Thermal management complex, and battery pack and energy storage system comprising the same

Abstract

Provided is a thermal management complex, including a protective layer (30); and a heat barrier layer (20) provided on at least one surface of the protective layer (30), wherein the protective layer (30) includes a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the surface, provided with the heat barrier layer (20), of the protective layer (30) is modified, and the heat barrier layer (20) includes a silicone-based resin matrix.

Description

[0001] WA12247S / Mk

[0002] THERMAL MANAGEMENT COMPLEX, AND BATTERY PACK AND ENERGY

[0003] STORAGE SYSTEM COMPRISING THE SAME

[0004] [Technical Field]

[0005] Embodiments relate to a thermal management complex and a battery pack and energy storage system including the same.

[0006] [Background Art]

[0007] The present application relates, in particular, to a thermal management complex used in lithium-ion batteries to delay or prevent thermal runaway of the batteries.

[0008] The demand for electrochemical energy storage devices such as lithium-ion batteries continues to increase due to the growth of application fields such as electric vehicles and grid energy storage systems, as well as other multi-cell battery application fields such as electric bicycles, uninterrupted power battery systems, and replacements for lead acid batteries. As their use increases, thermal management methods are needed. For large applications such as grid storage and electric vehicles, multiple electrochemical cells connected in series and parallel arrays are often used, which can lead to thermal runaway. When a cell is in a thermal runaway mode, the heat generated by the cell can induce a thermal runaway propagation reaction in cells adjacent thereto, potentially causing a cascading effect that could ignite the entire battery.

[0009] Therefore, as the demand for batteries with a reduced risk of thermal runaway increases, there is a need for the development of components capable of preventing or delaying the spread of heat, energy, or both to surrounding cells.

[0010] [Disclosure]

[0011] [Technical Problem]

[0012] 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 thermal management complex capable of preventing heat diffusion between battery cells when thermal runaway occurs, and a battery pack and energy storage system including the thermal management complex. WA12247S / Mk

[0013] 2

[0014] [Technical Solution]

[0015] In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a thermal management complex, including: a protective layer; and a heat barrier layer provided on at least one surface of the protective layer, wherein the protective layer includes a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer includes a silicone-based resin matrix.

[0016] The surface of the protective layer may be modified by at least one method of corona discharge, plasma treatment, sand mat processing, ozone exposure treatment, flame exposure treatment, high-voltage electric shock exposure treatment, and ionizing radiation treatment. A centerline average roughness (Ra) of the surface of the surface-modified protective layer may be 10 nm to 30 nm. A maximum height roughness (Rmax) of the surface of the surface-modified protective layer may be 200 nm to 600 nm. A ten-point median roughness (Rz) of the surface of the surface-modified protective layer may be 200 nm to 600 nm. A root mean square roughness (Rq) of the surface of the surface-modified protective layer may be 10 nm to 40 nm. A water contact angle of the surface of the surface-modified protective layer may be 30° to 70°.

[0017] The protective layer may have a heat shrinkage rate of 0.3% or less at 300°C.

[0018] The thermal management complex may have a peel strength of 0.01 kg / cm or more according to ASTM D3330. The thermal management complex may have a tensile strength of 1 MPa to 100 MPa according to ASTM D412. The thermal management complex may have an elongation of 30% to 200% according to ASTM D412.

[0019] The protective layer may include a polyimide-based resin, an epoxy -based resin, an amino-based resin, a phenol-based resin, a polyester-based resin, a polyurethane resin, or a combination thereof.

[0020] The thermal management complex may further include an adhesive layer disposed between the heat barrier layer and the protective layer, wherein the adhesive layer includes a silicone-based, urethane-based, acrylic-based, rubber-based, polyester-based, polyamide-based, epoxy -based, vinyl alkyl ether-based, fluorine-based adhesive or a combination thereof. WA12247S / Mk

[0021] 3

[0022] The heat barrier layer may have a thickness of 500 JMH to 5000 JMH, and the protective layer may have a thickness of 5 JMH to 100 JMH.

[0023] In accordance with another aspect of the present invention, there is provided a battery pack, including: a secondary battery cell; and a thermal management complex disposed on one side of the secondary battery cell, wherein the thermal management complex includes a protective layer and a heat barrier layer disposed on at least one surface of the protective layer, the protective layer includes a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer includes a silicone-based resin matrix.

[0024] In accordance with yet another aspect of the present invention, there is provided an energy storage system, including: a battery pack; and a motor driven by power supplied from the battery pack, wherein the battery pack includes: a secondary battery cell; and a thermal management complex disposed on one side of the secondary battery cell, wherein the thermal management complex includes a protective layer and a heat barrier layer disposed on at least one surface of the protective layer, the protective layer includes a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer includes a silicone-based resin matrix.

[0025] [Advantageous effects]

[0026] A thermal management complex according to the present invention includes a protective layer; and a heat barrier layer provided on at least one surface of the protective layer, wherein the protective layer includes a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the side surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer includes a silicone- based resin matrix. WA12247S / Mk

[0027] 4

[0028] By disposing a protective layer including a resin having a small thermal expansion coefficient on the surface of the heat barrier layer including the silicone-based resin matrix, improved insulating properties can be provided when heat is applied from the outside.

[0029] In addition, by modifying the surface, in contact with the heat barrier layer, of the protective layer, the surface roughness can be increased, so that the adhesive force between the protective layer and the heat barrier layer can be increased, thereby increasing the peel strength of a finally produced thermal management complex.

[0030] Further, by disposing the thermal management complex according to the present invention between secondary battery cells, the phenomenon of heat being transferred to adjacent cells when thermal runaway occurs can be suppressed or prevented. Accordingly, the thermal management complex according to the present invention can have improved thermal runaway suppression or prevention performance.

[0031] [Description of Drawings]

[0032] FIG. 1 illustrates the sectional view of a thermal management complex according to an embodiment.

[0033] FIG. 2 illustrates the sectional view of a thermal management complex according to another embodiment.

[0034] FIG. 3 specifically illustrates the sectional view of the thermal management complex according to an embodiment.

[0035] FIG. 4 illustrates the sectional view of a thermal management complex having a structure in which first inorganic filler particle and second inorganic filler particles are bound to a binder during thermal runaway.

[0036] FIG. 5 illustrates a thermal management complex positioned between two secondary battery cells.

[0037] FIG. 6 illustrates a battery pack.

[0038] FIG. 7 illustrates a vehicle equipped with a battery pack.

[0039] FIGS. 8 to 11 illustrate AFM photographs of the surface of the thermal management WA12247S / Mk

[0040] 5 complex according to an example.

[0041] FIGS. 12 to 15 illustrate AFM photographs of the surface of the thermal management complex according to a comparative example.

[0042] FIG. 16 illustrates a photo of a peel strength test for the surface of the thermal management complex according to an example.

[0043] FIG. 17 illustrates a photo of a peel strength test for the surface of the thermal management complex according to a comparative example.

[0044] [Best Mode]

[0045] In the description of embodiments, it will be understood that when each part, surface, layer or substrate is referred to as being “on” or “under” another part, surface, layer or substrate, the part, surface, layer or substrate can be directly on another part, surface, layer or substrate or intervening part, surface, layer or substrate, and criteria for “on” and “under” will be provided based on the drawings. Elements in the following drawings may be exaggerated, omitted, or schematically illustrated for conveniences and clarity of explanation, and the sizes of elements do not reflect their actual sizes completely.

[0046] Thermal management complex

[0047] A thermal management complex according to the present invention includes a protective layer; and a heat barrier layer provided on at least one surface of the protective layer, wherein the protective layer includes a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the side surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer includes a silicone- based resin matrix.

[0048] FIG. 1 illustrates the sectional view of a thermal management complex according to an embodiment. FIG. 2 illustrates the sectional view of a thermal management complex according to another embodiment. WA12247S / Mk

[0049] 6

[0050] Referring to FIG. 1, a thermal management complex 2 according to an embodiment may include a first protective layer 30; and a heat barrier layer 20 disposed on at least one surface of the first protective layer 30.

[0051] The heat barrier layer 20 may be disposed on the first protective layer 30. The heat barrier layer 20 may be bonded to an upper surface of the first protective layer 30. The heat barrier layer 20 may be adhered to the upper surface of the first protective layer 30. The heat barrier layer 20 may be in close contact with the upper surface of the first protective layer 30.

[0052] In addition, referring to FIG. 2, a thermal management complex 3 according to another embodiment may further include a second protective layer 40.

[0053] The second protective layer 40 may be disposed on the heat barrier layer 20. The second protective layer 40 may sandwich the first protective layer 30 together with the heat barrier layer 20. The second protective layer 40 may be bonded to an upper surface of the heat barrier layer 20. The second protective layer 40 may be in close contact with the upper surface of the heat barrier layer 20. The second protective layer 40 may be adhered to the upper surface of the heat barrier layer 20.

[0054] Protective layer

[0055] The protective layers 30 and 40 may include a polymer film having high heat resistance and mechanical strength.

[0056] The protective layers 30 and 40 may protect the heat barrier layer 20. The protective layers 30 and 40 may protect the heat barrier layer 20 from external thermal shock and physical shock.

[0057] The protective layers 30 and 40 may include a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C. The protective layers 30 and 40 may include a resin having a thermal expansion coefficient of 7 ppm / °C to 45 ppm / °C, 10 ppm / °C to 40 ppm / °C, or 10 ppm / °C to 30 ppm / °C in a temperature range of 100°C to 200°C.

[0058] The thermal expansion coefficient is a thermal expansion change pattern, measured by TMA (Q400, TA Co.), in the protective layer when the force pulling the protective layer is set to WA12247S / Mk

[0059] 0.2 N or less, and the temperature is increased in a temperature range including a temperature range of 100°C to 200°C at a temperature elevation rate of l°C / min to 10°C / min or 4°C / min to 6°C / min.

[0060] As described above, at least one side surface of the heat barrier layer 20 of the thermal management complex according to the present invention includes the protective layers 30 and 40 containing the resin having a low thermal expansion coefficient, the deformation due to heat may be alleviated, thereby improving heat resistance. In addition, the warpage of the sheet that may occur as the heat barrier layer 20 is foamed may be suppressed, thereby maintaining or increasing the mechanical strength.

[0061] The surfaces of the protective layers 30 and 40 in contact with the heat barrier layer 20 may be surface-modified for the purpose of increasing the adhesion, retention properties, etc. with the heat barrier layer 20. For example, physical treatments such as corona discharge treatment, plasma treatment, sand mat processing, ozone exposure treatment, flame exposure treatment, high-voltage electric shock exposure treatment, and ionizing radiation treatment; chemical treatments such as chromic acid treatment; and surface treatments such as adhesion facilitation treatment using a coating agent (undercoat agent) may be performed. The surface treatment for increasing adhesion is preferably performed on all the surfaces of the protective layers 30 and 40 on the side of the heat barrier layer 20. Preferably, the surfaces of the protective layers 30 and 40 in contact with the heat barrier layer 20 may be treated by corona discharge treatment.

[0062] The centerline average roughness (Ra) of the surface of each of the surface-modified protective layers may be 10 nm to 30 nm, 10 nm to 20 nm, or 11 nm to 15 nm.

[0063] The centerline average roughness (Ra) may be defined by Equation 1 below:

[0064] [Equation 1]

[0065] The maximum height roughness (Rmax) of the surface of the surface-modified protective layer may be 200 nm to 600 nm, 210 nm to 580 nm, or 220 nm to 570 nm. WA12247S / Mk

[0066] 8

[0067] The maximum height roughness (Rmax; maximum peak-to-valley) may be defined as the largest value among height deviations between peaks and valleys in five adjacent reference lengths.

[0068] The ten-point median roughness (Rz) of the surface of the surface-modified protective layer may be 200 nm to 600 nm, 220 nm to 550 nm, or 240 nm to 500 nm.

[0069] The ten-point median roughness (Rz) may be defined as a difference between the average of the five highest peaks and the average of the five lowest valleys in one reference length.

[0070] The root mean square roughness (Rq) of the surface of the surface-modified protective layer may be 10 nm to 40 nm, 12nm to 35 nm, or 15 nm to 30 nm.

[0071] The root mean square roughness (Rq) may be defined by Equation 2 below:

[0072] [Equation 2]

[0073] The water contact angle of the surface of the surface-modified protective layer may be 30° to 70°. The water contact angle of the surface of the surface-modified protective layer may be 35° to 65°. The water contact angle of the surface of the surface-modified protective layer may be 40° to 60°. The water contact angle of the surface of the surface-modified protective layer may be 45° to 55°. The protective layer may lower the water contact angle of the surface, compared to before the surface modification.

[0074] The water contact angle is obtained by, after dropping a drop of water on the surface of the surface-modified protective layer using a contact angle measurer (Phoenix 300 Touch, SEO Co.), measuring the angle between the protective layer and the water droplet.

[0075] The wetting energy of the surface of the surface-modified protective layer may be 20 mN / m to 60 mN / m. The wetting energy of the surface of the surface-modified protective layer may be 30 mN / m to 58 mN / m. The wetting energy of the surface of the surface-modified protective layer may be 35 mN / m to 55 mN / m. The wetting energy of the surface of the surface-modified protective layer may be 40 mN / m to 50 mN / m. WA12247S / Mk

[0076] 9

[0077] The wetting energy may be measured according to ASTM D5946 using a contact angle measurer (Phoenix 300 Touch, SEO Co.).

[0078] The surface of the surface-modified protective layer may have a negative spreading coefficient. The spreading coefficient of the surface of the surface-modified protective layer may be -50 mN / m to -5 mN / m. The spreading coefficient of the surface of the surface- modified protective layer may be -40 mN / m to -10 mN / m. The spreading coefficient of the surface of the surface-modified protective layer may be -30 mN / m to -20 mN / m. When the surface of the surface-modified protective layer satisfies the range, a liquid can form a liquid droplet without wetting the protective layer even if the liquid is dropped on the surface of the protective layer, which means that the adhesion of the surface in contact with the heat barrier layer is increased.

[0079] The spreading coefficient may be measured according to ASTM D5946 using a contact angle measurer (Phoenix 300 Touch, SEO Co.).

[0080] The work of adhesion of the surface of the surface-modified protective layer may be 93 mN / m to 150 mN / m, 95 mN / m to 130 mN / m, 100 mN / m to 125 mN / m, or 110 mN / m to 120 mN / m.

[0081] The work of adhesion may be measured according to ASTM D3330 using a universal tensile tester (UTM, Instron Co.).

[0082] As described above, the surface roughness may be increased and the contact angle may be lowered by modifying the surfaces of the protective layers 30 and 40 in contact with the heat barrier layer 20. Accordingly, the adhesive force between the protective layers 30 and 40 and the heat barrier layer 20 may be increased, so that a finally produced thermal management complex may have excellent peel strength.

[0083] The protective layers 30 and 40 may include a polyimide-based resin, an epoxy -based resin, an amino-based resin, a phenol-based resin, a polyester-based resin, a polyurethane resin, or a combination thereof. Preferably, the protective layers 30 and 40 may include a polyimide- based resin.

[0084] The protective layers 30 and 40 may have a tensile strength satisfying about 100 MPa or WA12247S / Mk

[0085] 10 more, 150 MPa or more, or 200 MPa or more and 700 MPa or less, 670 MPa or less, 650 MPa or less, or 600 MPa or less in the longitudinal direction (MD) or the transverse direction (TD).

[0086] The tensile strength may be measured by the Project Impact Assessment with Measurement & Verification (PIAM Method) standard.

[0087] In addition, the protective layers 30 and 40 may have an elongation satisfying 30% or more, 40% or more, 45% or more or 50% or more and 150% or less, 130% or less, 100% or less, or 95% or less in the longitudinal direction (MD) or the transverse direction (TD).

[0088] The elongation may be measured by the Project Impact Assessment with Measurement & Verification (PIAM Method) standard.

[0089] In addition, the protective layers 30 and 40 may have a tensile modulus satisfying 1.0 GPa or more, 1.5 GPa or more, or 2.0 GPa or more and 15.0 GPa or less, 12.0 GPa or less, 10.0 GPa, or 8.0 GPa or less.

[0090] The tensile modulus may be measured by the Project Impact Assessment with Measurement & Verification (PIAM Method) standard.

[0091] The protective layers 30 and 40 may have a heat shrinkage rate of 0.3% or less at about 300°C. Specifically, the protective layers 30 and 40 may have a heat shrinkage rate of less than about 0.28%, less than about 0.25% or less than about 0.2% at about 300°C in the longitudinal direction (MD) or the transverse direction (TD).

[0092] The protective layers 30 and 40 may have a heat shrinkage rate of less than about 0.5%, less than about 0.4%, less than about 0.3% or less than about 0.2% in the longitudinal direction (MD) or the transverse direction (TD) under the condition of being left at about 200°C for about 2 hours. The heat shrinkage rate may be measured according to the IPC TM650 2.2.4A standard.

[0093] In addition, in the protective layers 30 and 40, the coefficient of thermal expansion from about 100°C to about 200°C may be less than about 50 ppm, less than about 40 ppm, less than about 30 ppm, or less than about 25 ppm in the longitudinal direction (MD) or the transverse direction (TD).

[0094] Since the protective layers 30 and 40 has the mechanical properties and thermal properties as described above, the heat barrier layer 20 may be effectively protected. WA12247S / Mk

[0095] 1 1

[0096] Accordingly, the thermal management complex according to an embodiment may have improved thermal runaway prevention performance.

[0097] In particular, when a heat source of about 600°C is placed on the protective layers 30 and 40 and the thermal management complex according to an embodiment is left for about 30 minutes, the temperature of the upper surface of the heat barrier layer 20 may be less than about 300°C, less than about 290°C, less than about 280°C, less than about 270°C, less than about 260°C or less than about 250°C.

[0098] In addition, when a heat source of about 1400°C is disposed on the protective layers 30 and 40 and the thermal management complex according to an embodiment is left for about 5 minutes, the temperature of the upper surface of the heat barrier layer 20 may be less than about 300°C, less than about 290°C, less than about 280°C, less than about 270°C, less than about 260°C or less than about 250°C.

[0099] The thickness of each of the protective layers 30 and 40 may be about 5 JMH to about 100 JMH. The thickness of the protective layers 30 and 40 may be about 10 / / m to about 80 JMH, about 15 JMH to about 60 JMH or about 20 JMH to about 40 JMH.

[0100] Since the protective layers 30 and 40 have the thickness as described above, they may have improved insulation performance and improved mechanical properties. Since the protective layers 30 and 40 have the thickness as described above, they may effectively suppress the expansion of the battery in a thermal runaway process.

[0101] Heat barrier layer

[0102] The heat barrier layer 20 may have a thickness of about 500 JMH to about 5000 JMH.

[0103] The heat barrier layer 20 may have a thickness of about 500 JMH to about 3000 JMH. The heat barrier layer 20 may have a thickness of about 1000 JMH to about 2000 JMH.

[0104] The heat barrier layer 20 may have a density of about 0.3 g / cm3to about 0.7 g / cm3, about 0.2 g / cm3to about 0.6 g / cm3or about 0.3 g / cm3to about 0.5 g / cm3.

[0105] The Shore OO hardness of the heat barrier layer 20 may be about 20 to about 100, about 15 to about 80, about 20 to about 110 or about 30 to about 80. The Shore OO hardness may be WA12247S / Mk

[0106] 12 measured according to ISO 868.

[0107] The heat barrier layer 20 may have a compression force deflection of about 10 kPa to about 100 kPa, about 15 kPa to about 90 kPa, about 20 kPa to about 80 kPa or about 15 kPa to 70 kPa. The compression force deflection (CFD) may be measured according to ASTM D1056.

[0108] The heat barrier layer 20 may have a tensile strength of about 1 MPa to about 10 MPa, about 2 MPa to about 10 MPa, about 1 MPa to about 20 MPa or about 2 MPa to about 8 MPa. In addition, the heat barrier layer 20 may have an elongation of about 50% to about 300%, about 60% to about 250%, about 70% to about 200% or about 80% to about 180%. The tensile strength and the elongation may be measured according to ASTM D412.

[0109] The flame retardancy grade of the heat barrier layer 20 may exceed VI . The flame retardancy grade of the heat barrier layer 20 may be V0. The flame retardancy grade may be measured by UL94.

[0110] The heat barrier layer 20 may be formed by curing a silicone-based resin composition according to an embodiment. The heat barrier layer 20 may include the silicone-based resin composition according to an embodiment.

[0111] The silicone-based resin composition may include polysiloxane.

[0112] The polysiloxane may include a reactive functional group. The polysiloxane may include a vinyl group. Each of both terminals of the poly siloxane may include a vinyl group.

[0113] The silicone-based resin composition may include the polysiloxane in a content of about 11 wt% to about 70 wt%, about 20 wt% to about 65 wt%, about 30 wt% to about 60 wt%, about 30 wt% to 55 wt% or about 30 wt% to about 53 wt% based on the total weight of the composition.

[0114] The poly siloxane may be represented by Formula 1 below: WA12247S / Mk

[0115] [Formula 1]

[0116] In Formula 1, R1may be a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 18 carbon atoms, and R2may be an alkenyl group. In addition, in Formula 1, e may be 1 to 1500, and f may be 0 to 20. In Formula 1, e may be 10 to 1000, and f may be 0 to 15.

[0117] The poly siloxane may be represented by Formula 2 below:

[0118] [Formula 2]

[0119] In Formula 2, g may be 1 to 1500. G may be 10 to 1200. G may be 20 to 1000.

[0120] The polysiloxane may include a first polysiloxane, a second polysiloxane and a third polysiloxane.

[0121] The first polysiloxane may include a reactive functional group. The first polysiloxane may include a vinyl group. Each of both terminals of the first polysiloxane may include a vinyl group.

[0122] The first poly siloxane may be represented by Formula 1 :

[0123] The first poly siloxane may be represented by Formula 2 :

[0124] The first polysiloxane may have a weight average molecular weight (Mw) of about 10,000 g / mol to about 60,000 g / mol. The first poly siloxane may have a weight average molecular weight of about 20,000 g / mol to about 55,000 g / mol. The first polysiloxane may have a weight average molecular weight of about 35,000 g / mol to about 50,000 g / mol. The WA12247S / Mk

[0125] 14 first polysiloxane may have a weight average molecular weight of about 40,000 g / mol to about 50,000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0126] In the first polysiloxane, the kinematic viscosity at 25°C may be about 15,000 mPa-s to 25,000 mPa-s. In the first polysiloxane, the kinematic viscosity at 25°C may be about 16,500 mPa-s to 24,000 mPa-s. In the first polysiloxane, the kinematic viscosity at 25°C may be about 19,000 mPa-s to 23,000 mPa-s. The kinematic viscosity of the first polysiloxane may be a value at 25°C as measured by an Ostwald viscometer. The kinematic viscosity of the first polysiloxane may be a value at 25°C measured by a rotary viscometer. When the viscosity is measured, a shear rate may be about 10 s'1.

[0127] The first polysiloxane may be included in a content of 10 wt% to 50 wt% based on the total weight of the silicone-based resin composition. The first poly siloxane may be included in a content of 15 wt% to 45 wt% based on the total weight of the silicone-based resin composition. The first polysiloxane may be included in a content of 20 wt% to 40 wt% based on the total weight of the silicone-based resin composition.

[0128] The second polysiloxane may include a reactive functional group. The second poly siloxane may include a vinyl group. Each of both terminals of the second poly siloxane may include a vinyl group.

[0129] The second polysiloxane may be represented by Formula 1. the second polysiloxane may be represented by Formula 2.

[0130] The second polysiloxane may have a weight average molecular weight (Mw) of about 5,000 g / mol to 30,000 g / mol. The second polysiloxane may have a weight average molecular weight of about 10,000 g / mol to 25,000 g / mol. The second polysiloxane may have a weight average molecular weight of about 12,000 g / mol to 20,000 g / mol. The second polysiloxane may have a weight average molecular weight of about 15,000 g / mol to 18,000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0131] In the second polysiloxane, the kinematic viscosity at 25°C may be about 700 mPa-s to 1,300 mPa-s. In the second polysiloxane, the kinematic viscosity at 25°C may be about 750 mPa-s to 1,200 mPa-s. In the second polysiloxane, the kinematic viscosity at 25°C may be WA12247S / Mk

[0132] 15 about 780 mPa-s to 1,180 mPa-s. The kinematic viscosity of the second polysiloxane may be a value at 25°C as measured by an Ostwald viscometer. The kinematic viscosity of the second polysiloxane may be a value at 25°C measured by a rotary viscometer. When the viscosity is measured, a shear rate may be about 10 s'1.

[0133] The second poly siloxane may be included in a content of 1 wt% to 30 wt% based on the total weight of the silicone-based resin composition. The second poly siloxane may be included in a content of 5 wt% to 25 wt% based on the total weight of the silicone-based resin composition. The second poly siloxane may be included in a content of 10 wt% to 20 wt% based on the total weight of the silicone-based resin composition.

[0134] The third polysiloxane may include a reactive functional group. The third polysiloxane may include a vinyl group. Each of both terminals of the third poly siloxane may include a vinyl group.

[0135] The third polysiloxane may be represented by Formula 1.

[0136] The third polysiloxane may be represented by Formula 2.

[0137] The third polysiloxane may have a weight average molecular weight (Mw) of about 1,000 g / mol to 20,000 g / mol. The third polysiloxane may have a weight average molecular weight of about 5,000 g / mol to 18,000 g / mol. The third polysiloxane may have a weight average molecular weight of about 7,000 g / mol to 15,000 g / mol. The third polysiloxane may have a weight average molecular weight of about 9,000 g / mol to 13,000 g / mol. The weight average molecular weight may be measured based on polystyrene.

[0138] In the third polysiloxane, the kinematic viscosity at 25°C may be 350,000 mPa-s to 700,000 mPa-s. In the third polysiloxane, the kinematic viscosity at 25°C may be about 400,000 mPa-s to 650,000 mPa-s. In the third polysiloxane, the kinematic viscosity at 25°C may be about 450,000 mPa-s to 600,000 mPa-s. The kinematic viscosity of the third polysiloxane may be a value at 25°C as measured by an Ostwald viscometer. The kinematic viscosity of the third poly siloxane may be a value at 25°C measured by a rotary viscometer. When the viscosity is measured, a shear rate may be about 10 s'1.

[0139] The third polysiloxane may be included in a content of 0.01 wt% to 5 wt% based on the WA12247S / Mk

[0140] 16 total weight of the silicone-based resin composition. The third poly siloxane may be included in a content of 0.1 wt% to 2 wt% based on the total weight of the silicone-based resin composition. The third polysiloxane may be included in a content of 0.5 wt% to 1.5 wt% based on the total weight of the silicone-based resin composition.

[0141] A weight ratio of the first poly siloxane to the second poly siloxane may be about 6 : 1 to about 1 : 1. The weight ratio of the first poly siloxane to the second poly siloxane may be about 5 : 1 to about 1 : 1. The weight ratio of the first poly siloxane to the second poly siloxane may be about 4 : 1 to about 2 : 1.

[0142] A weight ratio of the first poly siloxane to the third poly siloxane may be about 6 : 1 to about 1 : 1. The weight ratio of the first poly siloxane to the third poly siloxane may be about 5 : 1 to about 1 : 1. The weight ratio of the first poly siloxane to the third poly siloxane may be about 4 : 1 to about 2 : 1.

[0143] The silicone-based resin composition may include a crosslinking agent.

[0144] The crosslinking agent may include a siloxane containing a hydrogen group. Each of both terminals of the crosslinking agent may include a siloxane containing a hydrogen group. The crosslinking agent may include a hydrogenated polysiloxane.

[0145] The crosslinking agent may be represented by Formula 3 below:

[0146] [Formula 3] where R3may be a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 18 carbon atoms, and R4may be a hydrogen atom. In addition, in Formula 3, h may be 1 to 1500, and i may be 0 to 20. In Formula 3, h may be 10 to 1000, and i may be 0 to 20. In Formula 3, h may be 1 to 1500, and i may be 0.

[0147] The crosslinking agent may be represented by Formula 4 below: WA12247S / Mk

[0148] 17

[0149] [Formula 4]

[0150] In Formula 4, j may be 1 to 1500, 10 to 1000, or 100 to 1500.

[0151] The crosslinking agent may have a weight average molecular weight (Mw) of about 500 g / mol to about 6000 g / mol. Preferably, the crosslinking agent may have a weight average molecular weight (Mw) of about 1000 g / mol to about 5000 g / mol, about 1500 g / mol to about 4500 g / mol, or about 2000 g / mol to about 4000 g / mol.

[0152] The viscosity at 25°C of the crosslinking agent may be about 1 mm2 / g to about 50 mm2 / g, about 10 mm2 / g to about 40 mm2 / g, or about 20 mm2 / g to about 30 mm2 / g.

[0153] The crosslinking agent may be included in an amount of 0.1 wt% to 20 wt%, preferably 1 wt% to 15 wt%, or 3 wt% to 10 wt% based on the total weight of the silicone-based resin composition.

[0154] A silicone-based composition according to the present invention may generate hydrogen gas by the reaction of the siloxane containing the hydrogen group of the crosslinking agent with water (H2O) to form micropores. However, when the silicone-based resin composition contains only pure water (H2O), a problem of not mixing within the silicone resin composition may occur.

[0155] Accordingly, the silicone-based resin composition according to the present invention may include a hydrophobic control agent. The hydrophobic control agent may include polysiloxane and water (H2O). Even if water (H2O) is included in the silicone resin composition, a hydrophobic control agent in the form of an emulsifier may be used to ensure that phase separation does not occur and the composition is well mixed.

[0156] The content of water in the hydrophobic control agent may be 40 wt% to 80 wt%, 45 wt% to 75 wt%, or 50 wt% to 70 wt% based on the total weight of the hydrophobic control agent.

[0157] In addition, the hydrophobic control agent may control the hydrophobicity of the WA12247S / Mk

[0158] 18 silicone-based resin composition according to an embodiment. The hydrophobic control agent may strongly adhere the silicone-based resin composition according to an embodiment to a heterogeneous film or sheet. As the amount of water (H2O) contained in the hydrophobic control agent increases, the adhesive force between the silicone-based resin composition and the heterogeneous film or sheet may be improved.

[0159] The hydrophobic control agent may include a hydroxyl group. The hydrophobic control agent may include octadecyl hydroxy polyglycol ether.

[0160] The hydrophobic control agent may be represented by Formula 5 below:

[0161] [Formula 5]

[0162] In Formula 5, k may be 1 to 20, 1 to 10, or 1 to 5.

[0163] In Formula 5, R5may be a substituted or unsubstituted alkyl group having 1 to 30, 3 to 20, or 5 to 15 carbon atoms.

[0164] The hydrophobic control agent may be represented by Formula 6 below:

[0165] [Formula 6]

[0166] In Formula 6, 1 may be 1 to 20, 1 to 10 or 1 to 5.

[0167] The viscosity at 25°C of the hydrophobic control agent may be about 1,000 mPa- s to about 20,000 mPa s, about 3,000 mPa s to about 15,000 mPa s or about 5,000 mPa s to about 10,000 mPa s.

[0168] The hydrophobic control agent may be included in an amount of 0.01 wt% to 5 wt%, preferably 0.1 wt% to 3 wt% or 0.1 wt% to 2 wt% based on the total weight of the silicone-based WA12247S / Mk

[0169] 19 resin composition.

[0170] The silicone-based resin composition may include a leveling agent.

[0171] The leveling agent may include a polysiloxane having no or little reactive functional group. In the leveling agent, the content of the reactive functional group may be 0 mol% to about 0.05 mol%. In the leveling agent, the content of the reactive functional group may be less than 0.05 mol%, less than about 0.04 mol%, less than about 0.03 mol%, less than about 0.02 mol%, less than about 0.01 mol%, or less than about 0.005 mol%.

[0172] The reactive functional group may include hydrogen, hydroxy or a vinyl group. The reactive functional group may exclude an alkyl group.

[0173] The leveling agent may be represented by Formula 7 below:

[0174] [Formula 7]

[0175] In Formula 7, R5may be an alkyl group having 1 to 18 carbon atoms, and m may be 1 to 1500, 10 to 1500, 10 to 1000, 20 to 1500, or 30 to 1500.

[0176] The leveling agent may be represented by Formula 8 below:

[0177] [Formula 8]

[0178] In Formula 8, n may be 1 to 1500, 10 to 1500, 10 to 1000, 20 to 1500, or 30 to 1500. WA12247S / Mk

[0179] 20

[0180] The viscosity at 25°C of the leveling agent may be about 1 mPa- s to about 100 mPa s, about 10 mPa s to about 80 mPa s, or about 31 mPa s to about 39 mPa s.

[0181] The leveling agent may enable the silicone-based resin composition to be effectively mixed. That is, the leveling agent may perform a lubricant function in the silicone-based resin composition.

[0182] In addition, the leveling agent may control the viscosity of the silicone-based resin composition. The leveling agent may be a viscosity modifier that modifies the viscosity of the silicone-based resin composition. In particular, since the leveling agent lowers the viscosity of the silicone-based resin composition, the silicone-based resin composition may form a coating layer to have high flatness.

[0183] In addition, since the leveling agent hardly contains the reactive functional group, the silicone resin composition may have long-term storage stability when it is manufactured and transported.

[0184] The leveling agent may be included in an amount of 0.1 wt% to 20 wt%, preferably 1 wt% to 15 wt% or 3 wt% to 10 wt% based on the total weight of the silicone-based resin composition.

[0185] The silicone-based resin composition may include a catalyst.

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

[0187] Examples of the catalyst include organic titanate esters such as platinum- divinyltetramethyldisiloxane complex, tetrabutyl titanate, and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxybi s(acetylacetate)titanium and diisopropoxybis(ethylacetoacetate)titanium; organoaluminum compounds such as aluminum tris(acetylacetonate) and aluminum tri s(ethyl acetoacetate); organic zirconium compounds such as zirconium tetra(acetyl acetonate) and zirconium tetrabutylate; organic tin 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 such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of WA12247S / Mk

[0188] 21 alkali metals such as potassium acetate; dialkyl hydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; and guanidyl group-containing organosilicon compounds.

[0189] The viscosity at 25°C of the catalyst may be about 100 mPa s to about 1,500 mPa s, about 300 mPa s to about 1,300 mPa s or about 500 mPa s to about 1,100 mPa s.

[0190] The catalyst may be included in an amount of 0.01 wt% to 5 wt%, preferably 0.1 wt% to 3 wt% or 0.1 wt% to 1 wt% based on the total weight of the silicone-based resin composition.

[0191] The silicone-based resin composition may include a stabilizer.

[0192] The stabilizer may be used to stabilize a platinum catalyst. In addition, the stabilizer may be used to extend the shelf life of the silicone-based resin composition. The stabilizer may be used to extend the shelf life of a first silicone-based resin composition to be described below.

[0193] The viscosity at 25°C of the stabilizer may be about 1 mPa s to about 50 mPa s, about 5 mPa- s to about 40 mPa- s or about 10 mPa- s to about 20 mPa- s.

[0194] The stabilizer may be included in an amount of 0.01 wt% to 5 wt%, preferably 0.1 wt% to 3 wt% or 0.1 wt% to 1 wt% based on the total weight of the silicone-based resin composition.

[0195] The stabilizer may include octylphosphonic acid.

[0196] The silicone-based resin composition may further include a reaction inhibitor.

[0197] The reaction inhibitor may be 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-l- cyclohexanol; ene-yne compounds such as 3-methyl-3-penten-l-yne and 3,5-dimethyl-3-hexen- 1-yne; curing reaction inhibitors such as hydrazine-based compounds, phosphine-based compounds, and mercaptan-based compound; and the like.

[0198] The viscosity at 25°C of the reaction inhibitor may be about 300 mPa- s to about 1,400 mPa s, about 500 mPa- s to about 1,200 mPa s, or about 600 mPa- s to about 1,000 mPa s.

[0199] The reaction inhibitor may be included in an amount of 0.01 wt% to 5 wt%, preferably 0.1 wt% to 3 wt% or 0.1 wt% to 1 wt% based on the total weight of the silicone-based resin composition. WA12247S / Mk

[0200] 22

[0201] The silicone-based resin composition may include inorganic filler particles.

[0202] The inorganic filler particles may include first inorganic filler particles and / or second inorganic filler particles.

[0203] The first inorganic filler particles may have an average particle diameter of 0.7 JMH to 20 JMH. The first inorganic filler particles may have an average particle diameter of 1 / / m to 10 JMH. The first inorganic filler particles may have an average particle diameter of 1 JMH to 6 JMH.

[0204] The first inorganic filler particles may have a specific surface area of 0.4 m2 / g to 8 m2 / g, 2 m2 / g to 6 m2 / g, or 4.4 m2 / g to 5 m2 / g. The specific surface area may be measured by the ISO 9277 method.

[0205] The first inorganic filler particles may be included in a content of 1 wt% to 15 wt% based on the total weight of the silicone-based resin composition. The first inorganic filler particles may be included in a content of 3 wt% to 15 wt% based on the total weight of the silicone-based resin composition. The first inorganic filler particles may be included in a content of 5 wt% to 13 wt% based on the total weight of the silicone-based resin composition.

[0206] As an embodiment, the first inorganic filler particles may include quartz.

[0207] The second inorganic filler particles may have an average particle diameter of 1 nm to 100 nm. The second inorganic filler particles may have an average particle diameter of 1 nm to 80 nm. The second inorganic filler particles may have an average particle diameter of 1 nm to 60 nm.

[0208] The second inorganic filler particles may have a specific surface area of 100 m2 / g to 500 m2 / g, 200 m2 / g to 450 m2 / g, or 270 m2 / g to 330 m2 / g. The specific surface area may be measured by the ISO 9277 method.

[0209] The second inorganic filler particles may be included in a content of 1 wt% to 15 wt% based on the total weight of the silicone-based resin composition. The second inorganic filler particles may be included in a content of 3 wt% to 15 wt% based on the total weight of the silicone-based resin composition. The second inorganic filler particles may be included in a content of 5 wt% to 13 wt% based on the total weight of the silicone-based resin composition.

[0210] As an embodiment, the second inorganic filler particles may include fumed silica. WA12247S / Mk

[0211] 23

[0212] The second inorganic filler particles have an average particle diameter of nm units smaller than that of the first inorganic filler particles, and thus have a large specific surface area, thereby further increasing the adsorption capacity of the silicone-based resin composition.

[0213] In addition, a ratio of the average particle diameter of the first inorganic filler particles to the average particle diameter of the second inorganic filler particles may be about 5: 1 to about 100:1, about 4: 1 to about 100:1, about 7: 1 to about 50: 1, about 10: 1 to about 100: 1 or about 15: 1 to about 80:1.

[0214] Since the first inorganic filler particles and the second inorganic filler particles have the above-described average particle size ratio, they may be uniformly distributed within a heat barrier layer described below. Accordingly, the first inorganic filler particles and the second inorganic filler particles may be uniformly packed within the heat barrier layer.

[0215] The silicone-based resin composition may include reactive particles.

[0216] The reactive particles may include first reactive particles and / or second reactive particles.

[0217] The content of the first reactive particles may be higher than the content of the second reactive particles. The size of the second reactive particles is smaller than that of the first reactive particles, and as the content of the second reactive particles having a small particle size decreases, the foaming rate of the silicone resin composition increases.

[0218] The first reactive particles may be included in a content of 13 wt% to 30 wt% based on the total weight of the silicone-based resin composition. The first reactive particles may be included in a content of 13 wt% to 25 wt% based on the total weight of the silicone-based resin composition. The first reactive particles may be included in a content of 15 wt% to 20 wt% based on the total weight of the silicone-based resin composition.

[0219] As an embodiment, the first reactive particles may include aluminum hydroxide. Specifically, the first reactive particles may include aluminum trihydrate.

[0220] The second reactive particles may include at least one of lithium, sodium, potassium, magnesium, calcium, strontium, zinc, boron, and zirconium. As an embodiment, the second reactive particles may include zinc borate.

[0221] The second reactive particles may be included in a content of 0.5 wt% to 2 wt% based WA12247S / Mk

[0222] 24 on the total weight of the silicone-based resin composition. The second reactive particles may be included in a content of 0.7 wt% to 1.7 wt% based on the total weight of the silicone-based resin composition. The second reactive particles may be included in a content of 1 wt% to 1.5 wt% based on the total weight of the silicone-based resin composition.

[0223] The first inorganic filler particles and the second inorganic filler particles have a large specific surface area due to the very small average particle diameters thereof, thereby having excellent adsorption capacity. During thermal runaway, the first reactive particles and the second reactive particles may generate a binder that binds the first inorganic filler particles and the second inorganic filler particles to each other.

[0224] The binder may connect the first inorganic filler particles and the second inorganic filler particles to each other, thereby forming a porous inorganic barrier layer.

[0225] When heat is applied from the outside, the first reactive particles and the second reactive particles may react with silicon and oxygen contained in a silicone-based resin matrix, thereby forming the binder. By the external heat, a silicate including an element contained in the first reactive particles and second reactive particles may be formed.

[0226] As an embodiment, when aluminum hydroxide and zinc borate are included as the reactive particles, a porous inorganic barrier layer may be formed by connecting inorganic filler particles, i.e., quartz and fumed silica, to each other. Here, the binder may include aluminazine borate-silicate.

[0227] Accordingly, even if the heat barrier layer is sintered by external heat, it may have mechanical strength due to the inorganic filler particles and the binder. That is, after the heat barrier layer is sintered, a porous inorganic barrier layer containing the inorganic filler particles and the binder may be formed.

[0228] Here, the inorganic barrier layer includes pores with a high porosity present between the inorganic filler particles and between the binder.

[0229] Accordingly, the inorganic barrier layer may have improved mechanical strength and improved insulation properties.

[0230] The silicone-based resin composition may include a first silicone-based resin WA12247S / Mk

[0231] 25 composition and a second silicone-based resin composition.

[0232] The first silicone-based resin composition may include the polysiloxane and the catalyst, and the second silicone-based resin composition may include a crosslinking agent including a reactive hydrogen group.

[0233] At least one of the first silicone-based resin composition and the second silicone-based resin composition may include inorganic filler particles. The inorganic filler particles are the same as described above.

[0234] At least one of the first silicone-based resin composition and the second silicone-based resin composition may include reactive particles that generate a binder bonded to the inorganic filler particles by heat. The reactive particles and the binder are the same as described above.

[0235] At least one of the first silicone-based resin composition and the second silicone-based resin composition may include at least one of the first poly siloxane, the second poly siloxane and the third polysiloxane. The first polysiloxane, the second polysiloxane and the third polysiloxane are the same as described above.

[0236] As an embodiment, the first silicone-based resin composition may include the first polysiloxane, the second polysiloxane, the second inorganic filler particles, the first reactive particles, the second reactive particles, the catalyst, the leveling agent, the stabilizer and the hydrophobic control agent.

[0237] As an embodiment, the second silicone-based resin composition may include the first polysiloxane, the second polysiloxane, the third polysiloxane, the first inorganic filler particles, the second inorganic filler particles, the crosslinking agent and the reaction inhibitor .

[0238] At least one of the first silicone-based resin composition and the second silicone-based resin composition may have a higher viscosity than the first polysiloxane.

[0239] At least one of the first silicone-based resin composition and the second silicone-based resin composition may have a lower viscosity than the second polysiloxane.

[0240] At least one of the first silicone-based resin composition and the second silicone-based resin composition may have a viscosity of 10,000 mPa-s to 90,000 mPa-s at 25°C.

[0241] The kinematic viscosity at 25°C of the first silicone-based resin composition may be WA12247S / Mk

[0242] 26 about 10,000 mPa s to 60,000 mPa s. The kinematic viscosity at 25°C of the first silicone- based resin composition may be about 10000 mPa s to 40000 mPa s. The kinematic viscosity at 25°C of the first silicone-based resin composition may be about 10000 mPa s to 32000 mPa s. The kinematic viscosity at 25°C of the first silicone-based resin composition may be about 15000 mPa- s to 30000 mPa- s. The kinematic viscosity of the first silicone-based resin composition may be a value at 25°C as measured by an Ostwald viscometer. The kinematic viscosity of the first silicone-based resin composition may be a value at 25°C measured by a rotary viscometer. When the viscosity is measured, a shear rate may be about 10 s'1.

[0243] The second silicone-based resin composition may have a viscosity of 10,000 mPa s to 90,000 mPa s at 25°C. The kinematic viscosity at 25°C of the second silicone-based resin composition may be about 10000 mPa s to 40000 mPa s. The kinematic viscosity at 25°C of the second silicone-based resin composition may be about 12000 mPa- s to 32000 mPa s. The kinematic viscosity at 25°C of the second silicone-based resin composition may be about 15000 mPa- s to 30000 mPa- s. The kinematic viscosity of the second silicone-based resin composition may be a value at 25°C as measured by an Ostwald viscometer. The kinematic viscosity of the second silicone-based resin composition may be a value at 25°C measured by a rotary viscometer. When the viscosity is measured, a shear rate may be about 10 s'1.

[0244] The silicone-based resin composition according to an embodiment may have a pot life of about 15 minutes to about 35 minutes at about 25°C. Accordingly, the silicone-based resin composition according to an embodiment may have an appropriate curing speed and may form a silicone foam layer having a low thickness variation.

[0245] FIG. 3 specifically illustrates the sectional view of the thermal management complex according to an embodiment. FIG. 4 illustrates the sectional view of a thermal management complex having a structure in which first inorganic filler particles and second inorganic filler particles are bound to a binder during thermal runaway.

[0246] Referring to FIG. 3, the heat barrier layer includes silicone-based resin matrix 100, first inorganic filler particle 210, second inorganic filler particles 220, first reactive particles 310 and second reactive particles 320.

[0247] The silicone-based resin matrix 100 includes a plurality of micropores 110. WA12247S / Mk

[0248] 27

[0249] The micropores may have an average particle diameter of about 1 nm to about 100 nm, about 5 nm to about 50 nm, about 10 nm to about 200 nm, about 20 nm to about 100 nm or about 1 nm to about 30 nm.

[0250] Since the micropores have the average particle diameter as described above, it may effectively block heat.

[0251] The heat barrier layer may have a porosity of about 30 vol% to about 80 vol%, about 35 vol% to about 70 vol%, about 40 vol% to about 80 vol% or about 50 vol% to about 80 vol%.

[0252] Since the heat barrier layer has the porosity as described above, it may effectively block heat and absorb external impact.

[0253] The silicone-based resin matrix 100 may be formed by curing the silicone-based resin composition according to an embodiment. The silicone-based resin matrix 100 may include the poly siloxane and the crosslinking agent. In addition, the silicone-based resin matrix 100 may further include the leveling agent, the catalyst, the stabilizer, the hydrophobic control agent and the reaction inhibitor. The silicone-based resin matrix 100 may be formed by a silicone-based resin formed by curing the components.

[0254] Accordingly, the silicone-based resin matrix 100 may include the poly siloxane, the crosslinking agent, the leveling agent, the catalyst, the stabilizer, the hydrophobic control agent and the reaction inhibitor in the above-described contents.

[0255] The heat barrier layer may form an inorganic insulating layer by heat generated from the outside. The heat barrier layer may form the inorganic insulating layer by high heat generated from a battery, etc. For example, the inorganic insulating layer may be formed by thermally treating the heat barrier layer at a temperature higher than about 600°C for about 5 minutes or more. For example, the inorganic insulating layer may be formed by thermally treating the heat barrier layer at about 600°C to about 800°C for about 5 minutes to about 1 hour.

[0256] The heat barrier layer may form a binder 400 due to the heat. The binder 400 may be formed by reacting the silicone-based resin matrix 100, the first reactive particles 310 and the second reactive particles 320. For example, the silicone-based resin matrix, the first reactive particles and the second reactive particles may be sintered by the heat, thereby forming the binder 400. WA12247S / Mk

[0257] 28

[0258] As shown in FIG. 3, the inorganic insulating layer may include the first inorganic filler particles 210, the second inorganic filler particles 220 and the binder 400.

[0259] The second inorganic filler particles 220 may be disposed between the first inorganic filler particles 210.

[0260] The binder 400 may connect the first inorganic filler particles 210 and the second inorganic filler particles 220 to each other. That is, the binder 400 may be connected to the first inorganic filler particles 210. In addition, the binder 400 may be connected to the second inorganic filler particles 220. The binder 400 may perform a network function that connects the first inorganic filler particles 210 and the second inorganic filler particles 220 to each other. In addition, the binder may perform a support function that supports the first inorganic filler particles and the second inorganic filler particles.

[0261] Accordingly, the inorganic insulating layer may have a porous structure. That is, the inorganic insulating layer may be a porous inorganic layer.

[0262] The binder 400 may include an element contained in the silicone-based resin matrix 100; an element contained in the first reactive particles 310; and an element contained in the second reactive particles 320. That is, the binder 400 may include silicate. The binder 400 may include aluminum-silicate. The binder 400 may include a silicate containing at least one of lithium, sodium, potassium, magnesium, calcium, strontium, zinc, boron, phosphorus, and zirconium. The binder 400 may include alumina-zinc borate-silicate.

[0263] Accordingly, the binder 400 may have improved heat resistance and mechanical strength. Accordingly, the heat barrier layer may form the inorganic insulating layer by external heat, and effectively block thermal runaway.

[0264] In particular, during the process of forming the binder 400, oxygen and hydrogen contained in the silicone-based resin matrix 100 and the first reactive particles 310 may react to form water. Water generated in this way may minimize impact due to external heat.

[0265] In addition, the first inorganic filler particles 210 and the second inorganic filler particles 220 may have high heat resistance and may be uniformly packed. Accordingly, the inorganic insulating layer may have uniform pores.

[0266] Accordingly, the inorganic insulating layer may have improved mechanical strength and WA12247S / Mk

[0267] 29 high insulating properties. Accordingly, the thermal runaway prevention sheet according to an embodiment may form the inorganic insulating layer to prevent or reduce the thermal runaway phenomenon of a cell adjacent to a cell where thermal runaway occurs.

[0268] The thermal management complex according to the present invention may further include an adhesive layer disposed between the heat barrier layer and the protective layer.

[0269] The adhesive layer may include a silicone-based, urethane-based, acrylic-based, rubberbased, polyester-based, polyamide-based, epoxy-based, vinyl alkyl ether-based, fluorine-based adhesive or a combination thereof. Due to the presence of the adhesive layer, the peel strength of the thermal management complex according to an embodiment may increase.

[0270] The thermal management complex according to an embodiment may have a peel strength of 0.01 kg / cm or more, 0.05 kg / cm or more, 0.07 kg / cm or more, or 0.1 kg / cm or more according to ASTM D3330. At the same time, the thermal management complex according to an embodiment may have a peel strength of 5 kg / cm or less, 3 kg / cm or less, or 1 kg / cm or less according to ASTM D3330.

[0271] The peel strength may be measured according to ASTM D3330 standards.

[0272] The thermal management complex may have a tensile strength of 1 MPa to 100 MPa, 10 MPa to 95 MPa, or 15 MPa to 90 MPa. The thermal management complex may have an elongation of 30% to 200%, 35% to 190%, or 40% to 180%.

[0273] The tensile strength and elongation of the thermal management complex may be measured according to ASTM D412 standards.

[0274] FIG. 5 illustrates a thermal management complex positioned between two secondary battery cells. FIG. 6 is a drawing for explaining a battery pack according to an embodiment, and FIG. 7 is a drawing for explaining a vehicle according to an embodiment.

[0275] Referring to FIGS. 5 to 7, a battery pack 1 may include secondary battery cells 13 and 15; and a thermal runaway prevention sheet 7 disposed between the secondary battery cells 13 WA12247S / Mk

[0276] 30 and 15. The thermal runaway prevention sheet may be at least one thermal runaway prevention sheet according to the previous embodiment.

[0277] The secondary battery cells 13 and 15 may be provided as a pouch-type secondary battery, a square secondary battery, or a cylindrical secondary battery. The secondary battery cells 13 and 15 may be provided in multiple units. The plural secondary battery cells 13 and 15 may be accommodated inside a pack case 50 to be described below. The plural secondary battery cells 13 and 15 may be stacked within the pack case 50 described below along the horizontal direction of the pack case 50.

[0278] The battery pack 1 may include at least one battery module 10; and the pack case 50 for packing the at least one battery module 10.

[0279] The battery pack 1 may be installed in a vehicle V as a fuel source for the vehicle V. For example, the battery pack 1 may be installed as a fuel source in an electric vehicle, a hybrid vehicle, or a vehicle V using the battery pack 1 in other ways.

[0280] The battery pack 1 may be applied to various devices. Specifically, the battery pack 1 may be applied to means of transportation such as electric bicycles, electric vehicles, hybrids, or Energy Storage Systems (ESS), but is not limited thereto and may be applied to various devices in which secondary batteries can be used.

[0281] As described above, the battery pack 1 according to the present embodiment, and a device, apparatus, and equipment such as the vehicle V including the battery pack 1 include the thermal management complex 7 described above, so that a battery pack 1 having all the advantages due to the thermal management complex 7 described above, a device, apparatus, and equipment such as a vehicle V including the battery pack 1, and the like may be implemented.

[0282] The thermal management complex according to the present invention includes a heat barrier layer, and the heat barrier layer includes first inorganic filler particle, second inorganic filler particles, first reactive particles and second reactive particles.

[0283] The first inorganic filler particles and the second inorganic filler particles have a large specific surface area due to the very small average particle diameters thereof, thereby having excellent adsorption capacity. During thermal runaway, the first reactive particles and the second reactive particles may generate a binder that binds the first inorganic filler particles and WA12247S / Mk

[0284] 31 the second inorganic filler particles to each other.

[0285] When heat is applied from the outside, the first reactive particles and the second reactive particles may react with silicon and oxygen contained in a silicone-based resin matrix, thereby forming the binder. By the external heat, a silicate including an element contained in the first reactive particles and second reactive particles may be formed. For example, a binder containing alumina-zinc borate-silicate may be formed by external heat.

[0286] Accordingly, even if the heat barrier layer is sintered by external heat, it may have mechanical strength due to the inorganic filler particles and the binder. That is, after the heat barrier layer is sintered, a porous inorganic barrier layer containing the inorganic filler particles and the binder may be formed.

[0287] Here, the inorganic barrier layer may include pores with a high porosity present between the inorganic filler particles and between the binder.

[0288] Accordingly, the inorganic barrier layer may have improved mechanical strength and improved insulation properties.

[0289] The binder may connect the first inorganic filler particles and the second inorganic filler particles to each other, thereby forming a porous inorganic barrier layer and, accordingly, inhibiting or preventing heat transfer to an adjacent cell.

[0290] Accordingly, the thermal runaway prevention sheet according to the present invention may have improved thermal runaway prevention performance.

[0291] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples to make the effects of the present invention more clear, but the present invention is not limited thereto.

[0292] Preparation examples

[0293] A-l : First polysiloxane represented by Formula a below, having a molecular weight of 46,600 g / mol, and having a viscosity of about 19,000 mPa s to about 23,000 mPa s at 25°C: WA12247S / Mk

[0294] 32

[0295] [Formula a]

[0296] A-2: Fumed silica (specific gravity: 2.2 g / cm3, average particle diameter: 10 to40 nm)

[0297] A-3: Quartz (average particle diameter: 3 JMH)

[0298] B: Crosslinking agent (methylhydrogenpolysiloxane) having a viscosity of about 20 mm2 / s to 25 mm2 / s at 25 °C and represented by Formula b below:

[0299] [Formula b]

[0300] C-l : Second polysiloxane represented by Formula a, having a molecular weight of about 16,500 g / mol, and a viscosity of about 780 mPa s to about 1,180 mPa s at 25°C.

[0301] C-2: Third poly siloxane represented by Formula a, having a molecular weight of about 110,000 g / mol, and a viscosity of about 350,000 mPa s to about 700,000 mPa s at 25°C.

[0302] D: Leveling agent represented by Formula c below and having a viscosity of about 31 mPa- s to about 39 mPa s at 25°C. [Formula c]

[0303] ML 'j ni,

[0304] E: Alumina trihydrate (KH-5R)

[0305] F: Zinc borate compound (ZB-03)

[0306] G: Platinum-divinyltetramethyldisiloxane WA12247S / Mk

[0307] 33

[0308] H: Octylphosphonic acid

[0309] I: Octadecyl hydroxy polyglycol ether having a solid content of 37% to 40% and a viscosity of about 5,000 mPa- s to 10,000 mPa s at 25°C

[0310] J: Ethynyl cyclohexanol

[0311] 5

[0312] (1) A-l and A-2 were mixed in a weight ratio of 7 : 3 to prepare a first polysiloxane composition having an ethenyl group at its terminal (viscosity: 0.6 ~ 1.8 mio mPa s). Accordingly, C-l, D, E, F, G, H and I were added in contents shown in Table 1 below, thereby preparing the first silicone-based resin composition.

[0313] 10 [Table 1 ]

[0314] (2) Next, A-l and A-2 were mixed in a weight ratio of 7 : 3 to prepare a first poly siloxane WA12247S / Mk

[0315] 34 composition having an ethenyl group at its terminal. In addition, A-l and A-3 were mixed in a weight ratio of 3 : 7 to prepare a second poly siloxane composition. Accordingly, B, C-l, C-2 and J were added in contents shown in Table 2 below, thereby preparing a second silicone-based resin composition. [Table 2]

[0316] Examples 1 to 5

[0317] (3) A polyimide film (PI Advanced Materials Co., GF series, thickness: 25 JMH, thermal expansion coefficient: 16 ppm / °C (longitudinal direction, MD) and 17 ppm / °C (transverse direction, TD)) was surface-modified by corona discharge. Next, the prepared first silicone- based resin composition and second silicone-based resin composition were mixed in a weight ratio of 1 : 1, and then coated on the surface-modified polyimide film.

[0318] The coating layer was cured at about 60°C for about 5 minutes, thereby manufacturing thermal management complexes according to Table 3 below. WA12247S / Mk

[0319] 35

[0320] [Table 3 J

[0321] Comparative Example 1

[0322] A thermal management complex was manufactured in the same manner as in Example 1, except that a polyimide film was not subjected to surface modification by corona discharge.

[0323] Comparative Example 2

[0324] A single layer of MICA sheet was used.

[0325] Experimental Example Experimental Example 1 - Surface analysis WA12247S / Mk

[0326] 36

[0327] In the thermal management complex manufactured in each of Example 1 and Comparative Example 1, the surface where the polyimide film came into contact with the coating layer was cut into a size of 20 JMH X 20 JMH, and then the surface of the thermal management complex was analyzed using an atomic force microscope (AFM) under the following equipment and conditions. Results are shown in FIGS. 8 to 15. FIGS. 8 to 11 illustrate AFM photographs of the surface of the thermal management complex according to Example 1. FIGS. 12 to 15 illustrate AFM photographs of the surface of the thermal management complex according to a comparative example.

[0328] Specifically, the maximum height roughness (Rmax), the ten-point median roughness (Rz), the centerline average roughness (Ra) and the root mean square roughness (Rq) are summarized in Table 4.

[0329] - Analysis equipment: XE-100(Park Systems, Korea)

[0330] - Scan size: 20 JMH X 20 JMH

[0331] - Scan rate: 0.4Hz - Environment: Air

[0332] - Mode: Non-contact

[0333] - Cantilever: NCHR

[0334] WA12247S / Mk

[0335] 37

[0336] [Table 4]

[0337] Experimental Example 2 - Analysis of mechanical properties of protective layer

[0338] In the thermal management complex manufactured in each of Example 1 and

[0339] Comparative Example 1, the water contact angle, the wetting energy, the spreading coefficient and the work of adhesion were measured. Measurement results are summarized in Table 5 below.

[0340] Specifically, the water contact angle was obtained by dropping a drop of water on the surface of the surface-modified protective layer using a contact angle measurer (Phoenix 300 Touch, SEO Co.), and then measuring the angle between the protective layer and the water droplet.

[0341] The wetting energy may be measured according to ASTM D5946 using a contact angle measurer (Phoenix 300 Touch, SEO Co.).

[0342] The spreading coefficient may be measured according to ASTM D5946 using a contact angle measurer (Phoenix 300 Touch, SEO Co.). The work of adhesion may be measured according to ASTM D3330 using a universal tensile tester (UTM, Instron Co.). WA12247S / Mk

[0343] 38

[0344] [Table 5]

[0345] Experimental Example 3 - Analysis of peel strength of thermal management complex In the thermal management complex manufactured in each of Example 1 and

[0346] Comparative Example 1, the peel strength was measured according to ASTM D3330 standards. Results are summarized in Table 6 and FIGS. 16 and 17 below. WA12247S / Mk

[0347] 39

[0348] [Table 6]

[0349] From Tables 4 to 6, it can be confirmed that the surface roughness of the thermal management complex surface-modified by corona discharge in Example 1 is larger than that of Comparative Example 1, so that the adhesive force between the heat barrier layer and the protective layer is excellent, resulting in a high peel strength.

[0350] Experimental Example 4 - Tensile strength and elongation

[0351] In the thermal management complex manufactured in each of Examples 1 to 4 and Comparative Examples 1 to 3, the tensile strength and the elongation were measured by the ASTM D412 test method. Measurement results are summarized in Table 7 below. WA12247S / Mk

[0352] 40

[0353] [Table 7]

[0354] Experimental Example 5 - Thermal insulation I

[0355] A heat of about 600°C was applied to the polyimide film surface of the thermal management complex manufactured in each of Examples 1 to 4 and Comparative Examples 1 and 2 for about 5 minutes. Next, the highest temperature was measured on the upper surface of the heat barrier layer. Measurement results are shown in Table 8 below.

[0356] Experimental Example 6 - Thermal insulation II A heat of about 1400°C was applied to the polyimide film surface of the thermal management complex manufactured in each of Examples 1 to 4 and Comparative Examples 1 and 2 for 30 seconds using a torch. At this time, the highest temperature was measured on the upper surface of the heat barrier layer. Measurement results are shown in Table 8 below. WA12247S / Mk

[0357] 41

[0358] Experimental Example 7 - Thermal peeling test

[0359] The thermal management complex manufactured in each of Examples 1 to 4 and Comparative Examples 1 and 2 was left in an oven at about 600°C for about 30 minutes. Next, the presence or absence of peeling between the sintered heat barrier layer and the polyimide film was observed. Results are shown in Table 8 below.

[0360] [Table 8] complexes manufactured according to Examples 1 to 4 may be seen to be similar to those of the thermal management complex of Comparative Example 1 that has not surface-modified. However, it can be confirmed from Table 8 that the thermal management complexes manufactured according to Examples 1 to 4 have improved insulation properties compared to Comparative Example 1, and prevent peeling between the heat barrier layer and the polyimide film after heat treatment. In addition, Comparative Example 2 was easily broken or cracked, so it was impossible to measure tensile strength, elongation and whether or not there was peeling. WA12247S / Mk

[0361] 42

[0362] [Description of Symbols]

[0363] 1 : battery pack

[0364] 3 : heat barrier layer

[0365] 5: protective layer 7: thermal management complex

[0366] 10: battery module

[0367] 13, 15: secondary battery cell

[0368] 50: pack case

[0369] 100: silicone-based resin matrix 110: micropore

[0370] 210: first inorganic filler particle

[0371] 220: second inorganic filler particle

[0372] 310: first reactive particle

[0373] 320: second reactive particle 400: binder

Claims

1. WA12247S / Mk43[CLAIMS]

1. A thermal management complex, comprising: a protective layer; and a heat barrier layer provided on at least one surface of the protective layer, wherein the protective layer comprises a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer comprises a silicone-based resin matrix.

2. The thermal management complex according to claim 1, wherein the surface of the protective layer is modified by at least one method of corona discharge, plasma treatment, sand mat processing, ozone exposure treatment, flame exposure treatment, high-voltage electric shock exposure treatment, and ionizing radiation treatment.

3. The thermal management complex according to claim 1, wherein a centerline average roughness (Ra) of the surface of the surface-modified protective layer is 10 nm to 30 nm.

4. The thermal management complex according to claim 1, wherein a maximum height roughness (Rmax) of the surface of the surface-modified protective layer is 200 nm to 600 nm.WA12247S / Mk44

5. The thermal management complex according to claim 1, wherein a ten-point median roughness (Rz) of the surface of the surface-modified protective layer is 200 nm to 600 nm.

6. The thermal management complex according to claim 1, wherein a root mean square roughness (Rq) of the surface of the surface-modified protective layer is 10 nm to 40 nm.

7. The thermal management complex according to claim 1, wherein a water contact angle of the surface of the surface-modified protective layer is 30° to 70°.

8. The thermal management complex according to claim 1, wherein the protective layer has a heat shrinkage rate of 0.3% or less at 300°C.

9. The thermal management complex according to claim 1, wherein the thermal management complex has a peel strength of 0.01 kg / cm or more according to ASTM D3330.

10. The thermal management complex according to claim 1, wherein the thermal management complex has a tensile strength of 1 MPa to 100 MPa according to ASTM D412.WA12247S / Mk45

11. The thermal management complex according to claim 1, wherein the thermal management complex has an elongation of 30% to 200% according to ASTM D412.

12. The thermal management complex according to claim 1, wherein the protective layer comprises a polyimide-based resin, an epoxy-based resin, an amino-based resin, a phenol-based resin, a polyester-based resin, a polyurethane resin, or a combination thereof.

13. The thermal management complex according to claim 1, further comprising an adhesive layer disposed between the heat barrier layer and the protective layer, wherein the adhesive layer comprises a silicone-based, urethane-based, acrylic-based, rubber-based, polyester-based, polyamide-based, epoxy-based, vinyl alkyl ether-based, fluorinebased adhesive or a combination thereof.

14. The thermal management complex according to claim 1, wherein the heat barrier layer has a thickness of 500 JMH to 5000 JMH, and the protective layer has a thickness of 5 JMH to 100 JMH.

15. A battery pack, comprising: a secondary battery cell; and a thermal management complex disposed on one side of the secondary battery cell,WA12247S / Mk46 wherein the thermal management complex comprises a protective layer and a heat barrier layer disposed on at least one surface of the protective layer, the protective layer comprises a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer comprises a silicone-based resin matrix.

16. An energy storage system, comprising: a battery pack; and a motor driven by power supplied from the battery pack, wherein the battery pack comprises: a secondary battery cell; and a thermal management complex disposed on one side of the secondary battery cell, wherein the thermal management complex comprises a protective layer and a heat barrier layer disposed on at least one surface of the protective layer, the protective layer comprises a resin having a thermal expansion coefficient of 5 ppm / °C to 50 ppm / °C in a temperature range of 100°C to 200°C, the surface, provided with the heat barrier layer, of the protective layer is modified, and the heat barrier layer comprises a silicone-based resin matrix.

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