Heat insulation composite material
阅读说明：本技术 隔热复合材料 (Heat insulation composite material ) 是由 刘婷婷 顾少卿 孙少敏 潘杰 赵忠印 加里·弗兰西斯·豪沃思 赛伦德拉·博吉拉勒·拉索德 于 2019-10-08 设计创作，主要内容包括：本发明提供一种用于电动汽车电池的延缓热扩散的隔热复合材料。所述隔热复合材料包括：硅橡胶层和无机纤维层。根据本发明的技术方案制备的隔热复合材料具有良好的隔热性能以及可压缩性,能够用于电动汽车电池以减少电池热失控的发生。(The invention provides a heat-insulating composite material for delaying heat diffusion for an electric vehicle battery. The thermal insulation composite comprises: a silicone rubber layer and an inorganic fiber layer. The heat insulation composite material prepared according to the technical scheme of the invention has good heat insulation performance and compressibility, and can be used for batteries of electric vehicles to reduce the occurrence of thermal runaway of the batteries.)
1. An insulating composite, comprising:
a silicone rubber layer; and
and an inorganic fiber layer.
2. The insulated composite of claim 1, wherein the silicone rubber layer has a thickness in the range of 0.2mm to 5 mm.
3. The insulated composite of claim 1, wherein the silicone rubber layer is cured from a silicone rubber precursor composition comprising, based upon the total weight of the silicone rubber precursor composition taken as 100 wt%:
35-70 wt% of a crosslinkable silicone oil;
1-10 wt% of a cross-linking agent;
10-50 wt% of a flame retardant; and
1-12 wt% of a water-loss endothermic filler.
4. A thermal insulation composite as claimed in claim 3, wherein the viscosity of the cross-linkable silicone oil is in the range of 100 to 10000 cSt.
5. The insulating composite of claim 3, wherein the cross-linkable silicone oil is a vinyl silicone oil.
6. The insulating composite of claim 3, wherein the cross-linking agent is a hydrogen-containing silicone oil.
7. A thermal insulation composite as claimed in claim 3, wherein the flame retardant is sodium silicate, zinc borate or mixtures thereof.
8. A thermal insulation composite as claimed in claim 3, wherein the water-loss endothermic filler is selected from aluminium hydroxide, magnesium hydroxide, barium hydroxide, hydrated sodium sulphate or mixtures thereof.
9. The insulating composite of claim 3, wherein the silicone rubber precursor composition comprises 4 to 10 weight percent of a water-loss endothermic filler.
10. The insulating composite of claim 3, wherein the silicone rubber precursor composition further comprises 0.1 to 10 weight percent of a polymerization catalyst that is a platinum-based catalyst or a peroxide catalyst.
11. The insulated composite of claim 3, wherein the silicone rubber precursor composition further comprises 1 to 10 weight percent of an inhibitor that is an alkynol inhibitor, a vinyl inhibitor, a cyclic double bond inhibitor, or a mixture thereof.
12. The insulated composite of claim 1, wherein the inorganic fiber layer has a thickness in a range of 0.2mm to 3 mm.
13. The insulated composite of claim 1, wherein the inorganic fibers in the inorganic fiber layer have an aspect ratio greater than 3: 1.
14. The insulated composite of claim 13, wherein the inorganic fibers are selected from one or more of the group consisting of: refractory ceramic fibers, metal oxide fibers, biosoluble inorganic fibers, glass fibers, crystalline fibers, amorphous fibers, mineral fibers, carbide fibers, and nitride fibers.
15. The insulated composite of claim 1, wherein the inorganic fiber layer comprises, based on 100 weight percent of the total weight of the inorganic fiber layer:
1-15 wt% binder;
5-85% by weight of a water-loss endothermic filler; and
10-80% by weight of inorganic fibers.
16. The insulating composite of claim 15, wherein the water-loss endothermic filler is selected from a metal hydroxide, a metal salt hydrate, or mixtures thereof.
17. The insulating composite of claim 15, wherein the water-loss endothermic filler is selected from aluminum hydroxide, magnesium hydroxide, barium hydroxide, hydrated sodium sulfate, or mixtures thereof.
18. The insulated composite of any of the preceding claims 1-17, comprising a silicone rubber layer and an inorganic fiber layer bonded to each other.
19. The insulated composite of any of the preceding claims 1-17, comprising one inorganic fiber layer and two silicone rubber layers, the two silicone rubber layers being located on opposite sides of the inorganic fiber layer and conforming thereto, respectively.
Technical Field
The invention relates to the technical field of batteries of electric vehicles, and particularly provides a heat-insulating composite material for delaying heat diffusion of batteries of electric vehicles.
Background
In recent years, the electric automobile production and sales volume keeps increasing at a high speed in the global market, particularly in the Chinese market. The electric automobile industry is moving towards revolution. Automobile manufacturers are working on the development of long-endurance electric vehicles (up to 200 miles endurance with a single charge). This would require the electric vehicle battery to have a larger battery capacity and a shorter charging time. The pursuit for the above technical effects brings about a potentially high risk that the failure rate of the lithium ion battery is increased, and even the thermal runaway phenomenon of the battery occurs.
Therefore, the thermal runaway problem of batteries for electric vehicles is gradually receiving much attention. To address the above issues, automotive manufacturers have adopted a variety of material designs to reduce the risk of thermal runaway in batteries. Currently, aerogel and mica are heat insulating materials that are of general interest and can be placed between cells in an electric vehicle battery to effectively reduce heat transfer between the cells. However, current aerogel products are very expensive. The general problem of mica sheet products is that the texture is hard and brittle, and there is a potential safety hazard. Therefore, it is of great significance to develop a thermal insulation material which can be used in the battery of the electric automobile and has good thermal insulation performance and compressibility and can delay thermal diffusion.
Disclosure of Invention
Starting from the technical problems set forth above, it is an object of the present invention to provide a thermal insulation composite material for an electric vehicle battery, which delays thermal diffusion, has good thermal insulation properties and compressibility, and can be used for an electric vehicle battery to reduce the occurrence of thermal runaway of the battery.
The present inventors have made intensive studies and completed the present invention.
According to one aspect of the present invention, there is provided an insulating composite comprising:
a silicone rubber layer; and
and an inorganic fiber layer.
According to certain preferred embodiments of the present invention, the thickness of the silicone rubber layer is in the range of 0.2mm to 5 mm.
According to certain preferred embodiments of the present invention, the silicone rubber layer is obtained by curing a silicone rubber precursor composition comprising, based on 100% by weight of its total weight:
35-70 wt% of a crosslinkable silicone oil;
1-10 wt% of a cross-linking agent;
10-50 wt% of a flame retardant; and
1-12 wt% of a water-loss endothermic filler.
According to certain preferred embodiments of the present invention, the viscosity of the crosslinkable silicone oil is in the range of 100 to 10000 cSt.
According to certain preferred embodiments of the present invention, the crosslinkable silicone oil is a vinyl silicone oil.
According to certain preferred embodiments of the present invention, the cross-linking agent is a hydrogen-containing silicone oil.
According to certain preferred embodiments of the present invention, the flame retardant is sodium silicate, zinc borate or mixtures thereof.
According to certain preferred embodiments of the present invention, the water-loss endothermic filler is selected from a metal hydroxide, a metal salt hydrate or a mixture thereof.
According to certain preferred embodiments of the present invention, the water-loss endothermic filler is selected from aluminum hydroxide, magnesium hydroxide, barium hydroxide, hydrated sodium sulfate or mixtures thereof.
According to certain preferred embodiments of the present invention, the silicone rubber precursor composition comprises 4 to 10 wt% of a water-loss endothermic filler.
According to certain preferred embodiments of the present invention, the silicone rubber precursor composition further comprises 0.1 to 10 wt% of a polymerization catalyst, which is a platinum-based catalyst or a peroxide catalyst.
According to certain preferred embodiments of the present invention, the silicone rubber precursor composition further comprises 1 to 10 wt.% of an inhibitor which is an alkynol inhibitor, a vinyl inhibitor, a cyclic double bond inhibitor or a mixture thereof.
According to certain preferred embodiments of the present invention, the thickness of the inorganic fiber layer is in the range of 0.2mm to 3 mm.
According to certain preferred embodiments of the present invention, the inorganic fibers in the inorganic fiber layer have an aspect ratio of greater than 3: 1.
According to certain preferred embodiments of the present invention, the inorganic fibers are selected from one or more of the group consisting of: refractory ceramic fibers, metal oxide fibers, biosoluble inorganic fibers, glass fibers, crystalline fibers, amorphous fibers, mineral fibers, carbide fibers, and nitride fibers.
According to certain preferred embodiments of the present invention, the inorganic fiber layer comprises, based on the total weight of the inorganic fiber layer taken as 100% by weight:
1-15 wt% binder;
5-85% by weight of a water-loss endothermic filler; and
10-80% by weight of inorganic fibers.
According to certain preferred embodiments of the present invention, the water-loss endothermic filler is selected from a metal hydroxide, a metal salt hydrate or a mixture thereof.
According to certain preferred embodiments of the present invention, the water-loss endothermic filler is selected from aluminum hydroxide, magnesium hydroxide, barium hydroxide, hydrated sodium sulfate or mixtures thereof.
According to certain preferred embodiments of the present invention, the insulating composite comprises a silicone rubber layer as described above and an inorganic fiber layer as described above attached to each other.
According to certain preferred embodiments of the present invention, the insulating composite comprises one inorganic fiber layer and two silicone rubber layers respectively located on opposite sides of the inorganic fiber layer and bonded thereto.
Compared with the prior art in the field, the invention has the advantages that: the heat-insulation composite material for delaying heat diffusion is flexible, is not easy to damage, has good heat-insulation performance, and can be used for batteries of electric vehicles to reduce the occurrence of thermal runaway of the batteries.
Drawings
FIG. 1 shows an insulating composite having a two-layer structure (silicone rubber layer/inorganic fiber layer) according to one embodiment of the present invention; and
fig. 2 shows an insulating composite having a three-layer structure (silicone rubber layer/inorganic fiber layer/silicone rubber layer) according to another embodiment of the present invention.
Detailed Description
It is to be understood that other various embodiments can be devised and modified by those skilled in the art in light of the teachings of this specification without departing from the scope or spirit of the disclosure. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
According to the technical scheme of the invention, the heat insulation composite material for delaying heat diffusion of the battery of the electric automobile is provided, and comprises the following components: a silicone rubber layer; and an inorganic fiber layer. Wherein the silicone rubber layer is capable of providing good thermal insulation at a lower temperature range and the inorganic fiber layer is capable of providing good thermal insulation at a higher temperature range, even up to about 800 ℃. The inorganic fiber layer also provides compressibility to the insulating composite such that it is not susceptible to damage during use. In addition, the silicone rubber layer can permeate into the inorganic fiber layer in the curing process, so that the hardness degree of the heat-insulation composite material is adjusted, and the compression performance of the heat-insulation composite material is further adjusted.
Specifically, the thickness of the silicone rubber layer is in the range of 0.2mm to 5 mm. By controlling the thickness of the silicone rubber layer within the above range, it is possible to maintain a sufficient heat insulating effect without significantly increasing the size of the silicone rubber layer.
The silicone rubber layer may be prepared by synthetic methods known in the art. Preferably, the silicone rubber layer is obtained by curing a silicone rubber precursor composition, for example, the silicone rubber precursor composition is coated on a substrate and cured. The silicone rubber precursor composition comprises, based on the total weight of the composition taken as 100 wt.%:
35-70 wt% of a crosslinkable silicone oil;
1-10 wt% of a cross-linking agent;
10-50 wt% of a flame retardant; and
1-12 wt% of a water-loss endothermic filler.
There is no particular limitation on the specific type of crosslinkable silicone oil that may be used to prepare the silicone rubber precursor composition. Preferably, the viscosity of the crosslinkable silicone oil is in the range of 100 to 10000 cSt. More preferably, the crosslinkable silicone oil is a vinyl silicone oil. The silicone rubber precursor composition comprises 35 to 70 wt% of a vinyl silicone oil, based on 100 wt% of the total weight of the composition. A specific example of a crosslinkable silicone oil which can be used in the present invention is a vinyl silicone oil produced by AB Andisil, which has a viscosity of 5000 cSt.
The silicone rubber precursor composition comprises a cross-linking agent for causing cross-linking of the cross-linkable silicone oil. Preferably, the cross-linking agent is hydrogen-containing silicone oil. The hydrogen-containing silicone oil is capable of causing polymerization of the vinyl silicone oil by hydrosilylation reaction. The silicone rubber precursor composition contains 1 to 10 wt%, preferably 3 to 10 wt%, of hydrogen-containing silicone oil based on 100 wt% of the total weight thereof. A specific example of the hydrogen-containing silicone oil that can be used in the present invention is a hydrogen-containing silicone oil produced by AB Andisil corporation.
The silicone rubber precursor composition includes 10 to 50 wt% of a flame retardant to provide a flame retardant effect. Preferably, the flame retardant is sodium silicate, zinc borate or a mixture thereof. Optionally, the flame retardant may also be a conventional halogen-based flame retardant such as a bromine or chlorine-based flame retardant, a nitrogen-based flame retardant, or a hydride-based flame retardant. Preferred examples of the flame retardant that can be used in the present invention include Expantrol (which is an aqueous solution containing 73 wt% sodium silicate, 17 wt% zinc borate and 10 wt% water) produced by 3M innovative limited.
The silicone rubber precursor composition also includes a water loss endothermic filler. In the present invention, unless otherwise specified, the term "water-loss endothermic filler" means an inorganic filler capable of losing water from a molecule upon heating and absorbing heat at the same time. The water loss heat absorption filler can remarkably reduce heat transfer through a water loss heat absorption process, and has a heat insulation effect. The silicone rubber precursor composition comprises from 1 to 12 wt% of the water-loss endothermic filler. Preferably, the silicone rubber precursor composition comprises from 4 to 10 wt% of the water-loss endothermic filler. The water-loss endothermic filler is selected from a metal hydroxide, a metal salt hydrate or a mixture thereof capable of losing water from the molecule upon heating. In particular, the water-loss endothermic filler is selected from aluminium hydroxide, magnesium hydroxide, barium hydroxide, hydrated sodium sulphate or mixtures thereof.
In order to promote the crosslinking reaction between the crosslinkable silicone oil and the crosslinking agent, preferably, the silicone rubber precursor composition contains 0.1 to 10% by weight of a polymerization catalyst. There is no particular limitation on the specific type of polymerization catalyst that may be employed. Preferably, the polymerization catalyst is a platinum-based catalyst or a peroxide catalyst. For example, a platinum catalyst manufactured by Heraeus corporation under the trademark Heraeus Karstedt Pt may be used.
Optionally, the silicone rubber precursor composition may further comprise 1 to 10 wt.% of an inhibitor. The inhibitor can be used to inhibit excessive curing of the silicone rubber precursor composition. Preferably, the inhibitor is an alkynol inhibitor, a vinyl inhibitor, a cyclic double bond inhibitor or a mixture thereof. Specific examples of inhibitors that may be used in the present invention include 1-ethynyl-1-cyclohexanol.
In addition to the silicone rubber layer described above, the thermal insulation composite according to the present invention further includes an inorganic fiber layer closely attached to the silicone rubber layer. The inorganic fiber layer serves to provide the thermal insulation composite with the required mechanical strength and is capable of providing good thermal insulation at higher temperature ranges, even up to around 800 ℃.
Specifically, the thickness of the inorganic fiber layer is in the range of 0.2mm to 3 mm. By controlling the thickness of the inorganic fiber layer within the above range, it is possible to maintain sufficient mechanical strength and heat insulation effect without significantly increasing the size of the silicone rubber layer.
According to certain embodiments of the present invention, the inorganic fiber layer comprises inorganic fibers, a binder, and a water-loss endothermic filler. Wherein the inorganic fiber layer comprises, based on the total weight of the inorganic fiber layer taken as 100 wt%:
1-15 wt% binder:
5-85% by weight of a water-loss endothermic filler: and
10-80% by weight of inorganic fibers.
According to certain embodiments, the inorganic fibers that may be used to prepare the inorganic fiber layer include, but are not limited to, heat-resistant biosoluble inorganic fibers, conventional heat-resistant inorganic fibers, or mixtures thereof.
For purposes of illustration and not limitation, suitable conventional heat-resistant inorganic fibers that can be used to prepare the inorganic fiber layer include heat-resistant ceramic fibers, alkaline earth silicate fibers, mineral wool fibers, glass fibers, and mixtures thereof.
In certain embodiments, the mineral wool fibers include, but are not limited to, at least one of rock wool fibers, slag wool fibers, basalt fibers, and glass wool fibers. Mineral wool fibers may be formed from basalt, industrial smelter slag, and the like, and typically contain silica, calcia, alumina, and/or magnesia. Glass wool fibers are typically made from a molten mixture of sand and recycled glass material.
Preferably, according to certain embodiments, the inorganic fibers useful for preparing the inorganic fiber layer are selected from one or more of the group consisting of: refractory ceramic fibers, metal oxide fibers, biosoluble inorganic fibers, glass fibers, crystalline fibers, amorphous fibers, mineral fibers, carbide fibers, and nitride fibers. In order to achieve the technical effect of the present invention, it is preferable that the thickness of the inorganic fiber layer is in the range of 0.2mm to 3 mm. Preferably, the aspect ratio of the inorganic fibers in the inorganic fiber layer is greater than 3: 1.
The inorganic fiber layer further comprises one or more binders. Suitable binders are inorganic binders, organic binders or combinations thereof. The organic binder may be provided in the form of a solid, liquid, solution, dispersion, latex, or the like. The organic binder may comprise a thermoplastic or thermoset binder that is a flexible material after curing. Examples of suitable organic binders include, but are not limited to, acrylic latex, (meth) acrylic latex, copolymers of styrene and butadiene, vinylpyridine, acrylonitrile, copolymers of acrylonitrile and styrene, vinyl chloride, polyvinyl chloride, copolymers of vinyl acetate and ethylene, polyamides, silicones, and the like. Other resinous binders include flexible thermosetting resins such as unsaturated polyesters, epoxy resins, and polyvinyl esters (e.g., polyvinyl acetate or polyvinyl butyral). According to certain embodiments, the multilayer thermal insulation composite uses an acrylic resin binder. The inorganic fiber layer according to the present invention may further comprise an inorganic binder. The inorganic binders include, but are not limited to, colloidal silica, colloidal alumina, colloidal zirconia, sodium silicate, and clays such as bentonite, hectorite, kaolinite, montmorillonite, palygorskite, saponite, or sepiolite, and the like. The inorganic fiber layer contains 1 to 15% by weight of a binder, based on 100% by weight of the total weight of the inorganic fiber layer.
Optionally, the inorganic fiber layer may further comprise a water-loss endothermic filler. In the present invention, unless otherwise specified, the term "water-loss endothermic filler" means an inorganic filler capable of losing water from a molecule upon heating and absorbing heat at the same time. The water loss heat absorption filler can remarkably reduce heat transfer through a water loss heat absorption process, and has a heat insulation effect. The inorganic fiber layer contains 5-85 wt% of a water-loss endothermic filler. The water-loss endothermic filler is selected from a metal hydroxide, a metal salt hydrate or a mixture thereof capable of losing water from the molecule upon heating. In particular, the water-loss endothermic filler is selected from aluminium hydroxide, magnesium hydroxide, barium hydroxide, hydrated sodium sulphate or mixtures thereof.
The inorganic fiber layer according to the present invention can be prepared by a general method according to the prior art, and can be commercially available. Commercially available examples of inorganic fiber layers that may be used in the present invention include alkali metal silicate fiber mats manufactured by TPF corporation under the designation 10951A.
The thermal insulation composite according to the present invention preferably has a double-layered structure to provide a good thermal insulation effect. Fig. 1 shows an insulating composite 1 having a two-layer structure (
There is no particular limitation on a specific method of preparing the thermal insulation composite according to the present invention, as long as the specific structure defined above can be obtained. Preferably, the thermal insulation composite may be prepared by the following method. First, a silicone rubber precursor composition containing various raw materials was formulated. Then, the silicone rubber precursor composition is applied onto a release film (e.g., a fluorine film), wherein the coating thickness of the silicone rubber precursor composition is adjusted by adjusting the coating gap of a film coater. Subsequently, the release film with the silicone rubber precursor composition was laminated with an inorganic fiber layer to obtain a composite body in which the side of the release film with the silicone rubber precursor composition was in contact with the inorganic fiber layer. And after the composite body is heated and cured, removing the release film from the composite body, thereby obtaining the heat insulation composite material.
The following detailed description is intended to illustrate the disclosure by way of example and not by way of limitation.
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