CN104062598B - A kind of lithium ion battery forces internal short-circuit security assessment method - Google Patents

A kind of lithium ion battery forces internal short-circuit security assessment method Download PDF

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Publication number
CN104062598B
CN104062598B CN201410306291.7A CN201410306291A CN104062598B CN 104062598 B CN104062598 B CN 104062598B CN 201410306291 A CN201410306291 A CN 201410306291A CN 104062598 B CN104062598 B CN 104062598B
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lithium ion
internal short
ion battery
battery
circuit
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CN201410306291.7A
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CN104062598A (en
Inventor
赵文娟
陈永平
黄璟
杨坚栋
吕成学
张静
陈瑶
吴江峰
高学锋
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Fengxian Entry-Exit Inspection And Quarantine Bureau Of People's Republic Of China (prc)
SHANGHAI DLG BATTERIY CO Ltd
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Fengxian Entry-Exit Inspection And Quarantine Bureau Of People's Republic Of China (prc)
SHANGHAI DLG BATTERIY CO Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a kind of lithium ion battery forces internal short-circuit security assessment method.Aperture is opened on lithium ion battery closed shell to be assessed, battery inside and outside pressure is consistent, then used charging method forces Li dendrite to generate until piercing through barrier film to cause internal short-circuit in negative pole, investigates whether now battery occurs thermal runaway phenomenon to assess its security performance.The inventive method is easy and simple to handle, can truly under extreme condition during analog charge Li dendrite produce and pierce through the situation that barrier film causes internal short-circuit, and newly-generated Li dendrite surface appearance identical it is contemplated that repeatability is good.

Description

A kind of lithium ion battery forces internal short-circuit security assessment method
Technical field
The present invention relates to lithium ion battery safety performance appraisal procedure, particularly a kind of lithium ion battery pressure internal short-circuit Security assessment method.
Background technology
Lithium ion battery has higher ratio with traditional secondary cell due to it compared with lead-acid battery, Ni-MH battery etc. Energy, has been widely applied to the different field such as consumer electronics product, electric bicycle, electric automobile, energy storage.Generally The positive electrode of the lithium ion battery such as transition metal oxide lithium salts such as cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4, in charged state Under belong to unstable compound, can decompose precipitated oxygen under the high temperature conditions, the oxygen of precipitation may with electrolyte in The combustibles such as the graphite material in combustible components, negative pole, charging product lithium carbon compound react and produce a large amount of heat energy, Heat energy may lead to further heat up and aggravate positive electrode and decompose analysis oxygen, eventually form " thermal runaway phenomenon " and lead to battery to fire Burn/blast.
Through researching and analysing, generally believe that in the industry initial hot conditionss are in most cases because the internal short-circuit of battery draws Rise, and it is the one of the main reasons leading to internal short-circuit that negative pole (locally) overcharge the Li dendrite being electrically generated to pierce through barrier film.
In order to improve the safety of lithium ion battery, each battery production enterprise is each in material, structure design, processing procedure management From having carried out numerous studies development, but how to evaluate the safety of battery especially just in case there is electricity in the case of internal short-circuit The security feature in pond is always a difficult problem.Famous UL standard is pacified in the electrokinetic cell about LEV and electric automobile Employ acupuncture in full evaluation to test (such as:ULSubject2271-2010 standard) occur in this kind of internal short-circuit assessing battery When security feature, its method is:
Battery is fully charged, lunged in the direction perpendicular to electrode surface with certain speed with the draw point of a diameter of 3mm Battery, keep pin in the battery a period of time, then observe battery whether explode, combustion phenomena.
This method is easy to implement, can simulated battery to a certain extent internal short-circuit phenomenon, but based on following Article two, reason, in the UL standard in other application field, acupuncture experiment is not specified as.
1) poor reproducibility:By the material of draw point, surface oxidation state, puncture the factors such as speed and affected too big, lead to test Occasionality increase, poor reproducibility.
2) similar external short circuit phenomenon can first be occurred before acupuncture causes internal short-circuit using so-called anti-needling structure, Thus cause barrier film Shutdown it is impossible to assessment under normal circumstances internal short-circuit when battery safety.
In other words, the safety that pin prick test is intended only as when simulated vehicle occurs unexpected in UL series standard is commented Estimate means, and be not the security assessment method that simulated battery occurs during internal short-circuit.
JIS standard proposes with nickel nail experimental evaluation internal short-circuit of battery safety (such as:JIS C8714:2007 standards), Its method is:
Battery recommends electric current with supplier, and constant-current charge, to 4.25V, turns constant-voltage charge to cut-off current at different temperatures 0.05C.After the completion of by battery proceed to temperature be 20 DEG C ± 5 DEG C, dew point be less than in -25 DEG C of environment, peel off sealing shell, take apart Battery bag simultaneously applies, in positive pole and negative electrode active material, the fritter nickel nail that interlayer puts into one " L " shape between barrier film, then rollback is former Shape, puts into and reinstalls sealing (must complete in 30min to sealing bag mouth from taking battery apart) in aluminum-plastic composite membrane bag in valve bag. After valve bag and battery place 45min ± 15min in specified temp temperature chamber, open aluminum plastic film, valve bag, take out battery and put It is placed on fixture, pushed in implantation nickel nail position vertical electrode surface with the speed of 0.1mm/s with the tool with rubber layer, until Battery stops pressure because internal short-circuit causes voltage drop to reach more than 50mV or pressure during 800N, observes whether battery fires Burn or explode.
This method can puncture, with true reappearance metallic foreign body, the situation that barrier film leads to internal short-circuit of battery, has good Repeatability.But open enclosed cell shell in dry environments, and implantation nickel nail is then re-closed between both positive and negative polarity, then enter It is a job that is extremely complex and needing high degree of skill that row such as heats, pushes at the operation, therefore there is no it at present in addition to JIS standard He adopts this method at well-known standard.
Content of the invention
It is an object of the invention to provide a kind of lithium ion battery forces internal short-circuit security assessment method, it is mainly used in Solve the problems of above-mentioned existing appraisal procedure, the inventive method can truly under extreme condition during analog charge, Li dendrite produces and pierces through barrier film and cause the situation of internal short-circuit, and newly-generated Li dendrite surface appearance identical it is contemplated that reappearing Property is good and easy and simple to handle.
Due under normal conditions, overcharge being carried out to lithium ion battery, the effect generating Li dendrite can not be reached.Cause CID (Current Interruption Device, current interrupt device) typically can be provided with for airtight lithium ion battery, when Generate because of gas during overcharge, inner pressure of battery increase leads to CID action cut-out to be charged so that Li dendrite life cannot be investigated Become and penetrate barrier film and positive contact forms the situation of internal short-circuit.
For achieving the above object, the technical scheme is that:
A kind of lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:Lithium to be assessed from Aperture is opened on sub- battery closed shell, is then electrically generated Li dendrite and causes internal short-circuit by overcharging, investigate now battery Whether there is thermal runaway.
Described lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:This lithium ion battery It is the hermetic type lithium ion battery with CID.
Described lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:Open aperture operation It is to carry out in -30 degrees Celsius of dew point or following dry environment.
Described lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:After unlatching aperture first With airtight adhesive tape by aperture temporary closure, then carry out overcharging electrically operated.
Described lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:Less than 2 hours Inside carry out overcharge experiment.
Described lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:The diameter of perforate is Fortunately between 0.5-2.0mm.
Described lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:Position of opening is best It is in inside battery space corresponding air chamber position, perforate depth is advisable to just break through closed shell wall thickness.
The mentality of designing of the inventive method is:The battery processing through perforate, the gas producing during overcharge, can So that outside is discharged into by perforate, cell internal pressure will not be occurred to raise and to lead to the safety device action that enclosed cell adds to be made Circuit is become to be cut off it can be ensured that Li dendrite generates until piercing through barrier film to cause internal short-circuit.Whether battery has occurred and that inside Short circuit, can reduce 50mV or more by, during constant-current charge, whether cell voltage moment (within 5 seconds) voltage and come Judge.Enter inside battery to testing issuable impact for reducing ambient atmosphere, perforate can in -30 degrees Celsius of dew point or Lower dry environment is carried out, then in the present context with the non-pressure-resistant seal measure such as adhesive tape by perforate temporary closure, return Carry out overcharge test in normal ambient environments.
Brief description
Fig. 1 is the schematic diagram that in the inventive method, cylinder type lithium battery punched.
Fig. 2 is square shaped duricrust lithium battery punching schematic diagram in the inventive method.
Specific embodiment
The invention discloses a kind of lithium ion battery forces internal short-circuit security performance assessing method, lithium to be assessed from On sub- battery closed shell open aperture (as Fig. 1,2, in figure 1 be air chamber punch position), then overcharge and be electrically generated lithium branch Crystalline substance, to cause internal short-circuit, investigates whether now battery occurs thermal runaway.
Alternately, this lithium ion battery is the hermetic type lithium ion battery with CID.
It is preferred that, opening aperture operation is to carry out in -30 degrees Celsius of dew point or following dry environment.
It is preferred that, open aperture temporary closure after aperture first with airtight adhesive tape, then carry out overcharging electrically operated.
It is preferred that, carry out overcharge experiment in less than 2 hours.
It is preferred that, the diameter of perforate is preferably between 0.5-2.0mm.
It is preferred that, preferably inside battery space corresponding air chamber position, perforate depth is with just for position of opening Penetrate closed shell wall thickness to be advisable.
To verify the superiority of the inventive method below by way of experiment further.
The test object of experiment:
(1) anti-acupuncture ternary cylindrical battery:The commercially available 18650 ternary 2200mAh batteries having " anti-acupuncture " structure, this battery Structure both positive and negative polarity outmost turns be uncoated active substance conducting base, when metal is needled into both positive and negative polarity can be formed whereby similar External short circuit effect, the possible Shutdown of barrier film, cause and during subsequent internal short-circuit, do not have high current generation.
(2) ceramic diaphragm ternary cylindrical battery:Coat 18650 ternarys that strengthening barrier film manufactures using aluminium oxide ceramics 2000mAh battery, because ceramic diaphragm has very high heat resistance, is typically considered to there is preferable safety.
Experimental technique:
With regard to aforementioned two kinds of test objects, the inventive method, JIS nickel is used to follow closely experimental technique, acupuncture experimental technique and UL respectively Abnormal charging measurement method is estimated, result such as table 1.
Embodiment 1
Take 4pcs anti-acupuncture ternary cylindrical battery, 1C4.2V constant-current constant-voltage charging to cut-off current 0.01C, then by battery Move on in the drying room that temperature 23+/- 2 DEG C dew point is less than -30 DEG C, electricity consumption is drilled in battery air chamber portion and opens the little of an a diameter of 1.0mm Hole, adhesive tape touch hole, removes drying room, 1C10V constant-current charge, terminates when one of aftermentioned phenomenon occurs:Battery temperature drops To low about 10 DEG C than peak value or generation (charging maximum duration is less than 8h) on fire from explosion.
Result:4 batteries all explode, and do not pass through.
Embodiment 2
Take 4pcs ceramic diaphragm ternary cylindrical battery, 1C4.2V constant-current constant-voltage charging to cut-off current 0.01C, then by electricity Pond moves on in the drying room that temperature 23+/- 2 DEG C dew point is less than -30 DEG C, and electricity consumption is drilled in battery air chamber portion and opens an a diameter of 1.0mm's Aperture, adhesive tape touch hole, removes drying room, 1C10V constant-current charge, terminates when one of aftermentioned phenomenon occurs:Battery temperature It is down to low about 10 DEG C or generation (charging maximum duration is less than 8h) on fire from explosion than peak value.
Result:4 batteries all do not occur to burn or explode, and pass through.
Comparative example 1
Take 4pcs anti-acupuncture ternary cylindrical battery, carry out acupuncture experiment by UL Subject2271-2010 standard, as a result 4 Battery does not all occur to burn or explode, and test is passed through.
Comparative example 2
Take 4pcs ceramic diaphragm ternary cylindrical battery, carry out acupuncture experiment, result by UL Subject2271-2010 standard 4 batteries all do not occur to burn or explode, and test is passed through.
Comparative example 3
Take 4pcs anti-acupuncture ternary cylindrical battery, carry out abnormal experiment of charging, 4 electricity as a result by UL1642-2010 standard Chi Jun does not occur to burn or explodes, and test is passed through.
Battery testing open-circuit voltage after experiment is 0V, and AC internal Resistance is ∞, illustrates that the CID of battery has broken Open.
Comparative example 4
Take 4pcs anti-acupuncture ternary cylindrical battery, use JIS C8714:2007 standards carry out nickel nail experiment as a result, 4pcs is electric There is phenomenon on fire in Chi Jun, test is not passed through.
Comparative example 5
Take 4pcs ceramic diaphragm ternary cylindrical battery, use JIS C8714:2007 standards carry out nickel nail experiment as a result, 4pcs All there is not blast or phenomenon on fire in battery, test is passed through.
Table 1, the Comparative result of different internal short-circuit safety evaluation method
As it can be seen from table 1 the inventive method has follows closely the suitable lithium ion battery security assessment effect of experiment with JIS nickel Really, the erroneous judgement situation of similar acupuncture experiment will not occur.The overcharge experiment of general UL standard cannot be in this experimental subject electricity Internal short-circuit is caused, thus cannot be carried out the assessment about security performance in the case of internal short-circuit in pond.
The inventive method is simple and convenient, and the nail experiment of result accuracy and JIS nickel is suitable, but easy and simple to handle and without the latter that The special expertise training of sample, has larger application value.
It is only presently preferred embodiments of the present invention in sum, be not used for limiting the practical range of the present invention.I.e. all The equivalence changes made according to the content of scope of the present invention patent and modification, all should be the technology category of the present invention.

Claims (6)

1. a kind of lithium ion battery force internal short-circuit security performance assessing method it is characterised in that:In lithium ion to be assessed Aperture is opened on battery closed shell, position of opening is in inside battery volume plenum corresponding site, is then given birth to by overcharge Become Li dendrite to cause internal short-circuit, investigate whether now battery occurs thermal runaway;This lithium ion battery is have CID airtight Type lithium ion battery.
2. lithium ion battery according to claim 1 force internal short-circuit security performance assessing method it is characterised in that:Open Opening aperture operation is to carry out in the dry environment below -30 degrees Celsius of dew point.
3. lithium ion battery according to claim 1 force internal short-circuit security performance assessing method it is characterised in that:Open Open aperture temporary closure after aperture first with airtight adhesive tape, then carry out overcharging electrically operated.
4. lithium ion battery according to claim 1 force internal short-circuit security performance assessing method it is characterised in that:? Carry out overcharge experiment in less than 2 hours.
5. lithium ion battery according to claim 1 force internal short-circuit security performance assessing method it is characterised in that:Open The diameter in hole is between 0.5-2.0mm.
6. lithium ion battery according to claim 1 force internal short-circuit security performance assessing method it is characterised in that:Open Hole location is defined by just breaking through closed shell wall thickness in inside battery space corresponding air chamber position, perforate depth.
CN201410306291.7A 2014-06-30 2014-06-30 A kind of lithium ion battery forces internal short-circuit security assessment method Expired - Fee Related CN104062598B (en)

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JP6245228B2 (en) * 2015-07-22 2017-12-13 トヨタ自動車株式会社 Inspection method for all-solid-state secondary battery and method for manufacturing all-solid-state secondary battery using the inspection method
CN107390137B (en) * 2017-08-16 2023-11-17 中国科学技术大学 Insulation puncture needle for evaluating safety performance of lithium ion battery
CN107645001A (en) * 2017-08-21 2018-01-30 上海空间电源研究所 A kind of experimental rig and test method for simulating lithium battery internal short-circuit
CN108267695B (en) * 2017-12-22 2020-08-11 江西瑞隆锂能科技有限公司 Analysis and test method based on forced lithium battery internal short circuit
US10739751B2 (en) 2018-06-18 2020-08-11 International Business Machines Corporation Apparatus for facilitating evaluating rechargeable batteries
CN109581241B (en) * 2018-12-07 2021-02-02 北京经纬恒润科技股份有限公司 Battery characteristic simulation method and device
CN109709137B (en) * 2018-12-28 2021-12-10 湖北雷迪特冷却系统股份有限公司 Battery water cooling plate temperature uniformity test equipment and method
CN110398699A (en) * 2019-06-26 2019-11-01 清华大学 Power battery thermal runaway method for early warning combined of multi-sensor information

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