current
Will be maintained at ICVAnd do not change.At this point it is possible to it is R that quantitative estimation goes out the internal short-circuit resistance of this lithium-ion-power cellISC=
VCV/ICV=2.93 Ω.
For being overdisharged to the lithium-ion-power cell of state-of-charge=-14.7%, this lithium-ion-power cell there occurs
Locally internal short-circuit.As shown in Figure 8, it is possible to use settled process is estimated for the internal short-circuit degree of this lithium-ion-power cell
Calculate.This lithium-ion-power cell is charged to state-of-charge=100%, and this lithium-ion-power cell is stood and monitors battery
Voltage.As shown in Figure 8, after a period of time Δ t=69174s, due to the existence of internal short-circuit, this joint lithium-ion-power cell
Electricity be state-of-charge=0 by emptying.According to discharge time and the electricity of releasing, it is estimated that this lithium-ion-power cell
Average discharge current be IElectric discharge=α * Q/ Δ t=1.38A, wherein Q represents the rated capacity of this lithium-ion-power cell, unit
It is As.Assuming that the average discharge volt of this lithium-ion-power cell is VAveragely=3.8V, then it is estimated that this lithium ion power is electric
The short-circuit resistance in pond is about RISC=VAveragely/IElectric discharge=2.75 Ω.
In step S170 of the present embodiment, the estimation result of the internal short-circuit in various degree obtained in combining step S160,
The MAP of lithium-ion-power cell internal short-circuit as of fig. 9 shown can be drawn.From described Fig. 9 it can be seen that at stage III
Leading portion, overdischarge state-of-charge is near-15%, the internal short-circuit resistance R of this lithium-ion-power cellISCAbout at 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 step S180 of the present embodiment, for this lithium-ion-power cell, can 9 produce with reference to the accompanying drawings
There is the lithium-ion-power cell of quantitative internal short-circuit resistance.Specifically, for producing, there is being somebody's turn to do of 1～10 Ω order of magnitude internal short-circuits
Money lithium-ion-power cell, should first choose this lithium-ion-power cell, and it is attached for-15% to be overdisharged to state-of-charge
Closely.
In sum, the present invention proposes the preparation method of a kind of internal short-circuit lithium-ion-power cell.The method is by right
Selected lithium-ion-power cell carries out overdischarge, and the overdischarge curve of acquisition is divided into M overdischarge feature stage.Selected
M criticizes described lithium-ion-power cell, and corresponding M overdischarge feature stage carries out overdischarge.Finally obtain multiple internal short-circuit resistance
With state-of-charge, the MAP of the internal short-circuit of described lithium-ion-power cell can be drawn.Then, can be right according to described MAP
One described lithium-ion-power cell electric discharge, thus internal short-circuit quantitative to this lithium ion power battery lossless, thus prepare
There is the internal short-circuit lithium-ion-power cell of quantitative internal short-circuit.The method by overdischarge induction internal short-circuit that the present invention proposes
Need not destroy the frame for movement of lithium-ion-power cell, favorable repeatability, it is possible to harmless quantitative induction lithium-ion-power cell
Internal short-circuit.It is thus possible to assess in various degree in the case of internal short-circuit quantitatively, the degree of danger of lithium-ion-power cell, also can
It is enough in exploitation internal short-circuit detection algorithm, and for the effectiveness of qualitative assessment internal short-circuit detection algorithm.The program is in assessment
Short circuit detection algorithm in early days has great importance, it will help improves the reliability of lithium-ion-power cell safety management, subtracts
The generation of few security of lithium-ion-power cell accident.The lithium ion with internal short-circuit in various degree can be produced by the method
Electrokinetic cell.The voltage of the lithium-ion-power cell with internal short-circuit that the method obtained, temperature-responsive is utilized to be out
Send out internal short-circuit early stage detection algorithm and data are provided, for verifying that the effectiveness of the internal short-circuit developed detection algorithm in early days is with reliable
Property.
Each technical characteristic of embodiment described above can combine arbitrarily, for making description succinct, not to above-mentioned reality
The all possible combination of each technical characteristic executed in example is all described, but, as long as the combination of these technical characteristics is not deposited
In contradiction, all it is considered to be the scope that this specification is recorded.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that, come for those of ordinary skill in the art
Saying, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for internal short-circuit lithium-ion-power cell, comprises the following steps:
S110, selected a lithium-ion-power cell；
S120, carries out performance test to described lithium-ion-power cell, it is thus achieved that the capacity of described lithium-ion-power cell, internal resistance,
Voltage and positive and negative pole material attribute；
S130, carries out overdischarge test, and obtains the overdischarge of described overdischarge test process described lithium-ion-power cell
Curve, the vertical coordinate unit of described overdischarge curve is overdischarge voltage, and abscissa unit is state-of-charge；
S140, is divided into M overdischarge feature stage according to overdischarge voltage by described overdischarge curve, and described M overdischarge is special
The stage of levying is the 1st overdischarge feature stage, the 2nd overdischarge feature stage ..., M overdischarge feature stage, each described mistake
A discharge characteristic stage corresponding overdischarge process；Described M is more than or equal to 3；
S150, takes M and criticizes described lithium-ion-power cell, described M criticize in every batch of described lithium-ion-power cell uniquely corresponding institute
State the described overdischarge feature stage of in M overdischarge feature stage, each described lithium ion power during described M is criticized
Battery over-discharge is to corresponding state-of-charge；
S160, each the described lithium-ion-power cell in criticizing described M carries out internal short-circuit test, it is thus achieved that during described M criticizes
The internal short-circuit resistance value of each described lithium-ion-power cell；
S170 is short in drawing described lithium-ion-power cell according to described internal short-circuit resistance value with described overdischarge SOC
The MAP on road, the abscissa of described MAP is state-of-charge, and the vertical coordinate of described MAP is internal short-circuit resistance；
S180, according to described MAP to a described lithium-ion-power cell overdischarge, induces the induction of this lithium-ion-power cell
Internal short-circuit.
2. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 1, it is characterised in that in step S120,
Performance test is carried out for selected lithium-ion-power cell and includes the volume test under given 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, it is characterised in that step S130 is concrete
Comprise the following steps:
S131, takes at least three described lithium-ion-power cells of joint；
S132, save described lithium-ion-power cells from described at least three select a joint lithium-ion-power cell as overdischarge lithium from
Sub-electrokinetic cell；
S133, described overdischarge lithium-ion-power cell is individually vented to state-of-charge be 0%；
S134, saves described at least three remaining described lithium-ion-power cell in described lithium-ion-power cell and charges to charged
State is 100%；
S135, saves described at least three the series connection of described lithium-ion-power cell and obtains lithium-ion-power cell module, use and walk
In rapid S120, identical electric current carries out overdischarge for this lithium-ion-power cell module, until described overdischarge lithium ion power
There is extensive precipitating metal dendrite in battery, shows voltage and level off to till 0V, thus obtain described overdischarge lithium ion and move
The discharge curve of power battery.
4. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 3, it is characterised in that in step S140,
Based on the performance test results in step S120, the degree separated out with metallic dendrite, as partitioning standards, divides described M mistake and puts
The electrical feature stage.
5. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 4, it is characterised in that in step S140,
With copper dendrite separate out degree as partitioning standards, described M overdischarge feature stage be respectively stage I, stage II, stage III,
Stage IV；Described stage I is by cell voltage continuous decrease, stopping declining to cell voltage；Described stage II starts from
Cell voltage stops declining, being more than zero to cell voltage Magnification；Described stage III starts from cell voltage Magnification and is more than
Zero, leveling off to a constant negative value to cell voltage；Described stage IV is for leveling off to a constant negative value from cell voltage
Stage afterwards.
6. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 1, it is characterised in that in step S150,
Described described M is criticized in each described lithium-ion-power cell be overdisharged in corresponding state-of-charge, institute
The batch that the overdischarge stage corresponding to corresponding state-of-charge of stating is corresponding with each described lithium-ion-power cell described
Identical.
7. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 1, it is characterised in that in S160, right
During described M criticizes, each described lithium-ion-power cell carries out the method for internal short-circuit test and includes constant current method of testing, and constant voltage is tested
One or more in method, and settled process.
8. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 7, it is characterised in that described constant current is tested
Method is: use constant current to have the lithium ion power of internal short-circuit simultaneously for a normal lithium-ion-power cell of joint and a joint
Battery carries out constant-current charge or electric discharge, according to normal lithium-ion-power cell with have internal short-circuit lithium-ion-power cell charging or
The difference value of discharge capacity carrys out the degree of qualitative assessment internal short-circuit.
9. the preparation method of internal short-circuit lithium-ion-power cell as claimed in claim 7, it is characterised in that described constant voltage is tested
Method is: the lithium-ion-power cell just with internal short-circuit is charged to a certain voltage VCVAfter, at this voltage VCVPlace carries out constant voltage and fills
Electricity, charging current is reduced to a certain numerical value ICVTime, if charging current maintains ICVAnd do not change, now quantitative estimation goes out
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, it is characterised in that described settled process
Comprise the following steps: lithium-ion-power cell is charged to a certain state-of-charge=α, this lithium-ion-power cell is stood and supervises
Survey cell voltage；When electricity emptying to the state-of-charge of this lithium-ion-power cell is zero, according to Δ t discharge time and releasing
Electricity α, the average discharge current estimating this lithium-ion-power cell is IElectric discharge=α * Q/ Δ t, wherein Q represents the volume of battery
Constant volume, unit is A s, it is assumed that the average discharge volt of this lithium-ion-power cell is VAveragely, then estimate this lithium ion and move
The internal short-circuit resistance of power battery is about RISC=VAveragely/IElectric discharge。
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