WO2021134733A1 - Matériau thermoplastique ignifuge utilisé pour un module de batterie au lithium et présentant une fonction d'inhibition de diffusion d'emballement thermique - Google Patents

Matériau thermoplastique ignifuge utilisé pour un module de batterie au lithium et présentant une fonction d'inhibition de diffusion d'emballement thermique Download PDF

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Publication number
WO2021134733A1
WO2021134733A1 PCT/CN2020/000002 CN2020000002W WO2021134733A1 WO 2021134733 A1 WO2021134733 A1 WO 2021134733A1 CN 2020000002 W CN2020000002 W CN 2020000002W WO 2021134733 A1 WO2021134733 A1 WO 2021134733A1
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Prior art keywords
flame
lithium battery
thermal runaway
thermoplastic material
retardant thermoplastic
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PCT/CN2020/000002
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English (en)
Chinese (zh)
Inventor
陈勳森
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耐特科技材料股份有限公司
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Priority to PCT/CN2020/000002 priority Critical patent/WO2021134733A1/fr
Publication of WO2021134733A1 publication Critical patent/WO2021134733A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the invention relates to a flame-retardant thermoplastic material, in particular to a flame-retardant thermoplastic material used for a lithium battery module and capable of inhibiting thermal runaway diffusion.
  • Lithium batteries are widely used in 3C products, power vehicles, energy storage systems, etc. Therefore, the safety of lithium batteries is a global issue. Even with multiple protections such as battery management systems (BMS) and mechanical structures, lithium batteries still have potential risks of heat and spontaneous combustion. In recent years, fires in energy storage power plants and electric vehicles have continued to occur. . For this reason, IEC 62619, UL 1973, UL 2580, JIS 8715-2, CNS 15387, GB/T 31485-2015 and other international standards have formulated test methods for thermal runaway of lithium batteries.
  • BMS battery management systems
  • Thermal Runaway IEC 62619 is defined as the phenomenon of rapid temperature rise caused by the exothermic reaction inside the cell.
  • Lithium batteries have high energy density and the electrolyte is flammable. Due to factors such as high temperature, overcharge, impact, electronic control system errors or process defects, the thermal runaway of the lithium battery causes prolonged burning.
  • the high temperature generated by thermal runaway of lithium batteries can often reach 600 ⁇ 1000°C.
  • the adjacent cells are also heated at the same time. If the upper limit temperature of the cell is exceeded (about 150°C), the adjacent cells will also self-radiate heat. The thermal runaway chain reaction that caused the battery system to burn completely.
  • the extended burn test uses external force assistance such as heating, acupuncture, overcharging, or the combination of the aforementioned methods to simulate the thermal runaway phenomenon of the battery cell inside the battery system to verify the suppression of thermal runaway diffusion of the battery system.
  • thermal management is very important for lithium battery module products, which is related to the service life of the lithium battery and the safety of the product.
  • the conversion of chemical energy and electric energy must cause energy loss, and the lost energy is released in the form of waste heat.
  • the cell that continuously emits heat will increase its temperature and dissipate heat to the environment through a suitable heat conduction path.
  • the covered bracket 20 has the largest contact area with the battery core 10
  • the currently commonly used bracket 20 is generally made of polymer materials with high manufacturing convenience and electrical insulation.
  • Polycarbonate (PC) is the current industry Commonly used materials.
  • PC Polycarbonate
  • the physical properties of PC cannot effectively slow down thermal runaway, so how to delay the chain reaction of thermal runaway burning and explosion of lithium battery modules has become an urgent issue to be solved at present.
  • the flame-retardant thermoplastic material for lithium battery modules and capable of inhibiting thermal runaway diffusion includes: polyamide, the weight percentage of which is 25 to 45%; lubricant, the lubricant is The weight percentage of the antioxidant is 0.1 to 2.0%; the antioxidant, the weight percentage of the antioxidant is 0.1 to 2.0%; the surfactant, the weight percentage of the surfactant is 0.1 to 2.0%; the toughening agent, the Toughening agent accounts for 0.1 to 20% by weight; non-toxic flame retardant, the non-toxic flame retardant accounts for 5 to 40% by weight; reinforced modifier, the reinforced modifier accounts for The weight percentage is 10 to 45%; the reinforcing material, the weight percentage of the reinforcing material is 0 to 20%.
  • the polyamide is nylon 6, nylon 66 or a combination thereof.
  • the non-toxic flame retardant is polyphosphate metal salts, melamine phosphates, melamine cyanurate, phosphate esters, borates or mixtures thereof.
  • the reinforcing modifier is a metal oxide and its derivatives, metal hydroxides and its derivatives, or metal silicates.
  • the reinforcing material is glass fiber, mineral fiber or kaolin.
  • the weight percentage of the lubricant is 0.2%.
  • the weight percentage of the antioxidant is 0.2%.
  • the surfactant is silicone resin and its weight percentage is 0.5%.
  • the battery module structure material with thermal runaway mitigation provided by the above-mentioned embodiments of the present invention has the beneficial effects that it can be used to manufacture lithium battery module structures, can slow down thermal runaway, resist burnout, and have good thermal conductivity properties.
  • Figure 1 is a diagram of the basic structure of a known lithium battery module
  • 2A to 2D are schematic diagrams of the experimental results of the material of the present invention with the formula of Example 1 in Table 2;
  • Figure 2A shows the appearance of the test piece before the gun burns
  • Fig. 2B shows the appearance of the test piece after the gun burns for 3 minutes
  • Fig. 2C shows the appearance of the test piece after the gun burns for 5 minutes
  • Fig. 2D shows that the test piece does not burn through
  • 3A and 3B are schematic diagrams of the experimental results of the materials of the present invention with the formula of Comparative Example 1 in Table 2;
  • Figure 3A shows the appearance of the test piece before the fire gun burns
  • Figure 3B shows the burn-through appearance of the test piece after the fire gun burns for 20 seconds
  • 4A and 4B are schematic diagrams of experimental results of the materials of the present invention with the formula of Comparative Example 2 in Table 2;
  • Figure 4A shows the appearance of the test piece before the fire gun burns
  • Figure 4B shows the burn-through appearance of the test piece after the fire gun burns for 18 seconds
  • 5A and 5B are schematic diagrams of the experimental results of the materials of the present invention with the formula of Comparative Example 3 in Table 2;
  • Figure 5A shows the appearance of the test piece before the fire gun burns
  • Figure 5B shows the burn-through appearance of the test piece after the fire gun burns for 26 seconds
  • Figure 6 is a schematic diagram of the structure of the present invention applied to a lithium battery module
  • FIG. 7 is a current-voltage curve diagram of the present invention applied to the discharge process of a lithium battery module
  • Figure 9 is a theoretical simulation analysis diagram of the present invention applied to a lithium battery module
  • 10A to 10C are structural appearance diagrams of the material stent of the present invention and the PC material stent in the acupuncture experiment;
  • FIG. 10A is a structural appearance view of the material stent of the present invention with a cell spacing of 2mm;
  • FIG. 10B is a structural appearance drawing of the material stent of the present invention with a cell spacing of 1mm;
  • FIG. 10C is a structural appearance view of a PC material stent with a cell spacing of 2mm;
  • Figure 11 is a graph of the temperature rise of the PC material stent after acupuncture in the acupuncture experiment
  • 12A and 12B are graphs of temperature rise after acupuncture on the difference in the distance between the battery cores of the material stent of the present invention in the acupuncture experiment;
  • FIG. 12A is a graph of the temperature rise after acupuncture of the material stent cell spacing of 2mm according to the present invention
  • Figure 12B is a graph of the temperature rise after acupuncture of the material stent cell spacing of 1mm according to the present invention
  • FIGS. 13A and 13B are schematic diagrams of the disassembly of the structure of the material stent of the present invention and the PC material stent after acupuncture;
  • FIG. 13A is a schematic diagram of the disassembly of the structure of the material stent of the present invention after acupuncture
  • FIG. 13B is a schematic diagram of the disassembly of the structure of the PC material stent after acupuncture.
  • the flame-retardant thermoplastic material for lithium battery modules provided by the present invention and capable of inhibiting thermal runaway diffusion includes polyamide, lubricants, antioxidants, surfactants, toughening agents, non-toxic flame retardants, reinforcing materials, and Strengthening modifier.
  • the polyamide is nylon 6, nylon 66 or a combination thereof, and the weight percentage of the polyamide is 25 to 45%.
  • the weight percentage of the lubricant is 0.1 to 2.0%.
  • the weight percentage of the antioxidant is 0.1 to 2.0%.
  • the weight percentage of the surfactant is 0.1 to 2.0%.
  • the weight percentage of the toughening agent is 0.1 to 20%.
  • the non-toxic flame retardant is a metal salt of polyphosphate, melamine phosphate, melamine cyanurate, phosphate, borate or a mixture thereof, and the non-toxic flame retardant accounts for 5 to 40% by weight .
  • the reinforcing modifier is metal oxide and its derivatives, metal hydroxide and its derivatives, or metal silicate, and the weight percentage of the reinforcing modifier is 10 to 45%.
  • the reinforcing material is glass fiber, mineral fiber or kaolin, and the weight percentage of the reinforcing material is 0 to 20%.
  • the lubricant accounts for 0.2% by weight
  • the antioxidant accounts for 0.2% by weight
  • the surfactant is silicone resin and accounts for 0.5% by weight.
  • Table 1 is a comparison table of the thermal conductivity of the flame-retardant thermoplastic material used in the lithium battery module and inhibiting thermal runaway diffusion (hereinafter referred to as the material of the present invention) and the currently commonly used lithium battery module bracket material, namely polycarbonate (PC) .
  • PC polycarbonate
  • PC Material of the invention unit Thermal conductivity 0.19 ⁇ 0.22 0.60 ⁇ 1.30 W/m-K
  • the thermal conductivity of the material of the present invention is much higher than that of the PC material, which effectively improves the problem of poor thermal conductivity of the plastic material.
  • the use of the material of the invention can slow down the temperature rise and thereby reduce the risk of thermal runaway of the battery cell.
  • Table 2 prepares the formula composition of several examples and several comparative examples. These examples have composition materials falling within the aforementioned composition formula range.
  • Table 3 is a comparison table of the results of the anti-burning experiment. It can be seen that the material test pieces of the several examples prepared in this embodiment will not be burned through by the flame (more than 3 minutes), and provide good anti-burning performance.
  • the lithium battery module structure made of the material of the present invention can effectively delay or prevent thermal runaway.
  • the material of the present invention has the function of preventing the burning of the lithium battery module from spreading to the other battery when thermal runaway occurs, so as to avoid the chain of the entire lithium battery module. Explosive combustion reaction allows personnel to quickly escape from the burning scene within a safe time.
  • test piece burns through to stop the experiment, and the time limit is at least 3 minutes;
  • UL94 is a plastic flammability standard issued by Underwriter Laboratories Inc. (UL). This standard classifies plastics according to their burning conditions. Among them, 5VA is classified as the highest level in the UL fire and flame retardant certification, and its test methods are as follows:
  • 5VB Start burning from the corner of the sample to ensure that the inner flame is in contact with the sample.
  • the burner is inclined at 20 ⁇ 5°, and the burning test time is 5 ⁇ 0.5 seconds each time, and a total of 5 burnings are carried out. The dripping of the test piece should not cause the cotton placed underneath to catch fire.
  • Test piece size 150*150*1.0(mm);
  • 5VA The flame acts on the center of the bottom surface of the flat sample, the burner is inclined 20 ⁇ 5°, and the inner flame contacts the sample. Act for 5 ⁇ 0.5 seconds, then remove the burner and keep it for 5 ⁇ 0.5 seconds, and stop after 5 actions. When all the afterflame and afterflame of the test piece have stopped, observe and record whether the sample is burned through.
  • Figures 2A to 2D are schematic diagrams of the experimental results of the material of the present invention with the formula of Example 1 in Table 2.
  • Figure 2A shows the appearance of the test piece before the fire gun burns
  • Figure 2B shows the appearance of the test piece after the fire gun burns for 3 minutes
  • Figure 2C shows the appearance of the test piece after burning the gun for 3 minutes. The appearance of the test piece after burning the gun for 5 minutes
  • Figure 2D shows that the test piece does not burn through.
  • 3A and 3B are schematic diagrams of the experimental results of the material of the present invention using the formula of Comparative Example 1 in Table 2, where FIG. 3A shows the appearance of the test piece before the gun is burned; FIG. 3B shows the burn-through appearance of the test piece after the gun is burned for 20 seconds.
  • 4A and 4B are schematic diagrams of the experimental results of the material of the present invention with the formula of Comparative Example 2 in Table 2, in which FIG. 4A shows the appearance of the test piece before the gun is burned; FIG. 4B shows the burn-through appearance of the test piece after the gun is burned for 18 seconds.
  • Fig. 5A and Fig. 5B are schematic diagrams of the experimental results of the material of the present invention with the formula of Comparative Example 3 in Table 2, where Fig. 5A shows the appearance of the test piece before the gun is burned; Fig. 5B shows the burn-through appearance of the test piece after the gun is burned for 26 seconds.
  • Test environment temperature 45°C;
  • Test time 60 minutes;
  • Figure 6 is a schematic diagram of the structure of the present invention applied to a lithium battery module. Each cell has a number on the top surface, namely, No. 1 to No. 12 cell.
  • Figure 7 is a current-voltage curve diagram of the discharge process, which is a comparison between the material of the present invention and the PC material.
  • Fig. 8 is a thermal test histogram of the discharge process. It can be seen that the lithium battery module holder applied by the material of the present invention can effectively reduce the temperature of the No. 7, No. 9 and No. 1 cells compared with the PC material.
  • Figure 9 is a verification diagram of theoretical simulation analysis performed against the above experimental conditions.
  • the material of the present invention can reduce the cell temperature by 10-15%.
  • the lithium battery module using the material of the present invention can effectively reduce the temperature rise of the cell of the lithium battery during the discharge process, thereby improving the efficiency and life of the lithium battery module.
  • This extended burning experiment is to simulate the thermal runaway phenomenon of the battery cell with the aid of acupuncture. Acupuncture is the most stringent method in the extended burning test to verify that the material of the present invention reduces heat conduction and flashover. Anti-burning effect.
  • This burning experiment compares the stent made from the material of the present invention (hereinafter referred to as the material stent of the present invention) with the stent made from the conventional flame-retardant PC material in the industry (hereinafter referred to as the PC material stent), and aims at the high capacity requirements of the terminal products , Test the best protection effect with different cell spacing.
  • Test environment temperature 60°C;
  • a steel needle with a needle diameter of 5mm and a speed of 5mm per second;
  • Table 4 is a comparison table of the results of acupuncture experiments.
  • Figures 10A to 10C are the appearance views of the material stent of the present invention and the PC material stent in the acupuncture experiment, in which Figure 10A is the structural appearance view of the material stent of the present invention with a cell spacing of 2mm; Figure 10B is the cell spacing of the material stent of the present invention 1mm structural appearance drawing; Figure 10C is a structural appearance drawing of the PC material bracket with a cell spacing of 2mm.
  • Figure 11 is a graph of the temperature rise of the PC material stent in the acupuncture experiment.
  • the highest temperature of the acupuncture cell is 495°C, and the adjacent cell exceeds 410°C and thermal runaway occurs.
  • Figures 12A and 12B are graphs showing the temperature rise after acupuncture with the cell spacing of the material stent of the present invention of 2mm and 1mm in the acupuncture experiment.
  • Figure 12A is the graph showing the temperature rise after acupuncture with the cell spacing of the material stent of the present invention at 2mm.
  • Figure 12B is a graph of the temperature rise after acupuncture with a cell spacing of 1mm in the material stent of the present invention, where the highest temperature of the acupuncture cell is 462°C, acupuncture The side cell does not exceed 150°C/voltage 8.3V.
  • FIGS. 13A and 13B are schematic diagrams of the disassembly of the material stent of the present invention and the structure of the PC material stent after acupuncture, in which Figure 13A is the schematic diagram of the disassembly of the material stent of the present invention after acupuncture; Figure 13B is the PC material stent after acupuncture Schematic diagram of structural disassembly.
  • the shell of the PC material bracket is smelted, the nickel sheet is smelted, and the structure is incomplete and the droplets are burnt inside, which can not produce a protective effect on the battery cell.
  • the whole structure of the material support of the present invention is kept intact regardless of the cell spacing of 2mm and 1mm, the nickel sheet is not burned, the cell is well protected, and the voltage of the adjacent cell is normal.
  • the PC material support melts in fire and the dripping has no protective effect on the battery cell, and the flame cannot be self-extinguished, and the continuous high temperature causes the second degree of burning.
  • the material support of the present invention produces a flame retardant layer after acupuncture with a cell spacing of 2mm and 1mm to cool down, isolate oxygen, and effectively suppress heat spread, so that the temperature of adjacent cells does not exceed the maximum allowable temperature of the cell to 150°C, avoiding second-degree burning .
  • the material of the present invention can inhibit the heat spread of the 18650 lithium battery after the battery core catches fire in the needle puncture experiment, and avoid the secondary damage caused by the explosion of the adjacent battery core.
  • the flame-retardant thermoplastic material provided by the present invention is suitable for lithium battery modules and has the effect of inhibiting thermal runaway diffusion.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un matériau thermoplastique ignifuge utilisé pour un module de batterie au lithium et présentant une fonction d'inhibition de diffusion d'emballement thermique. Plus particulièrement, l'invention concerne une structure applicable à un module de batterie, et en particulier, une matière plastique contenant un agent ignifuge non toxique et un modificateur d'amélioration. L'agent ignifuge non toxique consiste en des sels métalliques d'acide polyphosphorique, des phosphates de mélamine, des cyanurates de mélamine, des esters de phosphate, des borates ou un mélange de ceux-ci. Le modificateur d'amélioration consiste en des oxydes métalliques et des dérivés de ceux-ci, des hydroxydes métalliques et des dérivés de ceux-ci, ou des sels métalliques d'acide silicique. Par conséquent, la présente invention comprend des fonctions d'inhibition d'emballement thermique, de résistance à la propagation de combustion et de conduction thermique.
PCT/CN2020/000002 2020-01-03 2020-01-03 Matériau thermoplastique ignifuge utilisé pour un module de batterie au lithium et présentant une fonction d'inhibition de diffusion d'emballement thermique WO2021134733A1 (fr)

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PCT/CN2020/000002 WO2021134733A1 (fr) 2020-01-03 2020-01-03 Matériau thermoplastique ignifuge utilisé pour un module de batterie au lithium et présentant une fonction d'inhibition de diffusion d'emballement thermique

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PCT/CN2020/000002 WO2021134733A1 (fr) 2020-01-03 2020-01-03 Matériau thermoplastique ignifuge utilisé pour un module de batterie au lithium et présentant une fonction d'inhibition de diffusion d'emballement thermique

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610740A (zh) * 2015-01-30 2015-05-13 上海日之升新技术发展有限公司 一种新能源电池外壳专用料及其制备方法
CN106977908A (zh) * 2016-01-15 2017-07-25 株洲时代新材料科技股份有限公司 一种抗冲击耐刮擦导热尼龙复合材料及其制备方法
CN107189402A (zh) * 2017-07-07 2017-09-22 东莞市卡帝德塑化科技有限公司 用于制造锂电池电芯壳体的改性工程塑料材料及制备方法
JP6405811B2 (ja) * 2014-09-09 2018-10-17 東レ株式会社 ポリアミド樹脂組成物
WO2019155327A2 (fr) * 2018-02-12 2019-08-15 3M Innovative Properties Company Compositions durcissables, articles obtenus à partir de celles-ci, et leurs procédés de préparation et d'utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6405811B2 (ja) * 2014-09-09 2018-10-17 東レ株式会社 ポリアミド樹脂組成物
CN104610740A (zh) * 2015-01-30 2015-05-13 上海日之升新技术发展有限公司 一种新能源电池外壳专用料及其制备方法
CN106977908A (zh) * 2016-01-15 2017-07-25 株洲时代新材料科技股份有限公司 一种抗冲击耐刮擦导热尼龙复合材料及其制备方法
CN107189402A (zh) * 2017-07-07 2017-09-22 东莞市卡帝德塑化科技有限公司 用于制造锂电池电芯壳体的改性工程塑料材料及制备方法
WO2019155327A2 (fr) * 2018-02-12 2019-08-15 3M Innovative Properties Company Compositions durcissables, articles obtenus à partir de celles-ci, et leurs procédés de préparation et d'utilisation

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