Glass fiber impregnating compound, modified glass fiber, composite material, preparation method of composite material, battery and electric equipment

Abstract

The invention provides a glass fiber impregnating compound, a modified glass fiber, a composite material, a preparation method, a battery and electric equipment, and belongs to the technical field of composite materials. The preparation method of the glass fiber impregnating compound comprises the following steps: hydrolyzing a first coupling agent to obtain a hydrolysis system; and stirring the first mixed system containing the hydrolysis system and the film-forming agent to prepare the glass fiber impregnating compound. The mass of the first coupling agent is 5-15% of the mass of the glass fiber impregnating compound; and the mass of the film-forming agent is 3-15% of the mass of the glass fiber impregnating compound. When the glass fiber impregnating compound prepared by the preparation method of the glass fiber impregnating compound provided by the invention is used for treating a glass fiber matrix, a rough concave-convex structure can be formed on the surface of the glass fiber matrix, so that the specific surface area of the glass fiber matrix can be increased; and the interface bonding force between the glass fiber matrix and the resin in a composite material formed by the glass fiber matrix and the resin subsequently can be improved.

Description

Technical Field

[0001] The present application relates to the technical field of composite materials, and in particular to a glass fiber sizing agent, modified glass fiber, composite materials and preparation methods, batteries, and electrical equipment. Background Art

[0002] Composite materials formed by a glass fiber matrix and a resin can be used as engineering materials for batteries; however, in existing composite materials formed by a glass fiber matrix and a resin, the interface bonding strength between the glass fiber matrix and the resin is poor. Summary of the Invention

[0003] In response to the deficiencies in the prior art, the present application provides a glass fiber sizing, modified glass fiber, a composite material and a preparation method, a battery and an electrical device. The glass fiber sizing provided in the present application is applied to the surface of a glass fiber substrate to prepare modified glass fiber, which can improve the interfacial bonding strength between the glass fiber substrate and the resin in the composite material formed by the subsequent glass fiber substrate and resin, thereby improving the mechanical properties of the prepared composite material and reducing the attenuation of the mechanical properties of the prepared composite material under high temperature and high humidity conditions. The composite material is suitable for preparing structural parts in automobiles and batteries.

[0004] Surprisingly, it was discovered that when preparing a glass fiber sizing, increasing the amount of coupling agent used can form a rough structure on the surface of the glass fiber matrix, thereby significantly improving the bonding strength between the glass fiber matrix and the resin in the composite material formed by the subsequent glass fiber matrix and resin. Based on this, in a first aspect, the present application provides a method for preparing a glass fiber sizing, the method comprising: hydrolyzing a first coupling agent to obtain a hydrolysis system; and then stirring a first mixed system containing the hydrolysis system and a film-forming agent to prepare the glass fiber sizing. The mass of the first coupling agent is 5% to 15% of the mass of the glass fiber sizing; the mass of the film-forming agent is 3% to 15% of the mass of the glass fiber sizing.

[0005] By treating the glass fiber matrix with the glass fiber impregnating agent prepared by the preparation method of the glass fiber impregnating agent provided by the present application, a rough concave-convex structure can be formed on the surface of the glass fiber matrix, which is beneficial to increasing the specific surface area of the glass fiber matrix, and can improve the interfacial bonding force between the glass fiber matrix and the resin in the composite material formed by the subsequent glass fiber matrix and resin, which is beneficial to avoiding the mutual slip and separation of the glass fiber matrix and the resin under mechanical force in the composite material, and can improve the tensile strength, bending strength, impact strength and thermal deformation temperature of the composite material, and is also beneficial to inhibiting the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and can make the composite material have better mechanical properties, and is suitable for preparing structural parts in automobiles and batteries.

[0006] In some embodiments, the mass of the first coupling agent is 8% to 11% of the mass of the glass fiber sizing agent; the surface of the glass fiber matrix treated with the prepared glass fiber sizing agent can form a rough concave-convex structure, which is beneficial to further improve the interfacial bonding force between the glass fiber matrix and the resin, thereby improving the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0007] In some embodiments, the first coupling agent includes a silane coupling agent; the silane coupling agent contains at least one of an amino group, an epoxy group, and a double bond; the amino group, epoxy group, and / or double bond in the silane coupling agent can covalently react with the amino group, hydroxyl group, and / or double bond in the resin, which can further improve the interfacial bonding strength between the glass fiber matrix and the resin, thereby improving the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0008] In some embodiments, the film-forming agent contains epoxy groups; the epoxy groups in the film-forming agent can covalently react with the terminal functional groups of the resin molecules to further improve the interfacial bonding strength between the glass fiber matrix and the resin, and also help to avoid hydrolysis of the resin group.

[0009] In some embodiments, the first mixing system also includes a lubricant; the mass of the lubricant is 1% to 5% of the mass of the glass fiber impregnant; the glass fiber matrix is treated with a glass fiber impregnant containing a lubricant, and the impregnant can migrate to the surface of the glass fiber matrix to generate electrostatic repulsion, reduce intermolecular cohesion, and reduce the friction coefficient, thereby reducing the wear of the glass fiber matrix during subsequent composite processing with the resin, and improving the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0010] In some embodiments, the preparation method of the glass fiber sizing includes adjusting the pH value of the stirred system to 4-5. This helps improve the stability of the film-forming agent and further improves the interfacial bonding strength between the glass fiber matrix and the resin in the composite material subsequently formed by the glass fiber matrix and the resin.

[0011] In a second aspect, the present application provides a glass fiber sizing, which is prepared by the preparation method of the glass fiber sizing provided by any one of the first aspects above.

[0012] By treating the glass fiber matrix with the glass fiber impregnating agent provided in the present application, a rough concave-convex structure can be formed on the surface of the glass fiber matrix, which is beneficial to increasing the specific surface area of the glass fiber matrix, and can improve the interfacial bonding force between the glass fiber matrix and the resin in the composite material formed by the subsequent glass fiber matrix and resin, and can improve the tensile strength, bending strength, impact strength and thermal deformation temperature of the composite material. It is also beneficial to inhibit the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and the composite material has better mechanical properties, which is suitable for preparing structural parts in automobiles and batteries.

[0013] In a third aspect, the present application provides a method for preparing modified glass fiber, which comprises: applying the glass fiber impregnating agent provided in the second aspect above to the surface of a glass fiber substrate, and then drying the glass fiber impregnating agent on the surface of the glass fiber substrate.

[0014] The surface of the modified glass fiber provided in the present application has a rough concave-convex structure, which is beneficial to increasing the specific surface area of the glass fiber matrix, and can improve the interfacial bonding force between the modified glass fiber and the resin in the composite material formed by the subsequent modified glass fiber and resin, and can improve the tensile strength, flexural strength, impact strength and thermal deformation temperature of the composite material. It is also beneficial to inhibit the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and the composite material has better mechanical properties, which is suitable for preparing structural parts in automobiles and batteries.

[0015] In a fourth aspect, the present application provides a modified glass fiber, which is prepared using the preparation method of the modified glass fiber provided in the third aspect.

[0016] The surface of the modified glass fiber provided in the present application has a rough concave-convex structure, which is beneficial to increasing the specific surface area of the glass fiber matrix, and can improve the interfacial bonding force between the modified glass fiber and the resin in the composite material formed by the subsequent modified glass fiber and resin, and can improve the tensile strength, flexural strength, impact strength and thermal deformation temperature of the composite material. It is also beneficial to inhibit the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and the composite material has better mechanical properties, which is suitable for preparing structural parts in automobiles and batteries.

[0017] In a fifth aspect, the present application provides a method for preparing a composite material, which comprises: melt-kneading a second mixed system containing a resin and the modified glass fiber provided in the fourth aspect, and then performing a molding process to prepare the composite material.

[0018] The preparation method of the composite material provided in the present application adopts the modified glass fiber provided in the fourth aspect above, so that the interfacial bonding force between the modified glass fiber and the resin in the prepared composite material is relatively high, which can improve the tensile strength, flexural strength, impact strength and thermal deformation temperature of the composite material. It is also beneficial to inhibit the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and the composite material has good mechanical properties, which is suitable for preparing structural parts in automobiles and batteries.

[0019] In some embodiments, the second mixed system further includes a hindered phenol antioxidant and a phosphite antioxidant; the hindered phenol antioxidant includes at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl ester; and the phosphite antioxidant includes at least one of tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl diphosphite and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate. The above solution helps prevent hydrolysis of the resin and yellowing of the composite material, and can improve the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0020] In some embodiments, the mass of the resin is 50% to 85% of the mass of the composite material; or / and, the mass of the modified glass fiber is 10% to 50% of the mass of the composite material; or / and, the mass of the hindered phenol antioxidant is 0.1% to 0.5% of the mass of the composite material; or / and, the mass of the phosphite antioxidant is 0.1% to 0.5% of the mass of the composite material; or / and, the resin includes a thermoplastic polyester resin, and the thermoplastic polyester resin includes at least one of polybutylene terephthalate, polycarbonate, polyethylene terephthalate, poly1,4-cyclohexanedimethanol terephthalate, polyoxymethylene, polyamide, polyphenylene sulfide, polyetheretherketone and polyarylethernitrile; or / and, the second mixed system also includes a compatibilizer, and the mass of the compatibilizer is 1% to 10% of the mass of the composite material.

[0021] In a sixth aspect, the present application provides a composite material, which is prepared using the preparation method of the composite material provided in any one of the fifth aspects above.

[0022] The composite material provided in the present application has a high interfacial bonding force between the modified glass fiber and the resin, and the composite material has high tensile strength, flexural strength, impact strength and thermal deformation temperature. The composite material has a high mechanical strength retention rate under high temperature and high humidity conditions. The composite material has good mechanical properties and is suitable for preparing structural parts in automobiles and batteries.

[0023] In a seventh aspect, the present application provides a battery, the material of which includes the composite material provided in the seventh aspect above.

[0024] In some embodiments, the battery includes an output pole base, an annular gasket for the electrode terminal, an output pole protective cover, a fuse base, a high-voltage box base and a connector protective cover; the materials of the output pole base, the annular gasket for the electrode terminal, the output pole protective cover, the fuse base, the high-voltage box base and the connector protective cover all include the composite material provided in the seventh aspect above.

[0025] In some embodiments, the battery includes a BMS shell; the material of the BMS shell includes the composite material provided in the seventh aspect above.

[0026] In an eighth aspect, the present application provides an electrical device, which includes the battery provided in the eighth aspect.

[0027] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiment below. The accompanying drawings are for illustration purposes only and are not to be considered as limiting the present application. The same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0029] Figure 1 A schematic structural diagram of a vehicle provided for some embodiments of the present application.

[0030] Figure 2 Schematic diagram of the exploded structure of the battery provided in some embodiments of the present application.

[0031] Figure 3 A schematic structural diagram of a battery cell provided in some embodiments of the present application.

[0032] Figure 4 An exploded view of a battery cell provided in some embodiments of the present application.

[0033] Figure 5 This is the SEM characterization image of the glass fiber after treatment in step (3) of Example 1 of the present application.

[0034] Figure 6 This is the SEM characterization image of the glass fiber after treatment in step (3) of comparative example 2 of this application.

[0035] Figure 7 This is a SEM characterization image of the composite material prepared in Example 1 of the present application.

[0036] Figure 8 This is a SEM characterization image of the composite material prepared in Comparative Example 1 of this application.

[0037] Icon: 1000-vehicle; 100-battery; 10-housing; 11-accommodation space; 12-first part; 13-second part; 20-battery cell; 21-housing; 211-opening; 22-end cover assembly; 221-end cover; 222-electrode terminal; 23-electrode assembly; 24-current collecting member; 25-insulating protection member; 200-controller; 300-motor. DETAILED DESCRIPTION

[0038] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0040] In the description of the embodiments of this application, the technical terms "first" and "second" are used only to distinguish different objects and should not be understood to indicate or imply relative importance or implicitly specify the quantity, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, the meaning of "plurality" is more than two, unless otherwise clearly and specifically defined.

[0041] References to "embodiments" herein mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0042] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0043] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).

[0044] In the description of the embodiments of the present application, the technical terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc., indicating the orientation or position relationship, are based on the orientation or position relationship shown in the accompanying drawings, and are only for the convenience of describing the embodiments of the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the embodiments of the present application.

[0045] In the description of the embodiments of the present application, unless otherwise expressly specified or limited, technical terms such as "installed," "connected," "connected," and "fixed" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integration; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; internal connections between two components or interactions between two components. Those skilled in the art can understand the specific meanings of the above terms in the embodiments of the present application based on specific circumstances.

[0046] Currently, market developments indicate that power batteries are becoming increasingly widely used. They are not only used in energy storage systems such as hydropower, thermal, wind, and solar power plants, but are also widely used in electric vehicles like electric bicycles, electric motorcycles, and electric vehicles, as well as in military equipment and aerospace. As power battery applications continue to expand, market demand is also growing.

[0047] The power battery can be a lithium-ion battery or a sodium-ion battery. The BMS (i.e., battery management system) housing, the annular gasket of the electrode terminal, the output pole protective cover, the fuse base, the high-voltage box base, the output pole base, and the connector protective cover in the power battery can all be made of a composite material formed by glass fiber and resin. For example, the BMS housing in the battery is relatively thin, and the BMS housing will be affected by the high temperature and high humidity environment in the battery pack. Therefore, the material of the BMS housing is required to have high mechanical strength and not be easily shrunk or curled. It is also required that the material of the BMS housing has low mechanical performance attenuation under high temperature and high humidity conditions and is not easily affected by the high temperature and high humidity environment in the battery pack.

[0048] However, in the existing composite materials formed by glass fiber matrix and resin, the interfacial bonding strength between the glass fiber matrix and the resin is poor, resulting in poor mechanical properties of the composite materials formed by the glass fiber matrix and resin and high mechanical property attenuation under high temperature and high humidity conditions, which in turn leads to low mechanical strength of the structural parts in the power battery prepared using the composite materials, affecting the service life of the structural parts in the power battery.

[0049] Based on the above considerations, in order to improve the interfacial bonding strength between a glass fiber matrix and a resin in a composite material formed of a glass fiber matrix and a resin, the present application provides a method for preparing a glass fiber sizing. The method comprises: hydrolyzing a first coupling agent to obtain a hydrolysis system; and then stirring a first mixed system containing the hydrolysis system and a film-forming agent to prepare the glass fiber sizing. The mass of the first coupling agent is 5% to 15% of the mass of the glass fiber sizing; and the mass of the film-forming agent is 3% to 15% of the mass of the glass fiber sizing.

[0050] In the preparation method of the glass fiber impregnating agent provided in the present application, by adjusting the amount of the first coupling agent, a rough concave-convex structure can be formed on the surface of the glass fiber matrix, which is beneficial to increasing the specific surface area of the glass fiber matrix, and can improve the interfacial bonding force between the glass fiber matrix and the resin in the composite material formed by the subsequent glass fiber matrix and resin, which is beneficial to avoid the glass fiber matrix and the resin from sliding and separating from each other under mechanical force in the composite material, and can improve the tensile strength, flexural strength, impact strength and thermal deformation temperature of the composite material, and is also beneficial to inhibiting the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and can make the composite material have better mechanical properties, suitable for preparing structural parts in automobiles and batteries.

[0051] The glass fiber sizing prepared by the preparation method provided above can be used to treat a glass fiber matrix. The composite material formed by the treated glass fiber matrix and the resin can be used to prepare structural parts in power batteries (including but not limited to BMS housings, annular gaskets for electrode terminals, output pole protective covers, fuse bases, high-voltage box bases, output pole bases, and connector protective covers). The battery can be a battery cell, a module, a battery pack, etc. The battery can be used, but not limited to, in electrical equipment such as vehicles, ships, or aircraft. The power supply system of the electrical equipment can be composed of the battery disclosed in this application, which is conducive to improving the mechanical strength of the structural parts in the battery, thereby increasing the service life of the structural parts in the battery.

[0052] The embodiments of the present application provide an electrical device that uses a battery as a power source. The electrical device may be a vehicle, a mobile phone, a portable device, a laptop computer, a ship, a spacecraft, an electric toy, an electric tool, and the like. The vehicle may be a fuel vehicle, a gas vehicle, or a new energy vehicle. The new energy vehicle may be a pure electric vehicle, a hybrid vehicle, or an extended-range vehicle. The spacecraft may include an airplane, a rocket, a space shuttle, and a spacecraft. The electric toys may include fixed or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys. The electric tools may include metal cutting electric tools, grinding electric tools, assembly electric tools, and railway electric tools, such as electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact drills, concrete vibrators, and electric planers. The embodiments of the present application do not impose any special restrictions on the above-mentioned electrical devices.

[0053] For the convenience of description, the following embodiments are described by taking the electric device as a vehicle as an example.

[0054] Please refer to Figure 1 , Figure 1 This is a schematic diagram of the structure of a vehicle 1000 provided in some embodiments of the present application. A battery 100 is disposed within the vehicle 1000, and the battery 100 can be located at the bottom, front, or rear of the vehicle 1000. The battery 100 can be used to power the vehicle 1000, for example, as the operating power source of the vehicle 1000.

[0055] The vehicle 1000 may further include a controller 200 and a motor 300 . The controller 200 is used to control the battery 100 to supply power to the motor 300 , for example, to meet the power requirements of the vehicle 1000 during startup, navigation, and driving.

[0056] In some embodiments of the present application, the battery 100 can not only serve as the operating power source of the vehicle 1000, but also serve as the driving power source of the vehicle 1000, replacing or partially replacing fuel or natural gas to provide driving power for the vehicle 1000.

[0057] Figure 2 This is a schematic diagram of the exploded structure of the battery 100 provided in some embodiments of the present application. Figure 2 The battery 100 includes a box body 10 and a battery cell 20 , and the battery cell 20 is accommodated in the box body 10 .

[0058] The housing 10 is used to provide a storage space 11 for the battery cells 20. In some embodiments, the housing 10 may include a first portion 12 and a second portion 13, which overlap to define the storage space 11 for accommodating the battery cells 20. Of course, the connection between the first portion 12 and the second portion 13 can be sealed by a seal (not shown), such as a sealing ring, sealant, or the like.

[0059] The first part 12 and the second part 13 can be in various shapes, such as a cuboid, a cylinder, etc. The first part 12 can be a hollow structure with one side open to form a receiving 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 receiving cavity for accommodating the battery cell 20. The open side of the second part 13 covers the open side of the first part 12, thereby forming a box body 10 with a receiving space 11. Of course, if Figure 2 As shown, the first part 12 may be a hollow structure with one side open, and the second part 13 may be a plate-like structure. The second part 13 covers the open side of the first part 12 to form a box body 10 with an accommodating space 11.

[0060] In the battery 100, there can be one or more battery cells 20. If there are multiple battery cells 20, the multiple battery cells 20 can be connected in series, in parallel, or in a hybrid connection. A hybrid connection refers to a combination of series and parallel connections among the multiple battery cells 20. The multiple battery cells 20 can be directly connected in series, in parallel, or in a hybrid connection, and then the entire battery cell 20 can be housed within the housing 10. Alternatively, multiple battery cells 20 can be first connected in series, in parallel, or in a hybrid connection to form a battery module, and then the multiple battery modules can be connected in series, in parallel, or in a hybrid connection to form a single unit and housed within the housing 10. The battery cells 20 can be cylindrical, flat, rectangular, or other shapes. Figure 2 The example shows a case where the battery cell 20 is square.

[0061] In some embodiments, the battery 100 may further include a busbar component (not shown), and the multiple battery cells 20 may be electrically connected via the busbar component to achieve series connection, parallel connection, or mixed connection of the multiple battery cells 20 .

[0062] Figure 3 This is a schematic diagram of the structure of a battery cell 20 provided in some embodiments of the present application. Figure 4 This is an exploded view of a battery cell 20 provided in some embodiments of the present application. Figure 3 and Figure 4 The battery cell 20 may include a housing 21 , an end cap assembly 22 and an electrode assembly 23 . The housing 21 has an opening 211 , the electrode assembly 23 is accommodated in the housing 21 , and the end cap assembly 22 is used to cover the opening 211 .

[0063] The shape of the housing 21 can be determined according to the specific shape of the electrode assembly 23. For example, if the electrode assembly 23 is a rectangular parallelepiped structure, the housing 21 can also be a rectangular parallelepiped structure. Figure 3 and Figure 4 The case where the housing 21 and the electrode assembly 23 are square is exemplarily shown.

[0064] The shell 21 may be made of a variety of materials, such as copper, iron, aluminum, stainless steel, aluminum alloy, etc., and the embodiment of the present application does not impose any special restrictions on this.

[0065] The end cap assembly 22 includes an end cap 221 and an electrode terminal 222. The end cap assembly 22 is used to seal the opening 211 of the outer shell 21 to form a sealed installation space (not shown), which is used to accommodate the electrode assembly 23. The installation space is also used to accommodate an electrolyte, such as an electrolyte. The end cap assembly 22 serves as a component for outputting the electrical energy of the electrode assembly 23. The electrode terminal 222 in the end cap assembly 22 is used to electrically connect to the electrode assembly 23, that is, the electrode terminal 222 is electrically connected to the tab of the electrode assembly 23. For example, the electrode terminal 222 is connected to the tab through the current collecting member 24 to achieve electrical connection between the electrode terminal 222 and the tab.

[0066] It should be noted that the number of openings 211 of the outer shell 21 can be one or two. If the number of openings 211 of the outer shell 21 is one, the number of end cap assembly 22 can also be one, and two electrode terminals 222 can be provided in the end cap assembly 22. The two electrode terminals 222 are respectively used to electrically connect to the positive electrode tab and the negative electrode tab of the electrode assembly 23. If the number of openings 211 of the outer shell 21 is two, for example, the two openings 211 are provided on opposite sides of the outer shell 21, the number of end cap assemblies 22 can also be two, and the two end cap assemblies 22 are respectively covered at the two openings 211 of the outer shell 21. In this case, the electrode terminal 222 in one end cap assembly 22 can be a positive electrode terminal, which is used to electrically connect to the positive electrode tab of the electrode assembly 23; and the electrode terminal 222 in the other end cap assembly 22 can be a negative electrode terminal, which is used to electrically connect to the negative electrode tab of the electrode assembly 23.

[0067] In some embodiments, as Figure 4 As shown, the battery cell 20 may further include an insulating protective member 25 fixed to the periphery of the electrode assembly 23, and the insulating protective member 25 is used to insulate and isolate the electrode assembly 23 from the housing 21. Exemplarily, the insulating protective member 25 is a tape bonded to the periphery of the electrode assembly 23. In some embodiments, there are multiple electrode assemblies 23, and the insulating protective member 25 is arranged around the periphery of the multiple electrode assemblies 23, and the multiple electrode assemblies 23 are formed into an integral structure to maintain the structural stability of the electrode assembly 23. Among them, the electrode assembly 23 can be a wound electrode assembly or a laminated electrode assembly, and the embodiments of the present application are not limited thereto.

[0068] In this application, a method for preparing a glass fiber sizing includes: hydrolyzing a first coupling agent to obtain a hydrolysis system; and then stirring a first mixed system containing the hydrolysis system and a film-forming agent to prepare the glass fiber sizing. The mass of the first coupling agent is 5% to 15% of the mass of the glass fiber sizing; and the mass of the film-forming agent is 3% to 15% of the mass of the glass fiber sizing.

[0069] In the preparation method of the glass fiber sizing provided in the present application, by adjusting the amount of the first coupling agent to 5% to 15% of the mass of the glass fiber sizing, a rough concave-convex structure can be formed on the surface of the glass fiber matrix, which is beneficial to increasing the specific surface area of the glass fiber matrix, and can improve the interfacial bonding force between the glass fiber matrix and the resin in the composite material formed by the subsequent glass fiber matrix and resin, which is beneficial to avoid the glass fiber matrix and the resin from sliding and separating from each other under mechanical force in the composite material, and can improve the tensile strength, flexural strength, impact strength and thermal deformation temperature of the composite material, and is also beneficial to inhibiting the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and can make the composite material have better mechanical properties, suitable for preparing structural parts in automobiles and batteries.

[0070] In addition, the mass of the film-forming agent is 3% to 10% of the mass of the glass fiber sizing agent; the prepared glass fiber sizing agent can have a good bonding and bundling effect on the glass fiber matrix, so that the glass fiber matrix treated with the glass fiber sizing agent has good stiffness and bundling properties, which is beneficial to improving the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0071] As an example, the mass of the first coupling agent can be any value among 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% and 15% of the mass of the glass fiber sizing, or a range between any two values; the mass of the film-forming agent can be any value among 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12%, 13%, 14% and 15% of the mass of the glass fiber sizing, or a range between any two values.

[0072] As an example, the water used in preparing the glass fiber sizing may be deionized water.

[0073] In some embodiments, the mass of the first coupling agent is 8% to 11% of the mass of the glass fiber sizing agent; the surface of the glass fiber treated with the glass fiber sizing agent can form more rough concave-convex structures, which is beneficial to further improve the interfacial bonding strength between the glass fiber matrix and the resin.

[0074] In some embodiments, the first coupling agent includes a silane coupling agent; the first coupling agent forms a rough concave-convex structure on the surface of the glass fiber matrix. The first coupling agent includes a silane coupling agent, and the silane coupling agent can form a covalent connection with the surface of the glass fiber matrix and the surface of the resin, which is beneficial to further improve the interfacial bonding strength between the glass fiber matrix and the resin.

[0075] Furthermore, in some embodiments, the silane coupling agent contains at least one of an amino group, an epoxy group, and a double bond; in the above case, the amino group, the epoxy group, and / or the double bond in the silane coupling agent can covalently react with the amino group, the hydroxyl group, and / or the double bond in the resin, which can further improve the interfacial bonding strength between the glass fiber matrix and the resin, thereby improving the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0076] In some embodiments, the silane coupling agent includes at least one of γ-methacryloxypropyltrimethoxysilane, tetraethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, and 1,2-bis(trimethoxysilyl)ethane. Using the above-mentioned silane coupling agents can enhance the interfacial bonding strength between the glass fiber matrix and the resin.

[0077] It is understandable that the silane coupling agent is not limited to the substances listed above; in other feasible embodiments, the first coupling agent may also be other coupling agents, for example, a titanate coupling agent.

[0078] In some embodiments, the film-forming agent contains epoxy groups. In the above embodiment, the epoxy groups in the film-forming agent can covalently react with the terminal functional groups of the resin molecules, thereby further improving the interfacial bonding strength between the glass fiber matrix and the resin. The consumption of the terminal functional groups of the resin molecules by reacting with the epoxy groups in the film-forming agent also helps prevent hydrolysis of the resin groups. Therefore, the presence of epoxy groups in the film-forming agent helps improve the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0079] Furthermore, in some embodiments, the film-forming agent contains at least two epoxy groups. The above solution is conducive to further improving the interfacial bonding strength between the glass fiber matrix and the resin.

[0080] In some embodiments, the film-forming agent includes styrene-glycidyl methacrylate copolymer, which can increase the interfacial bonding strength between the glass fiber matrix and the resin.

[0081] It should be noted that the film-forming agent is not limited to the above substances. For example, the film-forming agent can also be mineral oil substances, hydrogenated vegetable oil substances, non-ionic surfactants or cationic surfactants, etc.; as an example, the film-forming agent can also be phenolic epoxy resin or polyurethane, etc.

[0082] In some embodiments, the aforementioned first mixing system also includes a lubricant; the glass fiber matrix is treated with a glass fiber impregnant containing a lubricant, and the impregnant can migrate to the surface of the glass fiber matrix to generate electrostatic repulsion, reduce intermolecular cohesion, and reduce the friction coefficient, thereby reducing the wear of the glass fiber matrix during subsequent composite processing with the resin, and improving the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0083] Furthermore, in some embodiments, the lubricant includes at least one of erucamide and fatty acid; this can reduce wear of the glass fiber matrix during subsequent composite processing with the resin, and can improve the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0084] Furthermore, in some embodiments, the fatty acid includes at least one of palmitic acid, stearic acid, oleic acid and lauric acid; this can reduce the wear of the glass fiber matrix during subsequent composite processing with the resin, and can improve the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0085] In some embodiments, the mass of the lubricant is 1% to 5% of the mass of the glass fiber sizing; this can reduce wear of the glass fiber matrix during subsequent composite processing with the resin and improve the mechanical properties of the composite material formed by the glass fiber matrix and the resin.

[0086] As an example, the mass of the lubricant can be any one of 1%, 1.5%, 2%, 2.5%, 3.5%, 4%, 4.5% and 5% of the mass of the glass fiber sizing, or any range therebetween.

[0087] In some embodiments, the hydrolysis step of the first coupling agent comprises: adding the first coupling agent to a water system with a pH of 3 to 4, and then stirring to obtain a hydrolysis system.

[0088] Furthermore, the hydrolysis step of the first coupling agent includes: mixing the first silane coupling agent and deionized water, adding a pH adjuster, adjusting the pH value to 3-4, then stirring at a speed of 800 rpm to 2000 rpm in a vacuum mixer, and then adding the first coupling agent, stirring for 15 minutes to 1 hour to obtain a hydrolysis system.

[0089] The hydrolysis pH value of the first coupling agent is 3 to 4, which can make the stability of the product after the hydrolysis of the first coupling agent better, and can make the hydrolysis reaction rate of the silane coupling agent faster and the condensation reaction slower, which is conducive to better adsorption of the first coupling agent on the surface of the glass fiber matrix, so that more silane coupling agent is adsorbed on the surface of the glass fiber matrix, which is more conducive to forming a rough concave-convex structure on the surface of the glass fiber matrix, which is conducive to increasing the specific surface area of the glass fiber matrix, and thus improving the interfacial bonding strength between the glass fiber matrix and the resin in the composite material formed by the subsequent glass fiber matrix and resin.

[0090] In some embodiments, the pH adjuster includes at least one of hydrochloric acid, citric acid, and acetic acid.

[0091] In some embodiments, the step of preparing the first mixed system includes: adding a film-forming agent, a lubricant, and water to a hydrolysis system and mixing them.

[0092] In some embodiments, the step of preparing the first mixed system includes: diluting the film-forming agent and the lubricant before mixing the hydrolysis system, the film-forming agent, the lubricant, and water.

[0093] As an example, the step of diluting the film-forming agent includes: diluting the film-forming agent emulsion with water; the step of diluting the lubricant includes: diluting the lubricant with water at a temperature of 15° C. to 55° C.

[0094] In some embodiments, the preparation method of the glass fiber impregnating agent includes: after stirring the first mixed system, adjusting the pH value of the stirred system to 4-5; this is beneficial to improving the stability of the film-forming agent and further improving the interfacial bonding strength between the glass fiber matrix and the resin in the composite material formed by the subsequent glass fiber matrix and the resin.

[0095] As an example, the pH value of the stirred system can be adjusted to any value among 4, 4.2, 4.5, 4.7, 4.9 and 5, or a range of values between any two of them.

[0096] In some embodiments, a pH adjuster is used to adjust the pH value of the stirred system to 4-5.

[0097] Furthermore, in some embodiments, the pH adjuster includes at least one of hydrochloric acid, citric acid, and acetic acid.

[0098] The present application provides a glass fiber sizing, which is prepared by the above-mentioned preparation method of the glass fiber sizing.

[0099] The present application provides a method for preparing modified glass fiber, which comprises: applying the aforementioned glass fiber sizing agent to the surface of a glass fiber substrate, and then drying the glass fiber sizing agent on the surface of the glass fiber substrate.

[0100] In some embodiments, the glass fiber matrix is chopped glass fiber. Further, in some embodiments, the glass fiber matrix is alkali-free chopped glass fiber.

[0101] As an example, the diameter of the glass fiber matrix is 8 μm to 13 μm.

[0102] The present application provides a modified glass fiber, which is prepared by the aforementioned method for preparing the modified glass fiber.

[0103] The surface of the modified glass fiber provided in the present application has a rough concave-convex structure, which is beneficial to increasing the specific surface area of the glass fiber matrix, and can improve the interfacial bonding force between the modified glass fiber and the resin in the composite material formed by the subsequent modified glass fiber and resin, and can improve the tensile strength, flexural strength, impact strength and thermal deformation temperature of the composite material. It is also beneficial to inhibit the attenuation of the tensile strength of the composite material under high temperature and high humidity conditions, so that the composite material has a higher mechanical strength retention rate under high temperature and high humidity conditions, and the composite material has better mechanical properties, which is suitable for preparing structural parts in automobiles and batteries.

[0104] The present application provides a method for preparing a composite material, which comprises: melt-kneading a second mixed system containing a resin and the modified glass fiber provided above, and then performing a molding process to prepare the composite material.

[0105] In some embodiments, the resin comprises a thermoplastic polyester resin.

[0106] In some embodiments, the thermoplastic polyester resin includes at least one of polybutylene terephthalate (PBT), polycarbonate (PC), polyethylene terephthalate (PET), poly(1,4-cyclohexanedimethylene terephthalate) (PCT), polyamide (PA6), polyoxymethylene (POM), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), and polyarylene ether nitrile (PEEN).

[0107] Furthermore, in some embodiments, the resins include a first resin and a second resin, both of which are PBT; wherein the melt index of the first resin (235°C, 2.16kg) is less than 20g / 10min, and the melt index of the second resin (235°C, 2.16kg) is 20g / 10min to 50g / 10min; and the mass ratio of the first resin to the second resin is (2 to 4):1; this is conducive to adjusting the melt index of the system for melt mixing to between 10g / 10min and 30g / 10min, so as to facilitate better implementation of melt mixing.

[0108] By way of example, in some embodiments, the viscosity of PBT is ≥ 1.0 dL / g.

[0109] It should be noted that, in other feasible implementations, the resin is not limited to the above substances and can be selected according to actual conditions.

[0110] In some embodiments, the aforementioned second mixing system further includes a compatibilizer, which can further promote the interface bonding between the modified glass fiber and the resin, thereby improving the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0111] Furthermore, in some embodiments, the mass of the compatibilizer is 1% to 10% of the mass of the composite material; this can further promote the interface bonding between the modified glass fiber and the resin, thereby improving the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0112] As an example, the mass of the compatibilizer may be at least one of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10% of the mass of the composite material.

[0113] In some embodiments, the compatibilizer contains an epoxy group; further, the compatibilizer contains at least two epoxy groups; and the compatibility between the resin and the modified glass fiber can be improved.

[0114] In some embodiments, the compatibilizer includes at least one of glycidyl methacrylate grafted polyolefin thermoplastic elastomer (POE-g-GMA), maleic anhydride grafted polyolefin thermoplastic elastomer (MAH-g-POE), ethylene-butyl acrylate binary copolymer, ethylene-butyl acrylate-glycidyl ester terpolymer, glycidyl methacrylate grafted ethylene-butyl acrylate copolymer (EBA-g-GMA) and ethylene-ethyl acrylate copolymer; the compatibilizer is selected from the above substances to promote the interfacial bonding between the modified glass fiber and the resin, thereby improving the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0115] Furthermore, the compatibilizer is selected from glycidyl methacrylate grafted ethylene-octene copolymer (for example, AX8900 from Arkema or BF7M from Sumitomo), which is beneficial to further improve the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0116] In some embodiments, the second mixing system further includes a hindered phenol antioxidant; or / and the second mixing system further includes a phosphite antioxidant. These solutions help prevent resin hydrolysis and yellowing of the composite material, and can improve the mechanical properties of the composite material formed by the modified glass fiber and resin.

[0117] Furthermore, in some embodiments, the mass of the hindered phenol antioxidant is 0.1% to 0.5% of the mass of the composite material; this helps to prevent the resin from hydrolyzing and the composite material from yellowing, and can improve the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0118] As an example, the mass of the hindered phenol antioxidant can be any value among 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% and 0.5% of the mass of the composite material, or any range between two values.

[0119] In some embodiments, the hindered phenol antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010) and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076); the use of the above substances as the hindered phenol antioxidant is beneficial to avoid hydrolysis of the resin and yellowing of the composite material, and can improve the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0120] It should be noted that, in other feasible embodiments, the hindered phenol antioxidant is not limited to the above substances.

[0121] In some embodiments, the mass of the phosphite antioxidant is 0.1% to 0.5% of the mass of the composite material; it can further promote the interface bonding between the modified glass fiber and the resin, thereby improving the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0122] As an example, the mass of the phosphite antioxidant can be any value among 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% and 0.5% of the mass of the composite material, or a range between any two values.

[0123] In some embodiments, the phosphite antioxidant includes at least one of tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl diphosphite (antioxidant PEPQ) and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (antioxidant PEP-36); the selection of the above substances as the phosphite antioxidant is beneficial to avoid hydrolysis of the resin and yellowing of the composite material, and can improve the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0124] It should be noted that, in other feasible embodiments, the phosphite antioxidant is not limited to the above substances.

[0125] In some embodiments, the aforementioned second mixed system includes both a hindered phenol antioxidant and a phosphite antioxidant, which is beneficial for further improving the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0126] In some embodiments, the mass of the resin is 50% to 85% of the mass of the composite material. As an example, the mass of the resin can be any of 50%, 55%, 60%, 65%, 70%, 75%, 80% and 85% of the mass of the composite material, or any range therebetween.

[0127] In some embodiments, the mass of the modified glass fiber may be 10% to 50% of the mass of the composite material. For example, the mass of the modified glass fiber may be any of 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, and 50% of the mass of the composite material, or any range therebetween.

[0128] In some embodiments, the second mixing system further includes a nucleating agent, which can accelerate the crystallization rate of the resin, increase the crystallization density of the resin, and promote the refinement of the resin grain size, thereby further improving the mechanical properties of the composite material formed by the modified glass fiber and the resin.

[0129] Furthermore, the mass of the nucleating agent is 0.1% to 0.5% of the mass of the composite material. As an example, the mass of the nucleating agent can be any value among 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% and 0.5% of the mass of the composite material, or a range between any two values.

[0130] In some embodiments, the nucleating agent includes at least one of nanosulfate, talc, silicon dioxide, metal carboxylates and their derivatives, calcium stearate, sarling resin, long-chain carboxylates, sodium montanate, calcium montanate, and sodium benzoate.

[0131] As an example, the nucleating agent may be NaV101 from Clariant.

[0132] In some embodiments, the aforementioned second mixing system further includes a second coupling agent. The second coupling agent can have a wetting effect on the resin surface, facilitating the adhesion of substances such as nucleating agents, hindered phenolic antioxidants, phosphite antioxidants, and masterbatches to the resin surface, thereby facilitating uniform dispersion of the components during subsequent melt extrusion and mixing. Furthermore, the second coupling agent can chemically bond with the resin surface and other components during the subsequent melt extrusion and mixing process, thereby improving the mechanical properties of the composite material.

[0133] Furthermore, in some embodiments, the mass of the second coupling agent is 0.1% to 0.5% of the mass of the composite material. As an example, the mass of the second coupling agent can be any value among 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% and 0.5% of the mass of the composite material, or any range therebetween.

[0134] In some embodiments, the second coupling agent includes a silane coupling agent.

[0135] Further, the second coupling agent includes at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane and γ-(2,3-epoxypropyloxy)propyltriethoxysilane.

[0136] In some embodiments, the aforementioned second mixing system further includes a masterbatch.

[0137] Furthermore, the mass of the masterbatch is 0.1% to 1% of the mass of the composite material. As an example, the mass of the masterbatch can be any value among 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% and 1.0% of the mass of the composite material, or a range between any two values.

[0138] It should be noted that this application does not limit the selection of masterbatches, and the selection can be made according to actual conditions.

[0139] As an example, the method for preparing the composite material includes the following steps:

[0140] (1) preparing raw materials for preparing composite materials;

[0141] (2) drying the resin at 120° C. to 130° C. for 4 to 6 hours to control the moisture content of the resin to below 0.03 wt % and setting aside;

[0142] (3) stirring and mixing the dried resin and the compatibilizer to obtain a first mixture;

[0143] (4) adding a second coupling agent to the first mixture and stirring and mixing to obtain a second mixture;

[0144] (5) Adding a hindered phenol antioxidant, a phosphite antioxidant, a nucleating agent and a masterbatch to the second mixture, stirring and mixing, and then adding modified glass fiber to the mixed system, melt-extruding, mixing and granulating; wherein the extrusion temperature is 200°C to 260°C.

[0145] It should be noted that, in other feasible implementations, the preparation method of the composite material is not limited to the above-mentioned method and can be adjusted according to actual conditions.

[0146] The present application provides a composite material, which is prepared using the above-mentioned method for preparing the composite material.

[0147] As an example, the composite material can be used to prepare BMS housings, output pole protective covers, fuse bases, annular gaskets for electrode terminals, high-voltage box bases, output pole bases, and connector protective covers in batteries; in addition, the composite material can also be used to prepare automobile window motor housings, wiper arms, silicon carbide chip packaged insulated gate bipolar transistors (IGBT housings), etc.

[0148] Next, one or more embodiments will be described in more detail with reference to the following examples. Of course, these examples do not limit the scope of one or more embodiments.

[0149] Example 1

[0150] (1) Prepare raw materials for preparing glass fiber sizing:

[0151] Weigh 10g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 4g of acetic acid (i.e., pH adjuster) and 72g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 10%, 12% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0152] (2) Preparation of glass fiber sizing:

[0153] Take 32 g of water, add 2 g of acetic acid to adjust the pH of the system to 3.3, and stir at 800 rpm in a vacuum stirrer for 20 min. Then, slowly add the first coupling agent weighed in step (1) into the vacuum stirrer, and continue stirring at 1000 rpm for 20 min to obtain a hydrolysis system.

[0154] The film-forming agent weighed in step (1) was stirred and mixed with 15 g of water to obtain a film-forming agent dilution solution.

[0155] The lubricant weighed in step (1) was stirred and mixed with 10 g of water at 30° C. to obtain a lubricant dilution solution.

[0156] The prepared hydrolysis system was poured into the reactor and stirred evenly. The film-forming agent dilution solution prepared above, the lubricant dilution solution prepared above and the remaining water were added to the reactor in sequence. Then, 2.0 g of acetic acid was added to the reactor to adjust the pH of the system in the reactor to 4.2. The mixture was stirred at 1200 rpm for 25 minutes to obtain the glass fiber sizing.

[0157] The total mass of water used in the preparation of the glass fiber sizing agent is the mass of the water weighed in step (1).

[0158] (3) Treatment of glass fiber:

[0159] An alkali-free long glass fiber with an average diameter of 10 μm was placed in a sizing agent tank containing the glass fiber sizing agent prepared in step (2) for 5 minutes, and then dried at 110° C. for 20 minutes. The dried alkali-free long glass fiber was then cut into short glass fibers with a length of 3.5 mm to obtain treated glass fibers.

[0160] (4) Prepare raw materials for preparing composite materials:

[0161] 3 kg of the glass fiber treated in step (3), 4.67 kg of the first resin, 2.0 kg of the second resin, 10 g of γ-(2,3-epoxypropoxy)propyltrimethoxysilane (i.e., the second coupling agent), 200 g of AX8900 (purchased from Arkema, i.e., a compatibilizer), 30 g of NAV101 (purchased from Clariant, i.e., a nucleating agent), 20 g of antioxidant 1010 (i.e., the first antioxidant), 20 g of antioxidant PEP-36 (i.e., the second antioxidant), and 50 g of masterbatch (purchased from Cabot Corporation, model 2014) were weighed respectively.

[0162] The first resin is TH6100, and the second resin is TH6082. TH6100 and TH6082 are purchased from Xinjiang Tunhe Resin Co., Ltd.

[0163] (5) Preparation of composite materials:

[0164] The first resin weighed in step (4), the second resin weighed in step (4), and the compatibilizer weighed in step (4) are added to a stirring barrel and stirred at 200 rpm for 1 minute; the second coupling agent is then added and stirred at 200 rpm for 1 minute; the first antioxidant weighed in step (4), the second antioxidant weighed in step (4), and the masterbatch weighed in step (4) are then added and stirred at 200 rpm for 1.5 minutes; the system in the stirring barrel and the glass fiber weighed in step (4) are then melt-extruded, mixed, and granulated to obtain a composite material. Among them, melt extrusion is divided into ten temperature zones, and the temperatures are 210℃~230℃, 220℃~240℃, 220℃~240℃, 220℃~240℃, 220℃~240℃, 220℃~240℃, 220℃~240℃, 220℃~240℃, 220℃~230℃, and 220℃~230℃.

[0165] Example 2

[0166] This embodiment provides a composite material. The difference between Example 2 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0167] Weigh 5g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 4.4g of acetic acid (i.e., pH adjuster) and 76.6g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 5%, 12% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0168] Example 3

[0169] This embodiment provides a composite material. The difference between Example 3 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0170] Weigh 15g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35COOH (i.e., lubricant), 3.5g of acetic acid (i.e., pH adjuster) and 67.5g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 15%, 12% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0171] Example 4

[0172] This embodiment provides a composite material. The difference between Example 4 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0173] Weigh 8g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 4.3g of acetic acid (i.e., pH adjuster) and 73.7g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 8%, 12% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0174] Example 5

[0175] This embodiment provides a composite material. The difference between Example 5 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0176] Weigh 11g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 3.3g of acetic acid (i.e., pH adjuster) and 71.7g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 11%, 12% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0177] Example 6

[0178] This embodiment provides a composite material. The only difference between Example 6 and Example 1 is that the γ-methacryloxypropyltrimethoxysilane (ie, the first coupling agent) in Example 1 is replaced by 3-chloropropyltrimethoxysilane.

[0179] Example 7

[0180] This embodiment provides a composite material. The difference between Example 7 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0181] Weigh 10g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 3g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 4g of acetic acid (i.e., pH adjuster) and 81g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 10%, 3% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0182] Example 8

[0183] This embodiment provides a composite material. The difference between Example 8 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0184] Weigh 10g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 10g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 4.2Xg of acetic acid (i.e., pH adjuster) and 73.8g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 10%, 10% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0185] Example 9

[0186] This embodiment provides a composite material. The only difference between Example 9 and Example 1 is that the styrene-glycidyl methacrylate copolymer (ie, the film-forming agent) in Example 1 is replaced by polyurethane.

[0187] Example 10

[0188] This embodiment provides a composite material. The difference between Example 10 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0189] Weigh 10g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 1g of stearic acid C 17 H 35COOH (i.e., lubricant), 4g of acetic acid (i.e., pH adjuster) and 73g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 10%, 12% and 1% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0190] Example 11

[0191] This embodiment provides a composite material. The difference between Example 11 and Example 1 is only that step (1) is different. In this embodiment, step (1) is as follows:

[0192] Weigh 10g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 5g of stearic acid C 17 H 35 COOH (i.e., lubricant), 4.2g of acetic acid (i.e., pH adjuster) and 68.8g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 10%, 12% and 5% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0193] Example 12

[0194] This embodiment provides a composite material. The only difference between Example 12 and Example 1 is that AX8900 (purchased from Arkema, i.e., a compatibilizer) in Example 1 is replaced by EBA-g-GMA.

[0195] Example 13

[0196] This embodiment provides a composite material. The only difference between Example 13 and Example 1 is that the antioxidant PEP-36 (ie, the second antioxidant) in Example 1 is replaced by antioxidant 168.

[0197] Example 14

[0198] This embodiment provides a composite material. The only difference between Example 14 and Example 1 is that antioxidant 1010 (ie, the first antioxidant) is not used in this embodiment, and the amount of antioxidant PEP-36 (ie, the second antioxidant) used is 40 g.

[0199] Example 15

[0200] This embodiment provides a composite material. The only difference between Example 15 and Example 1 is that the antioxidant PEP-36 (ie, the second antioxidant) is not used in this embodiment, and the amount of antioxidant 1010 (ie, the first antioxidant) used is 40 g.

[0201] Comparative Example 1

[0202] This comparative example provides a composite material. The only difference between comparative example 1 and example 1 is that the glass fiber used in step (4) and step (5) is a glass fiber that has not been treated with a glass fiber impregnating agent, and the glass fiber is an alkali-free chopped glass fiber with an average diameter of 10 μm and a length of 3.5 mm.

[0203] Comparative Example 2

[0204] This comparative example provides a composite material. The difference between Comparative Example 2 and Example 1 is only that step (1) is different. In this comparative example, step (1) is as follows:

[0205] Weigh 2g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 3.3g of acetic acid (i.e., pH adjuster) and 80.7g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 2%, 12% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0206] Comparative Example 3

[0207] This comparative example provides a composite material. The difference between Comparative Example 3 and Example 1 is only that step (1) is different. In this comparative example, step (1) is as follows:

[0208] Weigh 20g of γ-methacryloxypropyltrimethoxysilane (i.e., the first coupling agent), 12g of styrene-glycidyl methacrylate copolymer (i.e., the film-forming agent), 2g of stearic acid C 17 H 35 COOH (i.e., lubricant), 4.6g of acetic acid (i.e., pH adjuster) and 61.4g of water; wherein the mass of the first coupling agent, the mass of the film-forming agent and the mass of the lubricant account for 20%, 12% and 2% of the total mass of the first coupling agent, the film-forming agent, the lubricant, the pH adjuster and water, respectively.

[0209] The differences in the preparation parameters of the glass fiber sizing are detailed in Table 1.

[0210] Table 1 Differences in preparation parameters of glass fiber sizing

[0211]

[0212]

[0213] In Table 1, “ / ” indicates that the corresponding substance was not used. The proportion (%) of the first coupling agent refers to the proportion (%) of the mass of the first coupling agent in the total mass of the first coupling agent, film-forming agent, lubricant, pH adjuster and water. The proportion (%) of the film-forming agent refers to the proportion (%) of the mass of the first coupling agent in the total mass of the first coupling agent, film-forming agent, lubricant, pH adjuster and water. The proportion (%) of the lubricant refers to the proportion (%) of the mass of the first coupling agent in the total mass of the first coupling agent, film-forming agent, lubricant, pH adjuster and water.

[0214] The differences in the preparation parameters of the composite materials are detailed in Table 2.

[0215] Table 2 Differences in preparation parameters of composite materials

[0216]

[0217]

[0218] In Table 2, “ / ” indicates that the corresponding substance was not used.

[0219] Testing the properties of glass fibers and composite materials:

[0220] (1) Morphological characterization of glass fibers and composite materials

[0221] The glass fiber or composite material samples were tested using a ZEISS sigma 300 scanning electron microscope and referring to the standard JY / T010-1996. The morphology of the glass fiber or composite material samples was observed and SEM photos were taken.

[0222] (2) Tensile strength test of composite materials

[0223] The tensile strength of the composite materials was tested according to GB / T 1040-2006.

[0224] (3) Flexural strength and flexural elastic modulus test of composite materials

[0225] The flexural strength and flexural elastic modulus of the composite materials were tested in accordance with GB / T 9341-2008.

[0226] (4) Impact strength test of composite materials

[0227] The impact strength of composite materials was tested in accordance with GB / T 1843-2008.

[0228] (5) Thermal deformation temperature test of composite materials

[0229] The thermal deformation temperature of the composite material was tested according to GB / T1634-2004, with a test load of 0.45 MPa.

[0230] The properties of the composite materials are shown in Table 3.

[0231] Table 3 Properties of composite materials

[0232]

[0233]

[0234] The tensile strength of the composite material under high temperature (85°C) and high humidity (RH85%) conditions is shown in Table 4.

[0235] Table 4 Tensile strength of composite materials under high temperature (85°C) and high humidity (RH85%) conditions

[0236]

[0237] In Table 4, the attenuation of tensile strength (%) = [(T 0h -T) / T 0h ]×100%; where T 0h is the tensile strength of the composite material corresponding to the high temperature and high humidity treatment for 0 h, and T is the tensile strength of the composite material corresponding to different high temperature and high humidity treatment times.

[0238] Figure 5 This is the SEM characterization image of the glass fiber after being treated in step (3) of Example 1 of this application. Figure 6 This is the SEM characterization image of the glass fiber after treatment in step (3) of comparative example 2 of this application.

[0239] from Figure 5 and Figure 6 It can be seen that a rough concave-convex structure is formed on the surface of the glass fiber after being treated in step (3) of Example 1 of the present application, while the surface of the glass fiber after being treated in step (3) of comparative example 2 of the present application is relatively smooth; this indicates that the amount of coupling agent used in the glass fiber impregnating agent will affect the surface morphology of the prepared glass fiber. After the glass fiber is treated with the glass fiber impregnating agent prepared in step (2) of Example 1 of the present application, more rough concave-convex structures can be formed on the surface of the glass fiber.

[0240] Figure 7 This is a SEM characterization image of the composite material prepared in Example 1 of the present application. Figure 8 This is a SEM characterization image of the composite material prepared in Comparative Example 1 of this application.

[0241] from Figure 7 and Figure 8 It can be seen that Figure 7The glass fibers in the embodiment are basically completely coated with the resin, indicating that the interfacial bonding between the resin of Example 1 and the glass fibers treated with the glass fiber sizing agent is good; and Figure 8 The surface of the glass fiber in the comparative example 1 is relatively smooth, and the resin is not fully coated on the surface of the glass fiber, indicating that the interface bonding between the resin and the glass fiber in comparative example 1 is poor.

[0242] As can be seen from Table 3, the tensile strength, flexural strength, flexural elastic modulus, impact strength and heat deformation temperature of the composite materials prepared in Examples 1 to 15 are all superior to those of the composite materials prepared in Comparative Examples 1 to 3, indicating that the glass fiber treated with the glass fiber sizing provided in the present application can make the composite material formed by the glass fiber and the resin have higher mechanical properties.

[0243] The difference between Examples 1 to 5 and Comparative Examples 2 to 3 is that the amount of the first coupling agent used in preparing the glass fiber sizing is different. From the comparison between Examples 1 to 5 and Comparative Examples 2 to 3, it can be seen that the amount of the first coupling agent used in preparing the glass fiber sizing affects the mechanical properties of the composite material formed by the glass fiber and the resin; when the amount of the first coupling agent in the glass fiber sizing is too low or too high, it is not conducive to improving the mechanical properties of the composite material formed by the glass fiber and the resin.

[0244] The difference between Example 1 and Example 6 is that the first coupling agent used in the preparation of the glass fiber sizing is different. The structural formula of the first coupling agent in Example 1 contains an alkoxy group, while the structural formula of the first coupling agent in Example 6 does not contain an amino group, an epoxy group, or a double bond. From the comparison between Example 1 and Example 6, it can be seen that when the structural formula of the first coupling agent contains an alkoxy group, the mechanical properties of the composite material formed by the glass fiber and the resin can be further improved.

[0245] From the comparison between Example 1 and Example 9, it can be seen that compared with Example 9 in which the film-forming agent in the glass fiber sizing is selected from polyurethane, when the film-forming agent in the glass fiber sizing is selected from styrene-glycidyl methacrylate copolymer (i.e., Example 1), the mechanical properties of the composite material formed by the glass fiber and the resin can be further improved.

[0246] From the comparison between Example 1 and Examples 14-15, it can be seen that compared with Examples 14-15 in which only hindered phenol antioxidants (i.e., antioxidant 1010) or phosphite antioxidants (i.e., antioxidant PEP-36) are used as antioxidants in the preparation of the composite materials, when hindered phenol antioxidants and phosphite antioxidants are used as antioxidants in the preparation of the composite materials (i.e., Example 1), the mechanical properties of the composite material formed by glass fiber and resin can be further improved.

[0247] As can be seen from Table 4, the amount of the first coupling agent used in the preparation of the glass fiber sizing affects the attenuation of the mechanical properties of the composite material formed by the glass fiber and the resin under high temperature and high humidity conditions; when the amount of the first coupling agent in the glass fiber sizing is too low or too high, it is not conducive to reducing the attenuation of the mechanical properties of the composite material formed by the glass fiber and the resin under high temperature and high humidity conditions.

[0248] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

Claims

1. A method for preparing a glass fiber sizing, characterized in that: include: hydrolyzing the first coupling agent to obtain a hydrolysis system; Then, the first mixed system containing the hydrolysis system and the film-forming agent is stirred to prepare a glass fiber sizing agent; The mass of the first coupling agent is 5% to 15% of the mass of the glass fiber sizing agent; The mass of the film-forming agent is 3% to 15% of the mass of the glass fiber sizing agent.

2. The preparation method according to claim 1, characterized in that The mass of the first coupling agent is 8% to 11% of the mass of the glass fiber sizing agent.

3. The preparation method according to claim 1, characterized in that The first coupling agent includes a silane coupling agent; the silane coupling agent contains at least one of an amino group, an epoxy group and a double bond.

4. The preparation method according to any one of claims 1 to 3, characterized in that The film-forming agent contains epoxy groups.

5. The preparation method according to any one of claims 1 to 3, characterized in that The first mixing system also includes a lubricant; The mass of the lubricant is 1% to 5% of the mass of the glass fiber sizing agent.

6. The preparation method according to any one of claims 1 to 3, characterized in that The preparation method of the glass fiber sizing comprises: adjusting the pH value of the stirred system to 4-5.

7. A glass fiber sizing, characterized in that: The glass fiber sizing is prepared by the preparation method of the glass fiber sizing according to any one of claims 1 to 6.

8. A method for preparing modified glass fiber, characterized in that: include: The glass fiber sizing agent according to claim 7 is applied to the surface of a glass fiber substrate, and then the glass fiber sizing agent on the surface of the glass fiber substrate is dried.

9. A modified glass fiber, characterized in that: The modified glass fiber is prepared by the preparation method of the modified glass fiber according to claim 8.

10. A method for preparing a composite material, characterized in that: include: The second mixed system containing the resin and the modified glass fiber according to claim 9 is melt-kneaded and then molded to prepare a composite material.

11. The preparation method according to claim 10, characterized in that: The second mixed system also includes a hindered phenol antioxidant and a phosphite antioxidant; The hindered phenol antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; The phosphite antioxidant includes at least one of tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl diphosphite and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate.

12. The preparation method according to claim 11, characterized in that The mass of the resin is 50% to 85% of the mass of the composite material; or / and, the mass of the modified glass fiber is 10% to 50% of the mass of the composite material; or / and, the mass of the hindered phenol antioxidant is 0.1% to 0.5% of the mass of the composite material; or / and, the mass of the phosphite antioxidant is 0.1% to 0.5% of the mass of the composite material; Or / and, the resin includes a thermoplastic polyester resin; the thermoplastic polyester resin includes at least one of polybutylene terephthalate, polycarbonate, polyethylene terephthalate, poly(1,4-cyclohexanedimethanol terephthalate), polyoxymethylene, polyamide, polyphenylene sulfide, polyetheretherketone and polyarylethernitrile; Or / and, the second mixed system further includes a compatibilizer; the mass of the compatibilizer is 1% to 10% of the mass of the composite material.

13. A composite material, characterized in that The composite material is prepared by the method for preparing the composite material according to any one of claims 10 to 12.

14. A battery, characterized in that: The material of the battery includes the composite material according to claim 13.

15. The battery according to claim 14, characterized in that The battery includes an output pole base, an annular gasket for the electrode terminal, an output pole protective cover, a fuse base, a high-voltage box base and a connector protective cover; the material of the output pole base, the annular gasket for the electrode terminal, the output pole protective cover, the fuse base, the high-voltage box base and the connector protective cover all include the composite material.

16. The battery according to claim 14, characterized in that The battery includes a BMS shell; the material of the BMS shell includes the composite material.

17. An electrical device, characterized in that: The electrical device comprises the battery according to any one of claims 14 to 16.

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