CN110957545B - Detection method for thermal runaway diffusion in battery - Google Patents

Detection method for thermal runaway diffusion in battery Download PDF

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Publication number
CN110957545B
CN110957545B CN201911295550.XA CN201911295550A CN110957545B CN 110957545 B CN110957545 B CN 110957545B CN 201911295550 A CN201911295550 A CN 201911295550A CN 110957545 B CN110957545 B CN 110957545B
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battery
thermal runaway
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detection method
single battery
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CN110957545A (en
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李国华
王建涛
邵泽超
任志敏
罗茜
史晓岩
高可心
云凤玲
崔义
李阿林
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China Automotive Battery Research Institute Co Ltd
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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
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • H01M10/486—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring temperature
    • 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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  • Secondary Cells (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

The invention relates to a method for detecting thermal runaway diffusion in a battery, which comprises the following steps: step 1), preparing a single battery with multiple tabs; step 2), cutting off the electric contact connection between electrode layers in the single battery, and then sealing the single battery; step 3), establishing corresponding relations between the electrode layers and different positions of the single battery, performing thermal runaway test, and respectively obtaining sub-voltages of the electrode layers; and 4), judging the thermal runaway diffusion in the battery. According to the method, the occurrence sequence of the thermal runaway of the single battery and the position of the internal short circuit or the micro short circuit in the battery under different abuse conditions can be detected, the understanding of the thermal runaway explosion and the thermal propagation of the battery is deepened, and further improvement measures can be made pertinently. The method is simple and easy to implement, and can realize detection of the thermal runaway diffusion detection method in the battery.

Description

Detection method for thermal runaway diffusion in battery
Technical Field
The invention relates to the safety field of lithium ion batteries, in particular to a method for detecting thermal runaway diffusion in a battery.
Background
With the application of high-energy-density lithium ion batteries to automobiles and large energy storage power stations on a large scale, safety accidents occur at the moment, and further popularization and application of the lithium batteries are seriously influenced, and even the property and life safety of people are threatened. When the battery is subjected to thermal abuse, electrical abuse, and mechanical abuse, thermal runaway and explosion fires are liable to occur. If the preventive measure is improper, just cause peripheral electric core out of control easily, and then cause the thermal runaway diffusion of module and PACK rank. Especially large batteries such as large squares, large pouches and large cylinders tend to have difficulty in preventing thermal runaway diffusion, and one of the important reasons is that the generation and propagation of thermal runaway inside the cell and the destructive characteristics after runaway are not well understood. This is due to the many factors and complexity of the interior of the thermal runaway process of the monomer, and of course, the lack of a corresponding detection instrument or method. So that the understanding of the thermal runaway mechanism in the battery is quite rare, and the thermal runaway inside the single battery is still in a half black box state. Different runaway positions show different damage characteristics of thermal runaway, such as damage to a single body shell and action on a peripheral battery. If the electric core is out of control from which position, and the influence is generated after explosion, the understanding of the thermal runaway can be deepened so as to conveniently take corresponding measures to prevent and control the thermal runaway diffusion.
At present, whether the single thermal runaway is judged generally only by voltage drop and battery surface temperature, but the voltage detection of the battery can only be used for voltage change of the whole battery, and the thermal runaway can not be determined to be short circuit or thermal runaway from that place, and the thermal runaway can not be detected at the first time by adopting a three-electrode method. For example, patent CN201910364952.4 discloses a method and an apparatus for detecting thermal runaway of a battery, which includes obtaining voltage detection data of a plurality of voltage detection points in the battery and a plurality of temperature detection data of a plurality of temperature detection points in the battery; calculating the temperature rise rate of the battery according to the plurality of temperature detection data; and judging whether the battery is out of thermal runaway or not according to the voltage detection data, the temperature detection data and the temperature rise rate. Although the judgment of whether thermal runaway occurs or not is carried out according to the voltage, the temperature and the temperature rise rate, the method of detecting the thermal runaway diffusion in the single battery cannot be realized. The patent CN201720388036.0 carries out criterion and early warning of thermal runaway by detecting gas emitted by a battery; this detection method is very delayed: firstly, gas is exhausted due to thermal runaway, and time is required for the gas to reach a sensor; second, the delay of the gas sensor itself; thirdly, the thermal runaway condition in the battery cannot be detected. The detection of thermal runaway inside a battery is a particularly difficult problem, especially if a large battery is to know the location of thermal runaway or internal short circuit. Under the condition of multiple tabs, the condition that the tabs are continuous and cannot be separated on one hand, and on the other hand, the tabs are welded together, so that the tabs are integrated to reflect the highest pressure part in the battery and cannot reflect the internal voltage information of the battery; that is, when the battery has local thermal runaway inside the battery, the voltage outside the battery still shows the voltage of the runaway layer. Therefore, the single battery has the problems that the internal thermal runaway triggering position is difficult to detect and the internal short circuit position is difficult to confirm, and the thermal runaway positions of the battery under different abuse modes are different, so that the thermal runaway occurring positions and influences are more diversified. Therefore, there is a need for an effective method for detecting the thermal runaway position in the battery, so as to deepen the understanding of the thermal runaway occurrence mechanism and provide a direction for designing a safe and reliable battery.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a method for detecting thermal runaway diffusion in a battery.
One of the objectives of the present invention is to provide a method for detecting thermal runaway diffusion inside a battery, comprising the following steps:
step 1), preparing a single battery with multiple tabs;
step 2), cutting off the electric contact connection between electrode layers in the single battery, and then sealing the single battery;
step 3), establishing corresponding relations between the electrode layers and different positions of the single battery, performing thermal runaway test, and respectively obtaining sub-voltages of the electrode layers;
and 4), judging the thermal runaway diffusion in the battery.
According to the method, the occurrence sequence of the thermal runaway of the single battery and the position of the internal short circuit or the micro short circuit in the battery under different abuse conditions can be detected, the understanding of the thermal runaway explosion and the thermal propagation of the battery is deepened, and further improvement measures can be made pertinently. The method is simple and easy to implement, and can realize detection of the thermal runaway diffusion detection method in the battery.
According to some preferred embodiments of the present invention, in step 1), the unit cell comprises a discontinuous multi-tab positive plate, a negative plate and a diaphragm, wherein the discontinuous multi-tab positive plate is composed of a plurality of positive plate segments or laminations; and/or the single battery is manufactured by a lamination or winding process.
In the invention, the multi-tab battery is manufactured by a lamination or winding process (such as a cylindrical battery), and then is prepared into the multi-tab battery, and different sub-tabs are respectively positioned at different layers in the battery. If the battery is a laminated battery, the positive electrode tab and the negative electrode tab are respectively arranged on two sides of the battery and respectively correspond to each layer. After the battery is pre-charged, formed and divided in volume, before thermal runaway abuse, if the battery is a cylindrical battery, firstly removing a cover, then separating a positive electrode lug, and sealing the positive electrode lug by using glue to isolate air; in the case of a laminated cell, the positive and negative main electrode tabs are clipped off so that the sub-voltages of the different layers can be measured.
According to some preferred embodiments of the present invention, in step 2), the main tab of the single battery is removed, a sub-tab is arranged on a side edge of each segment of the discontinuous multi-tab positive plate, the width of the sub-tab is 2-6 mm, and the distance between the sub-tabs of different layers is at least 5mm, preferably 10-15 mm. In the invention, the sub-tabs between different layers keep a certain distance so as to ensure that each segment can obtain independent sub-voltage and facilitate battery packaging.
According to some preferred embodiments of the invention, in step 2), for the laminated cell, cutting off the electrical contact connection comprises cutting off the positive main tab and/or the negative main tab; and/or, for cylindrical cells, severing the electrical contact connection comprises removing the cap of the cylindrical cell and then separating the positive and/or negative electrode tabs.
According to some preferred embodiments of the present invention, the step 2) further includes the following processes for the unit cell: at least one of pre-charging, chemical conversion and volume separation is performed.
According to some preferred embodiments of the present invention, in step 3), different sub-tabs respectively correspond to pole pieces located in different layers inside the batteryPosition P of the fragment, noted as P1、P2、P3……PnWherein n is the number of positive plates, and obtaining the corresponding battery position P1、P2、P3……PnThe sub-voltage V of each electrode layer is denoted as V1、V2、V3……Vn。
According to some preferred embodiments of the present invention, in step 4), the sub-voltage dip is used as a basis for determining thermal runaway, and preferably, V is 0, it is determined that thermal runaway or internal short circuit occurs at the battery position P; and V is not equal to 0, judging that the thermal runaway or the internal short circuit does not occur at the battery position P.
According to some preferred embodiments of the invention, in step 4), the temperature increase is used as an aid to the determination that thermal runaway and/or internal short circuit has occurred.
According to some preferred embodiments of the present invention, in step 4), an analysis of short circuits or micro-short circuits within the unit cell is performed according to a voltage drop, and/or a propagation pattern of thermal runaway inside the unit cell is determined.
According to some preferred embodiments of the invention, the detection method is used for the diffusion process of thermal runaway inside the single cell under determined abuse conditions, including thermal abuse and/or mechanical abuse.
According to the method, the thermal runaway diffusion inside the large battery, such as a large soft package battery, a cylindrical battery and a laminated battery, can be detected, the sub-voltages of different layers are monitored, and then the thermal runaway position is judged according to the voltage drop and the corresponding position of a segment, or the position of the internal short circuit in the battery is judged. The method can detect the thermal runaway scenes of the battery in thermal abuse (such as hot box, burning, external heating and the like), mechanical abuse (such as extrusion, heavy impact and the like), and the like, the starting position of the thermal runaway inside the battery and the propagation direction of the thermal runaway, and can also estimate the propagation rate of the thermal runaway in the monomer through the time difference. The method is simple and feasible, and is convenient for experimental research.
The invention can simply detect the thermal runaway diffusion in the single battery by detecting the thermal runaway diffusion in the battery, and detect the information such as the position, the diffusion direction, the position of the internal short circuit or the micro short circuit and the like of the thermal runaway in the single battery. The method can be used for judging the positions of internal short circuits and micro short circuits of the single battery and researching the heat propagation direction and the heat runaway propagation rule in the single battery, has great guiding significance for understanding the heat runaway process and the generated result, deepens the understanding of the thermal runaway explosion and the heat propagation of the battery, and further can take improvement measures pertinently.
Drawings
FIG. 1 is a schematic view of the detection process of the present invention;
fig. 2 is a schematic view of the multi-tab battery process of the present invention;
fig. 3 is a schematic view of a multi-tab cell process of example 1 of the present invention;
FIG. 4 is a schematic diagram of the determination of the thermal runaway location of a monomer in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. The technical solution of the present invention is not limited to the following specific embodiments, and includes any combination of the specific embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
In the present invention, the specific techniques or conditions not specified in the examples are performed according to the techniques or conditions described in the literature in the art or according to the product specification. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The chemical raw materials used in the invention can be conveniently bought in domestic chemical product markets.
Fig. 1 shows a schematic diagram of a detection process according to an embodiment of the present invention, which includes collecting independent sub-voltages of each segment in multi-tab battery preparation, battery treatment, and thermal runaway abuse test, and determining a thermal runaway position and an internal thermal runaway diffusion law of a single battery according to a relationship between the thermal runaway position and a voltage drop.
Some embodiments of the invention provide a simple method for detecting thermal runaway diffusion in a battery, which comprises the following specific detection steps: firstly, preparing a multi-sub-lug battery, then processing the battery, cutting off the electrical contact connection between each layer, sealing the battery by using glue, and then monitoring the sub-voltage of each layer. And during the thermal runaway test, the voltage drop and the corresponding position of the segment are used for judging the thermal runaway, or the position of the internal short circuit in the battery is judged.
Step 1), preparing a positive electrode plate and a negative electrode plate with multiple sub-tabs, wherein the positive electrode plate and the negative electrode plate are composed of multiple layers of electrodes, and one more sub-tab is additionally arranged between every two layers of electrodes except for a normal tab;
the negative pole piece is also prepared by multilayer electrodes, and one more sub-tab is added between each layer of electrodes besides the normal tab, corresponding to the adjacent positive pole layer.
The battery is prepared by manufacturing a multi-tab electrode group by a lamination process, wherein positive tabs of different layers and corresponding negative tabs of different layers are manufactured. The width of the sub-tabs is 2-6 mm, and the distance between the sub-tabs on different layers is larger than 5mm, so that the battery can be conveniently packaged.
Step 2), battery treatment (as shown in fig. 2): after the battery is pre-charged, formed and divided in capacity, the main positive electrode lug and the main negative electrode lug are removed before thermal runaway abuse is carried out on the battery; the conductive sub-capability between the different layers is lost and the sealing is performed with glue to isolate the air so as to obtain the independent segment independent sub-voltages.
Step 3), collecting the sub-voltage of each segment during the thermal runaway abuse test, and marking the sub-voltage as V1、V2、V3……VnRespectively corresponding to the batteries P1，P2，P3……PnThe position voltage of (1).
And 4) taking the voltage suddenly reduced to zero as a thermal runaway judgment basis, and judging that the thermal runaway or the violent internal short circuit occurs at the battery position P if V is 0. And V is not equal to 0, the battery position P is judged not to generate thermal runaway, and meanwhile, the battery internal short circuit or micro short circuit can be judged according to the voltage drop.
Example 1
The present embodiment provides a method for detecting thermal runaway diffusion in a battery, in which a pole group is composed of a discontinuous positive pole piece, a discontinuous negative pole piece, and a diaphragm. And (4) making a multi-tab battery, removing the cover to separate the tabs after capacity grading before a thermal runaway abuse test, and sealing with glue. And judging the thermal runaway diffusion and the internal short circuit position according to the relation between the thermal runaway position and the pressure drop.
Step 1), preparing a discontinuous positive plate, namely cutting the positive plate into two sections, wherein the cut sections are about the length of the outermost circle of the battery, and then adhering the two sections together by using a high-temperature adhesive tape with the thickness of 15 microns, but leaving a gap, as shown in figure 3. And respectively welding the two broken pieces with lugs. The positive electrodes of different segments correspond to different positions of the battery after winding, and the position of the outer layer is P1The inner level is P2(ii) a The voltage of the outer layer is V through voltages at different positions of the single battery1Inner layer voltage of V2。
The negative electrode is a continuous pole piece.
And step 2), preparing the battery by welding a tab, injecting liquid, sealing, pre-charging and aging. Before thermal runaway abuse, the cover is removed, the positive pole lug is separated, and the positive pole lug is sealed by glue to isolate air, so that independent voltage of each segment is obtained.
Step 3), collecting the voltage of each segment during the thermal runaway abuse test, as shown in fig. 3: marked as V1、V2Outermost layer P corresponding to the position of the battery1And inner layer position P2。
And 4), judging the thermal runaway diffusion in the battery. As shown in FIG. 4, in the case of the battery heated externally, the outer layer voltage is gradually decreased first, and suddenly drops to 0V to some extent, while the outer surface temperature rises but exhibits a delay, i.e., V 10, the position of the battery or the outer electrode P is determined1Prior to position P2Thermal runaway or internal short circuit occurs. Only then is thermal runaway of the inner electrode caused. It can also be seen from this embodiment that, under external heat, the thermal runaway of the battery first occurs before the battery is heatedTo the inner layer electrode. Because the judgment by the temperature always has delay and the internal condition of the battery cannot be reflected in time, the method does not take the temperature as the judgment basis.
Example 2
The embodiment provides a method for detecting thermal runaway diffusion in a battery, which comprises battery preparation, battery processing, data monitoring, and establishment of a corresponding relation and identification. The preparation of the battery comprises the following steps: the pole group consists of a discontinuous multi-pole-lug positive pole piece, a discontinuous negative pole piece and a diaphragm. The pole group is prepared into a multi-sub pole lug battery, and the pole lug of the single battery is removed before the thermal runaway test, so that the pole lug is not contacted any more and is sealed by glue. The positive electrodes of different segments correspond to different positions of the battery or different layers (P)1，P2，P3… …) through sub-voltages (V) to different layers or different locations of the cell1、V2、V3… …) is detected. And judging the thermal runaway and thermal runaway diffusion or internal short circuit position according to the relationship between the thermal runaway and the voltage drop and the correspondence of the sub-voltage to the corresponding battery position or the electrode layer.
Step 1), preparing a positive electrode plate and a negative electrode plate with multiple sub-tabs, wherein the positive electrode plate and the negative electrode plate are composed of multiple layers of electrodes, and one more sub-tab is additionally arranged between every two layers of electrodes except for a normal tab;
the negative pole piece is also prepared by multilayer electrodes, and one more sub-tab is added between each layer of electrodes besides the normal tab, corresponding to the adjacent positive pole layer.
And preparing a multi-tab battery, wherein a multi-tab electrode group is manufactured by a lamination process, and positive tabs of different layers and corresponding negative tabs of different layers are prepared. The width of the sub-tabs is 2-6 mm, and the distance between the sub-tabs on different layers is larger than 5mm, so that the battery can be conveniently packaged.
Step 2), battery treatment: after the battery is pre-charged, formed and divided in capacity, the main positive electrode lug and the main negative electrode lug are removed before thermal runaway abuse is carried out, so that the conductive electron capability between different layers is lost, and the battery is sealed by glue to isolate air. To obtain separate segment-independent sub-voltages.
Step 3), thermal runaway abuse test is carried outSet the sub-voltages of each segment, denoted V1、V2、V3……VnRespectively corresponding to different layers P of the battery1、P2、P3……PnThe voltage of (c).
And 4) taking the voltage suddenly reduced to zero as a thermal runaway judgment basis, and judging that the thermal runaway or the violent internal short circuit occurs at the battery position P if V is 0. And V is not equal to 0, the battery position P is judged to be not thermally out of control, and meanwhile, the battery short circuit or micro short circuit can be identified according to the voltage drop.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A method for detecting thermal runaway diffusion in a battery is characterized by comprising the following steps:
step 1), preparing a single battery with multiple tabs;
step 2), cutting off the electric contact connection between electrode layers in the single battery, and then sealing the single battery;
step 3), establishing corresponding relations between the electrode layers and different positions of the single battery, performing thermal runaway test, and respectively obtaining sub-voltages of the electrode layers;
step 4), judging the thermal runaway diffusion in the battery;
in the step 1), the single battery comprises a discontinuous multi-tab positive plate, a negative plate and a diaphragm, wherein the discontinuous multi-tab positive plate is formed by winding or laminating a plurality of positive plate segments, and a sub-tab is arranged on the side edge of each segment of the discontinuous multi-tab positive plate; in the step 2), for the laminated single battery, cutting off the electrical contact connection comprises cutting off a positive electrode main lug and a negative electrode main lug; for a cylindrical cell, cutting the electrical contact connection includes removing the cap of the cylindrical cell and then separating the positive and negative tabs.
2. The detection method as claimed in claim 1, wherein the width of the sub-tabs is 2-6 mm, and the distance between the sub-tabs of different layers is at least 5 mm.
3. The detection method as claimed in claim 2, wherein the distance between the sub-tabs of different layers is at least 10-15 mm.
4. The detection method according to claim 1, wherein in step 2), the following processes are further included for the single battery: at least one of pre-charging, chemical conversion and volume separation is performed.
5. The detection method according to claim 4, wherein in step 3), different sub-tabs respectively correspond to positions P, denoted as P, of pole piece segments located in different layers in the battery1、P2、P3……PnWherein n is the number of positive plates, and obtaining the corresponding battery position P1、P2、P3……PnThe sub-voltage V of each electrode layer is denoted as V1、V2、V3……Vn。
6. The detection method according to claim 5, wherein in step 4), the sub-voltage dip is used as a basis for thermal runaway determination.
7. The detection method according to claim 6, wherein in step 4), if V =0, it is determined that thermal runaway or internal short circuit has occurred at the battery position P; and V is not equal to 0, judging that the thermal runaway or the internal short circuit does not occur at the battery position P.
8. The detection method according to claim 7, wherein in step 4), the temperature rise is used as an auxiliary means for determining the occurrence of thermal runaway and/or internal short circuit.
9. The detection method according to claim 6, wherein, in step 4), the analysis of the short circuit or micro short circuit inside the single battery is performed according to the voltage drop, and/or the propagation mode of the thermal runaway inside the single battery is determined.
10. The detection method according to any one of claims 1 to 9, wherein the detection method is used for the diffusion process of thermal runaway inside the single cell under determined abuse conditions, wherein the abuse conditions comprise thermal abuse and/or mechanical abuse.
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