Supermolecular lithium battery fire inhibitor as well as preparation method and application thereof

Abstract

The invention relates to the technical field of lithium ion battery safety, in particular to a supramolecular lithium battery fire inhibitor and a preparation method and application thereof. The supramolecular lithium battery fire inhibitor is prepared from the following raw materials in parts by weight: 10-50 parts of a supramolecular synergist, 30-90 parts of halogenated hydrocarbon and 0-20 parts of mineral oil, wherein the supramolecular synergist is prepared from perfluorohexanone and ethyoxyl (pentafluoro) cyclotriphosphazene. The supramolecular lithium battery fire inhibitor provided by the invention has relatively high electrical insulativity and efficient fire extinguishing characteristic, and the supramolecular acting force and fire extinguishing synergistic elements of the system are increased by introducing the supramolecular synergist, so that the stability, volatility and fire extinguishing efficiency of the inhibitor system are further improved, and the application value of the supramolecular lithium battery fire inhibitor is greatly increased.

Description

Technical Field

[0001] The present invention relates to the field of lithium ion battery safety technology, and in particular to a supramolecular lithium battery fire inhibitor, a preparation method and an application thereof. Background Art

[0002] Lithium batteries, with their advantages of high operating voltage, high energy density, high specific capacity, long cycle life, and fast response speed, are widely used in various fields and are closely related to people's lives. However, lithium batteries are prone to thermal runaway if they encounter external problems such as collision, extrusion, immersion in water, overcharging, and overheating during storage, transportation, and use. Fires caused by thermal runaway in lithium batteries have a unique chemical reaction mechanism, making them difficult to extinguish, prone to reignition, and highly dangerous. Lithium battery safety issues have severely restricted the rapid development of the new energy industry, and there is an urgent need for a fire suppressant suitable for lithium battery fires.

[0003] Currently, the inhibitors commonly used for lithium battery fire extinguishing include gas inhibitors, dry powder inhibitors, and water-based inhibitors. Commonly used gas inhibitors include CO2, heptafluoropropane, perfluorohexanone, etc., which mainly achieve the fire extinguishing effect by diluting oxygen. However, they have limited effect on lithium battery fires in open spaces and cannot suppress the re-ignition of the battery. Dry powder inhibitors achieve the fire extinguishing effect by isolating oxygen, and are less effective in cooling. After the fire is extinguished, the heat inside the lithium battery is difficult to dissipate, making it very easy for the re-ignition and explosion to occur. Water-based inhibitors are usually extinguished with pure water or by adding physical or chemical additives to water. Although they have a good cooling effect, water-based inhibitors have poor insulation properties and may cause short circuits during the fire extinguishing process, causing greater danger. Therefore, the development of a lithium battery inhibitor suitable for efficient fire extinguishing is an important problem that needs to be solved in this field. Summary of the Invention

[0004] The present invention aims to solve, at least to some extent, one of the technical problems in the related art. To this end, the present invention provides a supramolecular lithium battery fire suppressant, its preparation method, and application. The supramolecular lithium battery fire suppressant has high electrical insulation and efficient fire extinguishing properties, can quickly extinguish lithium battery fires, and prevent them from reigniting. The introduction of the supramolecular synergist increases the supramolecular force and fire extinguishing synergistic elements of the system, further improving the stability, volatility, and fire extinguishing efficiency of the suppressant system, greatly increasing its application value. In addition, the preparation process of the supramolecular lithium battery fire suppressant is simple, convenient for large-scale production, and has good application prospects.

[0005] To this end, the first aspect of the present invention provides a supramolecular lithium battery fire suppressant, wherein the raw materials for preparing the supramolecular lithium battery fire suppressant include 10 to 50 parts of a supramolecular synergist, 30 to 90 parts of a halogenated hydrocarbon, and 0 to 20 parts of a mineral oil;

[0006] Wherein, the supramolecular synergist comprises perfluorohexanone and ethoxy (pentafluoro) cyclotriphosphazene.

[0007] The supramolecular lithium battery fire suppressant provided by the present invention has high electrical insulation and efficient fire extinguishing properties. The introduction of the supramolecular synergist increases the supramolecular interaction force and fire extinguishing synergistic elements of the system, further improving the stability, volatility and fire extinguishing efficiency of the suppressant system, greatly increasing its application value.

[0008] According to an embodiment of the present invention, the mass ratio of the perfluorohexanone to the ethoxy(pentafluoro)cyclotriphosphazene is 1:(1-5).

[0009] According to an embodiment of the present invention, the halogenated hydrocarbon includes at least one of fluoroalkanes, chloroalkanes, chloroolefins, bromoolefins, bromoalkanes, and iodoalkanes.

[0010] According to an embodiment of the present invention, the halogenated hydrocarbon includes at least one of tetrachloroethylene, tetrachloroethane, tetrabromoethane, tetrabromoethylene, hexachloroethane, dibromotetrafluoroethane, dibromotetrachloroethane, tribromotrifluoroethane, 1,2-dibromo-1-chloro-1,2,2-trifluoroethane, dibromohexafluoropropane, trichloropentafluoropropane, hexachloropropylene, hexachlorobutadiene, dibromooctafluorobutane, dibromohexafluorocyclobutane, dichlorooctafluorobutane, dichlorohexafluorocyclobutane, diiodoperfluorobutane, and dibromoperfluorohexane.

[0011] According to an embodiment of the present invention, the mineral oil includes at least one of alkanes, cycloalkanes, and aromatic hydrocarbons.

[0012] The second aspect of the present invention provides a method for preparing the supramolecular lithium battery fire suppressant according to the first aspect, the preparation method comprising the following steps:

[0013] performing a first mixing treatment on the perfluorohexanone and the ethoxy(pentafluoro)cyclotriphosphazene to obtain the supramolecular synergist;

[0014] The supramolecular synergist, halogenated hydrocarbon and optional mineral oil are subjected to a second mixing process to obtain the supramolecular lithium battery fire suppressant through a cross-linking reaction.

[0015] According to the preparation method provided by the present invention, the supramolecular lithium battery fire suppressant can be prepared. The preparation method has a simple process, is convenient for large-scale production, and has good application prospects.

[0016] According to an embodiment of the present invention, the temperature of the first mixing treatment is 25-45°C.

[0017] According to an embodiment of the present invention, the time of the first mixing treatment is 6 to 12 hours.

[0018] According to an embodiment of the present invention, the temperature of the second mixing process is 60-100°C.

[0019] According to an embodiment of the present invention, the time of the second mixing treatment is 6 to 24 hours.

[0020] According to an embodiment of the present invention, the preparation method further includes the following steps: subjecting the halogenated hydrocarbon and the mineral oil to a third mixing treatment to obtain a mixed oil, subjecting the supramolecular synergist and the mixed oil to a second mixing treatment to obtain the supramolecular lithium battery fire suppressant through a cross-linking reaction.

[0021] According to an embodiment of the present invention, the temperature of the third mixing process is 50-80°C.

[0022] According to an embodiment of the present invention, the third mixing treatment is performed for 0.5 to 2 hours.

[0023] The third aspect of the present invention provides the use of the supramolecular lithium battery fire suppressant described in the first aspect or the supramolecular lithium battery fire suppressant obtained according to the preparation method described in the second aspect in lithium battery fire scenarios.

[0024] The supramolecular lithium battery fire suppressant prepared by the present invention has excellent fire extinguishing performance for lithium battery fires and has broad application prospects in lithium battery fire scenarios such as new energy vehicles, energy storage power stations, and electric bicycles.

[0025] The beneficial effects of the present invention compared to the prior art are as follows:

[0026] (1) The supramolecular lithium battery fire suppressant provided by the present invention increases the supramolecular interaction force and fire extinguishing synergistic elements of the system due to the introduction of the supramolecular synergist, thereby improving the stability of the suppressant system, reducing the storage cost of the suppressant and extending its service life. At the same time, the increase in fire extinguishing synergistic elements (such as P, N, F, etc.) enhances the fire extinguishing efficiency of the suppressant. In addition, the addition of the supramolecular synergist also increases the volatility of the suppressant system, improves its heat dissipation capacity, prevents lithium battery re-ignition, and reduces damage to electrical equipment after extinguishing the fire, greatly increasing its application value.

[0027] (2) The preparation method provided by the present invention has a simple process, low cost, and the obtained product has excellent performance and is suitable for large-scale production and application.

[0028] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0029] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be understood as limiting the present invention.

[0030] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the number of the technical features indicated. Therefore, features defined as "first" or "second" may explicitly or implicitly include one or more of such features. Furthermore, in the description of the present invention, unless otherwise specified, "plurality" means two or more.

[0031] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0032] In order to make the present invention more easily understood, certain technical and scientific terms are specifically defined below. Unless otherwise clearly defined elsewhere in this document, all other technical and scientific terms used herein have the meaning commonly understood by those skilled in the art to which the present invention belongs.

[0033] In this document, the terms “include” or “comprising” are open expressions, that is, including the contents specified in the present invention, but not excluding other contents.

[0034] As used herein, the terms "optionally," "optional," or "optionally" generally mean that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0035] According to an embodiment of the present invention, a first aspect of the present invention provides a supramolecular lithium battery fire suppressant, wherein the raw materials for preparing the supramolecular lithium battery fire suppressant include 10 to 50 parts of a supramolecular synergist, 30 to 90 parts of a halogenated hydrocarbon, and 0 to 20 parts of a mineral oil;

[0036] Wherein, the supramolecular synergist comprises perfluorohexanone and ethoxy (pentafluoro) cyclotriphosphazene.

[0037] The supramolecular lithium battery fire suppressant provided by the present invention increases the supramolecular interaction force and fire extinguishing synergistic elements of the system due to the introduction of the supramolecular synergist, thereby improving the stability of the inhibitor system, reducing the storage cost of the inhibitor and extending its service life. At the same time, the addition of fire extinguishing synergistic elements (such as P, N, F, etc.) enhances the fire extinguishing efficiency of the inhibitor. In addition, the addition of the supramolecular synergist also increases the volatility of the inhibitor system, thereby improving its heat dissipation capacity, preventing lithium battery re-ignition, and reducing damage to electrical equipment after extinguishing the fire, greatly increasing its application value.

[0038] According to a specific embodiment of the present invention, the raw materials for preparing the supramolecular lithium battery fire suppressant include 20-40 parts of supramolecular synergist, 40-80 parts of halogenated hydrocarbon, and 0-20 parts of mineral oil.

[0039] According to a specific embodiment of the present invention, the mass ratio of the perfluorohexanone to the ethoxy (pentafluoro) cyclotriphosphazene is 1:(1-5). As some specific examples, the mass ratio of the perfluorohexanone to the ethoxy (pentafluoro) cyclotriphosphazene can be 1:1, 1:2, 1:3, 1:4, 1:5, etc.

[0040] According to a specific embodiment of the present invention, the type of the halogenated hydrocarbon is not particularly limited. As some specific examples, the halogenated hydrocarbon includes at least one of fluoroalkanes, chloroalkanes, chloroolefins, bromoolefins, bromoalkanes, and iodinated alkanes. Specifically, the halogenated hydrocarbon includes at least one of tetrachloroethylene, tetrachloroethane, tetrabromoethane, tetrabromoethylene, hexachloroethane, dibromotetrafluoroethane, dibromotetrachloroethane, tribromotrifluoroethane, 1,2-dibromo-1-chloro-1,2,2-trifluoroethane, dibromohexafluoropropane, trichloropentafluoropropane, hexachloropropylene, hexachlorobutadiene, dibromooctafluorobutane, dibromohexafluorocyclobutane, dichlorooctafluorobutane, dichlorohexafluorocyclobutane, diiodoperfluorobutane, and dibromoperfluorohexane.

[0041] According to a specific embodiment of the present invention, the type of the mineral oil is not particularly limited. As some specific examples, the mineral oil includes at least one of alkanes, cycloalkanes, and aromatic hydrocarbons. Specifically, the mineral oil includes at least one of No. 10 transformer mineral oil, No. 25 transformer mineral oil, and No. 45 transformer mineral oil.

[0042] According to an embodiment of the present invention, a second aspect of the present invention provides a method for preparing the supramolecular lithium battery fire suppressant according to the first aspect, the preparation method comprising the following steps:

[0043] (1) The perfluorohexanone and the ethoxy(pentafluoro)cyclotriphosphazene are subjected to a first mixing treatment to obtain the supramolecular synergist.

[0044] After the first mixing treatment, a supramolecular force will be generated between the perfluorohexanone and the ethoxy (pentafluoro) cyclotriphosphazene, thereby obtaining the supramolecular synergist.

[0045] According to a specific embodiment of the present invention, the temperature of the first mixing process is 25-45°C. As some specific examples, the temperature of the first mixing process may be 25°C, 30°C, 35°C, 40°C, 45°C, etc.

[0046] According to a specific embodiment of the present invention, the time for the first mixing process is 6 to 12 hours. As some specific examples, the time for the first mixing process may be 6 hours, 8 hours, 10 hours, 12 hours, etc.

[0047] According to a specific embodiment of the present invention, the stirring speed of the first mixing process is 800-1500 r / min. As some specific examples, the stirring speed of the first mixing process may be 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, etc.

[0048] (2) subjecting the supramolecular synergist, halogenated hydrocarbon, and optionally mineral oil to a second mixing process to obtain the supramolecular lithium battery fire suppressant through a cross-linking reaction.

[0049] The supramolecular synergist, halogenated hydrocarbon and optional mineral oil are subjected to a second mixing process to cause cross-linking between the mixtures, thereby obtaining the supramolecular lithium battery fire suppressant.

[0050] According to a specific embodiment of the present invention, the temperature of the second mixing process is 60-100°C. As some specific examples, the temperature of the second mixing process may be 60°C, 70°C, 80°C, 90°C, 100°C, etc.

[0051] According to a specific embodiment of the present invention, the time for the second mixing process is 6 to 24 hours. As some specific examples, the time for the second mixing process can be 6 hours, 12 hours, 18 hours, 24 hours, etc.

[0052] According to a specific embodiment of the present invention, the stirring speed of the second mixing process is 800-1500 r / min. As some specific examples, the stirring speed of the second mixing process may be 800 r / min, 1000 r / min, 1200 r / min, 1500 r / min, etc.

[0053] According to a specific embodiment of the present invention, the preparation method further includes the following steps: subjecting the halogenated hydrocarbon and the mineral oil to a third mixing treatment to obtain a mixed oil, subjecting the supramolecular synergist and the mixed oil to a second mixing treatment to obtain the supramolecular lithium battery fire suppressant through a cross-linking reaction.

[0054] According to a specific embodiment of the present invention, the temperature of the third mixing process is 50-80°C. As some specific examples, the temperature of the third mixing process can be 50°C, 60°C, 70°C, 80°C, etc.

[0055] According to a specific embodiment of the present invention, the time of the third mixing process is 0.5 to 2 hours. As some specific examples, the time of the third mixing process can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, etc.

[0056] According to a specific embodiment of the present invention, the stirring speed of the third mixing process is 600-1200 r / min. As some specific examples, the stirring speed of the third mixing process may be 600 r / min, 800 r / min, 1000 r / min, 1200 r / min, etc.

[0057] According to an embodiment of the present invention, the third aspect of the present invention provides an application of the supramolecular lithium battery fire suppressant described in the first aspect or the supramolecular lithium battery fire suppressant obtained according to the preparation method described in the second aspect in a lithium battery fire scenario.

[0058] The supramolecular lithium battery fire suppressant prepared by the present invention has excellent fire extinguishing performance for lithium battery fires and has broad application prospects in lithium battery fire scenarios such as new energy vehicles, energy storage power stations, and electric bicycles.

[0059] Below, the scheme of the present invention will be explained in conjunction with embodiment.It will be understood by those skilled in the art that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention.In the embodiment, if specific technology or conditions are not indicated, the technology or conditions described in the literature in this area or the product instructions are used.The reagents or instruments used are not indicated by the manufacturer, and are all conventional products that can be obtained by commercial purchase.

[0060] Example 1

[0061] In this embodiment, the raw materials for preparing the supramolecular lithium battery fire suppressant include 30 parts of a supramolecular synergist, 60 parts of tetrachloroethane, and 10 parts of No. 25 mineral oil; wherein the supramolecular synergist includes 10 parts of perfluorohexanone and 20 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0062] The preparation method of the supramolecular lithium battery fire inhibitor comprises the following steps:

[0063] Weigh 10 parts by weight of No. 25 mineral oil into a sealed container, then weigh 60 parts of tetrachloroethane into the mineral oil, and react at 50°C and 800 rpm under magnetic stirring for 1 hour to obtain a mixed oil;

[0064] 10 parts of perfluorohexanone and 20 parts of ethoxy (pentafluoro) cyclotriphosphazene are reacted at 25° C. and 800 r / min under magnetic stirring for 6 hours to obtain a supramolecular synergist. Then 30 parts of the supramolecular synergist are added to the above-mentioned mixed oil and reacted at 60° C. and 800 r / min under magnetic stirring for 6 hours to cause cross-linking to obtain the supramolecular lithium battery fire suppressant.

[0065] The supramolecular lithium battery fire suppressant prepared in this example was used to conduct a lithium battery fire extinguishing test. The results are shown in Table 1.

[0066] Example 2

[0067] In this embodiment, the raw materials for preparing the supramolecular lithium battery fire suppressant include 30 parts of a supramolecular synergist, 60 parts of tetrachloroethane, and 10 parts of No. 25 mineral oil; wherein the supramolecular synergist includes 7.5 parts of perfluorohexanone and 22.5 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0068] The preparation method of the supramolecular lithium battery fire inhibitor comprises the following steps:

[0069] Weigh 10 parts by weight of No. 25 mineral oil into a sealed container, then weigh 60 parts of tetrachloroethane into the mineral oil, and react at 60°C and 1000 rpm under magnetic stirring for 1 hour to obtain a mixed oil;

[0070] 7.5 parts of perfluorohexanone and 22.5 parts of ethoxy (pentafluoro) cyclotriphosphazene are reacted at 45° C. and 1000 r / min under magnetic stirring for 12 hours to obtain a supramolecular synergist. Then, 30 parts of the supramolecular synergist is added to the above-mentioned mixed oil and reacted at 80° C. and 1000 r / min under magnetic stirring for 10 hours to cause cross-linking to obtain the supramolecular lithium battery fire suppressant.

[0071] The supramolecular lithium battery fire suppressant prepared in this example was used to conduct a lithium battery fire extinguishing test. The results are shown in Table 1.

[0072] Example 3

[0073] In this embodiment, the raw materials for preparing the supramolecular lithium battery fire suppressant include 30 parts of a supramolecular synergist, 60 parts of tetrachloroethane, and 10 parts of No. 25 mineral oil; wherein the supramolecular synergist includes 6 parts of perfluorohexanone and 24 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0074] The preparation method of the supramolecular lithium battery fire inhibitor comprises the following steps:

[0075] Weigh 10 parts by weight of No. 25 mineral oil into a sealed container, then weigh 60 parts of tetrachloroethane into the mineral oil, and react at 50°C and 800 rpm under magnetic stirring for 1 hour to obtain a mixed oil;

[0076] 6 parts of perfluorohexanone and 24 parts of ethoxy (pentafluoro) cyclotriphosphazene are reacted at 25° C. and 800 r / min under magnetic stirring for 6 hours to obtain a supramolecular synergist. Then 30 parts of the supramolecular synergist are added to the above-mentioned mixed oil and reacted at 60° C. and 800 r / min under magnetic stirring for 6 hours to cause cross-linking to obtain the supramolecular lithium battery fire suppressant.

[0077] The supramolecular lithium battery fire suppressant prepared in this example was used to conduct a lithium battery fire extinguishing test. The results are shown in Table 1.

[0078] Example 4

[0079] In this embodiment, the raw materials for preparing the supramolecular lithium battery fire suppressant include 20 parts of supramolecular synergist and 80 parts of tetrachloroethylene; wherein the supramolecular synergist includes 10 parts of perfluorohexanone and 10 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0080] The preparation method of the supramolecular lithium battery fire inhibitor comprises the following steps:

[0081] Weigh 80 parts of tetrachloroethylene;

[0082] 10 parts of perfluorohexanone and 10 parts of ethoxy (pentafluoro) cyclotriphosphazene are reacted at 25° C. and 800 r / min under magnetic stirring for 6 hours to obtain a supramolecular synergist, and then 20 parts of the supramolecular synergist are added to tetrachloroethylene and reacted at 60° C. and 800 r / min under magnetic stirring for 6 hours to cause cross-linking to obtain the supramolecular lithium battery fire suppressant.

[0083] The supramolecular lithium battery fire suppressant prepared in this example was used to conduct a lithium battery fire extinguishing test. The results are shown in Table 1.

[0084] Example 5

[0085] In this embodiment, the raw materials for preparing the supramolecular lithium battery fire suppressant include 40 parts of a supramolecular synergist, 40 parts of dibromohexafluoropropane, and 20 parts of No. 25 mineral oil; wherein the supramolecular synergist includes 6.7 parts of perfluorohexanone and 33.3 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0086] The preparation method of the supramolecular lithium battery fire inhibitor comprises the following steps:

[0087] Weigh 20 parts by weight of No. 25 mineral oil into a sealed container, then weigh 40 parts of dibromohexafluoropropane into the mineral oil, and react at 50° C. and 800 rpm under magnetic stirring for 1 hour to obtain a mixed oil;

[0088] 6.7 parts of perfluorohexanone and 33.3 parts of ethoxy (pentafluoro) cyclotriphosphazene were reacted at 25° C. and 800 r / min under magnetic stirring for 6 hours to obtain a supramolecular synergist. Then, 40 parts of the supramolecular synergist was added to the above-mentioned mixed oil and reacted at 60° C. and 800 r / min under magnetic stirring for 6 hours to cause cross-linking to obtain the supramolecular lithium battery fire suppressant.

[0089] The supramolecular lithium battery fire suppressant prepared in this example was used to conduct a lithium battery fire extinguishing test. The results are shown in Table 1.

[0090] Example 6

[0091] In this embodiment, the raw materials for preparing the supramolecular lithium battery fire suppressant include 30 parts of a supramolecular synergist, 30 parts of dibromooctafluorobutane, 30 parts of hexachloropropylene, and 10 parts of No. 25 mineral oil; wherein the supramolecular synergist includes 6 parts of perfluorohexanone and 24 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0092] The preparation method of the supramolecular lithium battery fire inhibitor comprises the following steps:

[0093] 10 parts by weight of No. 25 mineral oil were weighed and added to a sealed container, and then 30 parts of dibromooctafluorobutane and 30 parts of hexachloropropylene were weighed and added to the mineral oil. The mixture was reacted at 50° C. and 800 rpm under magnetic stirring for 1 hour to obtain a mixed oil.

[0094] 6 parts of perfluorohexanone and 24 parts of ethoxy (pentafluoro) cyclotriphosphazene are reacted at 25° C. and 800 r / min under magnetic stirring for 6 hours to obtain a supramolecular synergist. Then 30 parts of the supramolecular synergist are added to the above-mentioned mixed oil and reacted at 60° C. and 800 r / min under magnetic stirring for 6 hours to cause cross-linking to obtain the supramolecular lithium battery fire suppressant.

[0095] The supramolecular lithium battery fire suppressant prepared in this example was used to conduct a lithium battery fire extinguishing test. The results are shown in Table 1.

[0096] Comparative Example 1

[0097] This comparative example provides a lithium battery inhibitor and a preparation method thereof. The raw materials for preparing the lithium battery inhibitor include 30 parts of a synergist, 60 parts of tetrachloroethane, and 10 parts of No. 25 mineral oil; wherein the synergist includes 7.5 parts of perfluorohexanone and 22.5 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0098] The preparation method of the lithium battery inhibitor comprises the following steps:

[0099] Weigh 10 parts by weight of No. 25 mineral oil into a sealed container, then weigh 60 parts of tetrachloroethane into the mineral oil, and react at 50°C and 800 rpm under magnetic stirring for 1 hour to obtain a mixed oil;

[0100] 7.5 parts of perfluorohexanone and 22.5 parts of ethoxy (pentafluoro) cyclotriphosphazene were added to the above mixed oil, and reacted for 6 hours at 60° C. and 800 r / min under magnetic stirring to produce cross-linking to obtain a lithium battery inhibitor.

[0101] The lithium battery inhibitor prepared in this comparative example was used to carry out a lithium battery fire extinguishing test. The results are shown in Table 1.

[0102] Comparative Example 2

[0103] This comparative example provides a lithium battery inhibitor and a preparation method thereof. The raw materials for preparing the lithium battery inhibitor include 30 parts of a synergist, 60 parts of tetrachloroethane, and 10 parts of No. 25 mineral oil; wherein the synergist includes 30 parts of perfluorohexanone.

[0104] The preparation method of the lithium battery inhibitor comprises the following steps:

[0105] Weigh 10 parts by weight of No. 25 mineral oil into a sealed container, then weigh 60 parts of tetrachloroethane into the mineral oil, and react at 50°C and 800 rpm under magnetic stirring for 1 hour to obtain a mixed oil;

[0106] 30 parts of perfluorohexanone were added to the mixed oil, and the mixture was reacted at 60° C. and 800 r / min under magnetic stirring for 6 hours to cause cross-linking, thereby obtaining a lithium battery inhibitor.

[0107] The lithium battery inhibitor prepared in this comparative example was used to carry out a lithium battery fire extinguishing test. The results are shown in Table 1.

[0108] Comparative Example 3

[0109] This comparative example provides a lithium battery inhibitor and a preparation method thereof. The raw materials for preparing the lithium battery inhibitor include 30 parts of a synergist, 60 parts of tetrachloroethane, and 10 parts of No. 25 mineral oil; wherein the synergist includes 30 parts of ethoxy (pentafluoro) cyclotriphosphazene.

[0110] The preparation method of the lithium battery inhibitor comprises the following steps:

[0111] Weigh 10 parts by weight of No. 25 mineral oil into a sealed container, then weigh 60 parts of tetrachloroethane into the mineral oil, and react at 50°C and 800 rpm under magnetic stirring for 1 hour to obtain a mixed oil;

[0112] 30 parts of ethoxy (pentafluoro) cyclotriphosphazene were added to the above mixed oil, and the mixture was reacted at 60° C. and 800 r / min under magnetic stirring for 6 hours to cause cross-linking, thereby obtaining a lithium battery inhibitor.

[0113] The lithium battery inhibitor prepared in this comparative example was used to carry out a lithium battery fire extinguishing test. The results are shown in Table 1.

[0114] Comparative Example 4

[0115] This comparative example provides a lithium battery inhibitor and a preparation method thereof. The raw materials for preparing the lithium battery inhibitor include 60 parts of tetrachloroethane and 10 parts of No. 25 mineral oil.

[0116] The preparation method of the lithium battery inhibitor comprises the following steps:

[0117] 10 parts by weight of No. 25 mineral oil were added to a sealed container, and then 60 parts of tetrachloroethane were added to the mineral oil. The mixture was reacted at 50° C. and 800 rpm under magnetic stirring for 1 hour to obtain a lithium battery inhibitor.

[0118] The lithium battery inhibitor prepared in this comparative example was used to carry out a lithium battery fire extinguishing test. The results are shown in Table 1.

[0119] Comparative Example 5

[0120] This comparative example provides a lithium battery inhibitor and a preparation method thereof. The raw materials for preparing the lithium battery inhibitor include 10 parts of perfluorohexanone, 10 parts of ethoxy(pentafluoro)cyclotriphosphazene, and 80 parts of halogenated alkane; wherein the halogenated alkane includes 2-bromo-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, and the mass ratio of the two is 1:1.

[0121] The preparation method of the lithium battery inhibitor comprises the following steps:

[0122] Perfluorohexanone, ethoxy (pentafluoro) cyclotriphosphazene and halogenated alkane were weighed in parts by weight and mixed at 20° C. to obtain a lithium battery inhibitor.

[0123] The lithium battery inhibitor prepared in this comparative example was used to carry out a lithium battery fire extinguishing test. The results are shown in Table 1.

[0124] Comparative Example 6

[0125] This comparative example provides a lithium battery inhibitor and a preparation method thereof. The raw materials for preparing the lithium battery inhibitor include 10 parts of perfluorohexanone, 10 parts of pentafluoro(phenoxy)cyclotriphosphazene, and 80 parts of halogenated alkane; wherein the halogenated alkane includes 2-bromo-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, and the mass ratio of the two is 1:1.

[0126] The preparation method of the lithium battery inhibitor comprises the following steps:

[0127] Perfluorohexanone, pentafluoro(phenoxy)cyclotriphosphazene and halogenated alkane were weighed in parts by weight and mixed at 20° C. to obtain a lithium battery inhibitor.

[0128] The lithium battery inhibitor prepared in this comparative example was used to carry out a lithium battery fire extinguishing test. The results are shown in Table 1.

[0129] Test Case

[0130] The supramolecular lithium battery fire suppressant prepared in the example and the lithium battery suppressant prepared in the comparative example were subjected to a lithium battery fire extinguishing test. The test method is as follows:

[0131] A 100% SOC lithium battery and a heating plate were fixed on a test bench. The heating plate power was 1000W, and uniform heating was set at a heating rate of 20°C / min. A thermocouple was placed at the center of the side of the lithium battery to collect changes in the surface temperature of the lithium battery during the test. A fine water mist spray gun was set 60 cm above the lithium battery, and the spray gun pressure was set to 6.5MPa, the flow rate was 10L / min, and the atomization angle was 60°. After the test setup was completed, the heating device was started to heat the lithium battery until thermal runaway occurred, the battery safety valve opened, and the heating device was turned off. When a large amount of combustible gas was released from the safety valve and an open flame appeared, the fine water mist spray gun was started to extinguish the fire. The fire extinguishing time was observed. After the open flame was extinguished, the spraying was stopped and the observation was continued for 60 minutes to observe whether there was any re-ignition. The highest surface temperature of the lithium battery during the fire extinguishing process was recorded, and the cooling rate from the highest temperature to 200°C was calculated.

[0132] The main parameters of the test lithium battery are as follows:

[0133] Type: square aluminum shell ternary lithium battery;

[0134] Dimensions: 150mm×105mm×80mm (length×width×height);

[0135] Rated capacity: 150Ah;

[0136] Rated voltage: 3.7V;

[0137] Positive and negative electrode materials: the negative electrode is graphite, and the positive electrode is lithium nickel cobalt manganese oxide [Li(NiCoMn)O2];

[0138] Electrolyte composition: solvent is ethylene carbonate and propylene carbonate; solute is lithium hexafluorophosphate.

[0139] The above test method was used to test Examples 1-6 and Comparative Examples 1-4. The test results are shown in Table 1.

[0140] Table 1

[0141]

[0142]

[0143] Through the test results of Examples 1-6, it can be found that the supramolecular lithium battery fire suppressant provided by the present invention has an extinguishing time of less than 10s, a high fire extinguishing efficiency, a fast cooling rate, and no re-ignition phenomenon. The introduction of the supramolecular synergist increases the supramolecular force of the system, and as the supramolecular force is enhanced, the fire extinguishing time is reduced, the fire extinguishing efficiency is enhanced, and the cooling efficiency is increased, indicating that the increase in the supramolecular force has a positive effect on the inhibitor fire extinguishing efficiency, cooling rate, etc. Through the test results of Comparative Examples 1-6, it can be found that without the introduction of the supramolecular synergist, there is no supramolecular force, the inhibitor fire extinguishing efficiency is reduced, and comparative examples 2 and comparative examples 4 also re-ignite. In addition, the introduction of the supramolecular force also enhances the stability of the inhibitor system. With the presence of the supramolecular force, after standing for 24 hours, the system has no stratification and no turbidity, while without the presence of the supramolecular force, after standing for 24 hours, the system has more stratification and / or turbidity, thereby further reflecting the advantages of the supramolecular force and proving the superiority of the technical solution of the present invention.

[0144] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0145] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A supramolecular lithium battery fire suppressant, characterized in that: The raw materials for preparing the supramolecular lithium battery fire suppressant include 10 to 50 parts of supramolecular synergist, 30 to 90 parts of halogenated hydrocarbon, and 0 to 20 parts of mineral oil; Wherein, the supramolecular synergist comprises perfluorohexanone and ethoxy (pentafluoro) cyclotriphosphazene.

2. The supramolecular lithium battery fire suppressant according to claim 1, characterized in that: The mass ratio of the perfluorohexanone to the ethoxy(pentafluoro)cyclotriphosphazene is 1:(1-5).

3. The supramolecular lithium battery fire suppressant according to claim 1, characterized in that: The halogenated hydrocarbon includes at least one of fluoroalkanes, chloroalkanes, chloroolefins, bromoolefins, brominated alkanes, and iodinated alkanes; Optionally, the halogenated hydrocarbon includes at least one of tetrachloroethylene, tetrachloroethane, tetrabromoethane, tetrabromoethylene, hexachloroethane, dibromotetrafluoroethane, dibromotetrachloroethane, tribromotrifluoroethane, 1,2-dibromo-1-chloro-1,2,2-trifluoroethane, dibromohexafluoropropane, trichloropentafluoropropane, hexachloropropylene, hexachlorobutadiene, dibromooctafluorobutane, dibromohexafluorocyclobutane, dichlorooctafluorobutane, dichlorohexafluorocyclobutane, diiodoperfluorobutane, and dibromoperfluorohexane.

4. The supramolecular lithium battery fire suppressant according to claim 1, characterized in that The mineral oil includes at least one of alkanes, cycloalkanes and aromatic hydrocarbons.

5. The method for preparing the supramolecular lithium battery fire suppressant according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: performing a first mixing treatment on the perfluorohexanone and the ethoxy(pentafluoro)cyclotriphosphazene to obtain the supramolecular synergist; The supramolecular synergist, halogenated hydrocarbon and optional mineral oil are subjected to a second mixing process to obtain the supramolecular lithium battery fire suppressant through a cross-linking reaction.

6. The preparation method according to claim 5, characterized in that The temperature of the first mixing treatment is 25 to 45° C.; Optionally, the first mixing treatment is performed for 6 to 12 hours.

7. The preparation method according to claim 5, characterized in that The temperature of the second mixing treatment is 60-100°C; Optionally, the second mixing treatment is performed for 6 to 24 hours.

8. The preparation method according to claim 5, characterized in that The preparation method further comprises the following steps: subjecting the halogenated hydrocarbon and the mineral oil to a third mixing process to obtain a mixed oil; subjecting the supramolecular synergist and the mixed oil to a second mixing process to obtain the supramolecular lithium battery fire suppressant through a cross-linking reaction.

9. The preparation method according to claim 8, characterized in that The temperature of the third mixing treatment is 50-80°C; Optionally, the third mixing treatment lasts for 0.5 to 2 hours.

10. Use of the supramolecular lithium battery fire suppressant according to any one of claims 1 to 4 or the supramolecular lithium battery fire suppressant obtained by the preparation method according to any one of claims 5 to 9 in lithium battery fire scenarios.

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