Battery pack, fire extinguishing material, fire extinguishing product, and electric device

Abstract

The application provides a battery pack, fire extinguishing material, fire extinguishing product and electric device. The battery pack comprises a box body, a battery monomer and fire extinguishing particles. The box body has a containing space. The battery monomer is located in the containing space. The fire extinguishing particles are located in the containing space, and the fire extinguishing particles comprise a shell and fire extinguishing material in the shell. The fire extinguishing material comprises a first group and a second group. The first group comprises a halogenated hydrocarbon group and / or a halogenated ketone group. The second group comprises an organophosphorus group. The organophosphorus group is connected to the halogenated hydrocarbon group and / or the halogenated ketone group through a covalent bond. The battery pack has high reliability.

Description

Technical Field

[0001] This application relates to the field of battery technology, and in particular to a battery pack, fire extinguishing material, fire extinguishing product, and electrical device. Background Technology

[0002] As batteries are widely used in various fields, the requirements for their performance are becoming increasingly stringent. However, batteries in related technologies still suffer from low reliability. Summary of the Invention

[0003] This application provides a battery pack, fire extinguishing material, fire extinguishing product, and electrical device, wherein the battery pack has high reliability.

[0004] A first aspect of this application provides a battery pack, including a housing, battery cells, and fire extinguishing particles. The housing has a receiving space. The battery cells are located in the receiving space. The fire extinguishing particles are located in the receiving space, and the fire extinguishing particles include a shell and fire extinguishing material located within the shell. The fire extinguishing material includes a first group and a second group, wherein the first group includes a halogenated hydrocarbon group and / or a halogenated ketone group, and the second group includes an organophosphorus group, the organophosphorus group being covalently bonded to the halogenated hydrocarbon group and / or the halogenated ketone group.

[0005] In the battery pack provided in this application, the first group of the fire extinguishing material includes halogenated hydrocarbon groups and / or halogenated ketone groups, and the second group includes organophosphorus groups. The organophosphorus groups are covalently linked to the halogenated hydrocarbon groups and / or halogenated ketone groups. This increases the relative molecular weight of the fire extinguishing material, raising its melting and boiling points, thus reducing the risk of vaporization and decreased fire extinguishing effectiveness. Furthermore, the organophosphorus groups can synergistically capture combustion free radicals with either the halogenated hydrocarbon groups or the halogenated ketone groups, and can also block combustion pathways, significantly improving the fire extinguishing effect and reducing the likelihood of thermal runaway in the battery pack. Additionally, the presence of organophosphorus groups in the fire extinguishing material allows it to react with some of the harmful substances generated during the fire extinguishing process, reducing the mass of harmful substances. Therefore, the aforementioned fire extinguishing material not only reduces the occurrence of thermal runaway but also reduces the mass of harmful substances during the fire extinguishing process, resulting in higher reliability for the battery pack.

[0006] In some embodiments of this application, the halogenated hydrocarbon group includes a halogenated C1-10 alkyl group.

[0007] In some embodiments of this application, the haloketone group includes a halogenated C1-C10 ketyl group.

[0008] In the above-mentioned technical solution, the haloketone group can further improve the fire extinguishing effect of the fire extinguishing material, which can further reduce the probability of thermal runaway of the battery pack, thereby improving the reliability of the battery pack.

[0009] In some embodiments of this application, the halogenated hydrocarbon group includes a fully halogenated hydrocarbon group.

[0010] In some embodiments of this application, the perhalogenated hydrocarbon group includes one or more of perfluoropropane, perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane.

[0011] In some embodiments of this application, the haloketone group includes a perhaloketone group.

[0012] In some embodiments of this application, the perhalogenated ketone group includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, and perfluoroheptanone.

[0013] In the above-mentioned technical solutions, fully halogenated hydrocarbon groups and fully halogenated ketone groups can further improve the fire extinguishing effect of fire extinguishing materials.

[0014] In some embodiments of this application, the organophosphorus groups include phosphite groups and / or phosphate groups.

[0015] In some embodiments of this application, the phosphite group includes one or more of the following: dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibenzyl phosphite, perfluoromethyl phosphite, and di(trifluorosilane) phosphite.

[0016] In some embodiments of this application, the fire extinguishing material includes one or more compounds represented by formulas I to IV:

[0017]

[0018] In some embodiments of this application, the fire extinguishing particles include a first fire extinguishing particle and a second fire extinguishing particle. The first fire extinguishing particle includes a first shell and fire extinguishing material located inside the first shell. The second fire extinguishing particle includes a second shell and fire extinguishing material located inside the second shell. The ratio of the volume average particle size Dv150 of the first fire extinguishing particle to the volume average particle size Dv250 of the second fire extinguishing particle is (2-200):1.

[0019] In some embodiments of this application, the volume average particle size Dv150 of the first fire extinguishing particle is 10 μm to 20 μm, and the volume average particle size Dv250 of the second fire extinguishing particle is 0.1 μm to 5 μm.

[0020] In the above technical solution, the reasonable combination of the first fire extinguishing particle and the second fire extinguishing particle can improve space utilization and increase the packing density of the fire extinguishing particles, thereby helping to prevent thermal runaway of the battery pack and improve the reliability of the battery pack.

[0021] In some embodiments of this application, the thickness of the first housing is 0.02 μm to 1 μm.

[0022] In some embodiments of this application, the thickness of the second shell is 0.02 μm to 1 μm.

[0023] In the above-mentioned technical solution, the thickness of the first shell and the second shell is within the above-mentioned range, which can cover more fire extinguishing materials and improve storability and transportability.

[0024] In some embodiments of this application, the mass ratio of extinguishing material to first shell in the first extinguishing pellet is (50-99):(1-50).

[0025] In some embodiments of this application, the mass ratio of the fire extinguishing material to the first casing is (70-85):(15-30).

[0026] In the above-mentioned technical solution, the mass ratio of fire extinguishing material to the first shell is within the above-mentioned range, which can help improve the fire extinguishing effect, storability and transportability of the fire extinguishing particles.

[0027] In some embodiments of this application, the mass ratio of the extinguishing material to the second shell in the second extinguishing pellet is (50-99):(1-50).

[0028] In the above-mentioned technical solution, the mass ratio of the extinguishing material and the second shell is within the above-mentioned range, which can help improve the extinguishing effect, storability and transportability of the extinguishing particles.

[0029] In some embodiments of this application, the mass ratio of the fire extinguishing material to the second shell is (70-85):(15-30).

[0030] In the above-mentioned technical solution, the mass ratio of the extinguishing material and the second shell is within the above-mentioned range, which can help improve the extinguishing effect, storability and transportability of the extinguishing particles.

[0031] In some embodiments of this application, the battery pack includes multiple battery cells, with fire extinguishing particles located between two adjacent battery cells.

[0032] In the above technical solution, the fire extinguishing particles are located between two battery cells, which can increase the contact area between the fire extinguishing particles and the battery cells, and help the casing release the fire extinguishing material in response to preset conditions, thereby reducing the occurrence of thermal runaway.

[0033] In some embodiments of this application,

[0034] In some embodiments of this application, the material of the shell includes one or more of polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyurethane, and polyurea.

[0035] In the above technical solution, selecting the aforementioned material for the shell can improve the shell's sensitivity, enabling it to release fire extinguishing materials in a timely manner for fire suppression, thereby helping to reduce the occurrence of thermal runaway.

[0036] A second aspect of this application provides a fire extinguishing material comprising a first group and a second group. The first group comprises a halogenated hydrocarbon group and / or a halogenated ketone group. The second group comprises an organophosphorus group, wherein the organophosphorus group is covalently bonded to the halogenated hydrocarbon group and / or the halogenated ketone group.

[0037] In some embodiments of this application, the halogenated hydrocarbon group includes a halogenated C1-10 alkyl group.

[0038] In some embodiments of this application, the haloketone group includes a halogenated C1-C10 ketyl group.

[0039] In some embodiments of this application, the halogenated hydrocarbon group includes a fully halogenated hydrocarbon group.

[0040] In some embodiments of this application, the perhalogenated hydrocarbon group includes one or more of perfluoropropane, perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane.

[0041] In some embodiments of this application, the haloketone group includes a perhaloketone group.

[0042] In some embodiments of this application, the perhalogenated ketone group includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, and perfluoroheptanone.

[0043] In some embodiments of this application, the organophosphorus groups include phosphite groups and / or phosphate groups.

[0044] In some embodiments of this application, the phosphite group includes one or more of the following: dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibenzyl phosphite, perfluoromethyl phosphite, and di(trifluorosilane) phosphite.

[0045] In some embodiments of this application, the fire extinguishing material includes one or more compounds represented by formulas I to IV:

[0046]

[0047] The third aspect of this application provides a fire extinguishing product, including the fire extinguishing material of the second aspect of this application.

[0048] In some embodiments of this application, the fire extinguishing product includes one or more of the following: fire extinguishing capsule, aerogel heat insulation pad, fire extinguishing tape, and fire extinguisher.

[0049] In some embodiments of this application, the fire extinguishing capsule includes a shell and fire extinguishing material located within the shell.

[0050] In some embodiments of this application, the volume average particle size Dv50 of the fire extinguishing capsule is 0.1 μm to 20 μm.

[0051] In some embodiments of this application, the thickness of the shell is 0.02 μm to 1 μm.

[0052] In some embodiments of this application, the mass ratio of extinguishing material to shell is (50-99):(1-50).

[0053] In some embodiments of this application, the mass ratio of the fire extinguishing material to the shell is (70-85):(15-30).

[0054] In some embodiments of this application, the material of the shell includes one or more of polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyurethane, and polyurea.

[0055] The fourth aspect of this application provides an electrical device including a battery pack according to the first aspect of this application. Attached Figure Description

[0056] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the embodiments described below. The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of this application. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0057] Figure 1 This is a schematic diagram of the vehicle structure according to some embodiments of this application;

[0058] Figure 2 This is an exploded structural diagram of a battery according to some embodiments of this application.

[0059] Explanation of reference numerals in the attached figures:

[0060] 1000 - Vehicle; 100 - Battery pack; 10 - Box; 11 - Storage space; 12 - First part; 13 - Second part; 20 - Battery cell; 200 - Controller; 30 - Fire extinguishing particles; 31 - Shell; 32 - Fire extinguishing material; 300 - Motor. Detailed Implementation

[0061] The following detailed description, with appropriate reference to the accompanying drawings, specifically discloses embodiments of the battery pack, fire extinguishing material, fire extinguishing article, and electrical device of this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0062] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0063] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0064] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0065] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0066] In this application, a battery pack refers to a device capable of outputting electrical energy, which can be at least one battery cell or a battery module composed of multiple battery cells. A battery pack generally includes a housing for encapsulating one or more battery cells. The housing prevents liquids or other foreign matter from affecting the charging or discharging of the battery cells.

[0067] The battery cell can be a secondary battery or a primary battery; it can also be a lithium-sulfur battery, a sodium-ion battery, or a magnesium-ion battery, but is not limited to these. The battery cell can be cylindrical, flat, cuboid, or other shapes.

[0068] A battery cell includes an electrode assembly and an electrolyte. The electrode assembly consists of a positive electrode, a negative electrode, and a separator. The battery cell primarily functions by the movement of metal ions between the positive and negative electrodes. The positive electrode includes a positive current collector and a positive active material layer. The positive active material layer is coated on the surface of the positive current collector, and the uncoated current collector protrudes beyond the coated current collector, serving as the positive electrode tab. Taking a lithium-ion battery as an example, the positive current collector can be made of aluminum, and the positive active material can be lithium cobalt oxide, lithium iron phosphate, ternary lithium, or lithium manganese oxide, etc. The negative electrode includes a negative current collector and a negative active material layer. The negative active material layer is coated on the surface of the negative current collector, and the uncoated current collector protrudes beyond the coated current collector, serving as the negative electrode tab. The negative current collector can be made of copper, and the negative active material can be carbon or silicon, etc. To ensure that a large current can be carried without melting, multiple positive electrode tabs are stacked together, and multiple negative electrode tabs are stacked together. The diaphragm can be made of polypropylene (PP) or polyethylene (PE), etc. Furthermore, the electrode assembly can be a wound structure or a stacked structure; the embodiments of this application are not limited to these.

[0069] With the widespread use of batteries, higher demands are being placed on their performance. Battery reliability has always been a key performance indicator for both companies and consumers. High reliability reduces the occurrence of abnormal situations such as thermal runaway and the generation of large amounts of harmful substances. In related technologies, batteries are typically filled with perfluoroacetone or halocarbon fire extinguishing agents in the casing to reduce the occurrence of thermal runaway. However, perfluoroacetone or halocarbon fire extinguishing agents have low boiling points and are prone to vaporization at the high temperatures of thermal runaway, which reduces their fire extinguishing effectiveness and thus decreases battery reliability. Furthermore, these fire extinguishing agents also generate large amounts of harmful substances (such as hydrogen fluoride) during the fire extinguishing process, further reducing battery reliability.

[0070] In view of this, this application provides a battery pack, fire extinguishing material, fire extinguishing product and electrical device, wherein the battery pack has high reliability.

[0071] The battery packs disclosed in this application can be used, but are not limited to, in electrical devices such as vehicles, ships, or aircraft. Power systems incorporating the battery packs disclosed in this application and the electrical devices composed of those battery packs can be used.

[0072] This application provides an electrical device that uses a battery pack as a power source. The electrical device can be, but is not limited to, mobile phones, tablets, laptops, electric toys, power tools, electric vehicles, electric cars, ships, spacecraft, etc. Electric toys can include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc. Spacecraft can include airplanes, rockets, space shuttles, and spacecraft, etc.

[0073] For ease of explanation, the following embodiments will be described using a vehicle 1000 as an example of an electrical device according to an embodiment of this application.

[0074] Please refer to Figure 1 , Figure 1 This is a schematic diagram of the structure of a vehicle 1000 provided in some embodiments of this application. The vehicle 1000 can be a gasoline-powered vehicle, a natural gas-powered vehicle, or a new energy vehicle. The new energy vehicle can be a pure electric vehicle, a hybrid electric vehicle, or a range-extended electric vehicle, etc. A battery pack 100 is disposed inside the vehicle 1000, and the battery pack 100 can be located at the bottom, front, or rear of the vehicle 1000. The battery pack 100 can be used to power the vehicle 1000; for example, the battery pack 100 can serve as the operating power source for the vehicle 1000. The vehicle 1000 may also include a controller 200 and a motor 300. The controller 200 is used to control the battery pack 100 to supply power to the motor 300, for example, to meet the power needs of the vehicle 1000 during starting, navigation, and driving.

[0075] In some embodiments of this application, the battery pack 100 can not only serve as the operating power source for the vehicle 1000, but also as the driving power source for the vehicle 1000, replacing or partially replacing fuel or natural gas to provide driving power for the vehicle 1000.

[0076] This application provides a battery pack. Figure 2 An exploded view of the battery pack provided in the application embodiment. See also... Figure 2 The battery pack 100 includes a housing 10, individual battery cells 20, and fire extinguishing particles 30. The housing 10 provides a receiving space 11 for the individual battery cells 20 and the fire extinguishing particles 30. In some embodiments, the housing 10 may include a first portion 12 and a second portion 13, which overlap each other to define the receiving space 11 for accommodating the individual battery cells 20 and the fire extinguishing particles 30. Of course, the connection between the first portion 12 and the second portion 13 can be sealed by a sealant (not shown), such as a sealing ring, sealant, etc.

[0077] The first part 12 and the second part 13 can be of various shapes, such as cylinders, cuboids, hexagonal prisms, etc. The materials of the first part 12 and the second part 13 can be various, such as copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc., and this application embodiment does not impose any special limitations on this. The first part 12 can be a hollow structure with one side open to form a cavity for accommodating the battery cell 20, and the second part 13 can also be a hollow structure with one side open to form a cavity for accommodating the battery cell 20. The opening side of the second part 13 covers the opening side of the first part 12, thus forming a box 10 with an accommodating space 11. Of course, as... Figure 2 As shown, the first part 12 can also be a hollow structure with an opening on one side, and the second part 13 can be a plate-like structure. The second part 13 covers the opening side of the first part 12, thus forming a box 10 with a accommodating space 11.

[0078] In the battery pack 100, there can be one or more battery cells 20. If there are multiple battery cells 20, they can be connected in series, parallel, or in a mixed configuration. A mixed configuration means that multiple battery cells 20 are connected in both series and parallel. Multiple battery cells 20 can be directly connected in series, parallel, or in a mixed configuration, and then the whole assembly of multiple battery cells 20 is housed in the housing 10. Alternatively, multiple battery cells 20 can first be connected in series, parallel, or in a mixed configuration to form a battery module, and then multiple battery modules can be connected in series, parallel, or in a mixed configuration to form a whole assembly, which is then housed in the housing 10. The battery cell 20 can be cylindrical, flat, cuboid, or other shapes. Figure 2 An example is shown where the battery cell 20 is square.

[0079] In this embodiment of the application, the battery pack 100 may also include other structures. For example, the battery pack 100 may also include a busbar component for realizing electrical connection between multiple battery cells 20.

[0080] The battery pack 100 may also include a thermal management component for thermal management of the battery cells 20, so that the temperature of the battery cells 20 is within a set range, thereby ensuring the safety performance of the battery cells 20.

[0081] According to some embodiments of this application, this application provides a fire extinguishing material comprising a first group and a second group, wherein the first group comprises a halogenated hydrocarbon group and / or a halogenated ketone group, and the second group comprises an organophosphorus group, wherein the organophosphorus group is covalently linked to the halogenated hydrocarbon group and / or the halogenated ketone group.

[0082] In this article, a halogenated hydrocarbon group refers to a hydrocarbon group having one or more halogen substituents. For example, a halogenated hydrocarbon group may include one or more of the following: fluorobromocarbon group, fluorochlorobromocarbon group, hydrochlorofluorocarbon group, hydrobromofluorocarbon group, perfluorocarbon group, hydrofluorocarbon group, and fluoroiodocarbon group.

[0083] In this article, a haloketone group refers to a ketone group having one or more halogen substituents.

[0084] In this article, organophosphorus compounds are compounds containing carbon-phosphorus bonds or phosphoric acid derivatives containing organic groups.

[0085] In the embodiments of this application, the structure of the fire extinguishing material can be obtained by analysis using instruments and equipment well known in the art, such as infrared spectrometers, mass spectrometers, and nuclear magnetic resonance spectrometers.

[0086] In the fire extinguishing material provided in this application, the first group of the fire extinguishing material includes a halogenated hydrocarbon group and / or a halogenated ketone group, and the second group includes an organophosphorus group. The organophosphorus group is covalently linked to the halogenated hydrocarbon group and / or the halogenated ketone group. This not only increases the melting and boiling points of the fire extinguishing material, reducing the occurrence of vaporization and thus improving the fire extinguishing effect, but also allows the organophosphorus group to synergistically work with either the halogenated hydrocarbon group or the halogenated ketone group, i.e., synergistically capturing combustion free radicals. Furthermore, the organophosphorus group can block the combustion path, thereby greatly improving the fire extinguishing effect and reducing the occurrence of thermal runaway in the battery pack. In addition, the presence of the organophosphorus group in the fire extinguishing material can react with some of the harmful substances generated during the fire extinguishing process, thereby reducing the mass of harmful substances. Therefore, the above-mentioned fire extinguishing material not only reduces the occurrence of thermal runaway but also reduces the mass of harmful substances during the fire extinguishing process, thus enabling the battery pack to have higher reliability.

[0087] In some embodiments of this application, the halogenated hydrocarbon group includes a halogenated C1-10 alkyl group.

[0088] In this document, C1-C10 haloalkyl groups refer to C1-C6 alkyl groups having one or more halogen substituents. In the above embodiments, halogen-substituted C1-10 alkyl groups not only have high fire extinguishing effects but are also readily available, which helps to reduce the production cost of battery packs.

[0089] In some embodiments of this application, the haloketone group includes a halogenated C1-C10 ketyl group.

[0090] In this article, C1-C10 ketone alkyl groups refer to C1-C6 ketone alkyl groups having one or more halogen substituents.

[0091] In the above embodiments, the C1-C10 ketone alkyl groups can further improve the fire extinguishing effect of the fire extinguishing material, which can further reduce the probability of thermal runaway of the battery pack, thereby improving the reliability of the battery pack.

[0092] In some embodiments of this application, the halogenated hydrocarbon group includes a fully halogenated hydrocarbon group.

[0093] In some embodiments of this application, the perhalogenated hydrocarbon group includes one or more of perfluoropropane, perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane.

[0094] In some embodiments of this application, the haloketone group includes a perhaloketone group.

[0095] In some embodiments of this application, the perhalogenated ketone group includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, and perfluoroheptanone.

[0096] In the above embodiments, the perhalogenated hydrocarbon groups and perhalogenated ketone groups are covalently linked to organophosphorus groups, which can further increase the relative molecular weight of the fire extinguishing material, giving it a higher melting and boiling point, thereby improving the fire extinguishing effect, as well as its storage, processability, and transportation.

[0097] In some embodiments of this application, the organophosphorus groups include phosphite groups and / or phosphate groups.

[0098] In this paper, the phosphite group refers to the group having the atomic group shown in formula (1). In formula (1), *1, *2 and *3 are connecting bonds, representing single bonds.

[0099]

[0100] The phosphite group shown in formula (1) has monovalent atoms such as hydrogen atoms or monovalent atomic groups (e.g., phenyl, alkyl, other groups of atoms, etc.) bonded to bonding bonds *1 to *3. It should be noted that the valence of the atomic group refers to the number of other atoms or atomic groups that the atomic group can bond to (atomic valence).

[0101] In this document, a phosphate ester group refers to an oxygen atom covalently bonded to an alkyl or aryl group, wherein the oxygen atom is also covalently bonded to a phosphorus atom, which is bonded to an additional oxygen atom via a double bond.

[0102] In the above embodiments, the phosphite group and / or phosphate group are covalently linked to the first group. While improving the fire extinguishing effect of the fire extinguishing material, they can also capture some harmful acidic substances, such as hydrogen fluoride, generated during the fire extinguishing process by forming coordination bonds, thereby improving the reliability of the battery pack.

[0103] In some embodiments of this application, the phosphite group includes one or more of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibenzyl phosphite, perfluoromethyl phosphite, and di(trifluorosilane) phosphite.

[0104] In some embodiments of this application, the fire extinguishing material includes one or more compounds represented by formulas I to IV:

[0105]

[0106] This application also provides a fire extinguishing product, including the fire extinguishing material of any of the above embodiments.

[0107] In the embodiments of this application, the fire extinguishing product is not particularly limited and can be any molded article containing the above-mentioned fire extinguishing materials. For example, in some embodiments, the fire extinguishing product may include one or more of the following: fire extinguishing capsule, aerogel heat insulation pad, fire extinguishing tape, and fire extinguisher.

[0108] For ease of explanation, the following embodiments use a fire extinguishing capsule as an example of a fire extinguishing product according to an embodiment of this application.

[0109] In some embodiments of this application, the fire extinguishing capsule includes a shell and fire extinguishing material located within the shell, the fire extinguishing material including the fire extinguishing material in the above embodiments.

[0110] In some embodiments of this application, the volume average particle size Dv50 of the fire extinguishing capsule is 0.1 μm to 20 μm.

[0111] In this paper, Dv50 refers to the value of the particle size of the fire extinguishing capsules when the total volume is 50% after the capsules are added in ascending order. The Dv50 of the fire extinguishing capsules can be measured using instruments well-known in the art, such as a laser particle size analyzer.

[0112] In some embodiments of this application, the thickness of the shell is 0.02 μm to 1 μm.

[0113] In this paper, the shell thickness refers to the average value of the shell thickness of 50 fire extinguishing particles determined by scanning electron microscopy (SEM).

[0114] In the above embodiments, the thickness of the shell is within the above range, which can cover more fire extinguishing materials and improve storability and transportability.

[0115] In some embodiments of this application, the mass ratio of extinguishing material to shell is (50-99):(1-50).

[0116] In some embodiments of this application, the mass ratio of fire extinguishing material to shell is (70-85):(15-30).

[0117] In this paper, the mass ratio of extinguishing material to shell refers to the ratio of the mass content of extinguishing material in the extinguishing particles to the mass content of shell in the extinguishing particles, and can be tested using methods and instruments well known in the art. For example, thermogravimetric analysis (TGA) can be used.

[0118] In some embodiments of this application, the material of the shell includes one or more of polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyurethane, and polyurea.

[0119] In the above embodiments, selecting the aforementioned material for the shell can improve the shell's sensitivity, enabling it to release fire extinguishing materials in a timely manner for fire suppression, thereby helping to reduce the occurrence of thermal runaway.

[0120] In some specific embodiments of this application, the fire extinguishing capsule can be prepared by the following methods:

[0121] Weigh 1.5g of sodium salt powder of styrene-maleic anhydride copolymer and 1.5g of fire extinguishing material, pour them into 200mL of deionized water, stir evenly to obtain an aqueous system;

[0122] 30g of butyl stearate and 7.5g of 2,4-toluene diisocyanate were mixed evenly to obtain an oil phase system.

[0123] The aqueous phase system was placed in a shear emulsifier (7000 r / min), and then the oil phase system was poured into the aqueous phase system and emulsified for 10 min to obtain a suspension.

[0124] The suspension was transferred to a three-necked flask, and 10 mL of 4.5 g triethanolamine solution was added to the system while stirring continuously. The mixture was kept at 20 °C for 1 h, then at 30 °C for 2 h, and then at 3 h for 3 h. The mixture was then cooled and discharged. The resulting product was washed, filtered, and dried to obtain fire extinguishing particles.

[0125] This application also provides a battery pack 100, including a housing 10, battery cells 20, and fire extinguishing particles 30. The housing 10 has a receiving space 11. The battery cells 20 are located in the receiving space 11. The fire extinguishing particles 30 are located in the receiving space 11, and the fire extinguishing particles 30 include a shell 31 and fire extinguishing material 32 located within the shell 31. The shell 31 is configured to release the fire extinguishing material 32 in response to preset conditions.

[0126] In the battery pack provided in this application embodiment, both the battery cell 20 and the fire extinguishing particles 30 are located within the housing space 11 of the box 10. The shell 31 of the fire extinguishing particles 30 can release fire extinguishing material 32 in response to preset conditions to reduce the occurrence of thermal runaway of the battery pack 100. The first group of the fire extinguishing material 32 includes halogenated hydrocarbon groups and / or halogenated ketone groups, and the second group includes organophosphorus groups. The organophosphorus groups are covalently linked to the halogenated hydrocarbon groups and / or halogenated ketone groups. On the one hand, this can increase the relative molecular weight of the fire extinguishing material to increase its melting and boiling points, thereby reducing the occurrence of fire extinguishing material vaporization and resulting in a decrease in fire extinguishing effect, thus helping the fire extinguishing material to have a better fire extinguishing effect. On the other hand, it can enable the organophosphorus groups to play a synergistic role with either the halogenated hydrocarbon groups or the halogenated ketone groups, that is, to synergistically capture combustion free radicals. Moreover, the organophosphorus groups can also block the combustion path, thereby greatly improving the fire extinguishing effect of the fire extinguishing material, thereby reducing the occurrence of thermal runaway of the battery pack. Furthermore, the presence of organophosphorus groups in the extinguishing materials can react with some of the harmful substances produced during the extinguishing process, thereby reducing the amount of harmful substances. Therefore, the aforementioned extinguishing materials not only reduce the occurrence of thermal runaway but also reduce the amount of harmful substances produced during the extinguishing process, thus ensuring high reliability of the battery pack.

[0127] In some embodiments of this application, the fire extinguishing particles 30 include a first fire extinguishing particle and a second fire extinguishing particle. The first fire extinguishing particle includes a first shell and fire extinguishing material located inside the first shell. The second fire extinguishing particle includes a second shell and fire extinguishing material located inside the second shell. The ratio of the volume average particle size Dv150 of the first fire extinguishing particle to the volume average particle size Dv250 of the second fire extinguishing particle is (2-200):1.

[0128] In some embodiments of this application, the volume average particle size Dv150 of the first fire extinguishing particle is 10 μm to 20 μm, and the volume average particle size Dv250 of the second fire extinguishing particle is 0.1 μm to 5 μm.

[0129] In the above embodiments, the reasonable combination of the first fire extinguishing particles and the second fire extinguishing particles can improve space utilization and increase the packing density of the fire extinguishing particles, thereby helping to prevent thermal runaway of the battery pack and improve the reliability of the battery pack.

[0130] In some embodiments of this application, the thickness of the first housing is 0.02 μm to 1 μm.

[0131] In this paper, the thickness of the first shell refers to the average value of the thickness of the first shell of each of the 50 first extinguishing particles determined by scanning electron microscopy (SEM).

[0132] In some embodiments of this application, the thickness of the second shell is 0.02 μm to 1 μm.

[0133] In this paper, the thickness of the second shell refers to the average value of the thickness of the second shell of each of the 50 second fire extinguishing particles determined by scanning electron microscopy (SEM).

[0134] In the above embodiments, the thicknesses of the first shell and the second shell are respectively within the above range, which can cover more fire extinguishing materials and improve storability and transportability.

[0135] In the embodiments of this application, the mass ratio of the shell to the extinguishing material can be selected according to the outer diameter of the extinguishing particles or the thickness of the shell, which helps to balance the extinguishing effect, storability and transportation.

[0136] In some embodiments of this application, the mass ratio of extinguishing material to first shell in the first extinguishing pellet is (50-99):(1-50).

[0137] In some embodiments of this application, the mass ratio of the fire extinguishing material to the first casing is (70-85):(15-30).

[0138] In the above embodiments, the mass ratio of fire extinguishing material to the first shell is within the above range, which can help improve the fire extinguishing effect, storability and transportability of the fire extinguishing particles.

[0139] In some embodiments of this application, the mass ratio of the extinguishing material to the second shell in the second extinguishing pellet is (50-99):(1-50).

[0140] In the above embodiments, the mass ratio of the extinguishing material and the second shell is within the above range, which can help improve the extinguishing effect, storability and transportability of the extinguishing particles.

[0141] In some embodiments of this application, the mass ratio of the fire extinguishing material to the second shell is (70-85):(15-30).

[0142] In this paper, the mass ratio of extinguishing material to shell refers to the ratio of the mass content of extinguishing material in the extinguishing particles to the mass content of shell in the extinguishing particles, and can be tested using methods and instruments well known in the art. For example, thermogravimetric analysis (TGA) can be used.

[0143] In some embodiments of this application, the battery pack includes multiple battery cells, with fire extinguishing particles located between two adjacent battery cells.

[0144] In the above embodiment, the fire extinguishing particles are located between two battery cells, which can increase the contact area between the fire extinguishing particles and the battery cells, and help the casing release the fire extinguishing material in response to preset conditions, thereby reducing the occurrence of thermal runaway.

[0145] In some other embodiments of this application, multiple battery cells can be combined to form a battery module, and fire extinguishing particles can be disposed between two adjacent battery modules.

[0146] I. Implementation Examples

[0147] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0148] (1) Preparation of compounds

[0149] The preparation method of compound 1 shown in Formula I includes:

[0150] 1 mol of phosphorous acid was mixed with 1.5 mol of trifluoroiodoformane, and 5 g of FeSO4, 5 mL of H2O2 and 10 mL of dimethyl sulfoxide (DMSO) were added. The mixture was reacted at 60℃~80℃ for 6 h~8 h, and the intermediate product 1 with the following structural formula was obtained by separation.

[0151]

[0152] The above intermediate product was mixed with 2 mol of perfluoropentanone and reacted at 80℃~100℃ for 5h~8h to obtain compound 1 as shown in Formula I.

[0153] The preparation method of compound 2 shown in Formula II includes:

[0154] 1 mol of phosphorous acid was mixed with 1.5 mol of trifluoroiodoformane, and 5 g of FeSO4, 5 mL of H2O2 and 10 mL of dimethyl sulfoxide (DMSO) were added. The mixture was reacted at 60℃~80℃ for 6 h~8 h, and the intermediate product 2 with the following structural formula was obtained by separation.

[0155]

[0156] The above intermediate product was mixed with 2 mol of octafluoro-2-butanone and reacted at 80℃~100℃ for 5h~8h to obtain compound 2 as shown in formula II.

[0157] The preparation method of compound 3 shown in Formula III includes:

[0158] 1 mol of the phosphorous acid derivative with the following structural formula was mixed with 2 mol of octafluoro-2-butanone and reacted at 80℃~100℃ for 5h~8h to obtain compound 3 as shown in formula III.

[0159]

[0160] The preparation method of compound 4 shown in Formula IV includes:

[0161] Mixing 1 mol of phosphorous acid with 1.5 mol of trifluoroiodosilane yields intermediate 4, as shown in the following structural formula.

[0162]

[0163] The above intermediate product was mixed with 2 mol of octafluoro-2-butanone and reacted at 80℃~100℃ for 5h~8h to obtain compound 4 as shown in formula IV.

[0164] Example 1

[0165] (1) Preparation of fire extinguishing particles

[0166] Weigh 1.5g of sodium salt powder of styrene-maleic anhydride copolymer (CAS: 25736-61-2, purchased from Sigma-Aldrich) and 1.5g of the above compound 1, pour them into 200mL of deionized water, stir well to obtain an aqueous phase system;

[0167] 30g of butyl stearate and 7.5g of 2,4-toluene diisocyanate were mixed evenly to obtain an oil phase system.

[0168] The aqueous phase system was placed in a shear emulsifier (7000 r / min), and then the oil phase system was poured into the aqueous phase system and emulsified for 10 min to obtain a suspension.

[0169] The suspension was transferred to a three-necked flask, and 10 mL of 4.5 g of triethanolamine solution was added to the system while stirring continuously. The mixture was kept at 20 °C for 1 h, then at 30 °C for 2 h, and then at 3 h for 3 h. The mixture was then cooled and discharged. The resulting product was washed, filtered, and dried to obtain fire extinguishing particles. The fire extinguishing particles consist of a shell and fire extinguishing material located inside the shell. The shell is made of polyurea, and the fire extinguishing material is compound 1 mentioned above. The mass ratio of the fire extinguishing material to the shell is 80:20.

[0170] (2) Preparation of electrolyte

[0171] In a nitrogen atmosphere glove box (H2O < 0.1 ppm, O2 < 0.1 ppm), ethylene carbonate (EC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), and lithium hexafluorophosphate (LiPF6) were stirred and mixed evenly to obtain an electrolyte, wherein the volume ratio of EC, DEC, and EMC was 1:1:1, and the molar concentration of LiPF6 was 1 mol / L.

[0172] (3) Preparation of positive electrode sheet

[0173] LiNi, the positive electrode active material 0.8 Co 0.1 Mn 0.1 O2 (NCM811), conductive agent acetylene black, and binder polyvinylidene fluoride (PVDF) are mixed in N-methylpyrrolidone (NMP) solvent at a mass ratio of 95:3:2 to prepare a positive electrode slurry. The positive electrode slurry is uniformly coated on the surface of aluminum foil, and then dried, cold-pressed, and slit to obtain the positive electrode sheet.

[0174] (4) Preparation of negative electrode sheet

[0175] A negative electrode slurry is prepared by mixing graphite (the negative electrode active material), acetylene black (the conductive agent), styrene-butadiene rubber (SBR) (the binder), and sodium carboxymethyl cellulose (CMC-Na) (the thickener) in a deionized water solvent at a mass ratio of 96:2:1:1. The negative electrode slurry is then uniformly coated onto the surface of copper foil, and subsequently dried, pressed, trimmed, cut, and slit to form negative electrode sheets.

[0176] (5) Separating membrane

[0177] Polypropylene film is used as the separator.

[0178] (6) Preparation of battery cells

[0179] The positive electrode, separator, and negative electrode are stacked and wound in sequence to obtain an electrode assembly, with the separator positioned between the positive and negative electrodes. Tabs are welded to the electrode assembly, which is then placed in an aluminum casing and baked at 80°C to remove moisture. The electrolyte is then injected and the casing is sealed to obtain a non-charged battery. The non-charged battery then undergoes a series of processes including settling, hot and cold pressing, formation, shaping, and capacity testing to obtain a single battery cell.

[0180] (7) Battery pack preparation

[0181] The battery pack consists of 6 battery modules connected in series, and each battery module contains 6 individual battery cells.

[0182] Fire extinguishing particles made from compound 1 are filled between the battery modules in the battery pack.

[0183] Examples 2-9

[0184] The differences between Examples 2-9 and Example 1 are shown in Table 1.

[0185] Comparative Examples 1-4

[0186] Compared with Example 1, the difference between Comparative Examples 1 to 4 lies in the fire extinguishing material in the fire extinguishing particles, as shown in Table 1.

[0187] II. Testing Section

[0188] (1) Measurement of the mass ratio of extinguishing material to shell

[0189] 1. Weigh the sample and record its original mass;

[0190] 2. Place the sample in the thermogravimetric analyzer and heat the sample;

[0191] 3. During the heating process, the thermogravimetric analyzer will monitor and record the mass change of the sample in real time;

[0192] 4. The mass ratio of the extinguishing material to the shell can be inferred from the mass change.

[0193] (2) Boiling point test of fire extinguishing materials

[0194] By adding the fire extinguishing material into a fully automatic vapor pressure measuring instrument, the saturated vapor pressure of the material at different temperatures can be obtained. When the saturated vapor pressure is equal to the atmospheric pressure, the corresponding temperature is the boiling point.

[0195] (3) Thermal diffusion test

[0196] The battery was first discharged at 1C to 2.8V, left to stand for 1 hour, then charged at 0.2C to 4.3V, and left to stand for another hour. The battery mass m0 was recorded. The battery was then placed in a high-low temperature chamber, and the temperature was increased from room temperature to 130℃ at a rate of 5℃ / min and maintained for 30 minutes before heating was stopped. After this, the battery was observed at ambient temperature for 1 hour, and its mass m1 was recorded. The minimum mass of extinguishing material required to meet safety requirements was calculated using the following formula:

[0197] M g / Wh=(m1-m0) / (battery capacity×3.65)

[0198] The above testing procedure meets the safety requirements for power batteries for electric vehicles, GB 38031-2020.

[0199] (4) Measurement of hydrogen fluoride gas content

[0200] After the experiment, the atmosphere inside the sealed module was collected and subjected to gas chromatography to detect the HF content.

[0201] III. Analysis of Test Results for Each Embodiment and Comparative Example

[0202] Battery packs for each embodiment and comparative example were prepared according to the above method, and various performance parameters were measured. The results are shown in Table 1 below.

[0203] Table 1. Experimental results of Examples 1-9 and Comparative Examples 1-4

[0204]

[0205] Note: a / b in Table 1 represents the mass ratio of extinguishing material to shell.

[0206] As shown in Table 1, comparing the test results of Examples 1-9 and Comparative Examples 1-4, it can be seen that the first group of the fire extinguishing material includes halogenated hydrocarbon groups and / or halogenated ketone groups, and the second group includes organophosphorus groups. The organophosphorus groups are covalently linked to the halogenated hydrocarbon groups and / or halogenated ketone groups, which can reduce the occurrence of thermal runaway and reduce the mass of harmful substances during the fire extinguishing process, thus making the battery pack more reliable.

[0207] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A battery pack, characterized in that, include: The container has storage space; The battery cell is located in the accommodating space; Fire extinguishing particles are located in the containment space. The fire extinguishing particles include a shell and fire extinguishing material located within the shell. The fire extinguishing material includes a first group and a second group. The first group includes a halogenated hydrocarbon group and / or a halogenated ketone group. The second group includes an organophosphorus group. The organophosphorus group is covalently linked to the halogenated hydrocarbon group and / or the halogenated ketone group.

2. The battery pack according to claim 1, characterized in that, The haloalkyl groups include halosubstituted C1-10 alkyl groups; And / or, the haloketone group includes a halogenated C1-C10 ketyl group.

3. The battery pack according to claim 1, characterized in that, The halogenated hydrocarbon group includes a perhalogenated hydrocarbon group; optionally, the perhalogenated hydrocarbon group includes one or more of perfluoropropane, perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane. And / or, the haloketone group includes a perhaloketone group; optionally, the perhaloketone group includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, and perfluoroheptanone.

4. The battery pack according to any one of claims 1 to 3, characterized in that, The organophosphorus groups include phosphite groups and / or phosphate groups; Optionally, the phosphite group includes one or more of the following: dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibenzyl phosphite, perfluoromethyl phosphite, and di(trifluorosilane) phosphite.

5. The battery pack according to claim 4, characterized in that, The fire extinguishing material includes one or more compounds represented by formulas I to IV:

6. The battery pack according to claim 1, characterized in that, The fire extinguishing particles include a first fire extinguishing particle and a second fire extinguishing particle. The first fire extinguishing particle includes a first shell and the fire extinguishing material located inside the first shell. The second fire extinguishing particle includes a second shell and the fire extinguishing material located inside the second shell. The ratio of the volume average particle size Dv150 of the first fire extinguishing particle to the volume average particle size Dv250 of the second fire extinguishing particle is (2~200):

1. Optionally, the volume average particle size Dv150 of the first fire extinguishing particle is 10μm to 20μm, and the volume average particle size Dv250 of the second fire extinguishing particle is 0.1μm to 5μm. Optionally, the thickness of the first shell is 0.02 μm to 1 μm; and / or, the thickness of the second shell is 0.02 μm to 1 μm.

7. The battery pack according to claim 6, characterized in that, In the first extinguishing particles, the mass ratio of the extinguishing material to the first shell is (50-99):(1-50); optionally, the mass ratio of the extinguishing material to the first shell is (70-85):(15-30). And / or, in the second extinguishing particles, the mass ratio of the extinguishing material to the second shell is (50-99):(1-50); optionally, the mass ratio of the extinguishing material to the second shell is (70-85):(15-30).

8. The battery pack according to claim 1, characterized in that, The battery pack includes multiple battery cells, and the fire extinguishing particles are located between two adjacent battery cells.

9. The battery pack according to claim 1, characterized in that, The shell is made of one or more of polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyurethane, and polyurea.

10. A fire extinguishing material, characterized in that, The fire extinguishing materials include: The first group includes a haloalkyl group and / or a haloketone group; The second group includes an organophosphorus group, wherein the organophosphorus group is covalently linked to the haloalkane group and / or the haloketone group.

11. The fire extinguishing material according to claim 10, characterized in that, The haloalkyl groups include halosubstituted C1-10 alkyl groups; And / or, the haloketone group includes a halogenated C1-C10 ketyl group.

12. The fire extinguishing material according to claim 11, characterized in that, The halogenated hydrocarbon group includes a perhalogenated hydrocarbon group, and optionally, the perhalogenated hydrocarbon group includes one or more of perfluoropropane, perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane and perfluorooctane. And / or, the haloketone group includes a perhaloketone group, optionally, the perhaloketone group includes one or more of perfluoroacetone, perfluorobutanone, perfluoropentanone, perfluorohexanone, and perfluoroheptanone.

13. The fire extinguishing material according to any one of claims 10 to 12, characterized in that, The organophosphorus groups include phosphite groups and / or phosphate groups; The phosphite group includes one or more of the following: dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibenzyl phosphite, perfluoromethyl phosphite, and di(trifluorosilane) phosphite.

14. The fire extinguishing material according to claim 13, characterized in that, The fire extinguishing material includes one or more compounds represented by formulas I to IV:

15. A fire extinguishing product, characterized in that, Includes the fire extinguishing material as described in any one of claims 10 to 14; Optionally, the fire extinguishing product includes one or more of the following: fire extinguishing capsule, aerogel heat insulation pad, fire extinguishing tape, and fire extinguisher.

16. The fire extinguishing product according to claim 15, characterized in that, The fire extinguishing capsule includes a shell and the fire extinguishing material located inside the shell; Optionally, the volume average particle size Dv50 of the fire extinguishing capsule is 0.1 μm to 20 μm; Optionally, the thickness of the shell is 0.02 μm to 1 μm; Optionally, the mass ratio of the fire extinguishing material to the shell is (50-99):(1-50); Optionally, the mass ratio of the fire extinguishing material to the shell is (70-85):(15-30).

17. The fire extinguishing product according to claim 16, characterized in that, The shell is made of one or more of polyethylene, polypropylene, polyethylene terephthalate, polyamide, polyurethane, and polyurea.

18. An electrical appliance, characterized in that, The battery pack includes any one of claims 1 to 9.

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