Specification
Title of invention: resin composition
Technical field
[One]
Mutual citation with related applications
[2]
This application claims the interest of priority based on Korean Patent Application No. 10-2018-0035748 filed March 28, 2018 and Korean Patent Application No. 10-2019-0029278 filed March 14, 2019. All contents disclosed in the document of the application are included as part of this specification.
[3]
Technical field
[4]
This application relates to a resin composition.
Background
[5]
The secondary battery includes a nickel cadmium battery, a nickel hydride battery, a nickel zinc battery, or a lithium secondary battery, and a representative one is a lithium secondary battery.
[6]
Lithium secondary batteries mainly use lithium oxide and carbon materials as positive and negative active materials, respectively. The lithium secondary battery includes an electrode assembly in which a positive electrode active material and a negative electrode active material are applied, respectively, and an electrode assembly in which a negative electrode plate is disposed with a separator interposed therebetween, and a casing material for sealing and receiving the electrode assembly together with an electrolyte. And pouch-type secondary batteries. This single secondary battery may be referred to as a battery cell.
[7]
In the case of a medium or large-sized device such as a vehicle or a power storage device, a battery module in which a large number of battery cells are electrically connected to each other may be used to increase capacity and output, or a battery pack in which a plurality of such battery modules are connected may be used.
[8]
One of the methods of configuring a battery module or a battery pack as described above is to use an adhesive material capable of fixing a plurality of battery cells inside the battery module. In this case, the adhesive material may be injected into the battery module through an adhesive material injection hole formed on the surface of the battery module.
[9]
On the other hand, as an adhesive material that can be used for the above purpose, a two-component urethane adhesive composition may be mentioned. In addition, the two-component urethane-based adhesive composition may include a filler in order to secure heat dissipation performance required for the adhesive material for a battery module.
Detailed description of the invention
Technical challenge
[10]
An object of the present application is to provide a resin composition for a battery module excellent in storage stability and fairness.
[11]
Another object of the present application is to provide a resin composition for a battery module excellent in heat dissipation, adhesion, cold resistance, heat resistance, insulation, and adhesion reliability.
[12]
Another object of the present application is to provide a battery module and a battery pack.
[13]
All of the above and other objects of the present application can be solved by the present application described in detail below.
Means of solving the task
[14]
In an example related to the present application, the present application relates to a composition used in a battery module or battery pack. Specifically, the composition of the present application may be a composition injected into the case of the battery module and used to fix the battery cell within the module case by contacting one or more battery cells present in the battery module, as described below. .
[15]
In the present application, as the composition, a urethane-based composition may be used. Specifically, in the present application, a two-component urethane-based composition may be used. Two-part urethane refers to a polyurethane formed by mixing an isocyanate-based compound and a polyol-based compound, and is distinguished from a one-component polyurethane having a urethane group in a single composition.
[16]
In the case of the two-component polyurethane, a subject including polyol and a curing agent including an isocyanate may react at room temperature to be cured. That is, the composition of the present application may be a room temperature curing type. In the present application, the term "room temperature" is a state that is not particularly heated or reduced in temperature, and any temperature within the range of about 10 to 30°C, for example, about 15°C or more, about 18°C ​​or more, about 20°C or more, or It is about 23 ℃ or more, and may mean a temperature of about 27 ℃ or less. The curing reaction may be aided by a catalyst such as dibutyltin dilaurate (DBTDL), for example. Accordingly, the two-part urethane-based composition may include a physical mixture of the main component (polyol) and the curing agent component (isocyanate), and/or may include a reactant (cured product) of the main component and the curing agent component.
[17]
The two-component urethane-based composition of the present application may include a main composition part (or main part) including at least a polyol resin, and a curing agent composition part (or a curing agent part) including at least polyisocyanate. Accordingly, the cured product of the resin composition may include both the polyol-derived unit and the polyisocyanate-derived unit. In this case, the polyol-derived unit may be a unit formed by urethane reaction of a polyol with a polyisocyanate, and the polyisocyanate-derived unit may be a unit formed by urethane reaction of a polyisocyanate and a polyol.
[18]
In the composition, additives may be used in order to secure a use or a function required according to the use. For example, a filler may be used to secure thixotropy according to process needs, or to secure physical properties such as thermal conductivity, insulation, heat resistance (TGA analysis), and heat dissipation (thermal conductivity). The form or method in which the filler is included in the resin composition is not particularly limited. For example, the filler may be used to form a urethane-based composition in a state previously included in the main composition part and/or the curing agent composition part. Alternatively, in the process of mixing the main composition part and the curing agent composition part, it may be used in a manner in which a separately prepared filler is mixed together. And the filler may be used in excess as described below.
[19]
As such, when an excessive amount of filler is used as needed, the viscosity of the composition may increase, and this increase in viscosity has a problem of deteriorating the processability of injecting the composition into the battery module. The use of a dispersant may be considered to prevent viscosity increase due to the use of fillers. On the other hand, depending on the kind of dispersant, in the reaction with the isocyanate group in the composition, the functional group of the dispersant may be in a competitive relationship with the polyol that must participate in the urethane bond. If the urethane reaction between the polyol and the isocyanate does not sufficiently occur due to the presence of the dispersant functional group, the curing speed of the composition injected into the module may be slowed down. Leaks, the interface between parts is lifted, and parts are contaminated. In addition, insufficient curing becomes an obstacle to securing predetermined physical properties required for heat-dissipating adhesive materials. Therefore, while using the filler to prevent excessive viscosity increase due to the use of an excessive filler, it is necessary to secure an appropriate viscosity realization through an appropriate level of curing, and finally, the physical properties required for the heat dissipating adhesive material must be achieved. As a result of the inventors of the present application earnestly researching this point, they have come to complete the invention of the present application.
[20]
In this regard, the two-component urethane-based composition of the present application, in addition to the filler, includes an anionic dispersant to suppress an increase in viscosity due to the use of the filler.
[21]
Specifically, the composition may include less than 20 parts by weight of an anionic dispersant based on 100 parts by weight of the total amount of the ester-based polyol resin and the polyisocyanate. When the content of the anionic dispersant is adjusted within the above range, the increase in viscosity due to the filler through the dispersant can be suppressed, and at the same time, a reduction in curing reaction or delay in curing speed due to the reactor of the anionic dispersant can be prevented. The lower limit of the content of the anionic dispersant is not particularly limited, but may be about 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, or 10 parts by weight or more in consideration of the meaning of limiting the content of the anionic dispersant mentioned above.
[22]
In one example, the filler may be included in the main composition part and/or the hardener composition part. In addition, the dispersant may be included in the main composition part or the hardener composition part including the filler, and may be included in the main composition part or the hardener composition part regardless of whether the filler is included.
[23]
Specifically, when the dispersant is included in the main composition part and/or the curing agent composition part, the content of the dispersant may be included in an amount less than 20 parts by weight relative to the resin or compound component included in each composition part. When the content range is satisfied, the desired physical properties may be sufficiently achieved through the use of the filler while suppressing the disadvantages caused by the use of the filler and the dispersant, as described above.
[24]
For example, when a filler and a dispersant are included in the curing agent composition, the highly reactive isocyanate gradually reacts with the functional group of the dispersant at room temperature. The viscosity of the composition portion is increased, and as a result, the storage stability of the curing agent composition portion is reduced. Therefore, when the curing agent composition part includes a dispersant, the dispersant is preferably included in an amount of less than 20 parts by weight based on 100 parts by weight of polyisocyanate. When the above range is satisfied, the above-described problems related to the addition of a dispersant can be minimized while preventing excessive increase in viscosity due to the use of the filler.
[25]
In addition, when the filler and the dispersant are also included in the main composition part, the dispersant in the main composition part also reacts with the isocyanate as the main composition part and the hardener composition part are mixed, and the curing reaction of the urethane-based composition may be delayed. Similarly, when the content of the dispersant used in the main composition is adjusted to less than 20 parts by weight compared to 100 parts by weight of the polyol resin, an appropriate curing speed is given to the adhesive material injected into the battery module, and as a result, the cured composition has the desired properties. I can have it.
[26]
In one example, the anionic dispersant may be a phosphoric acid ester dispersant. The phosphoric acid ester-based dispersant is not particularly limited as long as it contains a unit represented by the following formula (1).
[27]
[Formula 1]
[28]

[29]
In Formula 1, each of R1 and R2 may independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or a polyalkylene oxide having n repeating units of an alkylene oxide having 1 to 4 carbon atoms. The repeating unit n may be 1 to 5.
[30]
The kind or polarity of another functional group or chemical structure bonded to one end of Formula 1 is not particularly limited. For example, the dispersant may be adsorbed on the surface of the filler through the functional group of Formula 1, and by other functional groups or chemical structures bonded to one end of the functional group of Formula 1, it is necessary to disperse steric hindrance and steric repulsion. (steric repulsion) or ionic repulsion (ionic repulsion) effect can be obtained if it is sufficient.
[31]
In one example, the dispersant may be included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total filler component. When the above range is satisfied, the viscosity increase due to the use of the filler can be appropriately controlled through the dispersant.
[32]
In one example, the main composition part or the curing agent composition part, the initial viscosity measured within 24 hours at room temperature after mixing the constituents of each composition part (for example, mixing a filler and a dispersant with polyol or isocyanate) (V 1 ) May be less than or equal to 1,000,000 cP. At this time, the initial viscosity (V 1) May be a viscosity value measured at a point of 2.5/s when measured in a shear rate range of 0.01 to 10.0/s using a rheological property meter (ARES). For example, when the curing agent composition portion includes an isocyanate, a filler, and a dispersant, the viscosity of the curing agent composition portion prepared by mixing them increases with time, and the viscosity value measured within 24 hours may be 1,000,000 cP or less. More specifically, the curing agent composition portion may have an initial viscosity value of 500,000 cP or less, 400,000 cP or less, 300,000 cP or less, or 200,000 cP or less. Similarly, when the main composition part includes a polyol, a filler, and a dispersant, the main composition part may have an initial viscosity value of 500,000 cP or less, 450,000 cP or less, 400,000 cP or less, and 350,000 cP or less. The lower limit of the initial viscosity value is not particularly limited, for example, the curing agent composition part may be 50,000 cP or more or 100,000 cP or more, and the main composition part may be 50,000 cP or more, 100,000 cP or more, 150,000 cP or more, or 200,000 cP or more. That the initial viscosity satisfies the above value means that the viscosity is not too large because the dispersion effect by the addition of the dispersant is sufficient, and as a result, it means that the injection process can be performed smoothly.
[33]
In another example, each of the main composition part or the curing agent composition part may satisfy the following relational expression 1 after at least 2 months elapse. At this time, after 2 months has passed, it may mean after 60 days or 1,440 hours have passed.
[34]
[Relationship 1]
[35]
V 2 /V 1 ≥ 2
[36]
In the above relational formula 1, V 1 is the initial viscosity of the main composition part or the curing agent composition part, and V 2 is the viscosity measured after a predetermined period of time exceeding 24 hours after mixing the components (with respect to the main composition part or the curing agent composition part) , V 2 is a viscosity value measured at a point of 2.5/s when measured in a shear rate range of 0.01 to 10.0/s using a rheological property meter (ARES). The fact that the viscosity value that becomes more than twice the initial viscosity is secured after at least 2 months has elapsed means that the storage stability of each composition part is excellent.
[37]
In one example, an ester-based polyol resin may be used as the polyol resin included in the main composition part. In the case of using an ester-based polyol, it is advantageous in securing excellent adhesion and adhesion reliability in the battery module after curing the resin composition.
[38]
In one example, as the ester-based polyol, for example, a carboxylic acid-based polyol or a caprolactone-based polyol may be used.
[39]
The carboxylic acid-based polyol can be formed by reacting a component including a carboxylic acid and a polyol (ex. diol or triol, etc.), and the caprolactone-based polyol includes caprolactone and a polyol (ex. diol or triol, etc.). It can be formed by reacting components. In this case, the carboxylic acid may be a dicarboxylic acid.
[40]
In one example, the polyol may be a polyol represented by Formula 2 or 3 below.
[41]
[Formula 2]
[42]

[43]
[Formula 3]
[44]

[45]
In Formulas 2 and 3, X is a unit derived from a carboxylic acid, and Y is a unit derived from a polyol. The unit derived from the polyol may be, for example, a triol unit or a diol unit. In addition, n and m may be any number.
[46]
In the above formula, the carboxylic acid-derived unit is a unit formed by reacting a carboxylic acid with a polyol, and the polyol-derived unit is a unit formed by reacting a polyol with a carboxylic acid or caprolactone.
[47]
That is, when the hydroxy group of the polyol and the carboxyl group of the carboxylic acid react, the water (HO 2 ) molecule is desorbed by the condensation reaction to form an ester bond. X in Formula 2 is the carboxylic acid forms an ester bond by the condensation reaction. It means the part excluding the ester bonded part after that. Further, Y is a portion excluding the ester bond after the polyol forms an ester bond by the condensation reaction. The ester bond is represented by Formula 2.
[48]
In addition, Y in Formula 3 also represents a portion excluding the ester bond after the polyol forms an ester bond with caprolactone. The ester bond is represented in Chemical Formula 3.
[49]
Meanwhile, in the above formula, when the polyol-derived unit of Y is a unit derived from a polyol containing three or more hydroxy groups, such as a triol unit, a branched structure may be implemented in the Y portion in the above formula.
[50]
In Formula 2, the type of the carboxylic acid-derived unit of X is not particularly limited, but in order to secure desired physical properties, a phthalic acid unit, an isophthalic acid unit, a terephthalic acid unit, a trimellitic acid unit, a tetrahydrophthalic acid unit, a hexahydrophthalic acid unit, Tetrachlorophthalic acid unit, oxalic acid unit, adipic acid unit, azelaic acid unit, sebacic acid unit, succinic acid unit, malic acid unit, glataric acid unit, malonic acid unit, pimelic acid unit, suberic acid unit, 2,2-dimethyl It may be any one unit selected from the group consisting of succinic acid unit, 3,3-dimethylglutaric acid unit, 2,2-dimethylglutaric acid unit, maleic acid unit, fumaric acid unit, itaconic acid unit, and fatty acid unit. . Considering the low glass transition temperature in the above-described range, an aliphatic carboxylic acid-derived unit may be preferable to an aromatic carboxylic acid-derived unit.
[51]
On the other hand, the type of the polyol-derived unit of Y in Formulas 2 and 3 is not particularly limited, but in order to secure desired physical properties, an ethylene glycol unit, a dieltyylene glycol unit, a propylene glycol unit, a 1,2-butylene glycol unit, 2,3-butylene glycol unit, 1,3-propanediol unit, 1,3-butanediol unit, 1,4-butanediol unit, 1,6-hexanediol unit, neopentyl glycol unit, 1,2-ethylhexyl Diol unit, 1,5-pentanediol unit, 1,9-nonanediol unit, 1,10-decanediol unit, 1,3-cyclohexanedimethanol unit, 1,4-cyclohexanedimethanol unit, glycerin unit, and It may be any one or more selected from the group consisting of trimethylolpropane units.
[52]
Meanwhile, in Formula 2, n is an arbitrary number, and the range may be selected in consideration of the desired physical properties of the resin composition or the cured resin layer. For example, n may be about 2 to 10 or 2 to 5.
[53]
In addition, in Formula 3, m is an arbitrary number, and the range may be selected in consideration of the desired physical properties of the resin composition or the cured resin layer. For example, m is about 1 to 10 or 1 to 5 days. I can.
[54]
When n and m in Formulas 2 and 3 are out of the above range, crystallinity expression of the polyol increases, and the injection processability of the composition may be adversely affected.
[55]
The molecular weight of the polyol may be adjusted in consideration of the low viscosity characteristics, durability or adhesiveness described below, and may be, for example, in the range of about 300 to 2,000. If it is out of the above range, the reliability of the resin layer after curing may be poor, or problems related to volatile components may occur.
[56]
In the present application, a polyisocyanate may mean a compound including two or more isocyanate groups.
[57]
In the present application, the type of polyisocyanate included in the curing agent composition portion is not particularly limited.
[58]
In one example, a non-aromatic isocyanate compound that does not contain an aromatic group may be used to secure desired physical properties. That is, it may be advantageous to use aliphatic or cycloaliphatic series. In the case of using an aromatic polyisocyanate, since the reaction rate may be too fast and the glass transition temperature of the cured product may be increased, it may be difficult to secure fairness and physical properties suitable for use of the composition of the present application.
[59]
For example, aliphatic or alicyclic polyisocyanate or a modified product thereof may be used. Specifically, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, or tetramethylene diisocyanate; Aliphatic cyclic polyisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanate methyl)cyclohexane diisocyanate or dicyclohexylmethane diisocyanate; Or any one or more of the above carbodiimide-modified polyisocyanate or isocyanurate-modified polyisocyanate; Etc. can be used. In addition, a mixture of two or more of the compounds listed above may be used.
[60]
The ratio of the polyol-derived resin component and the polyisocyanate-derived resin component in the resin composition is not particularly limited, and may be appropriately adjusted to enable a urethane reaction therebetween.
[61]
As described above, in order to secure heat dissipation (thermal conductivity) or to secure thixotropy according to process needs, an excessive amount of filler may be included in the composition. When an excessive amount of filler is used, the viscosity of the composition increases and the battery module Fairness when injecting the composition into the case of may deteriorate. Therefore, there is a need for sufficient low viscosity properties to include an excess of filler and not interfere with fairness. In addition, if only a low viscosity is shown, it is also difficult to secure fairness, so appropriate thixotropy is required, and during curing, it may be necessary to exhibit excellent adhesion, and the curing itself may need to proceed at room temperature. In addition, ester-based polyols are advantageous in securing adhesion after curing, but because they have strong crystallinity, they are highly likely to become waxy at room temperature, and there is a disadvantage in securing proper injection processability due to an increase in viscosity. Even if the viscosity is lowered through melting, due to the crystallinity that occurs naturally in the storage process, viscosity increase due to crystallization in the injection or application process of the composition that can be followed after mixing with the filler occurs. And, as a result, fairness may deteriorate. In consideration of this point, the ester-based polyol used in the present application may satisfy the following characteristics.
[62]
In the present application, the ester-based polyol may be amorphous or a polyol having sufficiently low crystallinity. In the above, "amorphous" means a case where the crystallization temperature (Tc) and melting temperature (Tm) are not observed in DSC (Differential Scanning calorimetry) analysis. The DSC analysis can be performed using a known apparatus, for example, Q2000 (TA Instruments Co., Ltd.). Specifically, the DSC analysis can be performed at a rate of 10°C/min (min) within the range of -80 to 60°C, for example, after raising the temperature from 25°C to 50°C at the rate, -70°C It can be made by reducing the temperature to, and raising the temperature to 50 ℃ again. In addition, "sufficiently low crystallinity" means that the melting point or melting temperature (Tm) observed in DSC analysis is less than 15°C, about 10°C or less, 5°C or less, 0°C or less, -5°C or less, -It means less than 10℃, or-less than 20℃. At this time, the lower limit of the melting point is not particularly limited, but, for example, the melting point may be about -80°C or higher, about -75°C or higher, or about -70°C or higher. When the polyol is crystallinity or does not satisfy the melting point range (at room temperature) when crystallinity is strong, the viscosity difference according to temperature tends to be large, so the dispersion of the filler and the viscosity of the final mixture in the process of mixing the filler and the resin It may adversely affect the process, deteriorate processability, and as a result, it may be difficult to satisfy the cold resistance, heat resistance, and water resistance required in the adhesive composition for a battery module.
[63]
1 is an example of determining the amorphous or sufficiently low crystallinity of the ester-based polyol, and is a graph showing DSC analysis results for several polyols. According to the present application, Sample #1 may be determined to be amorphous, and Sample #2 and #3 may be determined to have sufficiently low crystallinity. On the other hand, in the case of sample #4 with a melting temperature (Tm) of 33.52 ℃, it can be said that the crystallinity is high.
[64]
In one example, the polyol resin and the isocyanate component included in the urethane-based composition may have a glass transition temperature (Tg) of less than 0°C after curing. "Glass transition temperature after curing" means in this application, the room temperature and 30-70% relative humidity conditions against a 24-hour-cured state, 2250 cm as evidenced by FT-IR analysis -1 NCO peak based on the conversion rate in the vicinity of ( Conversion) may be a glass transition temperature measured for a cured product having 80% or more. The glass transition temperature may be measured after curing the polyol resin and the isocyanate component (without filler).
[65]
When the glass transition temperature range is satisfied, brittle characteristics can be secured within a relatively short time even at a low temperature at which the battery module or battery pack can be used, thereby ensuring impact resistance or vibration resistance. I can. On the other hand, if the above range is not satisfied, there is a possibility that tacky of the cured product is too high or thermal stability is deteriorated. In one example, the lower limit of the glass transition temperature of the urethane-based composition after curing may be -70°C or higher, -60°C or higher, -50°C or higher, -40°C or higher, or -30°C or higher, and the upper limit is -5 ℃ or less, -10 ℃ or less, -15 ℃ or less, or may be -20 ℃ or less.
[66]
In one example, at least, the filler included in the composition may be a thermally conductive filler. In the present application, the term thermally conductive filler may mean a material having a thermal conductivity of about 1 W/mK or more, about 5 W/mK or more, about 10 W/mK or more, or about 15 W/mK or more. Specifically, the thermal conductivity of the thermally conductive filler may be about 400 W/mK or less, about 350 W/mK or less, or about 300 W/mK or less. The type of the thermally conductive filler that can be used is not particularly limited, but may be a ceramic filler when insulating properties are considered together. For example, ceramic particles such as alumina, aluminum nitride (AlN), boron nitride (BN), silicon nitride, SiC or BeO may be used. The shape or ratio of the filler is not particularly limited, and is appropriately adjusted in consideration of the viscosity of the urethane-based composition, the possibility of sedimentation in the cured resin layer, the desired heat resistance or thermal conductivity, insulation, filling effect, or dispersibility. Can be. In general, as the size of the filler increases, the viscosity of the composition containing the filler increases, and the likelihood that the filler precipitates in the resin layer increases. In addition, as the size decreases, the thermal resistance tends to increase. Therefore, in consideration of the above points, a filler of an appropriate type and size may be selected, and if necessary, two or more fillers may be used together. In addition, it is advantageous to use a spherical filler in consideration of the amount to be filled, but a filler in a form such as a needle or plate may be used in consideration of network formation or conductivity. The thermal conductivity of the filler can be measured according to a known method, in which case,
[67]
In one example, the composition may include a thermally conductive filler having an average particle diameter in the range of 0.001 μm to 80 μm. In another example, the average particle diameter of the filler may be 0.01 µm or more, 0.1 µm or more, 0.5 µm or more, 1 µm or more, 2 µm or more, 3 µm or more, 4 µm or more, 5 µm or more, or about 6 µm or more. In other examples, the average particle diameter of the filler is about 75 μm or less, about 70 μm or less, about 65 μm or less, about 60 μm or less, about 55 μm or less, about 50 μm or less, about 45 μm or less, about 40 μm or less, about It may be 35 μm or less, about 30 μm or less, about 25 μm or less, about 20 μm or less, about 15 μm or less, about 10 μm or less, or about 5 μm or less. The average particle diameter may be measured using a particle size analysis (PSA) equipment. In one example, the average particle size may mean D(50), which is the 50th-ranked particle size when ranking particles from 1 to 100 for each size.
[68]
In order to obtain excellent heat dissipation performance, it may be considered that a thermally conductive filler is used in a high content. For example, the filler may be used within a range of about 50 to 2,000 parts by weight, based on 100 parts by weight of the total resin component, that is, the total amount of the ester-based polyol resin and polyisocyanate. In another example, the content of the filler may be used in excess of the total resin component. Specifically, based on 100 parts by weight of the total amount of the ester-based polyol resin and polyisocyanate, about 100 parts by weight or more, about 150 parts by weight or more, about 200 parts by weight or more, about 250 parts by weight or more, about 300 parts by weight or more, About 350 parts by weight or more, about 400 parts by weight or more, about 500 parts by weight or more, about 550 parts by weight or more, about 600 parts by weight or more, or about 650 parts by weight or more of a filler may be used. In one example, when the filler is used in the above range, it may be distributed in the same amount to the main composition part and the hardener composition part.
[69]
In one example, the moisture content of the filler may be 1,000 ppm or less. The moisture content can be measured with a karl fishcer titrator (KR831) under conditions of a relative humidity of 10% and a drift of 5.0 or less. In this case, the moisture content may be an average moisture content of all fillers used in the resin composition. In the present application, a filler that satisfies the above conditions may be selectively used, or after drying the filler to be used in an oven at a temperature of about 200° C., the moisture content of the filler may be adjusted to satisfy the moisture content range. In another example, the upper limit of the moisture content of the filler may be 800 ppm or less, 600 ppm or less, or 400 ppm or less, and the lower limit may be 100 ppm or more or 200 ppm or more.
[70]
As described above, when the thermally conductive filler is used in a high content, the viscosity of the main composition part including the filler, the curing agent composition part, or the composition including the same may increase. As described, if the viscosity of the resin composition is too high, the injection processability is not good, and accordingly, physical properties required for the resin layer may not be sufficiently implemented in the entire resin layer. In consideration of this point, it is preferable to use a liquid or low viscosity component capable of having sufficient flow as the resin component.
[71]
In one example, each of the ester-based polyol resin and the polyisocyanate component may have a viscosity of 10,000 cP or less. Specifically, the resin component may have a viscosity of 8,000 cP or less, 6,000 cP or less, 4,000 cP or less, 2,000 cP, or 1,000 CP or less. Preferably, the upper limit of the viscosity may be 900 cP or less, 800 cP or less, 700 cP or less, 600 cP or less, 500 cP or less, or 400 cP or less. Although not particularly limited, the lower limit of the viscosity of each resin component may be 50 cP or more or 100 cP or more. If the viscosity is too low, fairness may be good, but as the molecular weight of the raw material decreases, the possibility of volatilization increases, and heat resistance/cold resistance, flame retardance, and adhesion may deteriorate, and this disadvantage can be prevented by satisfying the lower limit range. The viscosity may be measured at room temperature using, for example, a Brookfield LV type viscometer.
[72]
In addition to the above, various types of fillers may be used. For example, in order to secure the insulating properties of the resin layer cured with the resin composition, use of a carbon (based) filler such as graphite may be considered. Alternatively, for example, a filler such as fumed silica, clay or calcium carbonate may be used. The form or content ratio of the filler is not particularly limited, and may be selected in consideration of the viscosity of the resin composition, the possibility of sedimentation in the resin layer, thixotropy, insulation, filling effect, or dispersibility.
[73]
In addition, the resin composition may further include a flame retardant or a flame retardant auxiliary. In this case, a known flame retardant may be used without particular limitation, and for example, a solid filler type flame retardant or a liquid flame retardant may be applied. Examples of the flame retardant include organic flame retardants such as melamine cyanurate and inorganic flame retardants such as magnesium hydroxide. If the amount of filler to be filled in the resin layer is large, a liquid-type flame retardant material (TEP, Triethyl phosphate or TCPP, tris(1,3-chloro-2-propyl)phosphate, etc.) may be used. In addition, a silane coupling agent capable of acting as a flame retardant enhancing agent may be added.
[74]
The composition may include the configuration as described above, and may be a solvent-type composition, an aqueous composition, or a solvent-free composition, but in consideration of convenience of the manufacturing process described below, a solvent-free type may be appropriate.
[75]
The composition of the present application may have physical properties suitable for use as described below after curing. Among the physical properties mentioned in the present specification, when the measured temperature affects the physical properties, the physical properties may be those measured at room temperature unless otherwise stated. In addition, the expression "after curing" in relation to physical properties may have the same meaning as described above in relation to the glass transition degree.
[76]
In one example, the resin composition has a predetermined adhesive strength at room temperature after curing (S 1). Specifically, the resin layer may have an adhesive strength of about 150 gf/10mm or more, 200 gf/10mm or more, 250 gf/10mm or more, 300 gf/10mm or more, 350 gf/10mm or more, or 400 gf/10mm or more. When the adhesive force satisfies the above range, appropriate impact resistance and vibration resistance can be secured. The upper limit of the adhesive force of the resin layer is not particularly limited, and for example, about 1,000 gf/10mm or less, 900 gf/10mm or less, 800 gf/10mm or less, 700 gf/10mm or less, 600 gf/10mm or less, or 500 gf/ It may be about 10 mm or less. If the adhesion is too high, there is a risk that the cured composition and the portion of the pouch to which it adheres are torn. Specifically, in the event of an impact such as to change the shape of the battery module due to an accident while driving a car, if the battery cell is attached too strongly through the cured resin layer, the pouch is torn and the dangerous substances inside the battery are exposed or exploded. can do. The adhesion can be measured for an aluminum pouch. For example, an aluminum pouch used for manufacturing a battery cell is cut to a width of about 10 mm, a resin composition is loaded on a glass plate, and the cut aluminum pouch is placed on the pouch's PET (poly(ethylene terephthalate)). ) After loading so that the surface and the resin composition are in contact, the resin composition is cured at 25° C. and 50% RH for 24 hours, and the aluminum pouch is subjected to a peel angle of 180° and 300 mm/min with a tensile tester (Texture analyzer). The adhesion can be measured while peeling at a peeling rate of.
[77]
In another example, the adhesive strength after curing of the resin composition may be maintained at a considerable level even under high temperature/high humidity. Specifically, in the present application, with respect to the adhesive force (S 1 ) after curing measured at room temperature, the % of the adhesive force (S 2 ) measured by the same method after performing a high temperature/high humidity acceleration test performed under a predetermined condition The ratio [(S 2 /S 1 ) x 100] may be 70% or more, or 80% or more. In one example, the high temperature/high humidity acceleration test may be measured after storing the same specimen as the specimen used to measure the room temperature adhesion for 10 days at a temperature of 40 to 100° C. and a humidity condition of 75% RH or more. When the above adhesion and relationship are satisfied, excellent adhesion durability can be maintained even when the use environment of the battery module changes.
[78]
In one example, the resin composition may have excellent heat resistance after curing. In this regard, when the composition of the present application does not contain a filler, when thermogravimetric analysis (TGA) is measured for a cured product of only the resin component, the temperature of 5% weight loss is 120°C. It can be more than that. In addition, when the composition of the present application includes a filler, when thermogravimetric analysis (TGA) is measured for the cured product of the resin composition, the remaining amount at 800° C. may be 70% by weight or more. In another example, the residual amount of 800° C. may be about 75% by weight or more, about 80% by weight or more, about 85% by weight or more, or about 90% by weight or more. In another example, the residual amount of 800° C. may be about 99% by weight or less. At this time, thermogravimetric analysis (TGA) may be measured in a range of 25 to 800°C at a temperature increase rate of 20°C/min in a nitrogen (N 2 ) atmosphere of 60 cm 3 /min . Heat resistance properties related to the thermogravimetric analysis (TGA) can be secured by controlling the type or content of resins and/or fillers.
[79]
In one example, the resin composition may have excellent electrical insulation after curing. In the battery module structure described below, when the resin layer exhibits a predetermined electrical insulating property, the performance of the battery module can be maintained and stability can be ensured. For example, the cured product of the resin composition may have an insulation breakdown voltage of about 10 kV/mm or more, 15 kV/mm or more, or 20 kV/mm or more, measured according to ASTM D149. The dielectric breakdown voltage is not particularly limited as the resin layer exhibits excellent insulation as the value increases, but considering the composition of the resin layer, about 50 kV/mm or less, 45 kV/mm or less, 40 kV/mm or less , 35 kV/mm or less, or 30 kV/mm or less. The dielectric breakdown voltage in the above range can be secured, for example, by adjusting the content of the filler and resin components described above.
[80]
In another example related to the present application, the present application relates to a battery module. The module includes a module case and a battery cell. The battery cell may be housed in the module case. One or more battery cells may exist in the module case, and a plurality of battery cells may be accommodated in the module case. The number of battery cells accommodated in the module case is not particularly limited as it is adjusted according to the use or the like. Battery cells accommodated in the module case may be electrically connected to each other.
[81]
The module case may include at least a sidewall and a lower plate forming an inner space in which the battery cells can be accommodated. In addition, the module case may further include an upper plate sealing the inner space. The sidewall, the lower plate, and the upper plate may be integrally formed with each other, or the module case may be formed by assembling separate sidewalls, lower plates and/or upper plates respectively. The shape and size of the module case is not particularly limited, and may be appropriately selected according to the purpose or the shape and number of battery cells accommodated in the internal space.
[82]
In the above, the terms upper plate and lower plate are terms of a relative concept used to distinguish them because there are at least two plates constituting the module case. In other words, it does not mean that the upper plate must be present on the upper side and the lower plate must be present on the lower side in the actual use state.
[83]
FIG. 2 is a view showing an exemplary module case 10, and is an example of a case 10 in the form of a box including one lower plate 10a and four side walls 10b. The module case 10 may further include an upper plate 10c sealing the inner space.
[84]
3 is a schematic view of the module case 10 of FIG. 2 in which the battery cells 20 are accommodated, as viewed from above.
[85]
Holes may be formed in the lower plate, sidewall and/or upper plate of the module case. As will be described later, the hole may be an injection hole used to inject a material for forming the resin layer, that is, a resin composition when a resin layer is formed by an injection process. The shape, number, and position of the holes may be adjusted in consideration of the injection efficiency of the resin layer-forming material. In one example, the hole may be formed in at least the lower plate and/or the upper plate.
[86]
In one example, the hole may be formed at about 1/4 to 3/4 point, about 3/8 to 7/8 point, or about the middle part of the total length of the side wall, the lower plate, or the upper plate. By injecting the resin composition through the injection hole formed at this point, it can be injected so that the resin layer has a wide contact surface. The 1/4, 3/4, 3/8, or 7/8 points are, for example, as shown in FIG. 4, the total length (L ), it is the ratio of the distance (A) to the formation position of the hole. In addition, the end (E) where the length (L) and the distance (A) are formed may be any end (E) as long as the length (L) and the distance (A) are measured from the same end (E). have. In FIG. 4, the injection hole 50a is located in an approximately middle portion of the lower plate 10a.
[87]
The size and shape of the injection hole are not particularly limited, and may be adjusted in consideration of the injection efficiency of the resin layer material to be described later. For example, the hole may be polygonal or amorphous, such as a circle, an oval, a triangle, or a square. The number of injection holes and their spacing are not particularly limited, and as described above, the resin layer may be adjusted to have a large contact area with the lower plate.
[88]
Observation holes (eg, (50b) in FIG. 4) may be formed at ends of the upper plate and the lower plate in which the injection holes are formed. The observation hole may be formed to observe whether the injected material is well injected to the end of the side wall, the lower plate, or the upper plate, for example, when the resin layer material is injected through the injection hole. The position, shape, size, and number of the observation holes are not particularly limited as long as they are formed to confirm whether the injected material is properly injected.
[89]
The module case may be a thermally conductive case. The term thermally conductive case means a case including a portion having a thermal conductivity of 10 W/mk or more, or at least as described above. For example, at least one of the above-described sidewall, lower plate, and upper plate may have the thermal conductivity described above. In another example, at least one of the sidewall, the lower plate, and the upper plate may include a portion having the thermal conductivity. For example, the battery module of the present application may include a first filler-containing cured resin layer in contact with the upper plate and the battery cell, and a second filler-containing cured resin layer in contact with the lower plate and the battery cell, as described later. However, at least the second filler-containing cured resin layer may be a thermally conductive resin layer, and accordingly, at least the lower plate may have thermal conductivity or may include a thermally conductive portion.
[90]
In the above, the thermal conductivity of the upper plate, lower plate, sidewall, or thermally conductive portion, which is thermally conductive, is 20 W/mk or more, 30 W/mk or more, 40 W/mk or more, 50 W/mk or more, 60 W/ mk or more, 70 W/mk or more, 80 W/mk or more, 90 W/mk or more, 100 W/mk or more, 110 W/mk or more, 120 W/mk or more, 130 W/mk or more, 140 W/mk or more , 150 W/mk or more, 160 W/mk or more, 170 W/mk or more, 180 W/mk or more, 190 W/mk or more, or 195 W/mk or more. The higher the thermal conductivity, the higher the value is, the more advantageous it is in terms of heat dissipation characteristics of the module, and thus the upper limit thereof is not particularly limited. In one example, the thermal conductivity is about 1,000 W/mK or less, 900 W/mk or less, 800 W/mk or less, 700 W/mk or less, 600 W/mk or less, 500 W/mk or less, 400 W/mk or less, It may be 300 W/mk or 250 W/mK or less, but is not limited thereto. The type of material exhibiting the above thermal conductivity is not particularly limited, and examples include metal materials such as aluminum, gold, pure silver, tungsten, copper, nickel or platinum. The module case may be entirely made of the thermally conductive material as described above, or at least a portion of the module case may be made of the thermally conductive material. Accordingly, the module case may include at least one portion having a thermal conductivity in the above-mentioned range or a portion having the above-mentioned thermal conductivity.
[91]
In the module case, the portion having the thermal conductivity in the above range may be a portion in contact with the resin layer and/or the insulating layer to be described later. In addition, the portion having the thermal conductivity may be a portion in contact with a cooling medium such as cooling water. In the case of having such a structure, heat generated from the battery cell can be effectively discharged to the outside.
[92]
The type of battery cells accommodated in the module case is also not particularly limited, and various known battery cells may be applied. In one example, the battery cell may be a pouch type. Referring to FIG. 5, the pouch-type battery cell 100 may typically include an electrode assembly, an electrolyte, and a pouch case.
[93]
5 is an exploded perspective view schematically showing the configuration of an exemplary pouch-type cell, and FIG. 6 is a combined perspective view of the configuration of FIG. 5.
[94]
The electrode assembly 110 included in the pouch-shaped cell 100 may have a form in which one or more positive plates and one or more negative plates are disposed with a separator therebetween. The electrode assembly 110 may be a winding type in which one positive plate and one negative plate are wound together with a separator, or a stack type in which a plurality of positive plates and a plurality of negative plates are alternately stacked with a separator interposed therebetween.
[95]
The pouch exterior material 120 may be configured in a form including, for example, an outer insulating layer, a metal layer, and an inner adhesive layer. These exterior materials 120 protect internal elements such as the electrode assembly 110 and the electrolyte, and include a thin metal film such as aluminum in consideration of supplementation and heat dissipation properties of the electrode assembly 110 and the electrolyte. I can. The metal thin film may be interposed between an insulating layer formed of an insulating material in order to secure electrical insulation from elements such as the electrode assembly 110 and an electrolyte or other elements outside the battery 100. In addition, the pouch may further include a polymer resin layer (substrate) such as PET.
[96]
In one example, the exterior material 120 may include an upper pouch 121 and a lower pouch 122, and at least one of the upper pouch 121 and the lower pouch 122 has a concave inner space (I) Can be formed. The electrode assembly 110 may be accommodated in the inner space I of the pouch. A sealing part S is provided on the outer circumferential surfaces of the upper pouch 121 and the lower pouch 122, and the sealing parts S are adhered to each other, so that the inner space in which the electrode assembly 110 is accommodated may be sealed.
[97]
Each electrode plate of the electrode assembly 110 is provided with an electrode tab, and one or more electrode tabs may be connected to the electrode lead. The electrode lead is interposed between the sealing portion S of the upper pouch 121 and the lower pouch 122 and exposed to the outside of the exterior material 120, thereby functioning as an electrode terminal of the secondary battery 100.
[98]
The shape of the pouch-type cell described above is only an example, and the battery cell applied in the present application is not limited to the above type. In the present application, known various types of pouch-type cells or other types of batteries may all be applied as battery cells.
[99]
The battery module of the present application may further include a resin layer. Specifically, the battery module of the present application may include a cured resin layer in which the filler-containing composition is cured. The cured resin layer may be formed from the urethane-based composition described above.
[100]
The battery module may include, as the resin layer, a first filler-containing cured resin layer in contact with the upper plate and battery cells, and a second filler-containing cured resin layer in contact with the lower plate and battery cells. At least one of the first and second filler-containing cured resin layers may include the cured product of the urethane-based composition described above, and thus may have a predetermined adhesion, cold resistance, heat resistance, and insulation as described above. In addition, the first and second filler-containing cured resin layers may have the following characteristics.
[101]
In one example, the resin layer may be a thermally conductive resin layer. In this case, the thermal conductivity of the thermally conductive resin layer may be about 1.5 W/mK or more, about 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or 4 W/mK or more. . The thermal conductivity is 50 W/mK or less, 45 W/mk or less, 40 W/mk or less, 35 W/mk or less, 30 W/mk or less, 25 W/mk or less, 20 W/mk or less, 15 W/mk Hereinafter, it may be 10 W/mK or less, 5 W/mK or less, 4.5 W/mK or less, or about 4.0 W/mK or less. When the resin layer is a thermally conductive resin layer as described above, the lower plate, the upper plate, and/or the sidewall to which the resin layer is attached may be a portion having a thermal conductivity of 10 W/mK or more. In this case, the portion of the module case showing the thermal conductivity may be a portion in contact with a cooling medium, for example, cooling water. The thermal conductivity of the resin layer is measured using a known hot disk device, and is a value measured according to, for example, ASTM D5470 standard or ISO 22007-2 standard. The thermal conductivity of the resin layer as described above can be secured, for example, by appropriately adjusting the filler contained in the resin layer and the content ratio thereof as described above.
[102]
In one example, the heat resistance of the resin layer or the battery module to which the resin layer is applied in the battery module is 5 K/W or less, 4.5 K/W or less, 4 K/W or less, 3.5 K/W or less, 3 K /W or less or about 2.8 K/W or less. When the resin layer or the battery module to which the resin layer is applied is controlled so that the thermal resistance within the above range is displayed, excellent cooling efficiency or heat dissipation efficiency can be ensured. The measurement of the thermal resistance may be calculated based on the temperature measured from the sensor by attaching a temperature sensor according to the cell position on the module while driving the battery module. The method of measuring the heat resistance is not particularly limited, and for example, the heat resistance may be measured according to ASTM D5470 standard or ISO 22007-2 standard.
[103]
In one example, the resin layer may be a resin layer formed to maintain durability even in a predetermined thermal shock test. The thermal shock test can be carried out in a manner known in the art. For example, when holding for 30 minutes at a low temperature of about -40°C and then raising the temperature to 80°C for 30 minutes as one cycle, the module case of the battery module after the thermal shock test repeated 100 times or It may be a resin layer that may not be peeled off or cracked from the battery cell. For example, when the battery module is applied to a product that requires a long warranty period (about 15 years or more in the case of a vehicle), such as a vehicle, the above-described level of performance may be required to secure durability.
[104]
In one example, the resin layer may be a flame retardant resin layer. In the present application, the term flame-retardant resin layer may mean a resin layer exhibiting a V-0 rating in UL 94 V Test (Vertical Burning Test). Through this, it is possible to secure stability against fire and other accidents that may occur in the battery module.
[105]
In one example, the resin layer may have a specific gravity of 5 or less. In another example, the specific gravity may be 4.5 or less, 4 or less, 3.5 or less, or 3 or less. A resin layer exhibiting a specific gravity in this range is advantageous for manufacturing a more lightweight battery module. As the specific gravity is lower, the lower the value is, the more advantageous it is to reduce the weight of the module, so the lower limit thereof is not particularly limited. For example, the specific gravity may be about 1.5 or more or 2 or more. Components added to the resin layer may be adjusted in order for the resin layer to exhibit specific gravity in the above range. For example, when the filler is added, a filler capable of securing a desired thermal conductivity even at as low a specific gravity as possible, that is, a filler having a low specific gravity by itself, or a filler having a surface treatment may be used.
[106]
In one example, it is preferable that the resin layer does not contain volatile substances. For example, the resin layer may have a nonvolatile content of 90% by weight or more, 95% by weight or more, or 98% by weight or more. In the above, the nonvolatile component and its ratio can be defined in the following manner. That is, the portion remaining after the resin layer is maintained at 100° C. for about 1 hour can be defined as a nonvolatile component. Therefore, the ratio of the non-volatile component can be measured based on the initial weight of the resin layer and the ratio after being maintained at 100° C. for about 1 hour.
[107]
In one example, it may be advantageous for the resin layer to have a low shrinkage during the curing process or after curing. Through this, it is possible to prevent the occurrence of delamination or voids that may occur during the manufacturing or use of the module. The shrinkage rate may be appropriately adjusted within a range capable of exhibiting the above-described effect, and may be, for example, less than 5%, less than 3%, or less than about 1%. Since the shrinkage ratio is more advantageous as the value is lower, the lower limit thereof is not particularly limited.
[108]
In one example, the resin layer may have a low coefficient of thermal expansion (CTE) in order to prevent peeling or voids that may occur during the manufacturing or use of the module. The coefficient of thermal expansion may be, for example, less than 300 ppm/K, less than 250 ppm/K, less than 200 ppm/K, less than 150 ppm/K, or less than about 100 ppm/K. The lower the value of the coefficient of thermal expansion is, the more advantageous it is, the lower limit thereof is not particularly limited. The method of measuring the coefficient of thermal expansion is not particularly limited. For example, by using TMA (Thermo Mechanical Analyze) in expansion mode, under 0.05 N load, it is measured at 5 ℃/min in the range of -40 to 125 degrees. The coefficient of thermal expansion can be measured in a way to check.
[109]
In one example, in order to impart excellent durability or impact resistance to the battery module, the resin layer may have an appropriate level of tensile strength. For example, the resin layer may be configured to have a Young's modulus of about 1.0 MPa or more. Young's modulus is measured in tensile mode at low temperature (about -40°C), room temperature (about 25°C), and high temperature (about 80°C) for each point within the range of -40 to 80°C, for example. It may be a slope value in the case of Young's modulus is measured lower as the temperature increases. For example, the resin layer of the present application may have a Young's modulus of 1.0 Mpa or more, more specifically, in the range of 10 to 500 Mpa within the section. When the Young's Modulus is less than the above range, the function of fixing a cell having a large weight is not good, and when the Young's Modulus is too large, since the brittle characteristic is strong, cracks may occur in an impact situation such as a vehicle collision.
[110]
In one example, it may be advantageous for the resin layer to exhibit an appropriate hardness. For example, if the hardness of the resin layer is too high, since the resin layer has brittle characteristics, reliability may be adversely affected. In consideration of these points, impact resistance and vibration resistance can be secured and durability of the product can be secured by adjusting the hardness of the resin layer. The resin layer, for example, has a hardness of less than 100, 99 or less, 98 or less, 95 or less, or 93 or less in Shore A type, or has a hardness of less than about 80, about 70 or less, or about 70 or less in Shore D type. It may be 65 or less or about 60 or less. The lower limit of the hardness is not particularly limited. For example, the hardness may be about 60 or more in the shore A type, or about 5 or more or about 10 or more in the shore 00 type. The hardness in the above range can be secured by adjusting the content of the filler. Shore hardness can be measured according to a known method using a hardness tester suitable for each type, such as a shore A hardness tester. Known methods include ASTM D2240 and the like.
[111]
By forming a cured resin layer that satisfies the above characteristics in the battery module as described above, a battery module having excellent durability against external shock or vibration can be provided.
[112]
In the battery module of the present application, at least one of the sidewall, the lower plate, and the upper plate in contact with the resin layer may be the thermally conductive sidewall, the lower plate, or the upper plate. Meanwhile, in the present specification, the term contact means, for example, the resin layer and the upper plate, the lower plate and/or the sidewall or the battery cell are in direct contact, or other elements, such as an insulating layer, are present therebetween. It can also mean a case. In addition, the resin layer in contact with the thermally conductive sidewall, the lower plate, or the upper plate may be in thermal contact with the object. In this case, in the thermal contact, the resin layer is in direct contact with the lower plate or the like, or another element such as an insulating layer to be described later exists between the resin layer and the lower plate. It may mean a state in which heat transfer from the battery cell to the resin layer and from the resin layer to the lower plate is not obstructed. In the above, that it does not interfere with the transfer of heat means that even when another element (ex. an insulating layer or a guiding part to be described later) exists between the resin layer and the lower plate, the total thermal conductivity of the other element and the resin layer. Is about 1.5 W/mK or more, about 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or 4 W/mK or more, or is in contact with the resin layer and This means that the total thermal conductivity of the lower plate, etc., is within the above range even when the other elements are present. The thermal conductivity of the thermal contact is 50 W/mK or less, 45 W/mk or less, 40 W/mk or less, 35 W/mk or less, 30 W/mk or less, 25 W/mk or less, 20 W/mk or less, 15 W/mk or less, It may be 10 W/mK or less, 5 W/mK or less, 4.5 W/mK or less, or about 4.0 W/mK or less. Such thermal contact can be achieved by controlling the thermal conductivity and/or thickness of the other element, if present.
[113]
The thermally conductive resin layer may be in thermal contact with the lower plate or the like, and may also be in thermal contact with the battery cell. Through the adoption of the structure as described above, it secures heat dissipation characteristics while significantly reducing various fastening parts or cooling equipment of modules that were previously required when configuring a general battery module or a battery pack that is an assembly of such modules. It is possible to implement a module in which more battery cells are accommodated per unit. Accordingly, in the present application, a smaller, lighter, and high-output battery module can be provided.
[114]
7 is an exemplary cross-sectional view of the battery module. In FIG. 6, the module includes: a case 10 including a side wall 10b and a lower plate 10a; It may have a shape including a plurality of battery cells 20 accommodated in the case and a resin layer 30 in contact with both the battery cells 20 and the case 10. 7 is a view of the resin layer 30 present on the lower plate 10a side, but the battery module of the present application may include a resin layer positioned on the upper plate side in the same shape as in FIG. 7.
[115]
In the above structure, the lower plate or the like in contact with the resin layer 30 may be a lower plate having thermal conductivity, as described above.
[116]
The contact area between the resin layer and the lower plate may be about 70% or more, about 75% or more, about 80% or more, about 85% or more, about 90% or more, or about 95% or more of the total area of ​​the lower plate. The upper limit of the contact area is not particularly limited, and may be, for example, 100% or less or about 100% or less.
[117]
When the upper plate or the lower plate is thermally conductive, and the cured resin layer in contact therewith is also thermally conductive, the thermally conductive portion or the thermally conductive lower plate may be a portion in contact with a cooling medium such as cooling water. That is, as schematically shown in FIG. 7, heat (H) can be easily discharged to the lower plate by the above structure, and by contacting the lower plate with the cooling medium (CW), even in a more simplified structure You can make it easier to dissipate heat.
[118]
Each of the first and second cured resin layers may have a thickness in a range of, for example, about 100 μm to 5 mm or about 200 μm to 5 mm. In the structure of the present application, the thickness of the resin layer may be set to an appropriate thickness in consideration of desired heat dissipation properties or durability. The thickness may be the thickness of the thinnest portion of the resin layer, the thickness of the thickest portion, or an average thickness.
[119]
As shown in FIG. 7, at least one surface inside the module case 10, for example, on a surface 10a in contact with the resin layer 30, a guiding unit capable of guiding the battery cell 20 accommodated ( 10d) may exist. At this time, the shape of the guiding part 10d is not particularly limited, and an appropriate shape may be employed in consideration of the shape of the applied battery cell. The guiding part 10d may be integrally formed with the lower plate or the like, or may be separately attached. The guiding part 10d may be formed of a thermally conductive material, for example, a metal material such as aluminum, gold, pure silver, tungsten, copper, nickel, or platinum in consideration of the aforementioned thermal contact. In addition, although not shown in the drawings, an interlayer paper or an adhesive layer may be present between the battery cells 20 to be accommodated. In the above, the separator may serve as a buffer during charging and discharging of the battery cell.
[120]
In one example, the battery module may further include an insulating layer between the module case and the battery cell or between the resin layer and the module case. FIG. 8 exemplarily shows a case in which the insulating layer 40 is formed between the guiding portion 10d formed on the lower plate 10a of the case and the resin layer 30. By adding an insulating layer, it is possible to prevent problems such as electric short-circuit phenomenon or fire occurrence due to contact between the cell and the case due to impact that may occur during use. The insulating layer may be formed using an insulating sheet having high insulating properties and thermal conductivity, or may be formed by coating or injection of an insulating material. For example, in a method of manufacturing a battery module to be described later, a process of forming an insulating layer before injection of the resin composition may be performed. A so-called TIM (Thermal Interface Material) or the like may be applied to the formation of the insulating layer. In another way, the insulating layer may be formed of an adhesive material, and for example, the insulating layer may be formed using a resin layer having a low or no filler content such as a thermally conductive filler. Resin components that can be used to form the insulating layer include acrylic resin, olefin resin such as PVC (poly(vinyl chloride)), PE (polyethylene), epoxy resin, silicone, or EPDM rubber ((ethylene propylene diene monomer rubber). Rubber components, etc. may be exemplified, but are not limited thereto. The insulation layer has an insulation breakdown voltage of about 5 kV/mm or more, about 10 kV/mm or more, and about 15 kV as measured in accordance with ASTM D149. /mm or more, 20 kV/mm or more, It may be 25 kV/mm or more or 30 kV/mm or more. The dielectric breakdown voltage is not particularly limited as it exhibits excellent insulation as the value increases. For example, the dielectric breakdown voltage of the insulating layer may be about 100 kV/mm or less, 90 kV/mm or less, 80 kV/mm or less, 70 kV/mm or less, or 60 kV/mm or less. The thickness of the insulating layer can be set in an appropriate range in consideration of the insulating properties or thermal conductivity of the insulating layer, for example, about 5 μm or more, about 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more , 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, or 90 μm or more. In addition, the upper limit of the thickness is not particularly limited, and may be, for example, about 1 mm or less, about 200 μm or less, 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, or 150 μm or less.
[121]
In another example related to the present application, the present application relates to a battery module, for example, a method of manufacturing the aforementioned battery module.
[122]
The manufacturing method of the present application includes the steps of injecting the resin composition into the module case; It may include accommodating a battery cell in the module case and forming the resin layer by curing the resin composition.
[123]
The order of the step of injecting the resin composition into the module case and the step of accommodating the battery cell in the module case is not particularly limited. For example, the resin composition may be first injected into the module case, and then the battery cell may be stored in that state, or the resin composition may be injected after the battery cell is first stored inside the module case.
[124]
As the resin composition, the resin composition described above can be used.
[125]
The method of injecting the resin composition into the module case is not particularly limited, and a known method may be applied. For example, a resin composition is poured into the opening of the module case to inject the resin composition, or the resin composition is injected through the above-described injection hole formed in the module case, and the resin composition is applied to both the battery cell and the battery module. A method of applying, etc. may be applied. For proper fixation, the injection process may be performed while constantly vibrating the battery module or battery cell.
[126]
The method of accommodating the battery cells in the module case into which the resin composition is injected or the module case before the composition is injected is not particularly limited.
[127]
The storage of the battery cells can be performed by placing the battery cells in an appropriate position in the module case in consideration of a desired arrangement or the like. In addition, when the cartridge structure is present, the above step may be performed by placing the battery cell in an appropriate position of the cartridge structure or inserting the cartridge structure in which the battery cell is located into the module case.
[128]
After accommodating the battery cells, adhesion between the battery cells or adhesion between the battery cells and the module case may be formed by curing the injected resin composition. The method of curing the resin composition is not particularly limited. In one example, when the composition is used, the resin composition may be cured by maintaining the resin composition at room temperature for a predetermined time. At a level that does not impair the thermal stability of the cell, heat may be applied for a certain period of time to accelerate curing. For example, before curing or in the curing process or in the storage or storage process of the battery cell, by applying heat in the range of less than 60°C, more specifically in the range of about 30°C to 50°C, reducing the tack time And improve fairness. A cured product capable of bonding between battery cells or bonding between battery cells and module case may have a conversion rate of at least 80% or more, as described above.
[129]
In another example of the present application, the present application relates to a battery pack, for example, a battery pack including two or more of the aforementioned battery modules. In the battery pack, the battery modules may be electrically connected to each other. A method of configuring a battery pack by electrically connecting two or more battery modules is not particularly limited, and all known methods may be applied.
[130]
The present application also relates to the battery module or to a device comprising the battery pack. An example of the device may be a vehicle such as an electric vehicle, but is not limited thereto, and may be a device for any purpose requiring a secondary battery as an output. In addition, a method of configuring the vehicle using the battery module or battery pack is not particularly limited, and a general method known in the related art may be applied.
Effects of the Invention
[131]
According to the present application, excellent storage stability and an appropriate curing speed may be provided for the adhesive urethane-based composition used to fix the battery cell in the module case.
Brief description of the drawing
[132]
1 shows an example of determining the amorphous property or sufficiently low crystallinity of an ester-based polyol according to an example of the present application.
[133]
2 shows an exemplary module case applicable in the present application.
[134]
3 schematically shows a form in which a battery cell is accommodated in a module case.
[135]
4 schematically shows an exemplary lower plate in which an injection hole and an observation hole are formed.
[136]
5 and 6 schematically illustrate an exemplary battery pouch that can be used as a battery cell.
[137]
7 and 8 schematically show the structure of an exemplary battery module.
[138]
References related to the drawings are as follows.
[139]
10: module case
[140]
10a: lower plate
[141]
10b: side wall
[142]
10c: top plate
[143]
10d: guiding part
[144]
20: battery cell
[145]
30: resin layer
[146]
50a: injection hole
[147]
50b: observation hall
[148]
40: insulating layer
[149]
100: pouch type cell
[150]
110: electrode assembly
[151]
120: exterior material
[152]
121: upper part
[153]
122: lower pouch
[154]
S: sealing part
Best mode for carrying out the invention
[155]
Hereinafter, the battery module of the present application will be described through Examples and Comparative Examples, but the scope of the present application is not limited by the ranges presented below.
[156]
Assessment Methods
[157]
1. Dispersibility
[158]
The initial viscosity (V 1 ) was measured with respect to the isocyanate-containing curing agent composition parts prepared in Examples and Comparative Examples . Specifically, after mixing the isocyanate, the filler and the dispersant, it was confirmed that the temperature drops to room temperature (about 25°C) within 24 hours, and a shear rate of 2.5/s at room temperature using a rheometer ( shear rate) standard viscosity was measured. The evaluation criteria are as follows. The higher the viscosity, the insufficient the dispersion effect due to the addition of the dispersant.
[159]
ㅇ: Viscosity is less than 500,000 cP
[160]
△: more than 500,000 and less than 1 million cP
[161]
X: more than 1 million cP
[162]
2. Storage stability
[163]
It was measured with respect to the isocyanate-containing curing agent composition portion prepared in Examples and Comparative Examples. Specifically, compared to the initial viscosity (V 1 ) measured within 24 hours after mixing the isocyanate, the filler, and the dispersant, the time taken until the viscosity (V 2 ) was 2 times or more was confirmed. The evaluation criteria are as follows. The shorter the time taken until the viscosity (V 2 ) is more than 2 times reached, the worse the storage stability is with respect to the reaction between the isocyanate and the dispersant.
[164]
ㅇ: 2 months or more
[165]
△: 1 month or more to less than 2 months
[166]
X: less than 1 month
[167]
3. Curing speed
[168]
The main composition part, the curing agent composition part, and the catalyst prepared in Examples and Comparative Examples were mixed, and evaluated according to the time when curing was completed. Completion of curing may mean that when the curing reaction occurs for 24 hours at room temperature and 30 to 70% relative humidity conditions, the NCO peak reference conversion rate confirmed by TF-IR analysis is 80% or more. . The shorter the time required to complete the curing, the faster the composition is injected into the module and then cured, which means that the required physical properties can be secured within a short time.
[169]
ㅇ: within 2 days
[170]
△: within one week
[171]
X: One week later
[172]
Examples and Comparative Examples
[173]
Example 1
[174]
Subject composition part : As a caprolactone-based polyol represented by Formula 2, the number of repeating units (m in Formula 2) is at a level of about 1 to 3, and the polyol-derived unit (Y in Formula 2) is 1,4- A composition containing a polyol containing butanediol was used. In addition, an alumina filler and a phosphoric acid-based anionic dispersant were mixed in the same amount as in Table 1 below. The polyol used is 100 g.
[175]
Curing agent composition part : A composition containing polyisocyanate (HDI, Hexamethylene diisocyanate) was used. In addition, an alumina filler and a phosphoric acid-based anionic dispersant were mixed in the same amount as in Table 1 below. The isocyanate used is 100 g.
[176]
In addition, the composition of the main composition and the composition of the curing agent composition were mixed with 0.1 wt% of DBTDL.
[177]
Example 2 and Comparative Examples 1 to 7
[178]
A two-part urethane-based composition was prepared in the same manner, except for the differences shown in Table 1 below.
[179]
[Table 1]
[180]

[181]
Physical properties were measured as described below for the prepared Examples and Comparative Examples. The results are shown in Table 2.
[182]
[Table 2]
[183]

[184]
As shown in Tables 1 and 2, it can be seen that in Comparative Examples 1 to 5, which do not have the configuration of the present application, the dispersibility is poor. In the case of these comparative examples, since the viscosity is excessively high, the experiment on storage stability or curing speed was not conducted because sufficient fairness cannot be secured when injecting into the actual battery module. In addition, in the case of Comparative Examples 6 and 7, it can be seen that the storage stability of the isocyanate and the curing speed of the entire composition were lowered compared to the examples due to the use of an excessive amount of the dispersant. In particular, the stability of isocyanate is related to the content of the dispersant contained in the curing agent, and the curing rate is considered to be related to the content of the total dispersant included in the main material and the curing agent. It is not a bad level, but it can be seen that the curing speed is not good.
Claims
[Claim 1]
Ester-based polyol resin-containing main composition; A polyisocyanate-containing curing agent composition portion; filler; And a phosphoric acid ester-based anionic dispersant, and comprising less than 20 parts by weight of the anionic dispersant based on 100 parts by weight of the total of the ester-based polyol resin and polyisocyanate.
[Claim 2]
The two-component urethane-based composition according to claim 1, wherein the main composition part or the curing agent composition part comprises a filler and an anionic dispersant.
[Claim 3]
The two-component urethane-based composition according to claim 2, comprising 50 to 2,000 parts by weight of a filler based on 100 parts by weight of the total amount of the ester-based polyol resin and polyisocyanate.
[Claim 4]
The two-part urethane-based composition according to claim 2, wherein the curing agent composition part comprises less than 20 parts by weight of the anionic dispersant relative to 100 parts by weight of polyisocyanate.
[Claim 5]
The two-part urethane-based composition of claim 2, wherein the main composition part comprises less than 20 parts by weight of the anionic dispersant based on 100 parts by weight of the ester-based polyol resin.
[Claim 6]
The two-part urethane-based composition according to claim 4 or 5, comprising 0.01 to 5 parts by weight of the anionic dispersant based on 100 parts by weight of the filler.
[Claim 7]
The two- component urethane-based composition of claim 2, wherein the main composition part or the curing agent composition part has an initial viscosity (V 1 ) of 1,000,000 cP or less measured within 24 hours at room temperature after mixing the constituents of each composition part (however, V 1 Is the viscosity value measured at the point of 2.5/s when measured in a shear rate range of 0.01 to 10.0/s using a rheological property meter (ARES)).
[Claim 8]
The two-component urethane-based composition according to claim 7, wherein the main composition part or the curing agent composition part satisfies the following relational formula 1 after at least two months elapse: [Relationship 1] V 2 /V 1 ≥ 2 (in the relational formula 1, V 1 is the initial viscosity of the main composition part or the curing agent composition part, V 2 is the viscosity measured after a predetermined period of time exceeding 24 hours after mixing the constituents, and V 2 is 0.01 to 1 using a rheological property meter (ARES). When measured in a range of shear rates up to 10.0/s, this is the viscosity value measured at the point of 2.5/s.)
[Claim 9]
The urethane-based resin composition of claim 1, wherein the filler has a moisture content of 1,000 ppm or less.
[Claim 10]
The method of claim 1, wherein the ester-based polyol is an amorphous polyol whose crystallization temperature (Tc) and melting temperature (Tm) are not observed in DSC (Differential Scanning calorimetry) analysis, or a two-part type having a melting temperature (Tm) of less than 15°C. Urethane-based composition.
[Claim 11]
The two-part urethane-based composition of claim 1, wherein each of the ester-based polyol resin and the polyisocyanate has a viscosity of less than 10,000 cP.
[Claim 12]
The two-part urethane-based composition of claim 1, wherein the resin component has a glass transition temperature (Tg) of less than 0°C after curing.
[Claim 13]
According to claim 1, wherein the ester-based polyol is a two-part urethane-based composition represented by the following Formula 2 or 3: [Chemical Formula 2] [Chemical Formula 3] However, in Formulas 2 and 3, X is a carboxylic acid-derived unit, and Y is a polyol It is a derived unit, n is a number within the range of 2 to 10, and m is a number within the range of 1 to 10.
[Claim 14]
The carboxylic acid-derived unit X is a phthalic acid unit, an isophthalic acid unit, a terephthalic acid unit, a trimellitic acid unit, a tetrahydrophthalic acid unit, a hexahydrophthalic acid unit, a tetrachlorophthalic acid unit, an oxalic acid unit, and adipic acid. Unit, azelaic acid unit, sebacic acid unit, succinic acid unit, malic acid unit, glataric acid unit, malonic acid unit, pimelic acid unit, suberic acid unit, 2,2-dimethylsuccinic acid unit, 3,3-dimethylglutaric acid Unit, 2,2-dimethylglutaric acid unit, maleic acid unit, fumaric acid unit, itaconic acid unit and one or more units selected from the group consisting of a fatty acid unit, a two-part urethane-based composition.
[Claim 15]
The method according to claim 13, wherein the polyol-derived unit Y is an ethylene glycol unit, a propylene glycol unit, a 1,2-butylene glycol unit, a 2,3-butylene glycol unit, a 1,3-propanediol unit, and 1,3. -Butanediol unit, 1,4-butanediol unit, 1,6-hexanediol unit, neopentyl glycol unit, 1,2-ethylhexyldiol unit, 1,5-pentanediol unit, 1,9-nonanediol unit, 1 ,10-decanediol unit, 1,3-cyclohexanedimethanol unit, 1,4-cyclohexanedimethanol unit, glycerin unit, and any one or two or more units selected from the group consisting of trimethylolpropane units Urethane-based composition.
[Claim 16]
The two-part urethane-based composition according to claim 1, wherein the polyisocyanate is a non-aromatic polyisocyanate.
[Claim 17]
The two-part urethane-based composition of claim 1, wherein the filler comprises alumina, aluminum nitride (AlN), boron nitride (BN), silicon nitride, SiC, or BeO.
[Claim 18]
A module case having an upper plate, a lower plate, and sidewalls, wherein an inner space is formed by the upper plate, the lower plate, and the sidewall; A plurality of battery cells present in the inner space of the module case; And a resin layer formed by curing the composition according to claim 1 and in contact with the plurality of battery cells.
[Claim 19]
A battery pack comprising one or more other battery modules according to claim 18.
[Claim 20]
A vehicle comprising the battery module according to claim 18 or the battery pack according to claim 19.