Battery module, method of manufacturing the same and curable resin composition included in battery module

Abstract

Provided is a battery module, including: a plurality of battery cells; a case for containing the battery cells; and a buffer part disposed between the battery cells in the case, wherein the buffer part includes: a silicone-based resin matrix disposed between the battery cells in the case; hollow microspheres inserted into the silicone-based resin matrix; and an inorganic heat-resistant layer disposed around the hollow microspheres.

Description

[0001] [DESCRIPTION]

[0002] [Invention Title]

[0003] BATTERY MODULE, METHOD OF MANUFACTURING THE SAME AND CURABLE RESIN COMPOSITION INCLUDED IN BATTERY MODULE

[0004] [Technical Field]

[0005] Embodiments relate to a battery module, a method of manufacturing the same and a curable resin composition included in the battery module.

[0006] [Background Art]

[0007] Secondary batteries that can be easily applied according to product groups and have electrical characteristics such as high energy density are universally applied to not only portable devices, but also electric vehicles (EVs) or hybrid vehicles (HEVs) driven by electric driving sources, etc. These secondary batteries are attracting attention as a new energy source for improving eco-friendliness and energy efficiency in that they do not generate any by-products due to the use of energy as well as the primary advantage of being dramatically able to reduce the use of fossil fuels.

[0008] Examples of the types of secondary batteries currently widely used include a lithium-ion battery, a lithium polymer battery, a nickel -cadmium battery, a nickel hydride battery, a nickelzinc battery, and the like. The operating voltage of these unit secondary battery cells, i.e., unit battery cells, is about 2.5 V to 4.5 V. Accordingly, when a higher output voltage is required, a plurality of battery cells are connected in series to constitute a battery pack. In addition, a plurality of battery cells may be connected in parallel to constitute a battery pack according to the charge / discharge capacity required for the battery pack. Accordingly, the number of battery cells included in the battery pack may be set in various ways according to a required output voltage or charge / discharge capacity.

[0009] Meanwhile, when configuring a battery pack by connecting a plurality of battery cells in series / parallel, it is general that a battery module including at least one battery cell is first configured, and other components are added using the battery module. Existing battery modules including battery cells that are composed of cylindrical cells generally include a plurality of cylindrical cells stacked on each other, a bus bar electrically connecting the plural cylindrical cells to each other, and a module case for accommodating various electronic components constituting the bus bar, the cylindrical cells and the battery module.

[0010] However, in the case of the existing battery modules, a predetermined gap between the cells is generated depending on the structural shape of the cylindrical cells, and the flow between the battery cells is frequently made when an external shock occurs, so that there is a risk of damage, etc. to the battery cells.

[0011] Therefore, there is a need for methods for providing a battery module capable of more stably supporting battery cells and of preventing damage to battery cells due to external impact, and providing a battery pack and vehicle including the battery module.

[0012] [Disclosure]

[0013] [Technical Problem]

[0014] Therefore, the present invention has been made in view of the above problems, and it is one object of the present invention to provide a battery module that has an improved production rate and can efficiently protect battery cells; a method of manufacturing the battery module; and a curable resin composition included in the battery module.

[0015] [Technical Solution]

[0016] In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a battery module, including: a plurality of battery cells; a case for containing the battery cells; and a buffer part disposed between the battery cells in the case, wherein the buffer part includes: a silicone-based resin matrix disposed between the battery cells in the case; hollow microspheres inserted into the silicone-based resin matrix; and an inorganic heat-resistant layer disposed around the hollow microspheres.

[0017] In the battery module according to the embodiment, the inorganic heat-resistant layer may include inorganic particles arranged adjacent to an outer surface of the hollow microspheres, wherein a ratio of a particle diameter of the hollow microspheres to a particle diameter of the inorganic particles is 30:1 to 30000:1.

[0018] In the battery module according to the embodiment, the hollow microspheres may include an organic resin, wherein the inorganic particles include an inorganic material selected from the group consisting of calcium carbonate, silica, calcium sulfate, barium sulfate, talc, talc powder, bentonite, kaolin, chalk powder, graphite, gypsum, electrically conductive carbon black, calcium chloride, iron oxide, aluminum oxide, potassium oxide, dolomite, wollastonite, titanium dioxide, silicate, and mica.

[0019] In the battery module according to the embodiment, the battery module may include a surface treatment agent coated around the inorganic particles, and the inorganic particles may be attached to the outer surface of the hollow microspheres.

[0020] In the battery module according to the embodiment, the surface treatment agent may include a fatty acid or a silane-based coupling agent.

[0021] In accordance with another aspect of the present invention, there is provided a curable resin composition for manufacturing a battery module, the curable resin composition includes: a silicone-based polymer; a curing catalyst; and a composite hollow filler, wherein the composite hollow filler includes: hollow microspheres; and an inorganic heat-resistant layer disposed around the hollow microspheres.

[0022] In the curable resin composition for manufacturing a battery module according to the embodiment, the inorganic heat-resistant layer may include inorganic particles arranged adjacent to an outer surface of the hollow microspheres, wherein a ratio of a particle diameter of the hollow microspheres and a particle diameter of the inorganic particles is 30:1 to 30000:1.

[0023] In the curable resin composition for manufacturing a battery module according to the embodiment, the hollow microspheres may include an organic resin, and the inorganic particles may include calcium carbonate, talc or silica.

[0024] In the curable resin composition for manufacturing a battery module according to the embodiment, the silicone-based polymer may include: a first organic polysiloxane including a vinyl group and having a viscosity of 10 mPa·s to 2000 mPa·s; and a third organic polysiloxane including a hydrogen group in a side chain thereof.

[0025] In the curable resin composition for manufacturing a battery module according to the embodiment, an average particle diameter of the hollow microspheres may be 5 μm to 300 μm, and an average particle diameter of the inorganic particles may be 0.02 μm to 0.2 μm.

[0026] In the curable resin composition for manufacturing a battery module according to the embodiment, the silicone-based polymer may further include: a second organic poly siloxane having a viscosity of 10000 mPa·s to 100000 mPa·s; and a fourth organic polysiloxane including a hydrogen group at a terminal thereof.

[0027] In the curable resin composition for manufacturing a battery module according to the embodiment, the composite hollow filler may have a pressure resistance of greater than 85%, wherein the pressure resistance is derived by a measurement method below:

[0028] [Measurement method]

[0029] 1) 7.5 wt% of the composite hollow filler and 92.5 wt% of glycerin are uniformly mixed to prepare a dispersion.

[0030] 2) A pressure of 20 MPa is applied to the dispersion for 30 minutes.

[0031] 3) The pressure resistance is obtained by dividing a volume of the pressed dispersion by an initial volume of the dispersion.

[0032] In accordance with yet another aspect of the present invention, there is provided a method of manufacturing a battery module, the method including: preparing a case for containing a plurality of battery cells thereinside; filling a curable resin composition into the case; and curing the curable resin composition to form a buffer part, wherein the curable resin composition includes: a silicone-based polymer; a curing catalyst; and a composite hollow filler, wherein the composite hollow filler includes: hollow microspheres; and an inorganic heat-resistant layer disposed around the hollow microspheres.

[0033] [Advantageous effects]

[0034] A battery module according to an embodiment includes a buffer part including hollow microspheres and an inorganic heat-resistant layer. In particular, the hollow microspheres can include an organic resin. Accordingly, the hollow microspheres can have high flexibility. In addition, the inorganic heat-resistant layer can be formed around the hollow microspheres.

[0035] Accordingly, the inorganic heat-resistant layer can protect the hollow microspheres from external thermal shock.

[0036] Accordingly, the buffer part is inserted between battery cells, thereby being capable of effectively absorbing physical impact due to the expansion and contraction of the battery cells. In particular, even if the pressure increases due to the expansion of the battery cells, the hollow microspheres cannot be destroyed. Accordingly, the buffer part can have improved durability even under external pressure. Therefore, the battery module according to the embodiment can effectively control the shrinkage and expansion of the battery cells while appropriately maintaining gaps between the battery cells.

[0037] In addition, since the inorganic heat-resistant layer is disposed on the hollow microspheres, the buffer part can effectively protect the hollow microspheres from thermal shock generated from the battery cells. That is, the inorganic heat-resistant layer can prevent the hollow microspheres from being deformed by heat from the battery cells. Therefore, the buffer part can have high heat resistance.

[0038] In addition, the inorganic heat-resistant layer can include a plurality of inorganic particles. That is, the inorganic heat-resistant layer can include inorganic particles that are independent of each other. Accordingly, the inorganic heat-resistant layer can be resistant to irreversible deformation by an external force. That is, even if the inorganic heat-resistant layer is deformed by an external force, the inorganic particles can return to their original positions. Accordingly, the inorganic heat-resistant layer can have improved durability even under external pressure. Therefore, the inorganic heat-resistant layer effectively protect the hollow microspheres.

[0039] Accordingly, the buffer part can effectively protect the battery cells. Therefore, since the battery module according to the embodiment includes the buffer part, it can have improved reliability.

[0040] [Description of Drawings]

[0041] FIG. 1 is a perspective view illustrating a battery module according to an embodiment. FIG. 2 is an exploded perspective view illustrating the battery module according to the embodiment.

[0042] FIG. 3 is a plan view illustrating a top surface of the battery module according to the embodiment.

[0043] FIG. 4 is a sectional view illustrating a cross-section of the battery module according to the embodiment.

[0044] FIG. 5 is a sectional view illustrating an enlarged cross-section of a buffer part.

[0045] FIG. 6 illustrates a battery pack.

[0046] FIG. 7 illustrates a vehicle in which the battery pack is mounted.

[0047] [Best Mode]

[0048] In the description of embodiments, in the case where it is described that each part, surface, layer or substrate is formed "on" or "under" each part, surface, layer or substrate, etc., “on” and “under” include both “directly” on or under another element and “indirectly” formed such that an intervening element is also present. In addition, criteria for “on” and “under” each element will be provided based on the drawings. The size of each component in the drawings may be exaggerated for explanation, and does not mean the size actually applied.

[0049] FIG. 1 is a perspective view illustrating a battery module according to an embodiment. FIG. 2 is an exploded perspective view illustrating the battery module according to the embodiment. FIG. 3 is a plan view illustrating a top surface of the battery module according to the embodiment. FIG. 4 is a sectional view illustrating a cross-section of the battery module according to the embodiment. FIG. 5 is a sectional view illustrating an enlarged cross-section of a buffer part.

[0050] Referring to FIGS. 1 to 5, the battery module according to the embodiment may include a battery cells 100, a module case 200, bus bars 300, a circuit board assembly 400, a support plate 500 and a buffer part 600.

[0051] The battery cells 100 are secondary batteries and may be pouch-type secondary batteries, prismatic secondary batteries, or cylindrical secondary batteries. The battery cells 100 may be cylindrical secondary batteries, i.e., cylindrical battery cells.

[0052] A plurality of battery cells 100 may be provided. The plural battery cells 100 may be accommodated in the module case 200 to be described below. The plural battery cells 100 may be laminated in the module case 200 to be described below along a horizontal direction of the module case 200.

[0053] The module case 200 may accommodate the battery cells 100 and various electronic components constituting a battery module 10. For this, the module case 200 may be provided with a predetermined accommodation space.

[0054] The module case 200 may include a case body 210 and a case cover 250.

[0055] The case body 210 includes an accommodation space therein, and may accommodate the plural battery cells 100, various electronic components constituting the battery module 10, and the like therein.

[0056] A plurality of cell insertion holes may be formed on an inner bottom surface of the case body 210. The plural cell insertion holes may be provided to correspond to the number of the plural battery cells 100.

[0057] Lower parts of the plural battery cells 100 may be inserted into the plural cell insertion holes. Accordingly, the plural battery cells 100 may be more stably accommodated in the module case 210.

[0058] In addition, an adhesive, etc. may be applied to the inside of the plural cell insertion holes. In this case, the plural battery cells 100 may be more stably fixed.

[0059] The case cover 250 may form an upper part of the module case 200, and may be coupled to the case body 210 to package the battery cells 100 inside the module case 200.

[0060] The bus bars 300 may be provided in the upper part of the plural battery cells 100 and may electrically connect the plural battery cells 100 to each other. A plurality of bus bars 300 may be provided, and the plural bus bars 300 may be disposed to be spaced apart from each other by a predetermined distance.

[0061] The circuit board assembly 400 may be electrically connected to the plural bus bars 300. The circuit board assembly 400 may sense the voltage, temperature, etc. of the battery cells 100. In addition, the circuit board assembly 400 may include a terminal for connecting to an external power source, etc., and may include a control board for managing the battery cells 100.

[0062] The support plate 500 may be disposed between the plural battery cells 100 and the plural bus bars 300 and may support the plural bus bars 300.

[0063] Referring to FIG. 4, the buffer part 600 serves to prevent the flow of the plural battery cells 100 and may be filled in spaces between the plural battery cells 100 in the lower part of the support plate 500.

[0064] The buffer part 600 may include a composite material capable of filling a predetermined space. The buffer part 600 may include a silicone-based curable resin composition. The plural battery cells 100 may be stably accommodated inside the module case 230 due to the buffer part

[0065] When manufacturing the battery module 10, the buffer part 600 may be filled inside the module case 200 through a dispenser unit accommodating the buffer part 600.

[0066] The buffer part 600 may be filled inside the case 210. The buffer part 600 may be entirely filled inside the case 210. The buffer part 600 may be filled between the battery cells 100. In addition, the buffer part 600 may be filled between the battery cells 100 and the case 210. The buffer part 600 may be arranged between the battery cells 100. The buffer part 600 may be in close contact with the battery cells 100. In addition, the buffer part 600 may be arranged between the battery cells 100 and the case 210. The buffer part 600 may be in close contact with an inner surface of the case 210.

[0067] Referring to FIG. 5, the buffer part 600 may include a silicone resin matrix 610 and a composite hollow filler 620.

[0068] The silicone resin matrix 610 may be filled inside the case 210. The silicone resin matrix 610 may be entirely filled inside the case 210. The silicone resin matrix 610 may be filled between the battery cells 100. In addition, the silicone resin matrix 610 may be filled between the battery cells 100 and the case 210. The silicone resin matrix 610 may be arranged between the battery cells 100. The silicone resin matrix 610 may be in close contact with the battery cells 100. In addition, the silicone resin matrix 610 may be arranged between the battery cells 100 and the case 210. The silicone resin matrix 610 may be in close contact with the inner surface of the case 210.

[0069] The silicone resin matrix 610 may be formed by curing a silicone-based curable resin composition.

[0070] The composite hollow filler 620 is disposed inside the silicone resin matrix 610. The composite hollow filler 620 may be inserted into the silicone resin matrix 610. The composite hollow filler 620 may be uniformly dispersed in the silicone resin matrix 610.

[0071] The composite hollow filler 620 may include hollow microspheres 621 and an inorganic heat-resistant layer 622.

[0072] The hollow microspheres 621 may be disposed in the silicone resin matrix 610. The hollow microspheres 621 may be inserted into the silicone resin matrix 610. The hollow microspheres 621 may be uniformly dispersed in the silicone resin matrix 610. Each of the hollow microspheres 621 includes a hollow 623 thereinside, and may have a spherical shape. In addition, the hollow microsphere 621 may include a shell surrounding the hollow 623.

[0073] The inorganic heat-resistant layer 622 is disposed around the hollow microsphere 621. The inorganic heat-resistant layer 622 may be disposed adjacent to an outer surface of the hollow microsphere 621. The inorganic heat-resistant layer 622 may be attached to the outer surface of the hollow microsphere 621.

[0074] The inorganic heat-resistant layer 622 may surround the hollow microspheres 621. The inorganic heat-resistant layer 622 may be coated on the outer surface of the hollow microsphere 621. The inorganic heat-resistant layer 622 may cover a part or all of the outer surface of the hollow microsphere 621.

[0075] In addition, the inorganic heat-resistant layer 622 may be disposed in the silicone resin matrix 610. The inorganic heat-resistant layer 622 may be inserted into the silicone resin matrix 610. The inorganic heat-resistant layer 622 may be uniformly dispersed in the silicone resin matrix 610.

[0076] As such, in this embodiment, the battery cells 100 may be more stably supported through the buffer part 600 and the flow of the battery cells 100 from external shocks may be more effectively prevented. Accordingly, in the present embodiment, the risk of damage to the battery cells 100 due to an external shock or the like may be significantly reduced.

[0077] To manufacture the buffer part, first, a silicone-based curable resin composition is prepared.

[0078] The silicone-based curable resin composition may include a first curable resin composition and a second curable resin composition.

[0079] The silicone-based curable resin composition includes a first organic polysiloxane. The first organic polysiloxane may be included in the first curable resin composition and / or the second curable resin composition.

[0080] The first curable resin composition may include the first organic polysiloxane.

[0081] The first organic polysiloxane may be represented by the following average composition formula (1):

[0082] R¹ₐSiO_b (1) In Compositional Formula (1), R1may represent one or more groups selected from the group consisting of a hydrogen atom, a hydroxy group, or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and a may be about 1.8 to about 2.2. a+b may be about 3.5 to about 8.

[0083] More particularly, a+b may be 4.

[0084] In Compositional Formula (1), the saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms represented by R1may be, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a 2-phenylethyl group or a 2-methyl-2-phenylethyl group; a halogenated hydrocarbon group such as a 3,3,3-trifluoropropyl group, a 2-(perfluorobutyl)ethyl group, a 2-(perfluorooctyl)ethyl group or a p-chlorophenyl group; or the like.

[0085] The first organic polysiloxane may have a weight average molecular weight (Mw) of about 100 g / mol to about 10000 g / mol. The first organic poly siloxane may have a weight average molecular weight of about 500 g / mol to about 7000 g / mol. The first organic polysiloxane may have a weight average molecular weight of about 700 g / mol to about 5000 g / mol. The first organic poly siloxane may have a weight average molecular weight of about 1000 to about 3000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0086] The first organic polysiloxane may have a kinematic viscosity of 10 mPa·s to 2000 mPa·s at 25° C. In the first organic polysiloxane, a kinematic viscosity at 25° C may be about 30 mPa·s to about 1000 mPa·s. The kinematic viscosity of the first organic polysiloxane may be a value at 25°C measured with an Ostwald viscometer.

[0087] Since the first organic polysiloxane has the weight average molecular weight and kinematic viscosity described above, the buffer part may have an appropriate bonding strength, an appropriate curing rate and an appropriate elasticity. In particular, since the first organic polysiloxane has the weight average molecular weight and kinematic viscosity described above, it may be easily injected between the secondary battery cells when forming the buffer part.

[0088] The first organic polysiloxane includes an alkenyl group bonded to a silicon atom, and at least two alkenyl groups may be included in one molecule of the first organic poly siloxane. 2 to 10 alkenyl groups may be included in one molecule of the first organic poly siloxane. 2 to 5 alkenyl groups may be included in one molecule of the first organic poly siloxane. 2 alkenyl groups may be included in one molecule of the first organic poly siloxane.

[0089] The first organic polysiloxane may be represented by the following average composition formula (2):

[0090] R¹ₐR²꜀SiOb (2)

[0091] In Compositional Formula (2), R1may be a hydrogen atom, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R2may be an alkenyl group. In Compositional Formula (2), a+c may be about 1.8 to about 2.2, and a+b+c may be about 3.5 to about 8. In Compositional Formula (2), a+b+c may be about 4. In Compositional Formula (2), a may be about 1.8 to about 2.2. In addition, c may be 0.0001 to 0.1.

[0092] The first organic poly siloxane may be represented by the following Chemical Formula (3).

[0093] [Chemical Formula 3]

[0094]

[0095] where R1may be a hydrogen atom, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R2may be an alkenyl group. In addition, in Chemical Formula 3, n may be 1 to 1500, and m may be 0 to 20. In Chemical Formula 3, n may be 10 to 1000, and m may be 0 to 20.

[0096] The first organic poly siloxane may be represented by the following Chemical Formula (4):

[0097] [Chemical Formula 4]

[0098]

[0099] where n may be 1 to 1500. n may be 10 to 1000.

[0100] The first organic polysiloxane may have a weight average molecular weight (Mw) of about 100 g / mol to about 10000 g / mol. The first organic poly siloxane may have a weight average molecular weight of about 500 g / mol to about 7000 g / mol. The first organic polysiloxane may have a weight average molecular weight of about 700 g / mol to about 5000 g / mol. The first organic poly siloxane may have a weight average molecular weight of about 1000 to about 3000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0101] In the first organic polysiloxane, a kinematic viscosity at 23°C may be 10 mPa·s to 2000 mPa·s. In the first organic polysiloxane, a kinematic viscosity at 23°C may be about 30 mPa·s to about 1000 mPa·s. In the first organic polysiloxane, a kinematic viscosity at 23°C may be about 100 mPa·s to about 700 mPa·s. The kinematic viscosity of the first organic polysiloxane may be a value at 23°C measured with an Ostwald viscometer.

[0102] The first organic polysiloxane may be included in a content of about 20 wt% to about 50 wt% in the first curable resin composition based on a total weight of the first curable resin composition. The first organic polysiloxane may be included in a content of about 25 wt% to about 45 wt% in the first curable resin composition based on a total weight of the first curable resin composition. The first organic poly siloxane may be included in a content of about 30 wt% to about 40 wt% in the first curable resin composition based on a total weight of the first curable resin composition.

[0103] The silicone-based curable resin composition may include a second organic polysiloxane. The second organic polysiloxane may be included in the first curable resin composition and / or the second curable resin composition.

[0104] The first curable resin composition may further include the second organic polysiloxane. The second organic polysiloxane may be a high-viscosity organic polysiloxane. The second organic polysiloxane may be represented by Compositional Formula (1), Compositional Formula (2), Chemical Formula 3 or Chemical Formula 4 described above. The second organic polysiloxane may have a viscosity of about 10000 mPa·s to 100000 mPa·s. The second organic polysiloxane may have a viscosity of about 20000 mPa·s to 70000 mPa·s.

[0105] The second organic polysiloxane may be included in a content of about 2 parts by weight to about 10 parts by weight in the first curable resin composition based on 100 parts by weight of the first organic poly siloxane. The second organic poly siloxane may be included in a content of about 3 parts by weight to about 8 parts by weight in the first curable resin composition based on 100 parts by weight of the first organic poly siloxane. The second organic polysiloxane may be included in a content of about 4 parts by weight to about 7 parts by weight in the first curable resin composition based on 100 parts by weight of the first organic polysiloxane.

[0106] Since the silicone-based curable resin composition contains the second organic polysiloxane in the content range, it may have an appropriate viscosity and an appropriate gel time. In particular, the silicone-based curable resin composition contains the second organic polysiloxane in the content range, it may have a high viscosity increase in the early stage of curing.

[0107] The silicone-based curable resin composition may include a chain extender. The chain extender may be included in the first curable resin composition and / or the second curable resin composition.

[0108] The first curable resin composition may further include the chain extender.

[0109] The chain extender may include a third organic polysiloxane containing a hydrogen group bonded to a silicon atom. The number of hydrogen groups per molecule of the third organic poly siloxane may be 1 to 10. The number of hydrogen groups per molecular of the third organic poly siloxane may be 2 to 10. The number of hydrogen groups per molecule of the third organic poly siloxane may be 2 to 5. The number of hydrogen groups per molecular of the third organic polysiloxane may be 2.

[0110] The third organic polysiloxane may be represented by Chemical Formula 5 below. [Chemical Formula 5]

[0111]

[0112] where R1may be a hydrogen atom, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R3may be a hydrogen atom. In addition, in Chemical Formula 5, n may be 1 to 1500, and m may be 0 to 20. In Chemical Formula 5, n may be 10 to 1000, and m may be 0 to 20. In Chemical Formula 5, n may be 1 to 1500, and m may be 0.

[0113] The third organic polysiloxane may be represented by Chemical Formula 6 below: [Chemical Formula 6]

[0114]

[0115] The third organic polysiloxane may have a viscosity of about 20 mPa·s to about 300 mPa·s at about 23°C. The third organic polysiloxane may have a viscosity of about 30 mPa·s to about 200 mPa·s at about 23 °C. The third organic polysiloxane may have a viscosity of about 40 mPa·s to about 150 mPa·s at about 23°C.

[0116] The third organic polysiloxane may be included in the first curable resin composition in a content of about 50 parts by weight to about 300 parts by weight based on 100 parts by weight of the first organic poly siloxane. The third organic poly siloxane may be included in the first curable resin composition in a content of about 70 parts by weight to about 250 parts by weight based on 100 parts by weight of the first organic poly siloxane. The third organic poly siloxane may be included in the first curable resin composition in a content of about 80 parts by weight to about 200 parts by weight based on 100 parts by weight of the first organic poly siloxane.

[0117] The silicone-based curable resin composition may include a crosslinking agent. The crosslinking agent may be included in the first curable resin composition and / or the second curable resin composition.

[0118] The first curable resin composition may further include the crosslinking agent. The crosslinking agent may include a fourth organic polysiloxane. The fourth organic poly siloxane may be represented by Chemical Formula 7 below: [Chemical Formula 7]

[0119]

[0120] In Chemical Formula 7, R1may be a hydrogen atom, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and R3may be a hydrogen atom. In addition, in Chemical Formula 7, n may be 1 to 1500, and m may be 1 to 500. In Chemical Formula 7, n may be 10 to 1000, and m may be 1 to 100.

[0121] The fourth organic polysiloxane may be represented by Chemical Formula 8 below: [Chemical Formula 8]

[0122]

[0123] In Chemical Formula 8, n may be 1 to 1500, and m may be 1 to 500. In Chemical Formula 8, n may be 10 to 1000, and m may be 1 to 100.

[0124] The fourth organic polysiloxane may have a viscosity of about 10 mPa·s to about 1000 mPa·s at about 23°C. The fourth organic polysiloxane may have a viscosity of about 50 mPa·s to about 500 mPa·s at about 23°C. The fourth organic polysiloxane may have a viscosity of about 60 mPa·s to about 400 mPa·s at about 23°C.

[0125] The crosslinking agent may be included in the first curable resin composition in a content of about 2 parts by weight to about 10 parts by weight based on 100 parts by weight of the first organic polysiloxane. The crosslinking agent may be included in the first curable resin composition in a content of about 3 parts by weight to about 8 parts by weight based on 100 parts by weight of the first organic poly siloxane. The crosslinking agent may be included in the first curable resin composition in a content of about 4 parts by weight to about 7 parts by weight based on 100 parts by weight of the first organic poly siloxane. The silicone-based curable resin composition may include the composite hollow filler. The composite hollow filler may be included in the first curable resin composition and / or the second curable resin composition. The first curable resin composition may include the composite hollow filler.

[0126] The composite hollow filler may include the hollow microspheres and the inorganic heat-resistant layer.

[0127] As described above, each of the hollow microspheres includes a hollow 623 thereinside, and may have a spherical shape. In addition, the hollow microsphere may include a shell surrounding the hollow.

[0128] The hollow microspheres may include an organic resin. The hollow microspheres may include a thermoplastic resin. The thermoplastic resin may include a polymer obtained by (co)polymerizing monomers such as (meth)acrylonitrile, (meth)acrylate monomers, styrene-based monomers, halogenated vinyl, halogenated vinylidene, vinyl acetate, butadiene, vinyl pyridine, and chloroprene. In addition, the thermoplastic resin may further include divinyl benzene, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3 -butylene glycol di(meth)acrylate, allyl(meth)acrylate, triacryl formal, triallyl isocyanurate, or the like. The thermoplastic resin may be a one-, two- or three-membered copolymer including at least one of methyl methacrylate, acrylonitrile and vinylidene chloride as a main component.

[0129] The hollow microspheres may be formed by a foaming agent. That is, the hollow may be formed by the foaming agent. That is, unexpanded microspheres containing the thermoplastic resin may be foamed and expanded by the foaming agent. Accordingly, the hollow microspheres may be formed.

[0130] As the foaming agent, n-pentane, isopentane, neopentane, butane or isobutane may be used. In addition, a hydrocarbon such as hexane or petroleum ether, a chlorinated hydrocarbon such as methyl chloride, methylene chloride, di chloroethane, dichloroethylene, tri chloroethane or trichloroethylene, or the like may be used as the foaming agent.

[0131] The unexpanded microspheres may have an average diameter (D50) of about 1 μm to about 50 μm. In addition, the unexpanded microspheres may have a density of about 1.1 g / cm3to about 1.5 g / cm3. The unexpanded microspheres may be heated to a predetermined temperature and expanded, so that the hollow microspheres may be formed. The heating may be carried out by various methods such as air heating, steam heating, microwave heating, infrared heating, or far-infrared heating. In addition, a heating temperature of the unexpanded microspheres may be about 100°C to about 200°C or about 110°C to about 180°C.

[0132] The hollow microspheres may be commercially obtained from products such as AkzoNobel's expancel series.

[0133] The hollow microspheres may have an average diameter (D50) of about 5 μm to about 300 μm, about 10 μm to about 250 μm, about 15 μm to about 200 μm, about 15 μm to about 150 μm, about 5 μm to about 50 μm, about 20 μm to about 70 μm, about 40 μm to about 100 μm or about 20 μm to about 120 μm.

[0134] the inorganic heat-resistant layer is disposed around the hollow microspheres. The inorganic heat-resistant layer may be disposed adjacent to the outer surface of the hollow microspheres. The inorganic heat-resistant layer may be attached to the outer surface of the hollow microspheres.

[0135] The inorganic heat-resistant layer may surround the hollow microspheres. The inorganic heat-resistant layer may be coated on the outer surface of the hollow microspheres. The inorganic heat-resistant layer may cover a portion or all of the outer surface of the hollow microspheres.

[0136] A thickness of the inorganic heat-resistant layer may be about 0.02 μm to about 3 μm, about 0.05 μm to about 2.5 μm, about 0.1 μm to about 2 μm or about 0.2 μm to about 2 μm.

[0137] The inorganic heat-resistant layer may include a plurality of inorganic particles.

[0138] The inorganic particles may include an inorganic material selected from the group consisting of calcium carbonate, silica, calcium sulfate, barium sulfate, talc, talc powder, bentonite, kaolin, chalk powder, graphite, gypsum, electrically conductive carbon black, calcium chloride, iron oxide, aluminum oxide, potassium oxide, dolomite, wollastonite, titanium dioxide, silicate and mica.

[0139] The inorganic particles may be at least one selected from the group consisting of calcium carbonate, silica and talc.

[0140] An average particle diameter (D50) of the inorganic particles may be about 0.02 μm to about 0.2 / / m, about 0.02 μm to about 0.3 / / m, about 0.02 μm to about 0.15 / / m, about 0.02 μm to about 0.1 JMH or about 0.02 μm to about 0.8 JMH.

[0141] A ratio of the average particle diameter of the hollow microspheres to the average particle diameter of the inorganic particles may be about 30:1 to about 30000:1, about 100:1 to about 20000:1, about 150:1 to about 20000:1, about 200:1 to about 15000:1 or about 300:1 to about 10000:1.

[0142] Since the hollow microspheres and the inorganic particles have the average particle diameters, the inorganic particles may be uniformly coated on the outer surface of the hollow microspheres.

[0143] The inorganic particles may be arranged on the outer surface of the hollow microspheres. The inorganic particles may be attached to the outer surface of the hollow microspheres. The inorganic particles may be in close contact with the outer surface of the hollow microspheres.

[0144] The composite hollow filler may further include a surface treatment agent.

[0145] The surface treatment agent may be coated on the surface of the inorganic particles. The surface treatment agent may surround the surface of the inorganic particles. The surface treatment agent may be chemically or physically bonded to the surface of the inorganic particles.

[0146] The inorganic particles may be attached to the hollow microspheres through the surface treatment agent.

[0147] The surface treatment agent may include a fatty acid-based compound or a silane-based coupling agent. The fatty acid-based compound may include a saturated fatty acid such as capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid or montanic acid or a fatty acid salt or alkyl ester thereof. The fatty acid salt may be an alkali metal salt, an ammonium salt, or an amine salt.

[0148] In addition, the surface treatment agent may include an unsaturated fatty acid such as oleic acid, linoleic acid or linolenic acid or an unsaturated fatty acid salt or alkyl ester thereof.

[0149] In addition, the surface treatment agent may include an OH group-containing fatty acid such as ricinoleic acid or 1,2-hydroxy stearic acid, an OH group-containing fatty acid salt thereof or an ester thereof with a monohydric or polyhydric alcohol; a dibasic acid such as adipic acid, azelaic acid, or sebacic acid, or a dibasic acid salt or mono- to dialkyl ester thereof; oligoesters or prepolymers of these compounds; or the like.

[0150] In addition, the surface treatment agent may include a resin acid-based compound, a sulfonic acid-based compound or an unsaturated carboxylic acid component-containing polymer-based compound.

[0151] Examples of the resin acid-based compound may include tall oil or rosin.

[0152] Examples of the sulfonic acid-based compound may include methanesulfonic acid, benzenesulfonic acid, p-toluene sulfonic acid, naphthalene sulfonic acid, derivatives thereof, and the like.

[0153] The unsaturated carboxylic acid component-containing polymer-based compound may include an ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid.

[0154] In addition, the unsaturated carboxylic acid component-containing polymer-based compound may include an ethylenically unsaturated mono-dicarboxylic acid such as maleic acid, fumaric acid or crotonic acid, or a half ester thereof; an anhydride of an ethylenically unsaturated dicarboxylic acid such as maleic acid or crotonic acid; and the like.

[0155] In addition, the silane-based coupling agent may be at least one selected from the group consisting of methacrylsilane, acrylsilane and isocyanuratesilane. More specfically, the silane-based coupling agent may be at least one selected from the group consisting of (methacryl): 3-methacryloxypropylmethyldimethoxy silane, (acryl): 3 -acryloxypropyltrimethoxy silane, (isocyanurate): tris-(trimethoxysilylpropyl)isocyanurate, (epoxy): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (amine): N-phenyl-3-aminopropyltrimethoxysilane and (vinyl): vinyltrimethoxy silane.

[0156] An average diameter (D50) of the composite hollow filler may be about 5 μm to about 300 μm, about 10 μm to about 250 μm, about 15 μm to about 200 μm, about 15 μm to about 150 μm, about 5 μm to about 50 μm, about 20 μm to about 70 μm, about 40 μm to about 100 μm or about 20 μm to about 120 μm.

[0157] A true density of the composite hollow filler may be about 0.05 g / cm3to about 0.5 g / cm3, about 0.07 g / cm3to about 0.4 g / cm3, about 0.08 g / cm3to about 0.35 g / cm3, about 0.05 g / cm3to about 0.2 g / cm3, about 0.1 g / cm3to about 0.3 g / cm3, about 0.15 g / cm3to about 0.4 g / cm3or about 0.1 g / cm3to about 0.3 g / cm3. The term "true density" is the quotient obtained by dividing the mass of the hollow filler sample by the true volume of the mass of the hollow filler, as measured by a gas pycnometer.

[0158] The composite hollow filler may have a specific surface area of about 1.9 m2 / g to about 2.7 m2 / g.

[0159] the composite hollow filler may have a collapse pressure under which 10% by volume collapses. The collapse pressure of the composite hollow filler may be about 250 psi to about 27000 psi.

[0160] The hollow filler may have a thermal conductivity of about 0.05 W / m K to about 0.2 W / m K.

[0161] In addition, the composite hollow filler may have a pressure resistance.

[0162] The pressure resistance may be measured by the following measurement method:

[0163] [Measurement method]

[0164] 1) About 7.5 wt% of the composite hollow filler and about 92.5 wt% of glycerin are uniformly mixed to prepare a dispersion.

[0165] 2) A pressure of about 20 MPa is applied to the dispersion for about 30 minutes.

[0166] 3) The pressure resistance is obtained by dividing the volume of the pressed dispersion by the initial volume of the dispersion.

[0167] In addition, in the measurement method, the initial volume of the dispersion may be one of about 50 ml, about 100 ml, about 200 ml, about 500 ml and about 1000 ml.

[0168] In addition, in the measurement method, one pressure of about 30 MPa, about 40 MPa or about 50 MPa may be applied to the dispersion.

[0169] In addition, in the measurement method, the pressure may be applied to the dispersion for about 40 minutes, about 50 minutes, about 60 minutes, about 70 minutes or about 80 minutes.

[0170] The pressure resistance of the composite hollow filler may be greater than about 0.85, greater than about 0.87 or greater than about 0.9.

[0171] Since the composite hollow filler has the pressure resistance, the buffer part may effectively buffer the expansion of the battery cells. In addition, since the composite hollow filler has the pressure resistance, the battery module according to the embodiment may have improved durability. The composite hollow filler may be manufactured by the following method.

[0172] The inorganic particles may be surface-treated with the surface treatment agent.

[0173] Next, the hollow microspheres and the surface-treated inorganic particles may be uniformly mixed in a dry state, so that the composite hollow filler may be manufactured. The temperature of the mixing process may be about 50°C to about 100°C.

[0174] The silicone-based curable resin composition may include an additive. The additive may be included in the first curable resin composition and / or the second curable resin composition. The first curable resin composition may further include an additive.

[0175] The additive may be at least one selected from the group consisting of a pigment, a dye, a clay, a surfactant, an oil, wollastonite, and fumed silica.

[0176] The "dye" means only a colored or fluorescent organic material, which imparts color to a substrate by selective absorption of light. The "pigment" generally means a colored, black, white or fluorescent particulate organic or inorganic solid that is insoluble in a vehicle or substrate into which it is incorporated and that is essentially unaffected by physical and chemical effects. The appearance of pigment is changed by selective absorption and / or scattering of light. A pigment generally retains the crystalline or particulate structure thereof throughout a coloring process. A pigment and a dye are well known in the art and need not be described in detail herein.

[0177] The clay may be a silicate containing a cation that may be selected from calcium, magnesium, aluminum, sodium, potassium and lithium cations, and mixtures thereof.

[0178] The surfactant may be a silicone polyether surfactant.

[0179] The oil may be castor oil. The oil may function as a rheology modifier.

[0180] The wollastonite is also known as calcium metasilicate, is a naturally occurring mineral, and may be added as a flame retardant.

[0181] The fumed silica may also be used as an additive to modify the rheology of these materials. The fumed silica may be obtained by high-temperature pyrolysis of volatile silicon compounds in an oxyhydrogen flame to produce finely divided silica.

[0182] The additive may be included in a content of about 2 parts by weight to about 10 parts by weight in the first curable resin composition based on 100 parts by weight of the first organic polysiloxane. The additive may be included in a content of about 3 parts by weight to about 8 parts by weight in the first curable resin composition based on 100 parts by weight of the first organic polysiloxane.

[0183] The second curable resin composition may include the first organic polysiloxane.

[0184] The first organic polysiloxane may be included in the second curable resin composition in a content of about 70 wt% to about 95 wt% based on the total weight of the second curable resin composition. The first organic polysiloxane may be included in the second curable resin composition in a content of about 75 wt% to about 95 wt% based on the total weight of the second curable resin composition. The first organic polysiloxane may be included in the second curable resin composition in a content of about 80 wt% to about 95 wt% based on the total weight of the second curable resin composition.

[0185] The silicone-based curable resin composition may include a curing catalyst. The curing catalyst may be included in the second curable resin composition. The curing catalyst accelerates curing of the silicone-based resin composition.

[0186] The curing catalyst may include a platinum-based catalyst.

[0187] Examples of the curing catalyst includes organic titanate esters such as a platinum-divinyltetramethyldisiloxane complex, tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxybis(acetylacetate)titanium and diisopropoxybis(ethylacetoacetate)titanium; organoaluminum compounds such as aluminum tris(acetylacetonate) and aluminum tris(ethylacetoacetate); organic zirconium compounds such as zirconium tetra(acetyl acetonate) and zirconium tetrabutylate; organotin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, and butyltin-2-ethylhexoate; metal salts of organic carboxylic acids such as tin naphthenate, tin oleate, tin butyrate, cobalt naphthenate, and zinc stearate; amine compounds and salts thereof, such as hexylamine and dodecylamine phosphate; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate; dialkyl hydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; and guanidyl group-containing organosilicon compounds.

[0188] The second curable resin composition may include the curing catalyst in a content of about 0.01 parts by weight to about 5 parts by weight based on 100 parts by weight of the second organic polysiloxane. The second curable resin composition may include the curing catalyst in a content of about 0.03 parts by weight to about 3 parts by weight based on 100 parts by weight of the second organic poly siloxane. The second curable resin composition may include the curing catalyst in a content of about 0.1 parts by weight to about 2 parts by weight based on 100 parts by weight of the second organic poly siloxane.

[0189] The silicone-based curable resin composition may include a reaction inhibitor. The reaction inhibitor may be included in the first curable resin composition and / or the second curable resin composition.

[0190] The second curable resin composition may include a reaction inhibitor. The reaction inhibitor may include at least one selected from the group consisting of acetylenic compounds such as 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; ene-yne compounds such as 3-methyl-3-pentene-1-yne and 3,5-dimethyl-3-hexen-1-yne; and curing reaction inhibitors such as a hydrazine-based compound, a phosphine-based compound, and a mercaptan-based compound.

[0191] The content of the reaction inhibitor may be about 0.0001 to about 10 parts by mass based on 100 parts by mass of the second organic poly siloxane.

[0192] The second curable resin composition may further include the composite hollow filler. That is, the composite hollow filler may be included in the first curable resin composition, may be included in the second curable resin composition, or may be included in both the first curable resin composition and the second curable resin composition.

[0193] The second curable resin composition may include the composite hollow filler in a content of about 3 parts by weight to about 20 parts by weight based on 100 parts by weight of the first organic polysiloxane. The second curable resin composition may include the composite hollow filler in a content of about 5 parts by weight to about 15 parts by weight based on 100 parts by weight of the first organic poly siloxane. The second curable resin composition may include the composite hollow filler in a content of about 6 parts by weight to about 14 parts by weight based on 100 parts by weight of the first organic poly siloxane.

[0194] The second curable resin composition may further include the additive. The second curable resin composition may include the additive in a content of about 0.1 parts by weight to about 5 parts by weight based on 100 parts by weight of the second organic poly siloxane.

[0195] The silicone-based resin composition may be prepared by a conventionally known silicone composition preparation method, and is not particularly limited.

[0196] The silicone-based resin composition may be prepared by mixing the first curable resin composition and the second curable resin composition.

[0197] In the silicone-based resin composition, a weight ratio of the first curable resin composition to the second curable resin composition may be about 0.5:1 to about 1:0.5. In the silicone-based resin composition, a weight ratio of the first curable resin composition to the second curable resin composition may be about 0.7:1 to about 1:0.7. In the silicone-based resin composition, a weight ratio of the first curable resin composition to the second curable resin composition may be about 0.8:1 to about 1:0.8.

[0198] For example, the silicone-based resin composition may be prepared by mixing the first curable resin composition and the second curable resin composition for 30 minutes to 4 hours using a mixer such as Trimix, Twin Mix, and Planetary Mixer (all are manufactured by Inoue Seisakusho Co., Ltd., registered trademarks), Ultra Mixer (manufactured by Mizuho Kogyo Co., Ltd., registered trademark), or Hibis Disper Mix (manufactured by Primix Co., Ltd., registered trademark). The temperature of the mixing process may be room temperature.

[0199] The silicone-based resin composition may include the hollow filler in a content of about 5 wt% to about 20 wt% based on the total weight. The silicone-based resin composition may include the hollow filler in a content of about 6 wt% to about 15 wt% based on the total weight. The silicone-based resin composition may include the hollow filler in a content of about 7 wt% to about 13 wt% based on the total weight.

[0200] The silicone-based resin composition may include the first organic polysiloxane in a content of about 50 wt% to about 80 wt% based on the total weight. The silicone-based resin composition may include the first organic poly siloxane in a content of about 55 wt% to about 75 wt% based on the total weight. The silicone-based resin composition may include the first organic poly siloxane in a content of about 60 wt% to about 75 wt% based on the total weight.

[0201] The silicone-based resin composition may include the second organic polysiloxane in a content of about 0.3 wt% to about 5 wt%. The silicone-based resin composition may include the second organic polysiloxane in a content of about 0.5 wt% to about 3 wt%. The silicone-based resin composition may include the second organic polysiloxane in a content of about 0.6 wt% to about 2 wt%.

[0202] The silicone-based resin composition may include the crosslinking agent in a content of about 0.3 wt% to about 5 wt%. The silicone-based resin composition may include the crosslinking agent in a content of about 0.5 wt% to about 3 wt%. The silicone-based resin composition may include the crosslinking agent in a content of about 0.6 wt% to about 2 wt%. The silicone-based resin composition may include the chain extender in a content of about 10 wt% to about 40 wt%. The silicone-based resin composition may include the chain extender in a content of about 15 wt% to about 35 wt%. The silicone-based resin composition may include the chain extender in a content of about 20 wt% to about 30 wt%.

[0203] In the silicone-based resin composition, a ratio of the weight of the first organic poly siloxane to the weight of the chain extender may be about 3: 1 to about 1.5:1. In the silicone-based resin composition, a ratio of the weight of the first organic poly siloxane to the weight of the chain extender may be about 2.5:1 to about 1.6:1.

[0204] The silicone-based resin composition may include the additive in a content of about 0.3 wt% to about 5 wt%. The silicone-based resin composition may include the additive in a content of about 0.5 wt% to about 3 wt%. The silicone-based resin composition may include the additive in a content of about 0.6 wt% to about 2 wt%.

[0205] The silicone-based resin composition may include the curing catalyst in a content of about 0.01 wt% to about 1 wt%. The silicone-based resin composition may include the curing catalyst in a content of about 0.02 wt% to about 0.9 wt%. The silicone-based resin composition may include the curing catalyst in a content of about 0.03 wt% to about 0.8 wt%.

[0206] The silicone-based resin composition may include the reaction inhibitor in a content of about 0.01 wt% to about 1 wt%. The silicone-based resin composition may include the reaction inhibitor in a content of about 0.02 wt% to about 0.9 wt%. The silicone-based resin composition may include the reaction inhibitor in a content of about 0.03 wt% to about 0.8 wt%.

[0207] Next, the battery cells 100 are disposed in the case body 210. The battery cells may be disposed in a seating part.

[0208] Next, the silicone-based curable resin composition is injected between the battery cells 100 in the case body 210.

[0209] Next, heat is applied to the injected silicone-based resin composition 601. Heat may be applied to an upper part of the injected silicone-based resin composition. Accordingly, the injected silicone-based resin composition is cured, thereby forming a buffer part.

[0210] The temperature of the upper part of the injected silicone-based resin composition may be about 60°C to about 150°C. The curing time of the injected silicone-based resin composition may be about 1 minute to about 10 minutes. The upper part of the injected silicone-based resin composition may be heated by an infrared heater.

[0211] The silicone-based resin composition may have a cone penetration.

[0212] The cone penetration of the silicone-based resin composition may be measured by the following method:

[0213] [Measurement method]

[0214] The silicone-based resin composition is sufficiently cured, thereby manufacturing a silicone resin block. The silicone-based resin composition is cured at about 60°C for about 1 hour, and a silicone-based resin block having a diameter of 60 mm and a height of 70 mm is manufactured. A penetration depth of the silicone-based resin block may be measured according to ISO 2137 using a 9.38 g hollow cone. When measuring the cone penetration, a one-quarter-scale cone is used.

[0215] The cone penetration of the silicone-based resin composition may be about 10 mm to about 70 mm. The cone penetration of the silicone-based resin composition may be about 20 mm to about 65 mm. The cone penetration of the silicone-based resin composition may be about 20 mm to about 60 mm.

[0216] Since the cone penetration of the silicone-based resin composition is within the above range, the silicone-based resin composition may perform a buffering action between the battery cells. In addition, since the cone penetration of the silicone-based resin composition is within the above range, the capping parts may easily seal the uncured silicone-based resin composition.

[0217] In addition, since the cone penetration of the silicone-based resin composition is within the above range, the battery cells may be properly fixed.

[0218] The battery module according to the embodiment includes a buffer part including hollow microspheres and an inorganic heat-resistant layer. In particular, the hollow microspheres may include an organic resin. Accordingly, the hollow microspheres may have high flexibility. In addition, the inorganic heat-resistant layer may be formed around the hollow microspheres. Accordingly, the inorganic heat-resistant layer may protect the hollow microspheres from external thermal shock.

[0219] Accordingly, the buffer part may be inserted between battery cells, thereby effectively absorbing the physical impact due to the expansion and contraction of the battery cells. In particular, even if the pressure increases due to the expansion of the battery cells, the hollow microspheres may not be destroyed. Accordingly, the buffer part may have improved durability even under external pressure. Therefore, the battery module according to the embodiment may effectively control the shrinkage and expansion of the battery cells while appropriately maintaining gaps between the battery cells.

[0220] In addition, since the inorganic heat-resistant layer is disposed on the hollow microspheres, the buffer part may effectively protect the hollow microspheres from thermal shock generated from the battery cells. That is, the inorganic heat-resistant layer may prevent the hollow microspheres from being deformed by heat from the battery cells. Accordingly, the buffer part may have high heat resistance.

[0221] In addition, the inorganic heat-resistant layer may include a plurality of inorganic particles. That is, the inorganic heat-resistant layer may include inorganic particles that are independent of each other. Accordingly, the inorganic heat-resistant layer may be resistant to irreversible deformation by an external force. That is, even if the inorganic heat-resistant layer is deformed by an external force, the inorganic particles may return to their original positions. Accordingly, the inorganic heat-resistant layer may have improved durability even under external pressure. Accordingly, the inorganic heat-resistant layer effectively protect the hollow microspheres.

[0222] Accordingly, the buffer part may effectively protect the battery cells. Accordingly, since the battery module according to the embodiment includes the buffer part, it may have improved reliability.

[0223] The silicone-based resin composition may have a contact angle.

[0224] The contact angle of the silicone-based resin composition may be measured according to the following measurement method:

[0225] [Measurement method]

[0226] The silicone-based resin composition is applied dropwise to a glass plate, and then a contact angle between an upper surface of the glass plate and the silicone-based resin composition drop is measured. The contact angle between the glass plate and the silicone-based resin composition may be measured at a time point of about 5 seconds.

[0227] A contact angle of the silicone-based resin composition may be about 10° to about 60°. The contact angle of the silicone-based resin composition may be about 15° to about 55°. The contact angle of the silicone-based resin composition may be about 17° to about 50°. The contact angle of the silicone-based resin composition may be about 15° to about 50°.

[0228] The silicone-based resin composition may have a contact angle reduction rate.

[0229] The contact angle reduction rate may be calculated by the following Equation 2:

[0230] [Equation 2]

[0231] Contact angle reduction rate = (contact angle at 0.25 sec - contact angle at 5 sec) / 4.75 sec

[0232] The contact angle reduction rate of the silicone-based resin composition may be about 57s to about 157s. The contact angle reduction rate of the silicone-based resin composition may be about 67s to about 147s. The contact angle reduction rate of the silicone-based resin composition may be about 77s to about 137s.

[0233] Since the silicone-based resin composition has a contact angle and contact angle reduction rate within the above ranges, the silicone-based resin composition may be easily injected between the battery cells. That is, the battery cells may have an exterior material such as a polymer film, and the silicone-based resin composition may have high wettability to the exterior material of the battery cells.

[0234] Accordingly, the silicone-based resin composition may be rapidly injected between the battery cells and may prevent an unfilled space from being generated.

[0235] The silicone-based resin composition may have thermal conductivity.

[0236] In addition, the first curable resin composition may have a contact angle. The contact angle of the first curable resin composition may be measured by the above measurement method.

[0237] A contact angle of the first curable resin composition may be about 10° to about 60°. The contact angle of the first curable resin composition may be about 15° to about 55°. The contact angle of the first curable resin composition may be about 17° to about 50°. The contact angle of the first curable resin composition may be about 15° to about 50°.

[0238] In addition, the second curable resin composition may have a contact angle. The contact angle of the second curable resin composition may be measured by the above measurement method.

[0239] A contact angle of the second curable resin composition may be about 10° to about 60°. The contact angle of the second curable resin composition may be about 15° to about 55°. The contact angle of the second curable resin composition may be about 17° to about 50°. The contact angle of the second curable resin composition may be about 15° to about 50°.

[0240] The first curable resin composition may have a contact angle reduction rate.

[0241] A contact angle reduction rate of the first curable resin composition may be about 67s to about 147s. The contact angle reduction rate of the first curable resin composition may be about 77s to about 137s.

[0242] The second curable resin composition may have a contact angle reduction rate.

[0243] A contact angle reduction rate of the second curable resin composition may be about 67s to about 147s. The contact angle reduction rate of the second curable resin composition may be about 77s to about 137s.

[0244] In addition, the silicone-based resin composition according to the embodiment may have hardness. The silicone-based resin composition may be measured by the following measurement method.

[0245] [Measurement method]

[0246] After the silicone-based resin composition according to the embodiment is sufficiently cured, a silicone-based resin sheet may be manufactured. The thickness of the silicone-based resin sheet may be one of about 5 mm to about 7 mm. The silicone-based resin composition according to the embodiment may be cured at about 60°C for about 1 hour, thereby manufacturing the silicone-based resin sheet. The thickness of the silicone-based resin sheet may be about 6 mm. Next, the hardness of the silicone-based resin sheet may be measured according to ISO 7619-1 or ASTM D2240, and may be derived from the hardness of the silicone-based resin composition.

[0247] The Shore A hardness of the silicone-based resin composition according to the embodiment may be about 3 to about 50, about 10 to about 50, about 20 to about 50, about 3 to about 30, about 5 to about 20, about 10 to about 50, about 5 to about 40 or about 20 to about 45.

[0248] Since the silicone-based resin composition according to the embodiment has the hardness, a battery may be effectively protected and firmly fixed.

[0249] In addition, the silicone-based resin composition according to the embodiment may have a flame retardancy rating of V-l or higher.

[0250] The flame retardancy rating is obtained by the UL94 test method, and the flame retardancy of the silicone-based resin sheet may be derived from the flame retardancy rating of the silicone-based resin composition according to the embodiment.

[0251] A density of the silicone-based resin sheet may be about 0.3 g / cm3to about 0.8 g / cm3, about 0.2 g / cm3to about 0.9 g / cm3, about 0.3 g / cm3to about 0.7 g / cm3, about 0.4 g / cm3to about 0.8 g / cm3, about 0.2 g / cm3to about 0.7 g / cm3or about 0.3 g / cm3to about 0.6 g / cm3.

[0252] The silicone-based resin composition according to the embodiment may have a pot life. The pot life of the silicone-based resin composition according to the embodiment may be measured by the following method.

[0253] The first curable resin composition and the second curable resin composition are uniformly mixed at about 23°C. Next, at this temperature, a viscosity of the mixed silicone-based resin composition is measured in real-time. Here, the pot life may be measured as a time for the viscosity of the mixed silicone-based resin composition to reach about 10000 mPa s.

[0254] The pot life of the silicone-based resin composition according to the embodiment may be about 5 minutes to about 60 minutes, about 7 minutes to about 50 minutes, about 6 minutes to about 40 minutes, about 10 minutes to about 30 minutes, about 5 minutes to about 20 minutes or about 15 minutes to about 30 minutes.

[0255] Since the silicone-based resin composition according to the embodiment has a pot life in the range, it may be effectively used in a process of manufacturing a battery pack.

[0256] FIG. 6 is a diagram for explaining a battery pack according to an embodiment, and FIG.

[0257] 7 is a diagram for explaining a vehicle according to an embodiment of the present invention.

[0258] Referring to FIGS. 6 and 7, a battery pack 1 may include at least one battery module 10 according to the above embodiment and a pack case 50 for packaging the at least one battery module 10.

[0259] The battery pack 1 may be provided in a vehicle V as a fuel source for the vehicle V. For example, the battery pack 1 may be provided in an electric vehicle, a hybrid vehicle, and other vehicles V that can use the battery pack 1 as a fuel source.

[0260] In addition, it is natural that the battery pack 1 may be provided in other devices, instruments, and facilities, such as an energy storage system using a secondary battery, in addition to the vehicle V.

[0261] As such, since the battery pack 1 according to the present embodiment and devices, instruments, and facilities, such as the vehicle V, including the battery pack 1 may include the above-described battery module 10, the battery pack 1 having all advantages due to the battery module 10, and devices, instruments, and facilities, such as the vehicle V, provided with the battery pack 1 may be implemented.

[0262] According to various embodiments as described above, the battery module 10 capable of more stably supporting the battery cells 100, and the battery pack 1 and vehicle V including the battery module 10 may be provided.

[0263] In addition, according to various embodiments as described above, the battery module 10 capable of improving the safety of the battery cells 100 by preventing damage to the battery cells 100 due to external shock, and the battery pack 1 and vehicle V including the battery module 10 may be provided.

[0264] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples for the purpose of clarifying the effects of the present invention, but the present invention is not limited thereto.

[0265] Manufacturing examples

[0266] A : Polysiloxane compound represented by Chemical Formula 4, having a viscosity of about 150 mPa·s to about 220 mPa·s at 23°C, and containing a silicon-bonded alkenyl group B : Polysiloxane compound represented by Chemical Formula 4, having a viscosity of about 40000 mPa·s to about 50000 mPa·s at 23°C, and containing a silicon-bonded alkenyl group

[0267] C-1 : Hydrogen polysiloxane compound represented by Chemical Formula 8, having a viscosity of about 150 mPa·s to about 250 mPa·s at 23°C, and having a hydrogen group bonded to a side chain thereof

[0268] C-2 : Hydrogen polysiloxane compound represented by Chemical Formula 6, having a viscosity of about 60 mPa·s to about 90 mPa·s at 23°C, and having a hydrogen group bonded to a terminal thereof

[0269] D: Platinum-divinyltetramethyldisiloxane complex

[0270] E: 1-ethynyl-1-cyclohexanol

[0271] F: Hollow composite filler (Japan Fillite, EMC-40, density 0.16 g / cm3) G: Colored pigment (ELASTOSIL® COLOR PASTE FL ULTRAMARINE BLUE RAL 5002)

[0272] The components were uniformly mixed at a speed of about 40 rpm at room temperature for one hour by means of a planetary mixer, thereby preparing first curable resin compositions as summarized in the following Table 1 and second curable resin compositions summarized in the following Table 2:

[0273]

Table 1

[0274]

[0275]

[0276]

Table 2

[0277]

[0278] Examples 1 to 14

[0279] The first curable resin composition and second curable resin composition prepared in each of the manufacturing examples were uniformly mixed as shown in Table 3 below. Next, the mixed resin composition was injected into the first aluminum mold and cured at about 60°C for about 1 hour. As a result, a silicone-based resin block having a diameter of about 60 mm, a height of about 70 mm and a cylindrical shape was manufactured.

[0280] In addition, the mixed resin composition was injected into the second aluminum mold under the above-described curing conditions, thereby manufacturing a silicone-based resin sheet having a thickness of about 6 mm.

[0281] [Table 3]

[0282]

[0283]

[0284] < Measurement examples>

[0285] 1. Hardness

[0286] The hardness of each of the silicone-based resin sheets manufactured in the examples was measured according to DIN EN ISO 7619-1.

[0287] 2. Density

[0288] The volume and weight of each of the silicone resin blocks manufactured in the examples were measured, and the density thereof was calculated.

[0289] 3. Cone penetration

[0290] The penetration depth of each of the silicone-based resin blocks manufactured in the examples was measured according to ISO 2137 using a 9.38 g hollow cone.

[0291] 4. Flame retardancy

[0292] Using a flame retardancy tester manufactured by Myungji Tech., the flame retardancy of each of the silicone resin sheets manufactured in the examples was measured in a vertical mode by the UL94 test method.

[0293] 5. Pot life

[0294] The pot life of each of the mixed resin compositions of the examples was measured at 2.5 rpm using a Brookfield viscometer, Model DV2T, at the time at which the viscosity was about 10,000 mPa- s. Here, the measurement temperature was room temperature.

[0295] 6. Contact angle

[0296] The mixed resin composition was dropped on glass in an amount of about 0.02 ml, and a contact angle over time was measured by a contact angle measurer (Phoenix 300 analyzer). Similarly, the contact angles of the first curable resin composition and the second curable resin composition were measured in the same manner.

[0297] As shown in Tables 4 to 6 below, the contact angles of the mixed resin composition and the first and second curable resin compositions were measured.

[0298] [Table 4]

[0299]

[0300] [Table 5]

[0301]

[0302]

[0303] [Table 6]

[0304]

[0305] As shown in Table 7 below, the hardness and flame retardancy of each of the silicone-based resin sheets, the cone penetration of each of the silicone resin blocks and the pot life of each of the mixed resin compositions, manufactured in the examples, were measured. [Table 7]

[0306]

[0307] As shown in Table 7, the silicone-based curable resin compositions of the examples exhibited appropriate hardness, appropriate mechanical strength, appropriate curing characteristics and improved flame retardancy.

[0308] [Description of Symbols]

[0309] cell 100

[0310] module case 200

[0311] bus bars 300

[0312] circuit board assembly 400

[0313] support plate 500

[0314] buffer part 600

Claims

1. [CLAIMS]2.

1. 3.A battery module, comprising:4.a plurality of battery cells;5.a case for containing the battery cells; and6.a buffer part disposed between the battery cells in the case,7.wherein the buffer part comprises:8.a silicone-based resin matrix disposed between the battery cells in the case;9.hollow microspheres inserted into the silicone-based resin matrix; and10.an inorganic heat-resistant layer disposed around the hollow microspheres.11.

2. 12.The battery module according to claim 1, wherein the inorganic heat-resistant layer comprises inorganic particles arranged adjacent to an outer surface of the hollow microspheres, wherein a ratio of a particle diameter of the hollow microspheres to a particle diameter of the inorganic particles is 30:1 to 30000:1.13.

3. 14.The battery module according to claim 2, wherein the hollow microspheres comprise an organic resin, wherein the inorganic particles comprise an inorganic material selected from the group consisting of calcium carbonate, silica, calcium sulfate, barium sulfate, talc, talc powder, bentonite, kaolin, chalk powder, graphite, gypsum, electrically conductive carbon black, calcium chloride, iron oxide, aluminum oxide, potassium oxide, dolomite, wollastonite, titanium dioxide, silicate, and mica.15.

4. The battery module according to claim 2, comprising a surface treatment agent coated around the inorganic particles, and16.the inorganic particles are attached to the outer surface of the hollow microspheres.17.

5. 18.The battery module according to claim 4, wherein the surface treatment agent comprises a fatty acid or a silane-based coupling agent.19.

6. 20.A curable resin composition for manufacturing a battery module, the curable resin composition comprises:21.a silicone-based polymer;22.a curing catalyst; and23.a composite hollow filler,24.wherein the composite hollow filler comprises:25.hollow microspheres; and26.an inorganic heat-resistant layer disposed around the hollow microspheres.27.

7. 28.The curable resin composition according to claim 6, wherein the inorganic heat-resistant layer comprises inorganic particles arranged adjacent to an outer surface of the hollow microspheres,29.wherein a ratio of a particle diameter of the hollow microspheres and a particle diameter of the inorganic particles is 30:1 to 30000:1.30.

8. 31.The curable resin composition according to claim 7, wherein the hollow microspheres comprise an organic resin, and the inorganic particles comprises calcium carbonate, talc or silica.32.

9. 33.The curable resin composition according to claim 8, wherein the silicone-based polymer comprises:34.a first organic polysiloxane comprising a vinyl group and having a viscosity of 10 mPa s to 2000 mPa s; and35.a third organic polysiloxane comprising a hydrogen group in a side chain thereof.36.

10. 37.The curable resin composition according to claim 7, wherein an average particle diameter of the hollow microspheres is 5 μm to 300 μm, and38.an average particle diameter of the inorganic particles is 0.02 μm to 0.2 μm.39.

11. 40.The curable resin composition according to claim 8, wherein the silicone-based polymer further comprises:41.a second organic polysiloxane having a viscosity of 10000 mPa·s to 100000 mPa·s; and a fourth organic polysiloxane comprising a hydrogen group at a terminal thereof.42.

12. 43.The curable resin composition according to claim 10, wherein the composite hollow filler has a pressure resistance of greater than 85%,44.wherein the pressure resistance is derived by a measurement method below:45.[Measurement method]46.1) 7.5 wt% of the composite hollow filler and 92.5 wt% of glycerin are uniformly mixed to prepare a dispersion.47.2) A pressure of 20 MPa is applied to the dispersion for 30 minutes.48.3) The pressure resistance is obtained by dividing a volume of the pressed dispersion by an initial volume of the dispersion.49.

13. 50.A method of manufacturing a battery module, the method comprising:51.preparing a case for containing a plurality of battery cells thereinside;52.filling a curable resin composition into the case; and53.curing the curable resin composition to form a buffer part,54.wherein the curable resin composition comprises:55.a silicone-based polymer;56.a curing catalyst; and57.a composite hollow filler,58.wherein the composite hollow filler comprises:59.hollow microspheres; and60.an inorganic heat-resistant layer disposed around the hollow microspheres.

Images