Patent Application
20230318126
The present disclosure relates to a secondary battery, and more particularly, to a secondary battery having a vent member.
Secondary batteries are highly applicable to various products and exhibit superior electrical properties such as high energy density, etc. Secondary batteries are commonly used not only in portable devices but also in electric vehicles (EVs) or hybrid electric vehicles (HEVs) driven by electrical power sources. The secondary battery is drawing attention as a new energy source for enhancing environment friendliness and energy efficiency in that the use of fossil fuels can be reduced greatly and no byproduct is generated during energy consumption.
Secondary batteries widely used at present include lithium ion batteries, lithium polymer batteries, nickel cadmium batteries, nickel hydrogen batteries, nickel zinc batteries and the like.
The secondary battery generally has a structure in which an electrode assembly including at least one unit cell having a positive electrode/separator/negative electrode structure is accommodated in a case of a laminate sheet in which an outer layer, a metal barrier layer and a sealant layer are sequentially laminated, and a sealant resin of the sealant layer is fused to seal the electrode assembly is sealed.
In the conventional secondary battery, the battery may ignite due to various causes such as a short circuit inside the secondary battery, overcharge or overdischarge, temperature control, or the like. At this time, thermal propagation where the temperature inside the secondary battery rises rapidly and simultaneously the heat is transferred to neighboring cells may be generated, which may further increase the fire.
In order to minimize damage to the electrode caused by gas when thermal propagation occurs—i.e., when the internal temperature of the secondary battery rises, directional venting characteristic is required to discharge the gas in one direction. However, the conventional secondary battery has a problem in that it is difficult to induce gas discharge in a specific direction.
Therefore, the present disclosure is directed to providing a secondary battery with improved safety by inducing gas discharge in a specific direction.
The present disclosure is directed to providing a secondary battery with improved safety by inducing gas discharge in a specific direction when gas is generated while securing a sealing property when the battery operates normally.
In one aspect of the present disclosure, there are provided secondary batteries according to the following embodiments.
The first embodiment provides a secondary battery, comprising:
In the second embodiment according to the first embodiment, a vent may occur between the middle layer and the lowermost layer.
In the third embodiment according to the first embodiment or the second embodiment, the first resin may have a melting point of 90° C. or above and lower than 100° C.
In the fourth embodiment according to any one of the first to third embodiments, the first resin may be a linear low-density polyethylene having a comonomer with a carbon number of 8.
In the fifth embodiment according to any one of the first to fourth embodiments, the first resin may have a poly dispersity index (PDI) of less than 2.6.
In the sixth embodiment according to the fourth or fifth embodiment, in the linear low-density polyethylene having a comonomer with a carbon number of 8, a content of the comonomer with a carbon number of 8 may be 12 weight % or more, based on 100 weight % of the linear low-density polyethylene having a comonomer with a carbon number of 8.
In the seventh embodiment according to any one of the first to sixth embodiments, the first resin may have a crystallization temperature of 80° C. to 90° C.
In the eighth embodiment according to any one of the first to seventh embodiments, the first resin may have a weight-average molecular weight of 100,000 g/mol to 250,000 g/mol.
In the ninth embodiment according to any one of the fourth to eighth embodiments, the linear low-density polyethylene having a comonomer with a carbon number of 8 may be polymerized in the presence of a metallocene catalyst.
In the tenth embodiment according to any one of the first to ninth embodiments, the case may include a sealing portion formed to seal the electrode assembly, the sealing portion may contain a sealant resin, and the linear low-density polyethylene of the vent member having a comonomer with a carbon number of 8 may have a lower melting point than the sealant resin.
In the eleventh embodiment according to any one of the first to tenth embodiments, the second resin may have a melting point of 100° C. to 130° C.
In the twelfth embodiment according to any one of the first to eleventh embodiments, the second resin may be a linear low-density polyethylene having a comonomer with a carbon number of 6 or more.
In the thirteenth embodiment according to any one of the first to twelfth embodiments, the second resin may have a poly dispersity index (PDI) of 2.6 to 4.
In the fourteenth embodiment according to the twelfth or thirteenth embodiment, in the linear low-density polyethylene having a comonomer with a carbon number of 6 or more, a content of the comonomer with a carbon number of 6 or more may be less than 12 weight %, based on 100 weight % of the linear low-density polyethylene having a comonomer with a carbon number of 6 or more.
In the fifteenth embodiment according to the any one of the first to fourteenth embodiments, the second resin may have a crystallization temperature of higher than 90° C. and 115° C. or below.
In the sixteenth embodiment according to any one of the first to fifteenth embodiments, the second resin may have a weight-average molecular weight of more than 250,000 g/mol and 400,000 g/mol or less.
In the seventeenth embodiment according to any one of the twelfth to sixteenth embodiments, the linear low-density polyethylene having a comonomer with a carbon number of 6 or more may be polymerized in the presence of a metallocene catalyst.
In the eighteenth embodiment according to any one of the first to seventeenth embodiments, the third resin may have a melting point of higher than 130° C.
In the nineteenth embodiment according to any one of the first to eighteenth embodiments, the third resin may include a high-density polyethylene, random polypropylene, or a mixture thereof.
In the twentieth embodiment according to any one of the first to nineteenth embodiments, the vent member may melt at 100° C. or above to vent a gas.
In the twenty first embodiment according to the twentieth embodiment, the vent member may be vented at a pressure of 1.5 atm or above.
In the twenty second embodiment according to any one of the first to twenty first embodiments, the vent member may have a maximum sealing strength of less than 6 kgf/15 mm at 100° C. or above.
In the twenty third embodiment according to any one of the first to twenty second embodiments, the vent member may have an average sealing strength of less than 4.5 kgf/15 mm at 100° C. or above.
In the twenty fourth embodiment according to any one of the first to twenty third embodiments, the vent member may have a maximum sealing strength of 6 kgf/15 mm or more at room temperature to 60° C.
In the twenty fifth embodiment according to any one of the first to twenty fourth embodiments, the vent member may have an average sealing strength of 4.5 kgf/15 mm or more at room temperature to 60° C.
In the twenty sixth embodiment according to any one of the tenth to twenty fifth embodiments, the vent region may be located in the sealing portion.
In the twenty seventh embodiment according to the twenty sixth embodiment, the vent region may be located in the sealing portion at a corner of the case.
In the twenty eighth embodiment according to any one of the first to twenty seventh embodiments, the secondary battery may be a pouch-type secondary battery.
A secondary battery according to an embodiment of the present disclosure includes a vent member having a structure of three or more layers, which includes a first resin in a lowermost layer, a second resin having a higher melting point than the first resin in an uppermost layer, and a third resin having a higher melting point than the second resin in a middle layer, so it is possible to induce gas to be discharged to the vent region and improve the rigidity of the vent member. Accordingly, the safety of the battery is improved.
The accompanying drawings illustrate a preferred embodiment of the present disclosure and together with the foregoing disclosure, serve to provide further understanding of the technical features of the present disclosure, and thus, the present disclosure is not construed as being limited to the drawing.
Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Prior to the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present disclosure on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.
Therefore, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the disclosure, so it should be understood that other equivalents and modifications could be made thereto without departing from the scope of the disclosure.
A secondary battery according to an embodiment of the present disclosure includes an electrode assembly; an electrode lead attached to the electrode assembly; a case configured to accommodate the electrode assembly therein; a lead film formed to surround a part of an outer surface of the electrode lead and interposed between the electrode lead and the case; a vent region formed in at least a part of the case; and a vent member inserted into the vent region and having a structure of three or more layers including a first resin in a lowermost layer, a second resin at in uppermost layer, and a third resin in a middle layer, wherein the second resin is a resin having a higher melting point than the first resin, and the third resin is a resin having a higher melting point than the second resin.
Referring to
The electrode assembly 12 includes a positive electrode plate, a negative electrode plate and a separator. In the electrode assembly 12, a positive electrode plate and a negative electrode plate may be sequentially laminated with a separator being interposed therebetween.
The positive electrode plate may include a positive electrode current collector made of a metal thin film having excellent conductivity—for example, an aluminum (Al) foil, and a positive electrode active material layer coated on at least one surface thereof. In addition, the positive electrode plate may include a positive electrode tab made of a metal material—for example, an aluminum (Al) material, at one side end thereof. The positive electrode tab may protrude from one side end of the positive electrode plate. The positive electrode tab may be welded to one side end of the positive electrode plate, or be bonded thereto using a conductive adhesive.
The negative electrode plate may include a negative electrode current collector made of a conductive metal thin film—for example, a copper (Cu) foil, and a negative electrode active material layer coated on at least one surface thereof. In addition, the negative electrode plate may include a negative electrode tab formed of a metal material—for example, a nickel (Ni) material, at one side end thereof. The negative electrode tab may protrude from one side end of the negative electrode plate. The negative electrode tab may be welded to one side end of the negative electrode plate, or be bonded thereto using a conductive adhesive.
The separator is interposed between the positive electrode plate and the negative electrode plate to electrically insulate the positive electrode plate and the negative electrode plate from each other. The separator may be a porous membrane so that lithium ions can pass between the positive electrode plate and the negative electrode plate. The separator may include, for example, a porous membrane using polyethylene (PE), or polypropylene (PP), or a composite film thereof.
An inorganic coating layer may be provided on the surface of the separator. The inorganic coating layer may have a structure in which inorganic particles are bonded to each other by a binder to form an interstitial volume between the particles.
The electrode assembly 12 may be a jelly-roll (winding-type) electrode assembly having a structure in which long sheet-type positive and negative electrodes are wound with a separator being interposed therebetween, a stacked (stack-type) electrode assembly having a structure in which a plurality of positive and negative electrodes cut into units of a predetermined size are sequentially stacked with a separator being interposed therebetween, a stack/folding type electrode assembly having a structure in which bi-cells or full-cells where positive and negative electrodes of a predetermined unit are stacked with a separator being interposed therebetween are wound, or the like.
The case 13 serves to accommodate the electrode assembly 12.
In an embodiment of the present disclosure, the case 13 may include an accommodation portion 13a for accommodating the electrode assembly 12, and a sealing portion 13b formed to seal the electrode assembly 12 as shown in
The sealing portion 13b may include a sealant resin, and the sealant resin may be fused along an outer circumference of the accommodation portion 13a to seal the electrode assembly 12.
In an embodiment of the present disclosure, the case 13 may be provided in a film form having a multilayer structure including an outer layer for protection against external impacts, a metal barrier layer for blocking moisture, and a sealant layer for sealing the case.
The outer layer may include a polyester-based film using polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, co-polyester, polycarbonate, nylon, or the like, and may be configured in a single layer or multiple layers.
The metal barrier layer may include aluminum, copper, or the like.
The sealant layer may include a sealant resin and may be formed in a single layer or multiple layers.
The sealant resin may include polypropylene (PP), acid-modified polypropylene (PPa), random polypropylene, ethylene propylene copolymer, or two or more thereof. The ethylene propylene copolymer may include, but is not limited to, ethylene-propylene rubber, ethylene-propylene block copolymer, and the like.
In an embodiment of the present disclosure, the case 13 may be in a pouch form.
The pouch-type case 13 may include an upper pouch and a lower pouch. When the case 13 includes an upper pouch and a lower pouch, after the upper pouch and the lower pouch are positioned so that the sealant resins thereof face each other, the facing sealant resins may be configured to be fused with each other by heat and pressure to seal the battery.
The fusion of the sealing portion 13b may be thermal fusion, ultrasonic fusion, or the like, but is not particularly limited as long as the sealing portion 13b can be fused.
The sealing portion 13b may be sealed on four or three peripheral sides of the battery case 13 in some embodiments. In the three-sided sealing structure, after the upper pouch and the lower pouch are formed on one pouch sheet, the boundary surface between the upper pouch and the lower pouch is bent so that the electrode assembly accommodation portions 13a formed on the upper pouch and the lower pouch overlap, and in this state, the edges of the remaining three sides are sealed except for the bending portion.
The electrode lead 11 may be accommodated in the case 13 so that a part thereof is exposed to the outside of the battery case 13 as shown in
The secondary battery 10 according to an embodiment of the present disclosure includes a lead film 14.
The lead film 14 surrounds a part of the outer surface of the electrode lead 11 and is interposed between the electrode lead 11 and the case 13. For example, the lead film 14 may be interposed between the electrode lead 11 and the sealing portion 13b of the case 13 in a region where the electrode lead 11 protrudes or extends away from the case 13 to help binding of the electrode lead 11 and the case 13.
Referring to
The vent member 15 may be attached to the case 13 by thermal fusion. In another example, the vent member 15 may be attached to the case 13 by an adhesive such as glue. In another example, the vent member 15 and the case 13 may be physically coupled to each other by means of a clip or the like. In another example, at least a part of the vent member 15 may be embedded in a film constituting the case 13, for example a sealant resin.
The vent member 15 has a structure of three or more layers. The vent member 15 includes a first resin in a lowermost layer 15a, a second resin in an uppermost layer 15b, and a third resin in a middle layer 15c. The vent member 15 contains resins having different melting points on one side and the other side, so that a vent may occur on one side of the vent member 15. Accordingly, it may be easy to adjust the vent to one direction. For example, a vent may occur on one side of the vent member 15 including the first resin with a lowest melting point.
If the rigidity of the vent member 15 is insufficient, an early vent may occur under the conditions prior to a desired temperature and pressure when the internal pressure of the cell is increased. If the third resin is included, since the third resin has a higher melting point than the first resin and the second resin, the rigidity of the vent member 15 may be improved, compared to the case where only the first resin and/or the second resin are included. Accordingly, it is possible to prevent an early vent from occurring in the condition prior to a desired temperature and pressure, when the internal pressure of the battery is increased.
The vent member 15 has an excellent sealing property for the case 13 in the normal temperature range, for example at room temperature to 60° C., and at a high temperature, for example as at 100° C. or above, the vent sealing strength of the case in which the vent member 15 is inserted may be lowered, which may realize or cause venting.
Referring to
For example, if the temperature of the battery increases excessively due to abnormal operation of the battery, the first resin contained in the lowermost layer 15a and having a lower melting point than the middle layer 15c and the uppermost layer 15b is melted. As the first resin melts, the sealing strength of the part in which the vent member is inserted decreases. Because the second resin has a higher melting point than the first resin, the lowermost layer 15a melts faster than the uppermost layer 15b. Accordingly, a vent may occur more easily in the lowermost layer 15a than in the uppermost layer 15b. Since the third resin has a higher melting point than the first resin and the second resin, even if the temperature of the battery rises, the middle layer 15c may not melt.
As shown in
In an embodiment of the present disclosure, the vent member 15 may be manufactured by laminating the first resin, the third resin and the second resin in order one after another and then fusing them. For example, the first resin, the third resin and the second resin may be laminated in order one after another and then thermally fused. In another example, the layers may be fused through an adhesive such as glue.
In an embodiment of the present disclosure, the vent member 15 may be vented at 100° C. or above. The vent member 15 may be vented earlier, compared to the case where only the second resin is included.
In an embodiment of the present disclosure, the vent member 15 may be vented at 100° C., for example at 100° C. to 120° C., to expel or exhaust gases from the accommodation portion to outside the secondary battery. In particular, the vent member 15 may be vented at a pressure of 100° C. or above and at a pressure of 1.5 atm or more. As the vent member 15 is vented in the aforementioned temperature range and/or the aforementioned pressure condition, it is possible to induce the gas to be discharged only during abnormal operation of the battery while allowing sealing of the battery during normal operation of the battery.
In an embodiment of the present disclosure, the vent member 15 may have a lower maximum sealing strength at 100° C. or above, compared to than the case where only the second resin is included. Accordingly, venting may occur earlier, compared to than the case where only the second resin is included.
In an embodiment of the present disclosure, the vent member 15 may have a maximum sealing strength of less than 6 kgf/15 mm or less than 5 kgf/15 mm or less than 4.5 kgf/15 mm or less than 3 kgf/15 mm or less than 2.6 kgf/15 mm at 100° C. or higher. In an embodiment of the present disclosure, the vent member 15 may have a maximum sealing strength of less than 6 kgf/15 mm or less than 5 kgf/15 mm or less than 4.5 kgf/15 mm or less than 3 kgf/15 mm or less than 2.6 kgf/15 mm at 100° C. to 120° C. In an embodiment of the present disclosure, the vent member 15 may have a maximum sealing strength of less than 3 kgf/15 mm or less than 2 kgf/15 mm or less than 1 kgf/15 mm or less than 0.5 kgf/15 mm or less than 0.1 kgf/15 mm or less than 0.05 kgf/15 mm at 120° C. or higher. If the vent member 15 satisfies the above-mentioned sealing strength in the above-mentioned temperature range, the sealing strength of the part of the case 13 in which the vent member 15 is inserted may be lowered at a high temperature, for example 100° C. or higher, so that the vent characteristic may be readily implemented.
In an embodiment of the present disclosure, the maximum sealing strength at room temperature to 60° C. may be further improved, compared to the case where the vent member 15 includes only the second resin. Accordingly, the rigidity of the vent member 15 is improved, and it is possible to more easily prevent an early vent prior to a desired temperature and pressure.
In addition, in an embodiment of the present disclosure, the vent member 15 may have a maximum sealing strength of 6 kgf/15 mm or more or 8 kgf/15 mm or more or 10 kgf/15 mm or more or 13 kgf/15 mm or more at room temperature to 60° C. If the vent member 15 satisfies the above-mentioned sealing strength in the above temperature range, even though the vent member 15 is inserted, the part of the case 13 in which the vent member 15 is inserted may have excellent sealing strength during normal operation of the battery, which may easily secure the sealing property of the battery.
In an embodiment of the present disclosure, the vent member 15 may have a maximum sealing strength of less than 6 kgf/15 mm at 100° C. or higher. The vent member 15 may have a maximum sealing strength of 6 kgf/15 mm or more at room temperature to 60° C. If the vent member 15 satisfies the sealing strength described above, the sealing strength of the part of the case 13 in which the vent member 15 is inserted may be lowered at a high temperature, for example at 100° C. or higher, so that the vent characteristic may be readily implemented. In addition, since the case 13 has excellent sealing strength during normal operation of the battery, the sealing property of the battery may be easily secured.
In an embodiment of the present disclosure, the vent member 15 may have a lower average sealing strength at 100° C. or above, compared to the case where only the second resin is included. Accordingly, venting may occur earlier, compared to the case where only the second resin is included.
In an embodiment of the present disclosure, the vent member 15 may have an average sealing strength of less than 4.5 kgf/15 mm or less than 3 kgf/15 mm or less than 2.1 kgf/15 mm at 100° C. or above. In an embodiment of the present disclosure, the vent member 15 may have an average sealing strength of less than 4.5 kgf/15 mm or less than 3 kgf/15 mm or less than 2.1 kgf/15 mm at 100° C. to 120° C. In an embodiment of the present disclosure, the vent member 15 may have an average sealing strength of less than 2 kgf/15 mm or less than 1 kgf/15 mm or less than 0.5 kgf/15 mm or less than 0.1 kgf/15 mm or less than 0.05 kgf/15 mm at 120° C. or higher. If the vent member 15 satisfies the above-mentioned sealing strength in the above-mentioned temperature range, the sealing strength of the part of the case 13 in which the vent member 15 is inserted may be lowered at a high temperature, for example at 100° C. or higher, so that the vent characteristic may be implemented more easily. If the vent member 15 satisfies the above-mentioned sealing strength in the above-mentioned temperature range, the sealing strength of the part of the case 13 in which the vent member 15 is inserted may be lowered at a high temperature, for example at 100° C. or higher, so that the vent characteristic may be implemented more easily.
In an embodiment of the present disclosure, the average sealing strength of the vent member 15 at room temperature to 60° C. may be further improved, compared to the case where only the second resin is included. Accordingly, the rigidity of the vent member 15 is improved, and it is possible to more easily prevent an early vent prior to a desired temperature and pressure.
In an embodiment of the present disclosure, the vent member 15 may have an average sealing strength of 4.5 kgf/15 mm or more or 5 kgf/15 mm or more or 6 kgf/15 mm or more or 7 kgf/15 mm or more or 8 kgf/15 mm or more at room temperature to 60° C. If the vent member 15 satisfies the above-mentioned sealing strength in the above temperature range, even though the vent member 15 is inserted, the part of the case 13 in which the vent member 15 is inserted may have excellent sealing strength during normal operation of the battery, thereby easily securing the sealing property.
In an embodiment of the present disclosure, the vent member 15 may have an average sealing strength of less than 4.5 kgf/15 mm at 100° C. or above. The vent member 15 may have an average sealing strength of 4.5 kgf/15 mm or more at room temperature to 60° C. If the vent member 15 has the above-mentioned sealing strength in the above-described temperature range, the sealing strength of the part of the case 13 in which the vent member 15 is inserted may be lowered at a high temperature, for example at 100° C. or higher, so that the vent characteristic may be easily implemented. In addition, since excellent sealing strength may be secured during normal operation of the battery, the sealing property of the battery may be easily secured.
The sealing strength of the vent member 15 according to temperature may be measured by conducting a tensile test at a speed of 5 mm/min, after cutting the part of the case in which the vent member 15 is inserted into a width of 15 mm and a length of 5 cm and then gripping both ends thereof using a UTM jig in a state where both ends are spread to 180°.
At this time, the maximum sealing strength means a maximum value when the case 13 is broken, and the average sealing strength means an average value when the case 13 is stretched by 8 mm at 4.5 kgf/15 mm when the maximum sealing strength is 4.5 kgf/15 mm or more and an average value when the case 13 is stretched by 8 mm at the maximum sealing strength when the maximum sealing strength is less than 4.5 kgf/15 mm.
In an embodiment of the present disclosure, the first resin may have a melting point of lower than 100° C. For example, the melting point of the first resin may be 90° C. or above and lower than 100° C., or 90° C. to 99° C., or 95° C. to 99° C. When the melting point of the first resin satisfies the above-mentioned range, the sealing strength of the part of the case 13 in which the vent member 15 is inserted is lowered at a high temperature, for example 100° C. or above, so that the vent characteristic may be more easily implemented. In particular, venting may occur earlier, compared to the case where only the second resin is included.
Even if the melting point of the first resin is lower than 100° C., since the first resin is used in the vent member 15 together with another resin that may compensate for the lower melting point, venting may occur more easily at high temperature, and the rigidity of vent member 15 may be improved. For example, during normal operation of the battery, the part of the case 13 in which the vent member 15 is inserted has excellent sealing strength, so the sealing property of the battery may be secured easily.
In this specification, the melting point of the resin may be measured using a differential scanning calorimeter (DSC). For example, the temperature of a sample is increased from 30° C. to 280° C. at 10° C./min, maintained at 280° C. for 10 minutes, cooled to 30° C. at 10° C./min, and then maintained at 30° C. for 10 minutes. Then, after increasing the temperature of the sample from 30° C. to 280° C. at 10° C./min, the melting point may be measured by maintaining the temperature at 280° C. for 10 minutes.
In an embodiment of the present disclosure, the poly dispersity index (PDI) of the first resin may be less than 2.6, or less than 2.59, or less than 2.551. The poly dispersity index (PDI) of the first resin may be 1 or more. Thus, a vent may occur more easily in the lowermost layer of the vent member containing the first resin.
In an embodiment of the present disclosure, the first resin may have a weight-average molecular weight of 100,000 g/mol to 250,000 g/mol, or 150,000 g/mol to 250,000 g/mol, or 180,000 g/mol to 220,000 g/mol. If the weight-average molecular weight of the first resin satisfies the above range, the first resin may more easily have a low melting point, for example a melting point of lower than 100° C., and thus, at a high temperature, for example at 100° C. or above, the sealing strength of the vent member may be more easily lowered, so an early vent may be induced more easily.
In this specification, the weight-average molecular weight and the poly dispersity index of the resin may be measured by gel permeation chromatography (GPC) under the following conditions:
In an embodiment of the present disclosure, the crystallization temperature of the sealant resin and the crystallization temperature of the first resin may be significantly different. For example, the difference between the crystallization temperature of the sealant resin and the crystallization temperature of the first resin may be 20° C. or more. If the difference between the crystallization temperature of the sealant resin and the crystallization temperature of the first resin satisfies the above-mentioned range, a vent may occur more easily in the lowermost layer of the vent member containing the first resin.
In an embodiment of the present disclosure, the crystallization temperature of the first resin may be 80° C. to 90° C., or 80° C. to 85° C. If the crystallization temperature of the first resin satisfies the above range, a vent may occur more easily in the lowermost layer of the vent member containing the first resin. In an embodiment of the present disclosure, the difference between the crystallization temperature of the sealant resin and the crystallization temperature of the first resin may be 20° C. or more, and the crystallization temperature of the first resin may be 80° C. to 90° C.
In this specification, the crystallization temperature may be measured using a differential scanning calorimeter (DSC). For example, the temperature of the sample may be increased from 30° C. to 280° C. at 10° C./min, maintained at 280° C. for 10 minutes, cooled to 30° C. at 10° C./min, and then maintained at 30° C. for 10 minutes. Then, after increasing the temperature of the sample from 30° C. to 280° C. at 10° C./min, the crystallization temperature may be measured by maintaining the temperature at 280° C. for 10 minutes.
In an embodiment of the present disclosure, the first resin may be a linear low-density polyethylene having a comonomer with a carbon number of 8. If the first resin is a linear low-density polyethylene having a comonomer with a carbon number of 8, the sealing strength of the case in which the vent member 15 is inserted may be lowered more easily at high temperatures, for example 100° C. or above.
In an embodiment of the present disclosure, in the linear low-density polyethylene having a comonomer with a carbon number of 8, the content of the comonomer with a carbon number of 8 may be 12 weight % or more, or 12 weight % to 20 weight %, or 12 weight % to 18 weight %, based on 100 weight % of the linear low-density polyethylene having a comonomer with a carbon number of 8. If the content of the comonomer with a carbon number of 8 satisfies the above-mentioned range, a vent may occur more easily in the lowermost layer of the vent member containing the first resin. In this specification, the comonomer content may be measured using an H-NMR. For example, after about 10 mg of a sample is completely dissolved in about 0.6 mL of trichloroethylene solvent using a heat gun, it may be sampled in an NMR tube and measured using the 11-1-NMR.
In an embodiment of the present disclosure, the linear low-density polyethylene having a comonomer with a carbon number of 8 may be polymerized in the presence of a metallocene catalyst. If the linear low-density polyethylene having a comonomer with a carbon number of 8 is polymerized in the presence of a metallocene catalyst, it may be more advantageous in terms of sealing strength and physical properties, compared to the case where it is polymerized in the presence of a Ziegler-Natta catalyst.
In an embodiment of the present disclosure, the first resin may have a melting point of lower than 100° C. and be a linear low-density polyethylene having a comonomer with a carbon number of 8. In an embodiment of the present disclosure, the first resin may have a poly dispersity index (PDI) of less than 2.6 and be a linear low-density polyethylene having a comonomer with a carbon number of 8. In an embodiment of the present disclosure, the first resin may have a crystallization temperature of 80° C. to 90° C. and be a linear low-density polyethylene having a comonomer with a carbon number of 8. In an embodiment of the present disclosure, the first resin may have a weight-average molecular weight of 100,000 g/mol to 250,000 g/mol and be a linear low-density polyethylene having a comonomer with a carbon number of 8.
In an embodiment of the present disclosure, the first resin may have a lower melting point than the sealant resin. If the first resin has a lower melting point than the sealant resin, the first resin may melt faster than the sealant resin at high temperatures. Accordingly, as the sealing strength of the part in which the vent member 15 is inserted is lower than the sealing strength of the part of the case containing the sealant resin, the vent characteristics may be implemented more easily.
In an embodiment of the present disclosure, the melting point of the second resin may be 100° C. to 130° C., or 105° C. to 130° C., or 110° C. to 125° C., or 115° C. to 125° C. If the melting point of the second resin satisfies the above-described range, the sealing strength of the part of the case 13 in which the vent member 15 is inserted is lowered at a high temperature, for example at 100° C. or above, so the vent characteristics may be implemented more easily.
In an embodiment of the present disclosure, the poly dispersity index (PDI) of the second resin may be 4 or less, or 3.8 or less, or 3.796 or less, or 3.5 or less, or 3.023 or less, or 3 or less, or 2.7 or less, or 2.674 or less. In addition, the poly dispersity index may be 2.6 or more. If the poly dispersity index of the second resin satisfies the above-mentioned range, the molecular weight distribution is narrow, so the sealing strength and physical properties may be more excellent during normal operation of the battery.
In an embodiment of the present disclosure, the weight-average molecular weight of the second resin is greater than 250,000 g/mol and to 400,000 g/mol or less, or 200,000 g/mol to 350,000 g/mol, or 230,000 g/mol to 300,000 g/mol. If the weight-average molecular weight of the second resin satisfies the above-mentioned range, the sealing strength may be further improved during normal operation of the battery.
In an embodiment of the present disclosure, the crystallization temperature of the sealant resin and the crystallization temperature of the second resin may be similar. For example, the difference between the crystallization temperature of the sealant resin and the crystallization temperature of the second resin may be 10° C. or less, or 5° C. or less. Also, the difference between the crystallization temperature of the sealant resin and the crystallization temperature of the second resin may be 0.1° C. or more. If the difference between the crystallization temperature of the sealant resin and the crystallization temperature of the second resin satisfies the above range, the fusion properties of the sealant resin and the second resin may be more excellent during normal operation of the battery.
In an embodiment of the present disclosure, the crystallization temperature of the second resin may be greater than 90° C. and 115° C. or less, or 95° C. to 110° C., or 100° C. to 110° C., or 105° C. to 110° C. If the crystallization temperature of the second resin satisfies the above range, the fusion properties of the sealant resin and the second resin may be more excellent.
In an embodiment of the present disclosure, the difference between the crystallization temperature of the sealant resin and the crystallization temperature of the second resin is 10° C. or less, and the crystallization temperature of the second resin may be higher than 90° C. and 115° C. or below.
In an embodiment of the present disclosure, the second resin may be a linear low-density polyethylene having a comonomer with a carbon number of 6 or more. If the second resin is a linear low-density polyethylene having a comonomer with a carbon number of 6 or more, the sealing property of the case 13 is excellent in the normal temperature range, for example at room temperature to 60° C., and at high temperature, for example at 100° C. or above, the strength of the case in which the vent member 15 is inserted may be lowered, which may realize or cause venting. For example, the second resin may include a linear low-density polyethylene having comonomer with a carbon number of 6 to 8.
In an embodiment of the present disclosure, in the linear low-density polyethylene having a comonomer with a carbon number of 6 or more, the content of the comonomer with a carbon number of 6 or more may be less than 12 weight %, or less than 11.8 weight %, or less than 10 weight %, or less than 9 weight %, or less than 8 weight %, or less than 7.6 weight %, compared to 100 weight % of the linear low-density polyethylene having a comonomer with a carbon number of 6 or more. The content of the comonomer with a carbon number of 6 or more may be 5 weight % or more, or 7.6 weight % or more, or 8 weight % or more, or 9.0 weight % or more, or 10 weight % or more, or 11.8 weight % or more, compared to 100 weight % of the linear low-density polyethylene having a comonomer with a carbon number of 6 or more. If the content of the comonomer with a carbon number of 6 or more satisfies the above-described range, it is possible to more easily prevent a problem that the sealing strength is lowered during normal operation of the battery due to a decrease in the packing density between molecules.
In an embodiment of the present disclosure, the linear low-density polyethylene having a comonomer with a carbon number of 6 or more may be polymerized in the presence of a metallocene catalyst. If the linear low-density polyethylene having a comonomer with a carbon number of 6 or more is polymerized in the presence of a metallocene catalyst, it will be more advantageous in terms of sealing strength and physical properties, compared to the case where it is polymerized in the presence of a Ziegler-Natta catalyst.
In an embodiment of the present disclosure, the second resin may have a melting point of 100° C. to 130° C. and be a linear low-density polyethylene having a comonomer with a carbon number of 6 or more. In an embodiment of the present disclosure, the second resin may have a poly dispersity index (PDI) of 2.6 or more and 4 or less and be a linear low-density polyethylene having a comonomer with a carbon number of 6 or more. In an embodiment of the present disclosure, the second resin may have a crystallization temperature of higher than 90° C. and 115° C. or below and be a linear low-density polyethylene having a comonomer with a carbon number of 6 or more. In an embodiment of the present disclosure, the second resin may have a weight-average molecular weight of greater than 250,000 g/mol and 400,000 g/mol or less and be a linear low-density polyethylene having a comonomer with a carbon number of 6 or more.
In an embodiment of the present disclosure, the second resin may have a lower melting point than the sealant resin. Accordingly, a vent may be induced more easily at a high temperature.
In an embodiment of the present disclosure, the melting point of the third resin may be higher than 130° C., or 131° C. to 140° C., or 132° C. to 138° C. If the melting point of the third resin satisfies the above range, it is possible to more easily improve the rigidity of the vent member 15.
In an embodiment of the present disclosure, the crystallization temperature of the first resin and the crystallization temperature of the third resin may be significantly different. For example, the difference between the crystallization temperature of the first resin and the crystallization temperature of the third resin is greater than the difference between the crystallization temperature of the first resin and the crystallization temperature of the sealant resin, so the fusion properties between the third resin and the first resin may be inferior to the fusion properties between the first resin and the sealant resin, so venting may occur more easily at the interface between the middle layer containing the third resin and the lowermost layer of the vent member containing the first resin, rather than at the interface between the first resin and the sealant resin.
In an embodiment of the present disclosure, the difference between the crystallization temperature of the first resin and the crystallization temperature of the third resin may be 30° C. or more. If the difference between the crystallization temperature of the first resin and the crystallization temperature of the third resin satisfies the above range, a vent may occur more easily between the middle layer containing the third resin and the lowermost layer of the vent member containing the first resin.
In an embodiment of the present disclosure, the crystallization temperature of the third resin may be higher than 115° C. For example, the crystallization temperature of the third resin may be 116° C. to 130° C., or 116° C. to 120° C. If the crystallization temperature of the third resin satisfies the above range, a vent may occur more easily between the middle layer containing the third resin and the lowermost layer of the vent member containing the first resin.
In an embodiment of the present disclosure, the difference between the crystallization temperature of the third resin and the crystallization temperature of the first resin is 30° C. or more, and the crystallization temperature of the third resin may be higher than 115° C.
In an embodiment of the present disclosure, the third resin may include high-density polyethylene, random polypropylene, or a mixture thereof.
In an embodiment of the present disclosure, the vent member 15 may have various shapes so that the gas is easily directed toward the vent region. For example, the vent member 15 may have a film shape.
The vent member 15 may be formed to have a predetermined thickness of a preset magnitude.
In an embodiment of the present disclosure, as shown in
Referring to
In an embodiment of the present disclosure, when the sealing portion 13b is sealed at three sides, the bent side of the case and one end of the vent member 15 may be in close contact.
In addition, the vent member 15 may be inserted into the case 13 so that the insertion length can be varied or the venting pressure and position can be controlled depending on the design. Here, the insertion length of the vent member 15 means a maximum value of the distance between one end and the other end of the vent member 15 based on the protruding direction of the electrode lead.
In an embodiment of the present disclosure, the insertion length of the vent member 15 may be smaller than the width of the sealing portion 13b. For example, the insertion length of the vent member 15 may be less than about 50% of the width of the sealing portion 13b. Here, the width of the sealing portion 13b means a maximum value of the distance between one end and the other end of the sealing portion 13b based on the protruding direction of the electrode lead 11.
In another embodiment of the present disclosure, the insertion length of the vent member 15 may be greater than the width of the sealing portion 13b. For example, the vent member 15 may be inserted through the accommodation portion 13a to be exposed to the outside of the case 13.
In an embodiment of the present disclosure, the vent member 15 may further include an adhesive layer for smoother placement.
Referring to
Referring to
The secondary battery according to an embodiment of the present disclosure includes a vent member, which has a structure of three or more layers including the first resin in a lowermost layer, the second resin in an uppermost layer and the third resin in a middle layer, so it is possible to more smoothly and quickly implement directional venting that may discharge gas in a specific direction by lowering the sealing strength at high temperature. Therefore, when a thermal runaway phenomenon occurs, namely when internal temperature of the secondary battery rises, damage to the electrode caused by the gas may be minimized. In addition, the rigidity of the vent member is improved to prevent early venting prior to a desired temperature and pressure.
In an embodiment of the present disclosure, the secondary battery may be a cylindrical, prismatic, or pouch-type secondary battery. Among them, the secondary battery may be a pouch-type secondary battery.
Hereinafter, the present disclosure will be explained in more detail with reference to exemplary embodiments. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth therein. It will be apparent that these exemplary embodiments are provided so that the present disclosure will be complete and understood easily by those skilled in the art.
A linear low-density polyethylene having a comonomer with a carbon number of 6 (LG Chem, Lucene™, SP311) (melting point: 119° C., comonomer content relative to the total resin content: 9 weight %, weight-average molecular weight: 270,756 g/mol, poly dispersity index: 2.674, crystallization temperature: 107° C.) having a thickness of 50 μm and polymerized in the presence of a metallocene catalyst was laminated on one surface of a high-density polyethylene (Sabic®, HDPE F04660, melting point: 135° C., weight-average molecular weight: 350,000 g/mol, crystallization temperature: 119° C.) having a thickness of 50 μm, and a linear low-density polyethylene having a comonomer with a carbon number of 8 (LG Chem, Lucene™, LF100) (melting point: 99° C., comonomer content relative to the total resin content: 16.3 weight %, weight-average molecular weight: 205,603 g/mol, poly dispersity index: 2.551, crystallization temperature: 83° C.) having a thickness of 50 μm and polymerized in the presence of a metallocene catalyst is laminated on the other surface of the high-density polyethylene, then thermally fused at 100° C., and cut to 100 mm in width to prepare a vent member.
An upper pouch and a lower pouch in which poly(ethylene terephthalate)/aluminum foil/polypropylene resin were sequentially laminated were placed so that the polypropylene resins thereof face each other, and then were accommodated in an electrode assembly in which a positive electrode, a separator and a negative electrode were stacked in order.
After that, the prepared vent member was inserted between the polypropylene resins, and then thermally fused at conditions of 200° C. and 0.08 MPa for 1.5 seconds to prepare a secondary battery.
An upper pouch and a lower pouch in which poly(ethylene terephthalate)/aluminum foil/polypropylene resin were sequentially laminated were placed so that the polypropylene resins thereof face each other, and then were accommodated in an electrode assembly in which a positive electrode, a separator and a negative electrode were stacked in order.
Then, the polypropylene resins were thermally fused to prepare a secondary battery.
An upper pouch and a lower pouch in which poly(ethylene terephthalate)/aluminum foil/polypropylene resin were sequentially laminated were placed so that the polypropylene resins thereof face each other, and then were accommodated in an electrode assembly in which a positive electrode, a separator and a negative electrode were stacked in order.
After that, a vent member having a thickness of μm and made of a linear low-density polyethylene (LG Chem, Lucene™, SP311) (melting point: 119° C., comonomer content relative to the total resin content: 9 weight %, weight-average molecular weight: 270,756 g/mol, PDI: 2.674, crystallization temperature: 107° C.) having a comonomer with a carbon number of 6 and polymerized in the presence of a metallocene catalyst was inserted between the polypropylene resins, and then thermally fused at conditions of 200° C. and 0.08 MPa for 1.5 seconds to prepare a secondary battery.
In the secondary batteries prepared in Example 1 and Comparative Example 2, a part of the case in which the vent member was inserted was cut to 15 mm in width and 5 cm in length at the following temperature, then both ends of the cut sample were opened at 180° and bite using a UTM jig, and then a tensile test was performed at a rate of 5 mm/min. The sealing strength of the case at this time is shown in Table 1 below.
In the secondary battery prepared in Comparative Example 1, a part of the case corresponding to the sealing portion was cut to 15 mm in width and 5 cm in length at the following temperature, then both ends of the cut sample were at 180° and bite using a UTM jig, and then a tensile test was performed at a speed of 5 mm/min. The sealing strength of the case at this time is shown in Table 1 below.
At this time, the maximum sealing strength means a maximum value when the case is broken, and the average sealing strength means an average value when the case is stretched by 8 mm at 4.5 kgf/15 mm if the maximum sealing strength is 4.5 kgf/15 mm or more, and means an average value when the case is stretched by 8 mm at the maximum sealing strength if the maximum sealing strength is less than 4.5 kgf/15 mm
As can be seen in Table 1, it may be found that in the secondary battery prepared in Example 1, the maximum sealing strength and the average sealing strength of the part of the case in which the vent member is inserted at room temperature to 60° C. are higher than the maximum sealing strength and the average sealing strength of the part of the case in which the vent member is inserted in the secondary battery prepared in Comparative Example 2 at room temperature to 60° C. Accordingly, the rigidity of the vent member 15 is improved compared to the case where only the second resin is included, thereby preventing early venting from occurring prior to a desired temperature and pressure.
In addition, it may be found that in the secondary battery prepared in Example 1, the maximum sealing strength and the average sealing strength of the case in which the vent member is inserted at 100° C. or above are lower than the maximum sealing strength and the average sealing strength of the part of the case in which the vent member is inserted in the secondary battery prepared in Comparative Example 1 at 100° C. or above. Accordingly, the secondary battery prepared in Example 1 may be vented more easily when the battery is heated to a high temperature due to an abnormal phenomenon, compared to the secondary battery prepared in Comparative Example 1.
In the secondary battery prepared in Comparative Example 1, the maximum sealing strength and the average sealing strength of the case at room temperature to 60° C. are similar to the maximum sealing strength and the average sealing strength of the part of the case in which the vent member is inserted at room temperature to 60° C. in the secondary battery prepared in Example 1, but the maximum sealing strength and the average sealing strength at 100° C. or above are significantly higher than the maximum sealing strength and the average sealing strength of the part of the case in which the vent member is inserted at 100° C. or above in the secondary battery prepared in Example 1. Thus, when the battery is heated to high temperature due to an abnormal phenomenon, the gas may be discharged in an unspecified direction to cause a chain ignition of the battery.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0049380 | Apr 2021 | KR | national |
The present application is a national phase entry under 35 U.S.C. § 371 of International Application No. PCT/KR2022/005497 filed on Apr. 15, 2022, which claims priority to Korean Patent Application No. 10-2021-0049380 filed on Apr. 15, 2021, the disclosures of which are incorporated herein by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/005497 | 4/15/2022 | WO |
