BR122024005859A2 - SECONDARY BATTERY BLOCK AND PROCESS FOR PREPARING A SECONDARY BATTERY BLOCK - Google Patents

Abstract

The present invention relates to an innovative secondary battery pack with improved thermal management useful for an all-electric vehicle (EV), a plug-in hybrid vehicle (PHEV), a hybrid vehicle (HEV), or battery packs used for batteries. from other vehicles and, more especially, the use of a specific material to thermally insulate a secondary battery block and further minimize the propagation of thermal runaway within a battery block. The secondary battery block comprises at least one battery module housing (102) in which there is disposed a plurality of battery cells (103) that are electrically connected together, a synthetic silicone rubber foam comprising a binder of silicone rubber and hollow glass beads, and the synthetic silicone rubber foam partially or completely fills the open space of the battery module housing (102) and/or covering the battery cells (103) and/or covering the housing module (102), and optionally, a cover covering the battery module housing (102).

Description

FIELD OF INVENTION CROSS REFERENCE TO RELATED PATENT APPLICATION

[001] The present application is an international application under the Patent Cooperation Treaty, which claims priority to Provisional Application US 1962/456,502, filed on February 8, 2017, the contents of which are incorporated herein by reference in its entirety .

FIELD OF INVENTION

[002] The present invention relates to an innovative secondary battery pack, in particular those comprising lithium-ion battery cells, with improved thermal management enabling use under extended conditions of extreme temperatures. More especially, the present invention relates to the use of a specific material to thermally insulate a secondary battery pack and further minimize the propagation of thermal excursions within a battery pack. Said secondary battery pack can be used in a fully electric vehicle (EV), a plug-in hybrid vehicle (PHEV), a hybrid vehicle (HEV) or in other vehicle batteries.

BACKGROUND OF THE INVENTION

[003] Batteries can be classified into primary and secondary batteries. Primary batteries, also known as disposable batteries, should be used until they are exhausted, after which they are simply replaced with one or more new batteries. Secondary batteries, more commonly referred to as rechargeable batteries, can be repeatedly recharged and reused, therefore offering economic, environmental and ease-of-use benefits compared to a disposable battery. Examples of secondary batteries may include nickel-cadmium batteries, nickel-metal hybrid batteries, nickel-hydrogen batteries, lithium secondary batteries, and the like.

[004] Secondary batteries, in particular lithium-ion batteries, have emerged as a key energy storage technology and are currently the main technology for consumer electronic devices, industrial, transportation and energy storage applications. power.

[005] Due to their high potential and their high energy and power densities, and also their good useful life, secondary batteries, at the moment, are the preferred battery technology, especially in the automotive industry, since It is currently possible to provide greater autonomy and adequate acceleration for electrically powered vehicles such as Hybrid Electric Vehicles (HEVs), Battery Electric Vehicles (BEVs) and Plug-In Hybrid Electric Vehicles (PHEVs). In today's automotive industry, different sizes and shapes of lithium-ion battery cells are being manufactured and subsequently assembled into blocks of different configurations. An automotive secondary battery pack generally consists of a large number of battery cells, sometimes several hundred, even thousands, to meet desired power and capacity needs.

[006] This change in powertrain technology, however, is not without its technological obstacles, since the use of an electric motor translates into the need for inexpensive batteries with high energy density, long useful life and capacity. to operate in a wide range of conditions. Although rechargeable battery cells offer a number of advantages over disposable batteries, this type of battery does not have its drawbacks. In general, most of the disadvantages associated with rechargeable batteries are due to the battery chemistries used, as these chemistries tend to be less stable than those used in primary cells. Secondary battery cells, such as lithium-ion cells, tend to be more prone to thermal management hot spots that occur when elevated temperatures trigger exothermic heat-generating reactions, further increasing the temperature and potentially triggering more deleterious reactions. . During this event, a large amount of thermal energy is rapidly released, heating the entire cell to a temperature of 850°C or higher. Due to the increase in temperature of the cell subjected to this temperature increase, the temperature of adjacent cells within the battery pack will also increase. If the temperature of these adjacent cells is allowed to rise unimpeded, they can also enter an unacceptable state with extremely high temperatures within the cell, causing a cascade effect in which the rise in temperature within a single cell propagates throughout the entire battery pack. . As a result, power to the battery pack is interrupted and the system employing the battery pack is more likely to incur extensive collateral damage due to the scale of damage and the release of associated thermal energy. In the worst case scenario, the amount of heat generated is great enough to lead to combustion of the battery as well as materials near the battery.

[007] Additionally, due to the characteristics of lithium-ion batteries, the secondary battery pack operates within an ambient temperature range of -20° C to 60° C. However, even when operating within this range temperature, the secondary battery pack may begin to lose its capacity or ability to charge or discharge if the ambient temperature drops below 0° C. Depending on the ambient temperature, the life cycle capacity or charge/discharge capacity of the battery can be greatly reduced as the temperature remains below 0°C. However, it may be unavoidable that the lithium-ion battery is used when the ambient temperature is outside the ideal ambient temperature range of 20°C to 25°C. ° C. These factors not only greatly reduce the vehicle's range, but also cause great damage to the battery. The deterioration in energy and available power at lower temperatures is attributed to the reduction in capacity and increase in internal resistance.

[008] Alluding to the above, in a battery or battery assembly with multiple cells, significant temperature variations may occur from one cell to the next, which is detrimental to the performance of the battery pack. To promote long life of the entire battery pack, the cells must be below the desired threshold temperature. To promote pack performance, the temperature differential between cells in the secondary battery pack must be minimized. However, depending on the thermal path to the environment, different cells will reach different temperatures. Furthermore, for the same reasons, different cells reach different temperatures during the charging process. Consequently, if a cell is at an increased temperature compared to other cells, its charging or discharging efficiency will be different and therefore it can be charged or discharged more quickly than other cells. This will cause a decline in the performance of the entire set.

[009] Various approaches have been employed to reduce the risk of controversial points or reduce the risk of thermal propagation. These can be found in US patent 8,367,233 which describes a battery block thermal management system comprising at least one housing failure port integrated into at least one wall of a battery block housing, in that the case failure port(s) remain closed during normal battery pack operation, and open during a battery pack thermal event, therefore providing a flow path for the Hot gas generated during the thermal event being exhausted out of the battery pack in a controlled manner.

[010] Another approach is to develop new cell chemistries and/or modify existing cell chemistries. Yet another approach is to provide additional shielding at the cell level, thereby inhibiting the flow of thermal energy from the cell subjected to thermal management contentious points propagating to adjacent cells. Yet another approach is to utilize a spacer assembly to maintain the position of the battery undergoing the thermal event in its predetermined location within the battery pack, therefore helping to minimize thermal effects on adjacent cells.

[011] Thermal insulation of a battery pack has also been described to reduce the risk of thermal excursions or their propagation. For example, US patent 2007/0,259,258 describes a battery of lithium generators in which the generators are stacked on top of each other and this stack is held in position surrounded by polyurethane foam. An embodiment is also described in which cooling fins are inserted between two generators.

[012] Patent DE 202005010708 describes a starting lead-acid electrochemical generator and an electrochemical generator for industrial use whose housing contains plastic foam such as polypropylene or polyvinyl chloride that contains closed pores.

[013] US patent 2012/0,003,508 describes a battery of lithium electrochemical generators, including a housing; a plurality of lithium electrochemical generators housed in the housing, each generator including a container; a rigid, flame-retardant, closed-porosity foam formed from an electrically insulating material that fills the space between the inner wall of the housing and the free surface of the side wall of the container of each electrochemical generator, the foam covering the free surface of the wall side of the container of each electrochemical generator in relation to a length that represents at least 25% of the height of the container. According to one embodiment, the foam consists of a material selected from the group comprising polyurethane, epoxy, polyethylene, melamine, polyester, formophenol, polystyrene, silicone or a mixture thereof, preferably being the polyurethane and the mixture of polyurethane and epoxy. The expansion of the polyurethane resin into the form of foam is described using the following chemical routes to obtain the foam: (a) the chemical route, that is, the reaction of water in the isocyanate producing CO2 that will cause the foam of the polyurethane; (b) the physical route, that is, the vaporization of a liquid with a low boiling point under the action of heat produced by the exothermic reaction between the isocyanate and the hydrogen donor compound, or (c) the air injection route .

[014] However, rigid foams that are typically produced by reacting a polyisocyanate with an isocyanate-reactive material such as polyol in the presence of a blowing agent do not exhibit the high compression set required when the foams are used to minimize the adverse effect of any fire and explosion linked to a thermal event.

[015] US patent 4,418,127 describes a lithium battery that is modular and has a plurality of cells, which has electrical connection means connecting the cells to the output terminals and ventilation means to release discharge by-products to a chemical purifier. The stainless steel cell housings are encapsulated in a modular aluminum box with a syntactic epoxy foam, said foam being syntactic in nature to reduce weight, and which are incorporated into it microballoons composed of compositions selected from the group consisting of glass and ceramics and additives to reduce flammability.

[016] Another important controversial point in the emerging field of electric vehicles is linked to the powertrains used that integrate the engine, automated manual powertrain, axles and wheels with the final drive to control the speed and generate greater torque to direct the vehicle. . The main difference from traditional fuel-guzzling vehicles is that there is no clutch or hydraulic torque converter in electric vehicles, therefore the overall system configuration is inherently less elastic, as the engine and powertrain system are directly mechanically coupled. This configuration has little passive damping effect that can dampen disturbances and avoid oscillations, which are mostly observed during travel in the low speed range. In fact, the dominant sound is magnetic noise which generates a whining noise at high frequencies. A vehicle that runs solely on an electric motor will also have less masked sound at low frequencies. This means that other noise requirements, such as for example component noise such as air or liquid cooling/heating for electric batteries, must be changed accordingly. Noise during regeneration (battery charging) when descending from the coast is also important. Therefore, due to the low damping in an electric vehicle and the lack of passive damping hardware compared to a conventional vehicle, a damping control strategy is necessary to minimize powertrain oscillations.

[017] While several approaches have been adopted to attempt to reduce the risk of thermal incursions, as well as the propagation of thermal energy throughout the battery pack, it is essential that if a thermal event occurs at the array level, the personal and ownership are minimized. As the number of cells in a battery increases, and as cell size increases, so does the need and benefit of providing adequate thermal management.

[018] Furthermore, there is still a need to better isolate battery cells, in particular lithium-ion batteries, from the adverse effect of low temperatures that are met when the weather reaches severe low temperatures that can reach -20° C. and even lower.

DESCRIPTION OF THE INVENTION

[019] In this context, one of the essential objectives of the present invention is to provide a new battery pack that provides adequate thermal management and minimizes personal and property risks due to uncontrolled thermal events, while still waiting.

[020] Another essential object of the present invention is to provide a new battery block that will provide damping control to minimize powertrain oscillations and better efficiency in controlling the propagation of noise originating from electric batteries while they are used.

[021] With the present invention, the claimed secondary battery block is expected to solve said problems linked to uncontrolled thermal excursions, in particular for lithium batteries, present efficient low-temperature insulation properties and provide a heat control strategy. damping to minimize powertrain oscillations.

[022] All these objectives, among others, are achieved by the present invention, which refers to a secondary battery block comprising: - at least one battery module housing (102) in which a plurality of battery cells are arranged battery (103) which are electrically connected together, - a silicone rubber synthetic foam comprising a silicone rubber binder and hollow glass beads, and said silicone rubber synthetic foam partially or completely filling the open space of said battery module housing (102) and/or partially or completely covering said battery cells (103) and/or partially or completely covering said module housing (102), and - optionally, a cover covering the battery module housing (102).

[023] To achieve this objective, the Depositor has demonstrated, to its credit, in a surprising and unexpected manner, that the selection of silicone rubber as a binder for a syntactic foam comprising hollow glass beads makes it possible to overcome the problems that were not solved by similar batteries using organic rubber syntactic foam.

[024] As used herein, the term "silicone rubber" includes the crosslinked product of any crosslinkable silicone composition. The term "syntactic silicone rubber foam" means a matrix produced from silicone rubber in which hollow glass beads are dispersed.

[025] Furthermore, it is well known that the range of an electric vehicle between charges is calculated at ambient temperature. Electric vehicle drivers are being told that the fragile temperature reduces available mileage. This loss is not only caused by the electrical heating of the cabin, but by the inherent slowdown of the battery's electrochemical reaction, which reduces capacity when it is cold. Therefore, the specific selection of silicone rubber as a binder within said synthetic foam makes it possible for said foam to present excellent insulation in relation to low temperatures close to or below the freezing point.

[026] Another advantage of using silicone rubber binders over organic rubber binders for a syntactic foam can be exemplified with the point of embrittlement (or loss of ductility), which is between -20° C and -30° C, for the typical organic rubber binder compared to -60° C to -70° C for the binders in accordance with the present invention.

[027] Another advantage is also linked to physical properties, such as elasticity, which remain efficient for a silicone rubber binder, even at temperatures at which organic rubber binders become brittle.

[028] Another advantage of using a synthetic silicone foam according to the present invention is that it has very low water absorption and therefore perfectly isolates the battery cells from unwanted water for their ideal uses. . In fact, unlike synthetic silicone foams, a standard silicone foam only contains the blown gas bubbles and has the voids completely or at least partially connected together, thus having an ability to absorb and diffuse water, characteristic that makes it difficult to use inside an electric vehicle where the battery packs are most often positioned under the vehicle or on the floor of the vehicle and therefore rainy driving conditions could lead to controversial issues with these materials.

[029] Since differences in temperatures affect the resistance, self-discharge rate, coulombic efficiency, as well as the irreversible capacity and power dissipation rates of battery cells, across a wide range of chemicals, the block secondary battery according to the present invention enables uniform thermal conditions for all cells of a battery pack or module. The probability of cellular state imbalance and premature failure of non-defective cells is therefore still minimized.

[030] According to a preferred embodiment, said synthetic silicone rubber foam is used as an encapsulation material disposed in said battery module housing (102) to at least partially encapsulate the plurality of battery cells (103 ) and/or outside the battery module housing (102) in a manner that at least partially encapsulates said battery module housing (102).

[031] In fact, the synthetic silicone rubber foam partially or completely fills the open space of said battery module housing and/or partially or completely covers said battery cells. The silicone rubber binder provides the syntactic foam with mechanical flexibility and thermal stability over a wide temperature range (e.g. from -70°C to 200°C). Furthermore, the decomposition of silicone rubber binder at thermal excess temperatures (up to 850°C) into silicone dioxide and silicone oxide absorbs a large amount of heat. Therefore, heat diffusion from the unit cell to neighboring unit cells can be effectively isolated by a thermal insulation barrier which is called synthetic silicone rubber foam. Thermal excursions are not propagated throughout the entire battery module and therefore the user's safety threat is avoided. Furthermore, for some battery modules that have the control circuit boards disposed in the battery module housing, the synthetic silicone rubber foam of the present invention may be disposed between the battery cells and the circuit board and between the battery cells and connection circuit to reduce the problem of battery heating caused by the circuit board and circuit.

[032] The silicone formulation contains hollow glass beads and, in a preferred embodiment, said hollow glass beads have melting points similar to those of a thermal event that occurs in a battery or a group of batteries in a block , so that heating softens and melts the glass, reducing heat transfer and protecting other batteries around the battery from overheating.

[033] According to a preferred embodiment, said battery cells (103) are of the lithium ion type.

[034] According to another preferred embodiment, the secondary battery pack, according to the present invention, which further comprises a plurality of heat dissipation members that are disposed at two or more interfaces between the battery cells and, at least one heat exchange member that integrally interconnects the heat dissipation members that is mounted to one side of the battery module housing (102), wherein the heat generated by the battery cells during charging and discharging of the cells of the battery is removed by the heat exchange member. It enables battery cell cooling with greater efficiency than conventional cooling systems, even with no gaps between battery cells or very small gaps between cells in the battery pack, therefore maximizing dissipation efficiency of heat from the secondary battery block and making it possible to further limit the free space within said secondary battery block.

[035] According to another preferred embodiment, the heat dissipation members according to the present invention are produced from a thermally conductive material that exhibits high thermal conductivity and the heat exchange member is provided with one or more cooling channels to enable a refrigerant such as a liquid or gas to flow through it.

[036] The heat dissipation members according to the present invention are not especially restricted, provided that each of the heat dissipation members is produced from a thermally conductive material, such as a metal plate that exhibits a conductivity high thermal.

[037] Preferably, the heat exchange member is provided with one or more cooling channels to enable a coolant to flow therethrough. For example, cooling channels to enable a coolant such as water to flow therethrough can be formed in the heat exchange member, thereby providing an excellent cooling effect with high reliability when compared with a structure. conventional air cooling.

[038] According to another preferred embodiment, the secondary battery block according to the present invention, which further comprises a refrigerant inlet distribution tube pipe, a refrigerant outlet distribution tube pipe and a plurality of heat exchange tubes as heat dissipation members and extending between the inlet and outlet distribution tube pipes, said heat exchange tubes are disposed at one or more interfaces between the battery cells and have a refrigerant passing through through to the exchange of heat generated from the battery cells during charging and discharging the battery cells.

[039] Hollow glass beads are used in the syntactic foam of the present invention and function to reduce the density of the foam. Hollow glass beads, and in particular hollow glass microspheres, are suitable for this application since, in addition to having excellent resistance to isotropic compression, they have the lowest density of any excipient that would be useful in the manufacture of syntactic foam. high compressive strength. The combination of high compressive strength and low density makes hollow glass microspheres the excipient with numerous advantages according to the present invention.

[040] According to one embodiment, the hollow glass beads are hollow microspheres of borosilicate glass, also known as glass bubbles or glass microbubbles.

[041] According to another embodiment, hollow borosilicate glass microspheres have true densities ranging from 0.10 grams per cubic centimeter (g/cc) to 0.65 grams per cubic centimeter (g/cc).

[042] The terms "true density" is the quotient obtained by dividing the mass of a sample of glass bubbles by the true volume of this mass of glass bubbles, measured by a gas pycnometer. The "true volume" is the total aggregate volume of the glass bubbles, not the total volume.

[043] According to another embodiment, the level of hollow glass beads is up to 80% of the volume charge in the syntactic silicone rubber foam or the liquid crosslinkable silicone composition precursor of said syntactic silicone rubber foam, as described below and, more preferably, between 5% and 70% by volume of the syntactic silicone rubber foam or liquid crosslinkable silicone composition precursor of said syntactic silicone rubber foam, as described below.

[044] According to a preferred embodiment, the hollow glass beads are selected from the 3M™ series of Floated Glass Bubbles (A16/500, G18, A20/1000, H20/1000, D32/4500 and the products of glass bubbles H50 / 10,000EPX) and 3M™ Series of Glass Bubbles (such as, but not limited to K1, K15, S15, K22, K20, S32, S32, S35, K37, XL38, S38, S38XHS, K46 , K42HS, S42XHS, S60, S60HS, ÍM16K, iM30K glass blister products) marketed by 3M Company. Said glass bubbles exhibit various crushing resistances ranging from 1.72 megapascals (250 psi) to 186.15 megapascals (27,000 psi) at which ten percent by volume of the first plurality of glass bubbles collapse. Other glass bubbles marketed by 3M such as 3M™ Glass Bubbles - Floated Series, 3M™ Glass Bubbles - HGS Series and 3M™ Glass Bubbles with Surface Treatment may also be used in accordance with the present invention .

[045] According to a preferred embodiment, said glass bubbles are selected from those that exhibit crushing resistances ranging from 1.72 megapascals (250 psi) to 186.15 megapascals (27000 psi), in which ten percent by volume of the first plurality of glass bubbles collapse.

[046] According to a most preferred embodiment, hollow glass beads are selected from the 3M™ Glass Bubbles series, S15, K1, K25, ÍM16K, S32 and XLD3000.

[047] To fill the free spaces with the synthetic silicone rubber foam, according to the present invention, it is possible: (a) to use a liquid crosslinkable silicone composition precursor of a synthetic silicone rubber foam comprising, the hollow glass beads, according to the present invention, - which, after injection or free flow, fills the free spaces and cures the crosslinking path, (b) or use a machined or previously molded block of a synthetic foam of silicone rubber that comprises the hollow glass beads that are inserted into the housing at the time of assembly.

[048] The use of a liquid crosslinkable silicone composition precursor of a synthetic silicone rubber foam comprising the hollow glass beads in the battery facilitates its filling compared to a standard liquid crosslinkable silicone precursor of a silicone foam as the foaming process of a standard foam creates the blown gas bubbles and have the voids completely or at least partially connected together, which causes numerous defects within the silicone foam obtained and filling problems .

[049] In fact, standard silicone foams are obtained through several methods, for example, adding a thermally decomposable blowing agent, or molding and curing while generating the hydrogen gas byproduct. In the method of adding a thermally decomposable blowing agent, the toxicity and odor of the decomposed gases are problems. The method of utilizing the hydrogen gas byproduct during the curing step suffers from problems such as the potential explosion of hydrogen gas and careful handling of the uncured composition during shelf-life storage. Furthermore, the gas generation method encounters difficulty in forming the controlled uniform cells.

[050] The use of expandable silicone rubber syntactic foam facilitates the filling of empty space within the battery block, since the expansion pressure pushes the foam into all cavities and recesses of the geometry to be filled. Furthermore, this method allows any geometry to be filled, which is not possible using prefabricated blocks.

[051] The silicone rubber that is used as a binder in syntactic foam according to the present invention, often referred to as silicone elastomers, is composed of three to four essential ingredients. These ingredients are (i) one or more reactive silicone polymers, (ii) optionally one or more excipients (iii) a crosslinking agent and (iv) a catalyst. In general, there are two main types of silicone rubber compositions that are heat vulcanized, (HTV) silicone rubber and room temperature vulcanization (RTV) silicone rubber. Heat vulcanized or high temperature vulcanization (HTV) silicone rubber compositions are often further differentiated as high consistency rubber (HCR) or liquid silicone rubber (LSR) depending on the uncured viscosity of the composition. The terms "room temperature vulcanization" (RTV) silicone rubber compositions, however, can be misleading, since some RTV compositions may require minimal heat to progress the reaction at a reasonable rate.

[052] The silicone rubber binder in which the hollow glass beads are dispersed can be obtained by curing either an addition-curing type organopolysiloxane composition, a peroxide-curing type organopolysiloxane composition, or an organopolysiloxane composition condensation type.

[053] Such silicone compositions are well known to those skilled in the art in the silicone field. The addition-cure type organopolysiloxane composition is preferably defined as primarily comprising (1) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups attached to the silicone atoms in a molecule, ( 2) from 0.1 to 50 parts by weight of an organohydrogen polysiloxane having at least two, preferably at least three hydrogen atoms attached to the silicone atoms (i.e., the SiH groups) in a molecule , and (3) a catalytic amount of an addition reaction catalyst. The peroxide curing type organopolysiloxane composition is preferably defined as principally comprising (1) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups attached to the silicone atoms in a molecule and (2 ) a catalytic amount of an organic peroxide. Condensation-type organopolysiloxane compositions that cross-link via polycondensation generally involve a silicone oil, generally a polydimethylsiloxane, with terminal hydroxyl groups, optionally prefunctionalized with a silane so as to have hydrolyzable and condensable ends and a cross-linking agent, a polycondensation catalyst, conventionally a tin salt or an alkyl titanate.

[054] According to a preferred embodiment, said synthetic silicone rubber foam is obtained by curing an organopolysiloxane (X) composition of the addition cure type. This embodiment offers several advantages over one-part systems (condensation-type organopolysiloxane compositions), especially in production environments. Since it is the catalyst and not moisture, such as in the case of a condensation cure silicone, that causes the cure, they do not present points of controversy with section thickness. In fact, they are advantageously used for applications such as encapsulation, encapsulation and large foundries. Addition-cure type organopolysiloxane compositions do not release reaction byproducts so they can cure indoors. Its curing can also be greatly accelerated by heat curing, however curing can be easily achieved without the need for heat, so that at room temperature 20° C (+/- 5° C), adjusting the level of inhibitor and/or catalyst which is a great advantage compared to peroxide curing which needs temperatures above 90°C.

[055] According to another preferred embodiment, the addition-curing type organopolysiloxane (X) composition comprises: (a) at least one organopolysiloxane (A) that has at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably, said alkenyl groups are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl, and, more preferably, said alkenyl groups are vinyl groups, (b) at least one silicone compound B that has at least two and preferably at least three hydrogen atoms attached to the silicone per molecule, (c) the hollow beads of glass (D) and preferably hollow microspheres of borosilicate glass, (d) a hydrosilylation catalyst (C), (e) optionally at least one cure rate controller (G) that reduces the rate of curing of the silicone composition, (f) optionally at least one reactive diluent (E) that reacts through the hydrosilylation reaction, and (g) optionally at least one additive (H) such as a pigment, a dye, clays, a surfactant, hydrogenated castor oil, wollastonite, aluminum trihydrate, magnesium hydroxide, halloysite, huntite hydromagnesite, expandable graphite, zinc borate, mica or a fumed silica.

[056] According to another preferred embodiment, the addition-curing type organopolysiloxane (X) composition comprises: (a) at least one organopolysiloxane (A) of the following Formula: - wherein: - R and R”, independently, are selected from each other, from the group consisting of a C1-C30 hydrocarbon radical and, preferably, R and R are the alkyl groups selected from the group consisting of methyl, ethyl, propyl, trifluoropropyl and phenyl e.g. most preferred. R is a methyl group, - R' is a C1-C20 alkenyl radical and preferably R' is selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and most preferably R' is a vinyl radical e - n is an integer having a value from 5 to 1,000, and preferably from 5 to 100, (b) at least one silicone compound (B) comprising, at least least two hydrogen atoms attached to the silicone per molecule and, preferably, a mixture of two silicone compounds (B) one, which comprises two telechelic hydrogen atoms attached to the silicone per molecule without any pendant hydrogen atoms attached to the silicone by molecule and, the others comprising at least three hydrogen atoms attached to the silicone per molecule, (c) an effective amount of hydrosilylation catalyst (C), and, preferably, a hydrosilylation catalyst (C) based on platinum, (d) the hollow glass beads (D) and, preferably, the hollow borosilicate glass microspheres, (e) optionally and preferably at least one reactive diluent (E) to reduce the viscosity of the composition and which reacts via the hydrosilylation reaction and is selected from the group consisting of: - a silicone compound comprising a single silicone hydride group per molecule and - an organic compound containing a single ethylenically unsaturated group, preferably said compound organic is an organic α-olefin containing from 3 to 20 carbon atoms, and most preferably selected from the group consisting of dodecene, tetradecene, hexadecene, octadecene and one of their combinations and all having a terminal vinyl group , - an organopolysiloxane having a single telechelic alkenyl group and, preferably, said telechelic alkenyl group is selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, more preferably, a vinyl group, (f ) optionally at least one additive (H) such as a pigment, a dye, clays, a surfactant, hydrogenated castor oil, wollastonite, aluminum trihydrate, magnesium hydroxide, halloysite, huntite hydromagnesite, expandable graphite, magnesium borate zinc, mica or a fumed silica, and (g) optionally at least one cure rate controller (G) that reduces the cure rate of the silicone composition.

[057] According to another preferred embodiment, the reactive diluent (E): - is selected from the group consisting of dodecene, tetradecene, hexadecene, octadecene or one of their combinations and all with a terminal vinyl group, or - is a liquid organopolysiloxane of Formula I - wherein - R and R2, independently, are selected from each other, from a C1-C30 hydrocarbon radical, and, preferably, are selected from the group consisting of methyl, ethyl, propyl, trifluoropropyl and phenyl, and , most preferably, are the methyl groups, - R1 is a C1-C20 alkenyl radical and, most preferably, R1 is selected from the group consisting of vinyl, allyl, hexenyl, decenyl or tetradecenyl and, most preferably, R1 is vinyl e - x is between 0 and 100, and is selected so as to decrease the viscosity of the addition-cure type organopolysiloxane (X) composition compared to the same composition without the reactive diluent.

[058] According to a preferred embodiment, organopolysiloxane (A) is selected from the group of dimethylpolysiloxanes containing terminal dimethylvinylsilyl groups.

[059] According to another preferred embodiment, in which: - the viscosity at 25° C of said organopolysiloxane (A) is between 5 mPa.s and 60,000 mPa.s; and, preferably, between 5 mPa.s and 5,000 mPa.s and, more preferably, between 5 mPa.s and 350 mPa.s, - the viscosity at 25° C of said silicone compound (B) comprising two hydrogen atoms telechelic compounds attached to the silicone per molecule without any hydrogen atom attached to the silicone per molecule, is between 5 and 100 mPa.s and - the viscosity at 25° C of said silicone compound (B) comprising at least three hydrogen atoms bonded to the silicone per molecule is between 5 and 2,000 mPa.s.

[060] All viscosities under consideration in the present invention correspond to a dynamic viscosity magnitude that is measured, in a manner known per se, at 25° C, with a Brookfield-type machine. In relation to fluid products, the viscosity under consideration in the present invention is the dynamic viscosity at 25° C, known as the "Newtonian" viscosity, that is, the dynamic viscosity that is measured, in a manner known per se, at a gradient of sufficiently low shear rate so that the measured viscosity is independent of the rate gradient.

[061] According to a preferred embodiment, the viscosities at 25° C of said organopolysiloxane (A) and said silicone compound (B) comprising at least two hydrogen atoms linked to the silicone per molecule are selected in a manner that the viscosity at 25° C of the addition-curing type organopolysiloxane composition (X) is between 500 mPa-s and 300,000 mPa-s, so that it can be injected into the battery module housing (102) . If the option of pouring the composition into the battery module housing (102) is selected, therefore, the components of said organopolysiloxane composition (X) of the addition cure type are selected such that their viscosity is between 500 mPa s to 5,000 mPa.s and, more preferably, between 500 mPa.s to 2,500 mPa.s.

[062] Examples of hydrosilylation catalysts (C) are hydrosilylation catalysts, such as the Karstedt catalyst shown in U.S. Patent 3,715,334 or other platinum or rhodium catalysts known to those skilled in the art, and also including platinum or rhodium catalysts. microencapsulated hydrosilylation, for example, those known in the art, as noted in U.S. Patent 5,009,957. However, the hydrosilylation catalysts relevant to the present invention may contain at least one of the following elements: Pt, Rh, Ru, Pd, Ni, for example, Raney nickel and combinations thereof. The catalyst is optionally coupled to an inert or active support. Examples of preferred catalysts that may be used include platinum-type catalysts such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum and olefin complexes, platinum complexes and 1,3-divinyl-1,1,3 ,3-tetramethyldisiloxane and powders on which platinum is supported, and the like. Platinum catalysts are fully described in the literature. In particular, there may be mentioned the complexes of platinum and an organic product described in U.S. Patents 3,159,601, 3,159,602 and 3,220,972 and in European Patents EP-A-057,459, EP-188,978 and EP-A-190,530 and the platinum and vinylated organopolysiloxane complexes described in U.S. Patents 3,419,593, 3,715,334, 3,377,432, 3,814,730 and 3,775,452, to Karstedt. In particular, platinum-type catalysts are especially desired.

[063] Examples of cure rate controller (G), which are also known as inhibitors, are designed to delay the cure of the silicone compound, if necessary. Curing rate controllers are well known in the art and examples of such materials can be found in U.S. Patents. U.S. Patent 3,923,705 relates to the use of cyclic siloxanes containing vinyl. U.S. Patent 3,445,420 describes the use of acetylenic alcohols. U.S. Patent 3,188,299 shows the effectiveness of heterocyclic amines. U.S. Patent 4,256,870 describes alkyl maleates used to control curing. Olefinic siloxanes may also be used as described in U.S. Patent 3,989,667. Polydiorganosiloxanes containing vinyl radicals have also been used and this technique can be seen in US Patents 3,498,945, 4,256,870 and 4,347, 346. The preferred inhibitors for this composition are methylvinylcyclosiloxanes, 3-methyl-1-butyn- 3-ol, and 1-ethynyl-1-cyclohexanol, more preferably, being 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane in amounts from 0.002% to 1. 00% silicone compound, depending on the desired cure rate.

[064] The cure rate controller (G) is preferably selected from: -1, 3,5,7-tetramethyl-1, 3,5,7-tetravinyl-cyclotetrasiloxane, - 3-methyl-1- butyn-3-ol and - 1-ethynyl-1-cyclohexanol.

[065] To obtain longer working time or "useful life", the amount of the cure rate controller (G) is adjusted to achieve the desired "useful life". The concentration of the catalyst inhibitor in the present silicone composition is sufficient to delay curing of the composition at room temperature without impeding or excessively prolonging curing at elevated temperatures. This concentration will vary widely depending on the particular inhibitor used, the nature and concentration of the hydrosilylation catalyst, and the nature of the organohydrogenpolysiloxane. Inhibitor concentrations as low as one mole of inhibitor per mole of platinum group metal will, in some cases, produce satisfactory storage stability and cure rate. In other cases, inhibitor concentrations of up to 500 or more moles of inhibitor per mole of platinum group metal may be required. The optimal concentration for a particular inhibitor in a given silicone composition can be easily determined through routine experimentation.

[066] According to a preferred embodiment, for said addition-curing type organopolysiloxane (X) composition, the proportions by weight of the organopolysiloxane (A), the reactive diluent (E), when present, and the silicone compound (B) are such that the total molar ratio of the hydrogen atoms attached to the silicone to the total alkenyl radicals attached to the silicone is within a range from 0.35 to 10, and preferably within a range from 0.4 to 1.5.

[067] Some additives (H) such as a pigment, a dye, clays, a surfactant, hydrogenated castor oil, wollastonite or a fumed silica (which modifies the flow of the silicone compound product) can also be used within said composition of organopolysiloxane (X) of the addition cure type.

[068] The term "dye" means only a colored or fluorescent organic substance, which imparts color to a substrate through selective absorption of light. The term "pigment" means an organic or inorganic particulate solid colored, black, white or fluorescent which are usually insoluble in the vehicle or substrate in which they are incorporated, and are essentially unaffected physically and chemically. Changes appearance through selective absorption and/or scattering of light. A pigment generally retains a crystal or particle structure throughout the coloring process. The pigments and dyes are well known in the art and do not need to be described in detail herein.

[069] Clays are products that are well known per se, which are described, for example, in the publication "Mineralogie des argiles [Mineralogy of clays], S. Caillere, S. Henin, M. Rautureau, 2nd Edition 1982, Masson" . Clays are silicates containing a cation that can be selected from calcium, magnesium, aluminum, sodium, potassium and lithium cations, and mixtures thereof. Examples of such products that may be mentioned include clays from the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also from the vermiculite, stevensite and chlorite families. These clays can be of natural or synthetic origin. The clay is preferably a bentonite or a hectorite, and these clays may be modified with a chemical compound selected from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkyl aryl sulfonates. and amine oxides and mixtures thereof. The clay that can be used, according to the present invention, is syntactic hectorites (also known as laponites), such as the products marketed by Laporte under the trade names Laponite XLG, Laponite RD and Laponite RDS (these products are magnesium and sodium and, in particular, lithium magnesium sodium silicates); bentonites, such as the product sold under the trade name Bentone HC by Rheox; aluminum and magnesium silicates, especially hydrated ones, such as the product sold by R.T. Vanderbilt Company under the trade name Veegum Ultra, or calcium silicates, in particular, which in syntactic form are marketed by the company CELITE ET WALSH ASS under the trade name Micro-Cel C.

[070] Various silicone polyether surfactants are available, but a preferred silicone polyether to thicken a silicone compound of the present invention would be SP 3300 from Elkem Silicones USA.

[071] Another additive (H) is preferably a rheology modifier such as Thixcin R, a hydrogenated castor oil, from Elementis Specialties, New Jersey, USA.

[072] Wollastonite, also known as calcium metasilicate, is a naturally occurring mineral that can be added as a flame retardant (amounts added will vary according to the application and will vary between 1 part by weight and 15 parts by weight). weight based on 100 parts by weight addition-curing organopolysiloxane (X) composition. The wollastonite that can be used in the present invention is a mined form, which has an acicular morphology, which is a needle-like shape. Preferred wollastonite grades are selected from materials supplied by NYCO®Minerals, Inc., Willsboro N.Y.

[073] Aluminum trihydrate (ATH) is a common flame retardant filler. It decomposes when heated above 180 to 200° C, at which point it absorbs heat and releases water to extinguish the flame. Magnesium hydroxide (MDH) has a higher thermal stability than ATH. Endothermic decomposition (heat absorption) begins at 300°C after which water is released which can act as a fire retardant.

[074] Huntite / Hydromagnesite mixtures (Mg3Ca(CO3)4 / Mg5Ca(CO3)4.4H2O. Huntite and hydromagnesite almost invariably occur as mixtures in nature. Hydromagnesite begins to decompose between 220° C (outdoors) ) and 250° C (under pressure in an extruder), which is high enough that it can be used as a flame retardant. In contrast, hydromagnesite releases water and absorbs heat, as do ATH and MDH. Huntite decomposes above 400°C, absorbing heat but releasing carbon dioxide.

[075] Fumed silicas can also be used as an additive (H) to change the rheology of these materials. Fumed silicas can be obtained through high temperature pyrolysis of a volatile silicone compound in an oxyrogen flame, producing a finely divided silica. This process, in particular, makes it possible to obtain hydrophilic silicas that have a large number of silanol groups on their surface, which would tend to thicken a silicone composition more than silica with low levels of silanol. Such hydrophilic silicas are marketed, for example, under the trade names Aerosil 130, Aerosil 200, Aerosil 255, Aerosil 300 and Aerosil 380 from Degussa and Cab-O-Sil HS-5, Cab-O-Sil EH-5, Cab- O-Sil. LM-130, Cab-O-Sil MS-55 and Cab-O-Sil M-5 from Cabot. It is possible to chemically modify the surface of said silica through a chemical reaction that causes a reduction in the number of silanol groups. It is possible, in particular, to replace the silanol groups with hydrophobic groups: therefore, a hydrophobic silica is obtained. The hydrophobic groups can be: - trimethylsiloxyl groups which, in particular, are obtained through the treatment of fumed silica in the presence of hexamethyldisilazane. Silicas treated in this manner are known as "silica silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R812 from Degussa and Cab-O-Sil TS-530 from Cabot, or dimethylsilyloxyl or polydimethylsiloxane groups which, in particular, are obtained through the treatment of fumed silica in the presence of polydimethylsiloxane or methyldichlorosilane.

[076] Silicas treated in this way are known as "dimethyl silica silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under the references Aerosil R972 and Aerosil R974 from Degussa and Cab-O-Sil TS-610 and Cab-O-Sil TS-720 from Cabot. The fumed silica preferably has a particle size that can be nanometer to micrometer, for example, ranging from about 5 to 200 nm.

[077] According to another preferred embodiment, said addition-curing type organopolysiloxane (X) composition is stored before use as a multi-component RTV comprising at least two separate packages which, preferably, are airtight, whereas the hydrosilylation catalyst (C) is not present in the same package with the silicone compound (B) or with the reactive diluent (E) when it is present and when it is a silicone compound comprising a single hydride group of silicone per molecule.

[078] According to another preferred embodiment, said addition-curing type organopolysiloxane (X) composition is stored before use as a multi-component RTV comprising at least two separate packages which, preferably, are airtight: (a) the first package (A1) comprising: - 100 parts by weight of at least one organopolyloxane (A), according to the present invention, and as defined above, - from 5 to 30 parts by weight of hollow glass beads (D), according to the present invention, and as defined above, and - from 0 to 30 parts and, preferably, from 5 to 30 parts by weight of, at least least, a reactive diluent (E) in accordance with the present invention, and as defined above, and - from 4 to 150 ppm platinum-based metal of a platinum-based hydrosilylation catalyst (C), ( b) the second package (A2) comprising: - 100 parts by weight of at least one organopolysiloxane (A), according to the present invention, and as defined above, - from 10 to 70 parts by weight of silicone compounds (B), one comprising two telechelic hydrogen atoms attached to the silicone per molecule, according to the present invention, and as defined above, - from 5 to 25 parts by weight of silicone compounds (B) comprising at least three hydrogen atoms attached to the silicone per molecule, according to the present invention, and as defined above, - from 5 to 30 parts by weight of hollow glass beads (D), according to the present invention, and as defined above, and - an effective amount of at least one cure rate controller (G) that reduces the cure rate.

[079] Another object of the present invention relates to a process for preparing a secondary battery block, according to the present invention, and as described above, which comprises the steps: (a) preparing at least a battery module housing (102) in which a plurality of battery cells (103) are arranged which are electrically connected together, (b) introducing into said battery module housing (102) the organopolysiloxane composition (X ) the type of addition curing, as defined in claim 3 or 11, (c) the complete or partial filling of the battery module housing (102), and (d) the possibility that curing occurs in such a way as to form a synthetic silicone rubber foam comprising a silicone rubber binder and hollow glass beads, and optionally (e) covering the battery module housing (102) with a lid.

[080] A preferred embodiment of the above process, according to the present invention, refers to the preparation of the organopolysiloxane composition (X) of the curing type through addition comprising the steps: (a) feeding, in a line base feed, of a liquid silicone base (MS1) comprising: (i) at least one organopolysiloxane (A) having at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing , from 2 to 14 carbon atoms, preferably, said alkenyl groups are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, more preferably, said alkenyl groups are vinyl groups, (ii) the hollow glass beads (D) and, preferably, the hollow borosilicate glass microspheres (D1), (iii) at least one silicone compound (B) having at least two and, preferably, at least least three hydrogen atoms bonded to the silicone per molecule, and (iv) optionally, a cure rate controller (G) that reduces the cure rate, (b) of the feed into a catalyst feed line, of a batch main catalyst (MC) comprising: (i) at least one hydrosilylation catalyst (C); and (ii) optionally, at least one organopolysiloxane (A) which has at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably said groups alkenyl are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, most preferably, said alkenyl groups are the vinyl groups; (c) feeding into an inhibitor supply line, a batch of inhibitor (Ml) comprising: (i) a cure rate controller (G) that reduces the cure rate; and (ii) optionally, at least one organopolysiloxane (A) which has at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably said groups alkenyl are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, most preferably, said alkenyl groups are the vinyl groups; and (d) optionally, feeding into an additive feed line, an additive master batch (MA), which comprises (i) at least one additive (H) such as a pigment, a dye, clays, a surfactant, hydrogenated castor oil, wollastonite, aluminum trihydrate, magnesium hydroxide, halloysite, huntite, hydromagnesite, expandable graphite, zinc borate, mica or a fumed silica, and (ii) optionally at least one organopolysiloxane (A) having at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably said alkenyl groups are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, more preferably, said alkenyl groups are vinyl groups; and (e) directing said liquid silicone base (MS1), said catalyst masterbatch (MC) and said inhibitor masterbatch (Ml) and, optionally, said additive masterbatch (MA) to a tank to obtain the organopolysiloxane composition (X) of the addition cure type.

[081] The first advantage of said preferred embodiment is in the fact that the crosslinking reaction rate for the organopolysiloxane composition (X) of the addition cure type is regulated through the addition of a cure rate controller (G) . Since the addition of this essential component is accomplished through the use of a specific feed line, the inhibitor level can be easily modified by the operator, enabling him to increase the cure rate or reduce the temperature at which rapid cure will occur. start. This is an important advantage, as the configuration of newly designed secondary battery blocks involves increasingly complex shapes, which means carefully adjusting the cure rate on a case-by-case basis.

[082] The second major advantage is that, at the moment, it is possible to reduce the level of inhibitor and, therefore, reduce the temperature at which rapid curing begins. This may be important if there are components inside the battery pack that are temperature sensitive.

[083] A preferred embodiment of the above process, according to the present invention, refers to the preparation of the cure-type organopolysiloxane composition through addition comprising the steps: (a) feeding into a base feed line , of a liquid silicone base (MS2) comprising: (i) at least one organopolysiloxane (A) having at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably, said alkenyl groups are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, more preferably, said alkenyl groups are the vinyl groups and (ii) at least one silicone compound (B) that has at least two and preferably at least three hydrogen atoms attached to the silicone per molecule, (iii) optionally, a cure rate controller (G) that reduces the cure rate curing, (b) feeding into a catalyst feed line, a master batch of catalyst (MC) comprising: (i) at least one hydrosilylation catalyst (C); and (ii) optionally, at least one organopolysiloxane (A) which has at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably said groups alkenyl are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, most preferably, said alkenyl groups are the vinyl groups; (c) feeding into an inhibitor supply line, a batch of inhibitor (Ml) comprising: (i) a cure rate controller (G) that reduces the cure rate; and (ii) optionally, at least one organopolysiloxane (A) which has at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably said groups alkenyl are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, most preferably, said alkenyl groups are the vinyl groups; and (d) optionally, feeding into an additive feed line, an additive master batch (MA), which comprises (i) at least one additive (H) such as a pigment, a dye, clays, a surfactant, hydrogenated castor oil, wollastonite, aluminum trihydrate, magnesium hydroxide, halloysite, huntite hydromagnesite, expandable graphite, zinc borate, mica or a fumed silica; (ii) optionally, at least one organopolysiloxane (A) that has at least two alkenyl groups attached to the silicone per molecule, said alkenyl groups each containing from 2 to 14 carbon atoms, preferably, said alkenyl groups are selected from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl and, most preferably, said alkenyl groups are vinyl groups; (e) directing said liquid silicone base (MS2), said catalyst main batch (MC) and said inhibitor main batch (Ml) and, optionally, said additive main batch (MA) to a stirred tank; and (f) operating said stirred tank, therefore, mixing said liquid silicone base (MS1), said catalyst masterbatch (MC) and said inhibitor masterbatch (Ml) and optionally said additive masterbatch (MA ), preferably using a high flow, low shear mixer and (g) adding the hollow glass beads (D) and, preferably, the hollow borosilicate glass microspheres (D1) to said stirring tank, of preferably, by means of gravity discharge or screw feeder to obtain the addition-curing type organopolysiloxane (X) composition.

[084] All components of the preferred embodiments of preparing the organopolysiloxane composition (X) of the addition-curing type were described above previously.

[085] According to a preferred embodiment, the secondary battery block, according to the present invention, is located inside a vehicle.

[086] It is understood that the term "vehicle", as used herein, is inclusive of motor vehicles, in general, such as passenger cars including sport utility vehicles (SUV), buses, trucks, various commercial vehicles, vessels including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles, and other vehicles powered by alternative fuels (e.g., fuels derived from other resources other than oil). As stated herein, a hybrid vehicle is a vehicle that has two or more power sources, for example, gasoline-powered and electric vehicles.

[087] In another preferred embodiment, the secondary battery block according to the present invention is located in an automotive motor vehicle.

[088] In another embodiment, the secondary battery block according to the present invention is located in a fully electric vehicle (EV), in a plug-in hybrid vehicle (PHEV), in a hybrid vehicle (HEV).

[089] In another embodiment, the secondary battery block according to the present invention is located in: an aircraft, a boat, a ship, a train or wall unit.

BRIEF DESCRIPTION OF THE FIGURES

[090] Figure 1 provides a top view of a secondary battery block without a cover with batteries inside the block.

[091] Figure 2 provides a perspective view of a secondary battery block with batteries within the block.

[092] Figure 3 provides a top view of batteries in a secondary battery block with synthetic silicone rubber foam, in accordance with the present invention, which fills the space between the batteries and the remaining space in the block.

[093] Figure 4 provides a top view of the battery cells in a secondary battery pack covered with the synthetic silicone rubber foam in accordance with the present invention, and with said foam filling the space between the batteries and the space remaining in the block.

[094] Figures 5 and 6 provide a schematic representation of two preferred embodiments of a method for producing an organopolysiloxane composition (X) of the curing type by addition in which the main batch of inhibitor (Ml) and the main batch of catalyst (MC) are fed separately to other components in order to control the cure rate.

[095] Figures (1) and (2) show that battery cells (103) can be very close to each other in a battery module housing (102). In one embodiment of the present invention, a crosslinkable silicone composition according to the present invention and precursor to a lightweight synthetic silicone rubber foam comprising a silicone rubber binder and hollow glass beads are poured into the module housing. (102) after the batteries have been placed and installed (Figure 3, 104) and yields to a synthetic silicone foam when cured (Figure 4, 105).

[096] Figure 5 shows a method for producing an organopolysiloxane composition (X) of the addition cure type, according to an embodiment of the present invention, in which said liquid silicone base (MS1) is stored in a storage tank (1), said catalyst main batch (MC) is stored in a storage tank (20), said inhibitor main batch (Ml) is stored in a storage tank (50) and said additive main batch (MA) is stored in a storage tank (65) and is fed separately into the respective supply lines (200), (210), (220) and (230), respectively. The storage tank (1) of the liquid silicone base (MS2) is connected to the agitation tank (80) through a feed pump (10), which can be any large displacement pump, and through a flow adjuster. optional feed rate (15). The catalyst main batch (MC) storage tank (20) is connected to the agitation tank (80) via a feed pump (25), which may be any small piston displacement pump, gear pump, micro motion injection pump or other positive displacement pump, and via an optional feed speed adjuster (30). The storage tank (50) of the main batch of inhibitor (Ml) is connected to the agitation tank (80) via a feed pump (55), which may be any small piston displacement pump, gear pump, microinjection pump or other positive displacement pump, and through an optional feed rate adjuster (60). The additive main batch (MA) storage tank (65) is connected to the agitation tank (80) via a feed pump (70), which may be any small piston displacement pump, gear pump, microinjection pump or other positive displacement pump and feed rate regulator (75). When said liquid silicone base (MS2), said catalyst main batch (MC) and said inhibitor main batch (Ml) and, optionally, said additive main batch (MA) are directed to said stirring tank (80); The resulting mixture is preferably mixed using a high flow, low shear mixer to produce the addition cure type organopolysiloxane (X) composition according to the present invention. Said composition, at present, is available to be introduced into said battery module housing (102) by means of (100) which may be by means of an injection apparatus or by means of a pump to enable free flow to fill the battery module housing clearances (102) and cure the crosslinking path.

[097] Figure 6 shows a method for producing an organopolysiloxane composition (X) of the addition cure type, according to another embodiment of the present invention, in which said liquid silicone base (MS2) is stored in a storage tank (1), said catalyst main batch (MC) is stored in a storage tank (20), said inhibitor main batch (Ml) is stored in a storage tank (50) and said additive main batch (MA) is stored in a storage tank (65) and is fed separately into the respective supply lines (200), (210), (220) and (230), respectively. The storage tank (1) of the liquid silicone base (MS2) is connected to the agitation tank (80) through a feed pump (10), which can be any large displacement pump, and through a flow adjuster. optional feed rate (15). The catalyst main batch (MC) storage tank (20) is connected to the agitation tank (80) via a feed pump (25), which may be any small piston displacement pump, gear pump, micro motion injection pump or other positive displacement pump, and via an optional feed speed adjuster (30). The storage tank (50) of the main batch of inhibitor (Ml) is connected to the agitation tank (80) via a feed pump (55), which may be any small piston displacement pump, gear pump, microinjection pump or other positive displacement pump, and through an optional feed rate adjuster (60). The additive main batch (MA) storage tank (65) is connected to the agitation tank (80) via a feed pump (70), which may be any small piston displacement pump, gear pump, microinjection pump or other positive displacement pump and feed rate regulator (75). When said liquid silicone base (MS2), said catalyst main batch (MC) and said inhibitor main batch (Ml) and, optionally, said additive main batch (MA) are directed to said stirring tank (80); the resulting mixture is preferably mixed using a high flow, low shear mixer. To said resulting mixture, the hollow glass beads (D) and, preferably, the hollow borosilicate glass microspheres (D1) which are stored in the storage tank (90), which is preferably a hopper, are transferred to said stirring tank (80) directly by gravity discharge or through the screw feeder (95) for the production of additional organopolysiloxane composition (X) of the curing type, according to the present invention. Said composition, at present, is available to be introduced into said battery module housing (102) by means of (100) which may be by means of an injection apparatus or by means of a pump to enable free flow to fill the battery module housing clearances (102) and cure the crosslinking path.

[098] Other advantages provided by the present invention will become evident from the following illustrative Examples.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION (I) DEFINITION OF COMPONENTS

[099] - Organopolysiloxane (A1) = polydimethylsiloxane with terminal units of dimethylvinylsilyl with a viscosity at 25° C ranging from 80 mPa.s to 120 mPa.s; - Organopolysiloxane (A2) = polydimethylsiloxane with terminal units of dimethylvinylsilyl with a viscosity at 25° C ranging from 500 mPa.s to 650 mPa.s; - Organopolysiloxane (B1) (CE) as chain extender = polydimethylsiloxane with terminal units of dimethylsilylhydride with a viscosity at 25° C ranging from 7 mPa.s to 10 mPa.s and Formula: M'DXM'.

[0100] Where: - D is a siloxy unit of Formula (CH3)2SiO2/2; - M' is a siloxy unit of formula (CH3)2(H)SiO1/2; - ex is an integer that varies from 8 to 11; - Organopolysiloxane (B2) (XL) as cross-linking agent, with a viscosity at 25° C ranging from 18 mPa.s to 26 mPa.s, more than 10 SiH reactive groups are present (on average from 16 to 18 SiH reactive groups): poly(methylhydrogen) (dimethyl)siloxane with SiH groups in the chains and terminal chains (α/w), - Hollow glass beads (D1): 3M™ Glass Bubbles Series S15, sold by 3M Company , Particle Size (50%) microns per volume = 55 microns, Isostatic Crush Resistance: Test Pressure 300 psi (2.07 MPa), True Density (g/cc) = 0.15, - Hollow Glass Beads (D2): 3M™ K25 Series Glass Bubbles, marketed by 3M Company, Particle Size (50%) microns by volume = 55 microns, Isostatic Crush Test Pressure 750 psi, True Density (g/cc) = 0.25, - Hollow Glass Beads (D3): 3M™ iM16K Glass Bubbles, marketed by 3M Company, (Particle Size (50%) microns by volume = 20 microns, Isostatic Crush Resistance Test Pressure 16,000 psi, True Density (g/cc) = 0.46, - Hollow glass beads (D4): 3M™ K1 Glass Bubbles, marketed by 3M Company, (Particle size (50%) microns per volume = 65 microns , Isostatic Crush Resistance Test Pressure 250 psi, True Density (g/cc) = 0.125, - Cure Rate Controller (G1): 1, 3,5,7-tetramethyl-1,3,5,7- tetravinyl-cyclotetrasiloxane, - Cure rate controller (G2): 1-ethynyl-1-cyclohexanol (ECH), - Cure rate controller (G3)-MB: 90% by weight Organopolysiloxane (A1) and 10 % by weight of cure rate controller (G2), - Catalyst (C): 10% platinum as Karstedt catalyst in 350 cS dimethylvinyldimer, sold by Johnson Matthey Company, - Catalyst (C-MB): 98% by weight of Organopolysiloxane (A1) and 2% by weight of Catalyst (C), - Reactive diluent (E) = 1-tetradecene. (II) EXAMPLES PART I TABLE 1 FORMULATION (1) OF THE PRESENT INVENTION OF TWO PARTS PRECURSOR OF A SILICONE RUBBER SYNTACTIC FOAM TABLE 2 FORMULATION (2) OF THE PRESENT TWO-PART INVENTION PRECURSOR OF A SILICONE RUBBER SYNTATIC FOAM - For the two-part formulation (1), parts A and B were combined as 6:1 in w/w (weight ratio) for preparing compositions (I) before curing; - For the two-part formulation (2), parts A and B were combined as 1:1 in w/w (weight ratio) for preparing compositions (II) before curing.

[0101] Each formulation (1) and (2) were poured before curing into the internal part of a battery module housing (102), in which a plurality of battery cells (103) were arranged, which were electrically conductive connected to each other. Curing occurred at room temperature to produce a synthetic silicone rubber foam comprising a silicone rubber binder and hollow glass beads that completely filled the open space of said battery module housing (102) and fully covered said battery cells (103). (III) EXAMPLES PART II

[0102] The following formulations were prepared: TABLE 3 FORMULATION (3) – COMPARATIVE TABLE 4 FORMULATION (4) – INVENTION TABLE 5 FORMULATION 5 – INVENTION TABLE 6 FORMULATION 6 – INVENTION TABLE 7 FORMULATION 7 – INVENTION TABLE 8 FORMULATIONS 8, 9 AND 10 (INVENTION) WITH (H AS SIH) / MOLAR RATIO OF VlNILA = 0.72 TABLE 9 FORMULATIONS 11, 12 AND 13 (INVENTION) - WITH (H AS SIH) / MOLAR RATIO OF VlNILE = 0.72 TABLE 10 FORMULATIONS 14, 15 AND 16 (INVENTION) - WITH (H AS SIH) / MOLAR PROPORTION OF VINYL = 0.72

[0103] Formulation (3) was mixed in a mixture ratio of 1:1 by weight and cured at room temperature (25° C) overnight for 16 hours to produce a cured silicone elastomer (syntactic silicone rubber foam). silicone).

[0104] Formulations (4) to (16) were mixed in a mixture ratio of 1:1 by weight and cured at room temperature (25° C) overnight for 16 hours to produce the synthetic rubber foams. silicone, according to the present invention.

[0105] Formulation (17) (comparative) was prepared by mixing, in a mixing ratio of 1:1 by weight, the two-part component sold by Elkem Silicones under the reference RTV-3040 (two-part component, polyaddition curing) and cured at room temperature (25° C) overnight for 16 hours to produce a cured silicone elastomer.

[0106] Formulation (18) (comparative) was prepared by mixing in a mixing ratio of 1:1 by weight of the two-part component sold by Elkem Silicones under the reference BluesilTMESA 7242 (which is a liquid curing silicone elastomer). two-component heat that crosslinks through a polyaddition) and was cured at room temperature (25° C) overnight for 16 hours to produce a cured silicone elastomer.

[0107] Formulation (19) was prepared based on Sakrete Concrete. The concrete used was from SAKRETE of North America, LLC located in Charlotte, North Carolina. The product is called SAKRETE High Strength Concrete Mix. The concrete sample was produced using the following process: - Pour 1 kg of the high strength concrete mixture into a container forming an indentation in the center of the concrete, - Sufficient water was added to obtain a viable mixture (70g), - The material was poured into a 51 mm diameter mold, - The material was worked into voids and then flattened with a metal spatula, - The material was allowed to harden until a thumb impression could not be left on the material, - A metal trowel was used to obtain a desired finish and leveling as the material was hardening, - The material was kept moist and under plastic for 7 days while constantly being kept at room temperature. TABLE 11 PHYSICAL PROPERTIES OF CURED PRODUCTS (SYNTATIC SILICONE FOAM) TABLE 12 THERMAL CONDUCTIVITY MEASUREMENT OF CURED SAMPLES

[0108] Thermal conductivity was measured using a 2500S Thermtest Hot Disk TPS (Transient Plane Source) Tester and is listed in Table 12. Table 12 shows that the example formulations, according to the present invention (Formulations of (4) a (16)) have lower thermal conductivity than comparative materials: formulation (17) (RTV 3040), formulation (18) (ESA 7242), formulation (19) (Sakrete Concrete) and formulation (3) (ESA 7200).

[0109] It is an advantage to have a thermally insulating material. If a battery or several batteries in the pack overheat, an insulating material around the battery will help prevent excessive heat from reaching the passenger area of an electric vehicle (car, truck, boat, train, plane, and the like).

[0110] Another advantage of the cured formulations (4) to (16), according to the present invention, is that they can absorb vibration. Resilience is related to vibration. The more resilient a material is, the more vibration is translated through the material. Using a Shore® model SRI Resiliometer, commonly referred to as a Bayshore Resiliometer, to quickly and accurately measure the "Rubber Property - Vertical Rebound Resilience" as described in ASTM D2632. The resilience of the example in accordance with the present invention and the comparative materials were measured and the results are described in Table 13. All formulations were mixed in a 1:1 mix ratio by weight and cured at room temperature during drying. night for 16 hours. A weight falls onto the test sample and rebounds above the test sample when it reaches the sample. When the weight reaches the sample and bounces high, it is more resistant. When the weight does not bounce as high, the material is less resilient. TABLE 13 RESILIENCE MEASUREMENT OF SOME OF THE CURED PRODUCTS

[0111] Table 13 shows that the comparative formulation has greater resilience and will translate vibration through the materials more easily while the cured formulations, according to the present invention, have lower resilience.

[0112] "Tan delta" is a shortened form of the terms "Tangent of Delta". Tan delta quantifies the way in which a material absorbs and disperses energy. It expresses the out-of-phase time relationship between an impact force and the resulting force that is transmitted to the supporting body. The tan delta is also known as the Loss Factor due to this loss of energy from the impact force through conversion and dispersion to a safer form of energy. Therefore, tan delta is ultimately an indication of the effectiveness of a material's damping capabilities. The higher the tan delta, the higher the damping coefficient, the more efficient the material will be in effectively absorbing and dispersing energy. The tan delta is equal to the ratio of the loss modulus to the storage modulus or tan(delta) = G"/G".

[0113] G"= loss modulus and G'= storage modulus. Higher values correlate with a material that dampens more effectively than those with lower values.

[0114] Table 14 below shows that examples of the materials of the present invention dampen better than the comparative material. TABLE 14 TAN DELTA MEASUREMENTS OF SOME OF THE CURED PRODUCTS

[0115] Tan delta measurements were performed using an Anton Parr MCR 302 at 25° C. G” and G’ were measured as the material cured. The tan delta was calculated from these two values. The cured sample of the synthetic silicone foams prepared from the addition-cured type organopolysiloxane compositions, according to a preferred embodiment of the present invention, can advantageously be used as a cushioning material and fulfill the desired object within from the electric vehicle field who is eagerly looking for a damping control strategy to minimize powertrain oscillations.

[0116] The flame resistance of 3 cured materials, according to the present invention, was measured and is cited in Table 15. All formulations tested were self-extinguishing. TABLE 15 FLAME RESISTANCE RESULTS OF SOME CURED MATERIAL, ACCORDING TO THE PRESENT INVENTION (IV) EXAMPLES PART III TABLE 16 FORMULATION (20) – INVENTION

[0117] The formulation (20) (addition curing type organopolysiloxane composition) used for the preparation of a syntactic silicone rubber foam and compared with the syntactic silicone rubber foam prepared from the formulation (21) ( product cured with tin-catalyzed condensation). The ingredients are described respectively in Tables 16 and 17. TABLE 17 FORMULATION 21 - CONDENSATION CURED SILICONE RUBBER SYNTATIC FOAM

[0118] Battery blocks can have long distances that the insulation material (the liquid precursor, before cross-linking, of the synthetic silicone foam, according to the present invention,) needs to travel from the external air to fill the block. The comparative formulation (21) described above requires air humidity to cure quickly. The formulation was mixed at 25°C and allowed to sit at that temperature until it had cured sufficiently so that an initial durometer reading could be taken. The comparative condensation curable formulation (21) was also produced and allowed to rest in a similar manner as the formulation of the invention (20). Both samples were prepared and then allowed to rest after being poured onto an aluminum plate that had material 1 cm thick and 5.2 cm in diameter. A 5.2 cm face of the material was exposed to the air and no air (or air moisture) could move through the bottom or sides of the aluminum plate. This configuration is representative of what might happen in a typical drum block. Air with moisture may be present on one face of the encapsulation material for a battery, while much of the material is below the surface, depending on the moisture to migrate through the bulk of the encapsulation material.

[0119] In relation to the formulation of the invention (20), it took about 12 minutes to measure the hardness of the material in a Shore A interval. The hardness was about 15 Shore A. At one hour the hardness was 50 Shore A. Similar formulations achieved about 52 to 54 Shore A in the previous Examples. When checking the Condensation Curable Formulation (21), it took up to 1 hour and 42 minutes before a durometer measurement could be taken, and the value was 11.7 Shore A. When pressing the sample manually and then pulling a second sample (plate equivalent) aside, it was discovered that the lower half of the sample was still liquid. The test sample was only cured in one layer on top. This indicates that the condensation-cured material requires a significantly longer time to cure in a representative test setup than the formulation of the invention. It would be advantageous if the material cured more quickly to speed up production times when encapsulating batteries.

[0120] Another curing system, a peroxide curing system was tested. However, peroxides typically require heat to cure, which is a disadvantage. As shown above, the formulation of the invention (11) can be cured very quickly if desired, and no heat or energy is required for heating.

[0121] As below, a comparative formulation of peroxide (22) is described in Table 18. TABLE 18 FORMULATION 22 - COMPARATIVE FORMULATION CURED WITH PEROXIDE (22) WITH MIXING PROPORTION OF 1:1 BY WEIGHT OF PARTS A and B - DBPH = Varox®= consists of more than 90% by weight of 2,5-dimethyl-2,5-di (t-butylperoxy)hexane and is marketed by RT Vanderbilt - Organopolysiloxane (A3): poly(methylvinyl)(dimethyl )siloxane with terminal units of dimethylvinylsilyl with a viscosity at 25° C = 390 mPa.s.

[0122] Class and Grasso suggest curing silicones with a DBPH catalyst at 177° C for one hour (reference: Class, J.B.; Grasso, R.P., Efficiency of Peroxides for Curing Silicone Elastomers, Rubber Chemistry and Technology, September 1993 , Volume 66, No 4, pages 605-622). We follow this advice when curing our formulation as well. No post-curing was performed.

[0123] The same type of container was used to hold the material during curing (aluminum plate, one face open, 5.2 cm in diameter and 1 cm thick of the poured material). We kept an open face, since when encapsulating, it is common to pour it into a container and cure the material open to air. Putting a lid on the container to keep air out would be extra cost for the lid and extra time to secure the lid in a production environment. When cured for one hour at 177°C, the sample was removed from the oven. The surface facing the air has not been cured. This is not an uncommon phenomenon, but it was tested in these formulations to observe whether a formulation similar to the formulation of the invention would present the controversial points observed in other peroxide-cured silicone formulations. Once the uncured layer was removed, the comparative cured peroxide elastomer formulation (22) had a hardness of 20 Shore A.

[0124] Three ways to eliminate lack of curing at an interface containing oxygen are normally used in industry: - Removal of oxygen from the curing zone through the use of inert gas, through the use of waxes that migrate to the surface and form a barrier, or through the use of films that are in direct contact with the coating, - Increase the concentration of free radicals, increasing the level of peroxide, - Use chemicals that react with peroxy radicals.

[0125] All of these solutions to the lack of cure can work. However, heating would still be required for the sample and implementation of the solutions would require much more complicated formulations that alter the cured elastomer (i.e., waxes, chemicals that react with peroxy radicals, and the like) and more expensive formulations. (i.e. more free from peroxy radicals). (IV) EXAMPLES PART III

[0126] Formulations (23) to (27) were prepared according to Table 19. Thermal conductivity (W/mK) and specific gravity (g/cm3) were measured. Thermal conductivity was measured using a 2500S Thermtest Hot Disk TPS Tester (Transient Plane Source). TABLE 19 FORMULATIONS 23, 24, 25, 26 AND 27

Claims (7)

1. SECONDARY BATTERY BLOCK, comprising: (a) at least one battery module housing (102) in which a plurality of battery cells (103) are arranged that are electrically connected together, characterized by: (b ) a silicone rubber syntactic foam comprising a silicone rubber binder and hollow glass beads, and the silicone rubber syntactic foam partially or completely filling the open space of the battery module housing (102) and/or covering the battery cells (103) and/or covering the module housing (102), and (c) optionally, a cover covering the battery module housing (102), wherein said synthetic silicone rubber foam is obtained through of an organopolysiloxane (X) composition of the addition-curing type, and wherein the organopolysiloxane (X) composition of the addition-curing type comprises: (d) 100 parts by weight of an organopolysiloxane (A) which has at least two alkenyl groups attached to the silicone atoms in a molecule, (e) 0.1 to 50 parts by weight of an organohydrogenpolysiloxane (B) which has at least two, preferably at least three atoms of hydrogen attached to the silicone atoms in a molecule, and (f) a catalytic amount of an addition reaction catalyst (C). 2. SECONDARY BATTERY BLOCK according to claim 1, further comprising a refrigerant inlet distribution tube pipe, a refrigerant outlet distribution tube pipe and a plurality of heat exchange tubes as members of heat dissipation and extending between the inlet and outlet distribution tube pipes, said heat exchange tubes are arranged at one or more interfaces between the battery cells (103) and have a refrigerant passing through for heat exchange generated from the battery cells (103) during charging and discharging the battery cells (103). 3. SECONDARY BATTERY BLOCK, according to claim 1, characterized by being located inside a vehicle. 4. SECONDARY BATTERY BLOCK, according to claim 1, characterized by being located in an automotive motor vehicle. 5. SECONDARY BATTERY BLOCK, according to claim 1, characterized by being located in a fully electric vehicle (EV), in a plug-in hybrid vehicle (PHEV), in a hybrid vehicle (HEV). 6. SECONDARY BATTERY BLOCK, according to claim 1, characterized by being located in: an aircraft, a boat, a ship, a train or wall unit. 7. PROCESS FOR PREPARING A SECONDARY BATTERY BLOCK, as defined in any one of claims 1 to 6, characterized in that it comprises the steps: (a) preparing at least one battery module housing (102) in which a plurality of battery cells (103) are arranged which are electrically connected to each other, (b) introducing into the battery module housing (102) the organopolysiloxane composition (X) of the addition-curing type, (c) completely or partially filling the battery module housing (102), and (d) allowing curing to form a synthetic silicone rubber foam comprising a silicone rubber binder and hollow glass beads, and optionally (e) covering the battery module housing (102) with a cover.