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    • 专利摘要:
    combustion reduction mixture and combustion reduction process. Lithium-ion battery combustion reduction is achieved by positioning a mixture comprising a thermally destabilizing solid fluoropolymer and a fluorinated composition with respect to the battery, the positioning being effective to provide battery combustion reduction, the mixture being preferably semi-solid and with proximity to the battery to provide the effect of reducing combustion, referred to as a coating over at least a portion of the battery.
    公开号:BR112015004365B1
    申请号:R112015004365-8
    申请日:2013-08-30
    公开日:2021-08-10
    发明作者:Dennis J. Kountz；George Martin Pruce；James R. Hoover
    申请人:E.I Du Pont De Nemours And Company；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] This invention relates to the reduction of combustion derived from a lithium ion battery that had been compromised such as by short circuit. BACKGROUND OF THE INVENTION
    [002] A lithium ion battery (Li-ion battery) is a battery in which lithium ions move between oppositely charged electrodes to generate electricity.
    [003] The corruption (malfunction) of a lithium ion battery such as by short circuit within the battery, is known to be able to produce an uncontrolled thermal reaction that vaporizes combustible components within the battery, especially the electrolyte separating each anode of each battery cathode. Battery combustion involves ignition of the combustible vapors, especially after reaching the oxygen present in the air that comes in contact with the combustible vapors either inside the battery pack housing within which the battery is housed or outside the battery pack from which combustible vapors escape.
    [004] In an effort to stop the flow of electricity to the compromised battery, battery packs have been equipped with fuse protection that stops the flow of electricity after an excessive temperature rise caused by uncontrolled thermal reaction within the battery.
    [005] Due to the fact that the electrical method has not always been effective in reducing combustion, several other techniques have been tried.
    [006] Patent document US 2011/0177366 describes the formation of the battery pack case as a laminate of (i) a thermoconductive layer of metal or resin with high thermal conductivity such as an engineering plastic (ii) an absorbing layer of heat made of resin materials, ceramic materials or inorganic materials. Layer (i) forms the outer side of the housing and layer (ii) forms the inner side of the housing so that heat absorbed by layer (ii) is conducted away from the interior of the battery pack housing by layer (i) ). Fluorocarbon resin is described as a possible material for layer (ii), and polytetrafluoroethylene (PTFE) is described as an example of a resin with superior heat resistance. The PTFE heat absorbing layer is described as containing 20 to 70 parts by weight of particulate material called material B dispersed therein and PTFE is described as having excellent binding property [0073-0074]. The function of the particulate material B in layer (ii) is to undergo a thermal decomposition reaction that absorbs heat and expands layer (ii) to form an insulating layer in order to protect electronic devices outside the battery pack housing [0071] . Sodium carbonate hydrogen and aluminum hydroxide are described as examples of material B. As an apparent compensation for the insulating effect (ii) after heating, the battery pack is also provided with a sinusoidal conduit 25 (Fig. 2) to allow the escape of hot gases out of the battery pack housing and cooling the air of that gas as it circulates along the length of the conduit. The method of this patent publication is to try to prevent the emission of a high temperature flammable gas out of the interior of the battery pack by limiting the temperature rise within the battery pack and cooling the gas that escapes from the battery pack.
    [007] Patent document US 2009/0176148 describes the immersion of batteries in a container filled with a heat transfer fluid, and containing a heat exchanger at least partially filled with the heat transfer fluid, the fluid being a liquid or a gas such as water, glycols, perfluorocarbons, perfluoropolyethers, perfluoroamines, perfluoroethers, silicone oil and hydrocarbon oils and the heat exchanger contribute to the removal of heat from the submerged batteries [0037]. In one embodiment, the heat transfer fluid is a hydrofluoroether having a low boiling temperature, for example less than 80°C or even less than 50°C [0036], the vaporization of this fluid contributing to the removal of heat from immersed batteries [0032]. A disadvantage of this method for improving battery safety, i.e., combustion reduction, is that it is based on gas and/or liquid as the transfer fluid. Gas or liquids within the battery pack casing tend to escape after any opening that is formed in the casing when the casing is subjected to an impact.
    [008] Patent document US 2010/0047673 describes filling the space between the battery pack casing and the batteries contained within the casing with a non-flammable filling material in order to exclude air from inside the casing interior . In one embodiment, liquid or gas is used as a filler material and is either contained within a polypropylene bag or absorbed into a high polymer to provide a gel-like material [0048]. Example 12 describes the preparation of a filler material by kneading 90 wt% magnesium hydrogen carbonate powder which releases carbon dioxide when superheated with 10 wt% PTFE with a binding effect in a mortar, wherein the mixture The resultant is then molded into pellets, which then become the filler material within the battery casing [0081]. The person skilled in the art knows that PTFE must have a binding effect, PTFE must be the fine powder type made by polymerization of aqueous dispersion, followed by coagulation of the dispersed PTFE particles, the resulting clot being called the powder type fine PTFE. This fine PTFE powder, before sintering, fibrillates when subjected to shear when it occurs in mixtures in a mortar. The fibrils that make up the fibrillated PTFE act as a binding agent for particulate material such as the magnesium hydrogen carbonate used in example 12. We can see that in this application, PTFE is used for its binding capacity, the magnesium hydrogen carbonate being Magnesium is the fire retardant in the fill material.
    [009] There is still a need for an effective way of reducing combustion through a lithium ion battery. BRIEF DESCRIPTION OF THE INVENTION
    [010] The present invention satisfies this need through an embodiment that provides a novel combustion reduction composition as follows: A mixture for reducing combustion through a lithium ion battery comprising a thermally destabilizing solid fluoropolymer and a fluorinated composition.
    [011] This mixture is useful for improving the safety of lithium ion batteries through its reducing effect to prevent or extinguish combustion by the battery. The mixture can serve as a last line of defense against combustion, other safety features must be associated with the battery, eg fuse protection against failure.
    [012] Another embodiment of the present invention is the process for reducing combustion of a lithium ion battery, comprising positioning a mixture comprising a thermally destabilizing solid fluoropolymer and a fluorinated composition with respect to said battery, which is effective in providing said battery reduction of said combustion by said battery. Preferably, the mixture is at least close to the battery to provide the above mentioned combustion reduction effect. At least close means close to the battery or in contact with the battery. The simplest form of contact with the battery is formation of a coating on the battery. In one aspect of these embodiments the battery features an electrical connector and positioning the mixture includes forming a coating of said mixture at least on said electrical connector. An electrical connector includes more than one connector as you would expect since the battery features an anode and cathode. In another aspect of these embodiments, positioning the mixture includes forming a coating of said mixture on at least a portion of said battery. In yet another aspect of this embodiment, both the electrical connector and at least a portion of the battery are coated by the mixture.
    [013] The mixture and process of the present invention are applicable to one or more lithium ion batteries interconnected to provide electricity, ie, the positioning of the mixture is applied to each battery present that is contained within a battery pack housing to form a set of batteries.
    [014] In each of these embodiments, the fluoropolymer and fluorinated composition are preferably different from each other, either chemically or in state or both. Chemical differences will be discussed below. With regard to the difference in state, although the fluoropolymer is solid, it is preferred that the molecular weight of the fluorinated composition has a low molecular weight so that when mixed with the solid fluoropolymer, the resulting mixture is semi-solid in state or simply semi-solid. solid.
    [015] Semi-solid (semi-solid state) is understood as the fact that the mixture is neither gas nor liquid at temperatures that the lithium-ion battery (and battery pack) can expect to encounter without in use or when recharging when the battery is a rechargeable battery. Such temperatures include temperatures up to 40°C, sometimes up to 50°C and more, for example temperatures up to 60°C and even up to 80°C. The semi-solid state of the mixture differs from the liquid state in that it is not flowable under any of these temperatures at atmospheric pressure. On the other hand, the liquid state denotes flow in order to take the shape of its container, presenting at the same time a fixed volume. Rather than flowability, the semi-solid state of the mixture means that it exhibits rigidity whereby it remains where it is positioned in the battery casing. This placement of the mixture is facilitated by the semi-solid state characteristic of the mixture, namely that the mixture is sufficiently flowable under pressure to obtain strong contact with desired surfaces within the battery pack, for example the batteries and/or their connectors . The pressure applied can be just that of a hand spatula used to apply and spread the mixture where desired over the battery and/or connectors to form a coating therein within a battery pack housing. Once applied, and pressure removed, the semi-solid state of the mixture results in the mixture that does not flow out of its applied position at least at the above temperatures. Characteristic of the semi-solid state, the mixture has the consistency of wax, putty, or putty, whose rigidity can be controlled by the proportion of fluorinated composition in the mixture and the molecular weight of the fluorinated composition, as the molecular weight affects the viscosity of the fluorinated composition by itself.
    [016] Preferably, the fluorinated composition itself is a liquid under the above temperatures which means that the fluorinated composition has a boiling temperature higher than the specific maximum temperatures of those mentioned above that can occur in the battery and battery pack. For simplicity, these boiling temperatures can be considered based on atmospheric pressure (one atm (1MPa)).
    [017] The solid state of the fluoropolymer component of the semi-solid blend differs from the semi-solid state by exhibiting stiffness, but not by the pressure flowability mentioned above. Thus, the solid fluoropolymer does not have the consistency of wax, putty or putty. The mixture of solid fluoropolymer and liquid fluorinated composition provides the preferred semi-solid state of the resulting mixture. In one embodiment, the solid fluoropolymer itself resists deformation as indicated by exhibiting a tensile strength of at least 1 MPa (ASTM D638 at 23°C), preferably at least 5MPa. The semi-solid mixture can be considered to exhibit a tensile strength of zero due to the inability to form tensile specimens that have sufficient integrity to be tested for tensile strength.
    [018] In these embodiments, the semi-solid mixture provides a unique effect, in addition to the fact that each component of the mixture is non-flammable. The fluorinated composition and the destabilized solid fluoropolymer contribute to reduced combustion. By combustion reduction it is understood that combustion never takes place even if the corruption of the lithium ion battery is such that an uncontrolled exothermic reaction is expected or if combustion starts its intensity is reduced or the fire is extinguished too quickly. Reduced intensity means that when a plurality of lithium ion batteries are present within the battery pack casing, combustion tends to be limited to virtually the corrupted battery, which will be after it is quickly extinguished.
    [019] The components of the mixture are stable under the temperatures that may be encountered by the Li-ion battery and battery pack as mentioned above. At higher temperatures the destabilization of the solid fluoropolymer means that it undergoes decomposition which suppresses combustion. The same is true for the fluorinated compounding component of the mixture.
    [020] The molecular weight of the fluorinated composition is low in relation to the molecular weight of the solid fluoropolymer. The low molecular weight of the fluorinated composition provides high mobility to the composition under superheat that accompanies corruption of the lithium ion battery, thus facilitating the composition's access to the superheat area to reduce combustion. BRIEF DESCRIPTION OF THE DRAWINGS
    [021] Figure 1 is a schematic plan view of an array of four lithium ion batteries, including their electrical interconnection, showing an application embodiment of the semi-solid mixture of the present invention; - Figure 2 is a side view schematic of the battery arrangement of figure 1; - Figure 3 is a schematic plan view of a battery pack, cover removed, containing an arrangement of sixteen lithium ion batteries and their electrical interconnection showing another embodiment of application of the semi mixture - solid of the present invention; e- Figure 4 is a cross-sectional view of the battery pack of figure 3, cover in place, taken along line 4-4 of figure 3. DETAILED DESCRIPTION OF THE INVENTION
    [022] The batteries in figure 1 are lithium ion batteries 2, 4, 6, and 8, jelly-roll type where layers of anode, electrolyte and cathode are rolled to form a cylindrical shape housed inside a cylindrical can. The electrolyte, if not acting as a physical separator between the anode and cathode, will include a separator, into which the electrolyte is absorbed. The anode and cathode can also include current collectors. Battery anodes 2 and 4 are electrically connected in parallel by bus 14 and battery anodes 6 and 8 are electrically connected in parallel by bus 16. Bus 18 electrically interconnects buses 14 and 16 in series to form the positive terminal for the array of batteries as shown by the + symbol in figure 1. Busbars 20 and 22 electrically connect battery cathodes 2 and 4 and 6 and 8, respectively. Bus 24 electrically interconnects buses 20 and 22 to form negative terminal for the battery array as shown by the symbol - in figure 1.
    [023] The mixture of the present invention is present as a coating 26 on busbars 14, 16, 20, and 22 and their underlying anodes and cathodes as shown in Figure 1. The coating is formed by applying the mixture to the tops (anodes) and bottoms (cathodes) of batteries 2, 4, 6, and 8 and mixture pressure for close contact with current-carrying elements on the outside of each battery. In fact, the coating is formed on both the anode and cathode ends of the batteries and their associated busbars as shown in figure 2. If desired, the mixture can also be applied to form a coating over the uncoated lengths of busbars. 18 and 24 shown in figure 1. When current is concentrated at the anode ends of the batteries and the busbars that carry this current to the positive terminal, it is preferred that at least these busbars (electrical connectors) are sheathed by the semi-mixture. of the present invention. The anodes, cathodes and buses are all electrical connectors for each battery and the battery array. The mixture applied to the conductors and preferably to the battery as shown in figures 1 and 3 must be electrically non-conductive so as not to cause a short circuit.
    [024] Lithium ion battery can be of any type including prismatic lithium ion battery, with anode/electrolyte/cathode separator layers being stacked on top of one another and the resulting set of many anode layers /electrolyte/cathode separator is housed in an aluminum foil barrier layer that forms the battery can. This aluminum foil barrier that prevents electrolytes from escaping and isolating themselves from the atmosphere is often called a bag. A positive electrode and a negative electrode extend from the outside of the bag, forming the electrical interconnection between the layers of anodes and cathodes, respectively, inside the bag.
    [025] In another embodiment of the present invention, the mixture is positioned as a coating on the outside of the bag at least surrounding the electrodes and on the electrodes themselves after their interconnection with the device to be powered by the battery.
    [026] The Li-ion battery can be either a primary battery or a secondary battery. The secondary battery's recharging capability feature makes it a preferred battery for application of the present invention.
    [027] Figure 3 shows an array of sixteen lithium ion batteries 32, 34, 36 and 38 as the batteries of figure 1, but contained within an enclosure 28 to form a battery pack 30. The anodes and batteries 32 are electrically connected by bus 40, batteries 34 through bus 42, batteries 36 through bus 44, and batteries 38 through bus 46. Buses 40, 42, 44, and 46 are electrically interconnected by bus 48 to provide the positive terminal of the battery pack. The cathodes of batteries 32 are electrically connected by bus 50, batteries 34 by bus 52, batteries 36 by bus 54, and batteries 38 by bus 56. Buses 50, 52, 54, and 56 are electrically interconnected by bus 58 to provide the negative terminal of the battery pack. A mixture coating 60 of the present invention is formed on all surfaces of the batteries and their busbars as shown in Figure 3.
    [028] Figure 4 shows that the battery pack housing 28 consists of a bottom receptacle 64, inside which the battery array of figure 3 is positioned and the cover 62 in a closed position forming the housing 28. The mixture is deep enough to allow the mixture to form a coating 60 on all surfaces of the battery and its rails within the housing 28. One embodiment of achieving the formation of this coating is to first form a bed of the mixture within the bottom receptacle 64. Then, the array of electrically interconnected batteries can be pressed into this bed. The mixture that is forced upward by this compression can then be spread to form a coating over any uncoated upside-down surface (batteries and busbars), thus encapsulating the battery array and its busbars within the semi-solid mixture. If the amount of mix in the bed is insufficient to coat upward facing surfaces then the mix can be added and spread over any uncoated battery/bar surface. The housing 28 may then be closed by adding the cover 62 to the bottom receptacle 64. Li-ion prismatic batteries may be replaced by the jelly-roll batteries of Figures 1-4. The mixture does not need to fill all the space inside the casing as shown in figure 4; some empty space may exist. Alternatively, much of not all of the space within the enclosure can be filled with the mixture that encapsulates the battery array.
    [029] As we can see from the above description of placement of the mixture with respect to batteries and connectors, it is preferred that the mixture be semi-solid to allow for close contact, especially on irregularly shaped surfaces or surfaces that are not readily accessible. While the mixture can form a direct coating on one or more of these elements, the coating can also be indirect. For example, a battery might have a wrap and flammable film there, and the mixture would be formed as a coating on top of the wrap film.
    [030] With respect to the destabilizing solid fluoropolymer component of the mixture, preferably semi-solid, the fluoropolymer itself can present a wide variety of identities. In general, the fluoropolymer has a main chain of carbon atoms as a polymer chain: -CCC-CC-CCCCC-Cx-, where x is the number of additional carbon atoms present to provide, together with the substituents in the polymer chain, the molecular weight desired for the fluoropolymer, and makes the fluoropolymer solid. Fluoropolymers with molecular weights of at least 50,000 (Mn) are commercially available, making it convenient to use such fluoropolymers in their thermally destabilizing form in the blend of the present invention. Preferred fluoropolymers are those which are melt-processable copolymers of tetrafluoroethylene, for example comprising at least 40-99 mole percent tetrafluoroethylene (TFE) derived from repeating units (by polymerization) and 1-60 mole percent units derived from at least one another comonomer. Preferred comonomers with TFE to form by fluoropolymers are perfluoroolefins having 3 to 8 carbon atoms, such as hexafluoro propylene (HFP), and/or perfluoro(alkyl vinyl ether) (PAVE) in which the linear or branched alkyl group contains from 1 to 5 carbon atoms. Preferred PAVE monomers in these TFE copolymers and those described below are those in which the alkyl group contains 1, 2, or 3 carbon atoms, and the copolymer can be made using a variety of PAVE monomers. Preferred TFE copolymers include FEP (TFE/HFP copolymer and TFE/HFP/PAVE copolymer) and PFA (TFE/PAVE copolymer), with PAVE most preferably being perfluoro(ethyl vinyl ether)(PEVE) or perfluoro (propyl vinyl ether) (PPVE), or the combination of perfluoro (methyl vinyl ether) (PMVE) and PPVE, ie TFE/PMVE/PPVE copolymer, sometimes called MFA, less preferred is a fluoropolymer having -CH2- units in the polymer chain such as THV (TFE/HFP/VF2 copolymer). The FEP preferably contains 5 to 17% by weight of HFP, the balance being TFE, with PAVE content if present being 0.2 to 2% by weight based on the total weight of the FEP. The PFA preferably contains at least 2% by weight of PAVE, with the remainder being TFE, based on the total weight of the PFA.
    [031] Preferably, the fluoropolymer is at least 50% by weight fluorine, preferably at least 60% by weight, and more preferably at least 70% by weight fluorine, based on the total weight of the polymer chain (excludes end groups). In one embodiment of the present invention, if hydrogen is present in the repeating units constituting the polymer chain, it is preferred that hydrogen is only mono-substituted at any of the carbon atoms constituting the polymer chain or at any side group attached to the polymer chain, a since the presence of -CH2- can confer non-flammability of the fluoropolymer. Preferably, the hydrogen content, if any, is not more than 2% by weight, more preferably not more than 1% by weight, most preferably not more than 0.5% by weight, based on the total weight of the fluoropolymer. A small amount of hydrogen along the polymer chain may have the beneficial thermal destabilizing effect of the fluoropolymer, thus aiding its combustion reduction effect. In another embodiment of the present invention, the fluoropolymer is a perfluoropolymer. By per fluoropolymer is meant the fact that the monovalent substituents on the carbon atoms forming the polymer polymer chain are all fluorine atoms with the possible exception of end groups.
    [032] Unlike the fluorinated composition in the mixture when the fluorinated composition is itself in the liquid state, the fluoropolymer is in the solid state at least under the temperatures found by the lithium ion battery and its battery pack of up to 40 °C, sometimes up to 50°C and more, for example up to 60°C and even up to 80°C, at atmospheric pressure. At higher temperatures, the fluoropolymer can melt. Preferably, however, the melting temperature of the fluoropolymer is at least 200°C and no more than 315°C. Alternatively, the fluoropolymer can be one that softens upon heating, rather than having a distinct melting temperature. In each shell, the fluoropolymer is preferably melt flowable. However, the fluoropolymer remains solid under the Li-ion battery temperatures as mentioned above. Melt flowability can be characterized by a melt flow rate (MF) of at least 0.01 g/10 min, preferably at least 0.1 g/10 min, more preferably at least 5 g/10 min or at least 10 g/10 min min, all as measured in accordance with ASTM D 1238, under conditions of melting temperature and molten polymer weight that is prescribed for the specific fluoropolymer. For PFA and FEP, the prescribed temperature and weight is 372°C and 5 kg, respectively.
    [033] Fluoropolymers are known for their thermal stability, especially arising from the strong chemical bond between carbon and fluorine atoms that predominate in the fluoropolymer. It is common, however, for the fluoropolymer as a polymerizate to have thermally unstable moieties, especially unstable end groups, arising from ingredients that provide free radicals in the aqueous polymerization medium during the polymerization reaction. As the same as or greater than the total of at least 300 unstable end groups, more often at least 400 such end groups -COOH, -COF, and/or -CONH2. Per 106 carbon atoms may be present in the as-polymerized fluoropolymer. For example, the common persulfate polymerization initiator in the aqueous polymerization medium results in the formation of carboxyl end groups, -COOH, in the polymer chain. These groups decompose at elevated temperatures, indicating the thermal stability of the fluoropolymer. Decomposition is the splitting of the carboxyl end groups, leaving behind the reactive group CF2-, which can cause the formation of a new labile end group, perfluoro vinyl, -CF=CF2, which extends into the polymer chain. Before such destabilizing fluoropolymers are made available by manufacturers for commercial use, the fluoropolymer undergoes a stabilization process that replaces unstable end groups with stable end groups. For example, FEP is subjected to wet heat treatment at elevated temperatures to replace unstable end groups with the stable -CF2H end group. Both FEP and PFA undergo fluorination treatment to replace unstable end groups with the stable -CF3 end group.
    [034] The destabilisable solid fluoropolymer used in the present invention is preferably not end group stabilized, but is instead used in its thermally destabilizing form, i.e., the thermally unstable moieties, such as the end unstable groups, are present in the fluoropolymer. Heating by the Li-ion battery caused by such corruption as improper recharging or short circuiting results in heating of the solid fluoropolymer to cause decomposition of unstable portions. This decomposition results in non-combustible volatiles that are emitted from the fluoropolymer. These volatiles reduce combustion either by preventing it from occurring, confining it if it does, or by instantly extinguishing the fire.
    [035] A preferred destabilizing fluoropolymer is the aforementioned FEP, but with end groups that are not stabilized, thus having the unstable end groups mentioned above.
    [036] Another embodiment of thermally destabilizing fluoropolymer that contains thermally destabilizing groups such as -CH2-CH2- or -CH2- in the polymer chain in the small amount as mentioned above that provides thermal decomposition of the fluoropolymer without imparting flammability to the fluoropolymer. Such thermally unstable groups can be present in combination with thermally unstable end groups as described above. A preferred thermally destabilizing fluoropolymer which contains at least the thermally unstable polymeric (main) chain is the copolymer of TFE, HFP and ethylene, with the amount of ethylene in the copolymer being small to satisfy the above preferred maximum hydrogen contents. The TFE and HFP contents of the TFE/HFP/ethylene copolymer may be the same as for the above FEP dipolymer.
    [037] The destabilized solid fluoropolymer is preferably one that becomes flowable under heating provided by the corrupted lithium ion battery. In casing fluoropolymers that exhibit a melting temperature, such heating exceeds the melting temperature. The fluoropolymer softens sufficiently after such heating that it becomes molten and flowable or melts to become melt flowable. The heating provided by the corrupted battery changes the fluoropolymer from solid to liquid state. This fluoropolymer flow contributes to the exclusion of oxygen from combustible vapors arising from overheated electrolyte and/or firestop. The fusion flow may be sufficient to seal the opening in the battery pack casing from which combustible vapors would otherwise escape from the battery casing.
    [038] The battery pack housing material of construction can be any material that is non-flammable and provides the strength necessary for the integrity of the housing when subjected to expected conditions of use. The fluoropolymer used in the semi-solid blend may also be a battery pack housing material of construction, such as housing 28 in Figures 3 and 4. Preferably, however, as the material of construction, the fluoropolymer has a melting temperature of at least 240°C, more preferably at least 280°C. The preferred fluoropolymer is PFA as described above. The fluoropolymer, when PFA, can be destabilized or have thermally stable end groups and can be used as the sole material of construction for the shell or as a coating such as a metal shell. Another preferred material of construction of the casing or cladding is FEP, which is preferably stabilized at least when used as the casing material of construction.
    [039] With respect to the fluorinated composition component of the semi-solid mixture, unlike the fluoropolymer component which is solid, the fluorinated composition itself is preferably not solid under the temperatures that can be encountered by the battery and battery pack as above mentioned. It is not a gas at these temperatures. Preferably, the fluorinated composition itself is liquid at these temperatures. This liquid state means that the fluorinated composition in the mixture does not emit volatiles during temperatures up to 40°C, sometimes up to 50°C, or up to 60°C and even up to 80°C (atmospheric pressure). The boiling temperature of the fluorinated composition is preferably at least 100°C (an atmospheric pressure).
    [040] The liquid state results from the fluorinated composition with a low molecular weight in relation to the molecular weight of the solid fluoropolymer. Preferred fluorinated compositions are fluoropolyethers (FPE), preferably perfluoropolyethers (PFPE), both of which may have any chain structure in which oxygen atoms in the backbone of the molecules are separated by saturated fluorocarbon groups with 1-3 carbon atoms, preferably groups perfluorocarbon. More than one type of fluorocarbon group may be present in the molecule of fluorinated composition.
    [041] Representative structures are (-CFCF3-CF2-O-)n (I)(-CF2-CF2-CF2-O-)n (II)(-CF2-CF2-O-)n-(-CF2-O -)m (III)(-CF2-CFCF3-O-)n-(-CF2-O-)m (IV)
    [042] These structures are discussed by Kasai in J. Appl. Polymer Sci. 57, 797 (1995) and they are commercially available as certain KRYTOX® and FOMBLIN® lubricating oils. Preferably, FPE which includes PFPE has a carboxyl group at one or both ends of the chain structure of FPE and PFPE. For monocarboxyl FPE including PFPE, the other end of the molecule is usually perfluorinated but may contain a hydrogen atom. FPE and PFPE with a carboxyl group at one or both ends that can be used in the present invention have at least 2 ether oxygens, more preferably at least 4 ether oxygens, and even more preferably at least 6 ether oxygens, ie n in formulas above is at least 2, 4, or 6 and in the above formulas is at least 1, 2 or 3. Preferably, at least one of the fluorocarbon groups that separate ether oxygens, and more preferably at least two such fluorocarbon groups have 2 or 3 carbon atoms. Even more preferably, at least 50% of the fluorocarbon groups that separate ether and oxygen have 2 or 3 carbon atoms. Also, preferably, the FPE which includes PFPE has a total of at least 9 carbon atoms. The maximum value of n and m in the above formulas is preferably that which does not exceed the molecular weight at which the composition is liquid under the temperatures that can be encountered by the lithium ion battery and battery pack. While more than one FPE including PFPE may be used in the semi-solid blend of the present invention, preferably only one such FPE or PFPE is used. FPE and PFPE are considered a composition because as commercially available FPEs and PFPEs are usually a mixture of FPEs or mixtures of PFPEs, where the n value or m value shown is the average number of n and m groups present in the PFPE.
    [043] Especially PFPEs have a high thermal stability that allows them to be used as high temperature lubricants even when groups are present at one or both ends of the chain structure. The heat provided by the corrupted lithium ion battery, however, causes decarboxylation of the FPE or PFPE, similar to the decomposition of solid fluoropolymers with thermally unstable portions such as carboxyl end groups. Thus, when the fluorinated composition contains thermally unstable end groups such as carboxyl, this composition contributes to non-flammable volatiles reducing combustion similar to the effect of destabilizing solid fluoropolymer in the semi-solid mixture.
    [044] The mixture of the present invention can be made by mixing together with the fluorinated composition, preferably as a liquid with the solid fluoropolymer in particulate form, i.e., the thermally destabilizing solid fluoropolymer is particulate. The fluoropolymer particles can be those that result from the polymerization process to make the fluoropolymer eg aqueous dispersion, polymerization typically results in the formation of fluoropolymer particles with an average particle size of at most 0.5 micrometers as measured by the light scattering of laser. Recovery of the fluoropolymer particles from the aqueous polymerization medium results in the aggregation of the primary particles from the polymerization process to form secondary particles of agglomerated primary particles, with the secondary particles having an average particle size of 200 to 800 micrometers as measured by the dispersion of laser light (ASTM D 4464). The thermally destabilizing fluoropolymer particle size is preferably one that is effective to produce a homogeneous semi-solid mixture with the fluorinated composition.
    [045] The mixing process can be carried out at room temperature (15-25°C) for convenience. Mixing can be done manually or by mechanical means. The components are added to the mixing vessel and subjected to mixing. Since a solid is preferably being mixed with a liquid, mixing is complete when no concentration of either component is visible. Instead, a mixture that appears to be homogeneous, which is preferably semi-solid, is obtained. Fluoropolymer particles are generally white in color, and the fluorinated composition will be a colorless liquid with the result that a mixture exhibits a uniform white appearance.
    [046] Solid fluoropolymer is known for its non-stick characteristic, making it useful for non-stick cookware surfaces. Association with this feature is its incompatibility with other materials. Mixing fluoropolymer particles with an incompatible liquid will not produce a homogeneous mixture. Instead, the incompatible liquid will simply drain from the fluoropolymer particles. Most organic solvents are incompatible with fluoropolymer, i.e., particles do not dissolve in such solvents. The fluorinated composition in liquid form is sufficiently compatible as a thermally destabilizing fluoropolymer in particulate form to form a homogeneous mixture, i.e., the liquid fluorinated composition does not drain from the mixture.
    [047] The proportions of each component in the mixture are adjusted in order to obtain the deformability of the desired mixture at the time the mixture is formed into a coating on the lithium ion battery (batteries). For certain fluoropolymer particles, the proportion of fluorinated composition will vary as a function of the molecular weight of the composition as the molecular weight affects the liquid viscosity. Although the slurry coating on the lithium ion battery (or connectors) can harden when the battery is used at extremely low temperatures, it is the desired deformability for the process of forming a slurry coating on the battery. of lithium ions (batteries) or connectors which is aimed at establishing the method for mixing especially to obtain the preferred semi-solid state for mixing. For convenience, the coating process can be conducted at room temperature (15°-25°C).
    [048] Preferably, the mixture, preferably semi-solid, comprises 4 to 96% by weight of each fluorinated composition and destabilizing solid fluoropolymer components, based on the combined weight of those components for a total 100% by weight. On the same basis, preferred proportions are additionally 5 to 95% by weight of the fluorinated composition and 95 to 5% by weight of the solid fluoropolymer, 10 to 90% by weight of the fluorinated composition and 90 to 10% by weight of the solid fluoropolymer. 90% by weight of the fluorinated composition and 50 to 10% by weight of the solid fluoropolymer, and 50 to 85% by weight of the fluorinated composition and 50 to 15% by weight of the solid fluoropolymer.
    [049] The thickness of the semi-solid mixture coating formed on the lithium ion battery is preferably at least 25 micrometers (one mil). In the embodiment of figures 3 and 4, a much thicker coating is formed.
    [050] By way of example the lithium ion batteries in the array shown in figure 3 are 4.8v each, providing a voltage of 19.2 for the battery pack. The semi-solid mixture comprises tetrafluoroethylene/hexafluoro propylene (FEP) copolymer with a melt flow rate (MFR) of 30 g/10 min and hexafluoro propylene content of 10% by weight. The copolymer has a molecular weight (Mn) that exceeds 50,000 and has a melting temperature of 255°C. The copolymer is in the form of secondary particles with an average particle size of approximately 300 micrometers. The copolymer is a solid copolymer that exhibits a tensile strength greater than 5 MPa and is thermally destabilisable as indicated by its terminal unstable population being greater than 500 terminal unstable groups /106 carbon atoms, at least 90% of which are - COOH and the remainder comprising -CONH2. The mixture also comprises CF3CF2CF2-O-(-CFCF3-CF2-O-)n-CFCF3-COOH,
    [051] where n is an average value of 14, providing a molecular weight of approximately 2500, as the fluorinated composition, which is liquid at room temperature and has a boiling temperature greater than 100°C. These components are mixed together in a 50:50 weight ratio at room temperature and manually spatula-applied to the batteries and connectors (busbars) within the battery pack as shown in figures 3 and 4. The battery pack is equipped with thermocouples for monitor internal temperature at specific locations within the battery pack. A nail is driven through the battery pack cover to impale one of the Li-ion batteries for short circuit. An impaled battery is one that is located adjacent to a thermocouple. The thermocouple reveals that short circuiting of the battery by the nail is obtained, when the temperature measured by this thermocouple reveals a rapid increase in temperature. Steam visibly exits the casing. The steam ignites and is instantly extinguished by the semi-solid mixture coating.
    [052] Similar results are obtained when the aforementioned fluoropolyether of 2500 molecular weight is replaced by fluoropolyether with the same molecular structure, but with a greater number of repeating units n to provide a molecular weight of approximately 7500, the resulting mixture being the FEP is semi-solid in consistency.
    [053] Similar results are obtained when FEP is replaced by secondary particles of tetrafluoroethylene/hexafluoro propylene/ethylene copolymer with an average particle size of 300 micrometers, with the HFP content being 7.6% by weight and the weight of hydrogen provided by the copolymerized ethylene units is 0.13 % by weight. The copolymer also has a smaller amount of hydrogen present (0.006% by weight) as -C2H5 end groups derived from using ethane as the chain transfer agent in the polymerization to produce the copolymer. The copolymer has a molecular weight (Mn) that exceeds 50,000 and an MFR of 30 g/10 sec. The combustion result is similar to that when FEP is used.
    权利要求:
    Claims (5)
    [0001]
    1. MIXTURE FOR REDUCING COMBUSTION (26), by a lithium ion battery (2,4,6,8), characterized by comprising a solid fluoropolymer and a fluoropolyether, called fluoropolyether having oxygen atoms in the molecule's chain structure separated by saturated fluorocarbon groups having 1 to 3 carbon atoms, wherein the solid fluoropolymer is a thermally destabilized solid fluoropolymer having at least 300 thermally unstable end groups selected from -COOH, -COF and/or -CONH2 per 106 atoms of carbon.
    [0002]
    A MIXTURE according to claim 1, characterized in that said fluoropolyether is in the liquid phase so that a semi-solid mixture is formed at temperatures of up to 80°C when said fluoropolyether is mixed with said solid fluoropolymer, wherein semi-solid solid means that said mixture is neither a gas nor a liquid at said temperatures.
    [0003]
    A MIXTURE according to claim 1, characterized in that said fluoropolyether itself is in a liquid state at temperatures of up to at least 40°C.
    [0004]
    4. COMBUSTION REDUCTION PROCESS, by a lithium ion battery (2,4,6,8), characterized in that it comprises positioning a mixture (26) comprising solid fluoropolymer with respect to said battery, said mixture being effective to provide said reduction by said combustion of said battery, wherein the solid fluoropolymer is a thermally destabilized solid fluoropolymer having at least 300 thermally unstable end groups chosen from -COOH, -COF and/or -CONH2 per 106 carbon atoms, and said mixture (26 ) further comprises a fluoropolyether having oxygen atoms in the chain structure of the molecule separated by saturated fluorocarbon groups having 1 to 3 carbon atoms, said positioning including forming a coating of said mixture on at least a part of said battery (2 ,4,6,8).
    [0005]
    5. Process according to claim 4, characterized in that said battery has an electrical connector (14,16,18,22) and said positioning includes the formation of a coating of said mixture at least on said electrical connector.
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    同族专利:
    公开号 | 公开日
    CN104620410A|2015-05-13|
    CN104620410B|2017-12-05|
    TWI610987B|2018-01-11|
    TW201420691A|2014-06-01|
    US20140060859A1|2014-03-06|
    KR102095942B1|2020-04-01|
    JP2015536013A|2015-12-17|
    KR20150048739A|2015-05-07|
    JP6346184B2|2018-06-20|
    BR112015004365A2|2017-07-04|
    WO2014036360A1|2014-03-06|
    EP2891197B1|2018-11-14|
    EP2891197A1|2015-07-08|
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    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-06-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261694901P| true| 2012-08-30|2012-08-30|
    US61/694,901|2012-08-30|
    US201261703948P| true| 2012-09-21|2012-09-21|
    US61,703,948|2012-09-21|
    PCT/US2013/057447|WO2014036360A1|2012-08-30|2013-08-30|Mixture for abating combustion by a li-ion battery|
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