CELL POUCH FILM MAINTAINING OR INCREASING HIGH-TEMPERATURE SEALING STRENGTH, METHOD FOR PREPARING THE SAME, SECONDARY BATTERY USING THE CELL POUCH AND METHOD FOR MANUFACTURING THE SECONDARY BATTERY

Information

  • Patent Application
  • 20240222756
  • Publication Number
    20240222756
  • Date Filed
    December 28, 2023
    11 months ago
  • Date Published
    July 04, 2024
    4 months ago
  • CPC
    • H01M50/198
    • H01M50/105
    • H01M50/124
  • International Classifications
    • H01M50/198
    • H01M50/105
    • H01M50/124
Abstract
Disclosed is a cell pouch film, comprising at least an outer layer, a barrier layer, and a sealant layer structured in that order, wherein the sealant layer is formed by extrusion on the barrier layer, wherein the sealant layer has a glass transition temperature (Tg) of −10° C. to −7° C., and wherein a crystallinity of the sealant layer is 28% to 32%, a preparation method thereof, a secondary battery using the cell pouch film, and a manufacturing method for the secondary battery. The sealing strength of the pouch film may be maintained or increased at high temperatures, thereby providing excellent high-temperature stability, which prevents electrolyte leakage during battery use in high-temperature environments and ensures battery safety with fewer defects.
Description
CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to Korean Patent Application No. 10-2022-0189862, filed on Dec. 29, 2022, and all the benefits accruing therefrom under 35 U.S.C. § 119, the contents of which in its entirety are herein incorporated by reference.


BACKGROUND
1. Field

The present disclosure relates to a high-temperature sealing strength-maintaining or increasing cell pouch film, and a method for preparing the same, and specifically, the present disclosure relates to a cell pouch film wherein the sealant layer is formed by extrusion, and the high-temperature sealing strength may be maintained or increased by controlling a glass transition temperature and crystallinity of a sealant layer, a method for preparing the same, a secondary battery using the same, and a method for manufacturing the secondary battery.


2. Description of the Related Art

Lithium secondary batteries (LiB) are being applied to many applications based on various advantages such as high energy density and excellent output.


As a laminated film for encasing a secondary battery, with a multi-layer structure that surrounds an electrode group and an electrolyte of the secondary battery, a secondary battery pouch film is a key component material that determines the battery's stability, lifespan characteristics, and operational sustainability and requires mechanical flexibility and strength, high oxygen/water vapor barrier properties, high thermal sealing strength, chemical resistance to electrolyte solutions, electrical insulation, and high temperature stability, etc.


Cell pouch films typically consist of an outer layer, a barrier layer and an inner sealant layer.


The outer or outermost layer is composed of nylon or a blend of nylon and PET (polyethylene terephthalate), OPP (oriented polypropylene), polyethylene, and the like. The required properties of these outer layers or outermost layers include heat resistance, pinhole resistance, chemical resistance, formability, and insulation, etc.


The barrier layer requires formability as well as barrier properties against water vapor and other gases. In this respect, metals with formability such as aluminum (Al), iron (Fe), copper (Cu), and nickel (Ni) etc. are used in the barrier layer, and aluminum is currently used the most.


Since the sealant layer which is an inner layer is in contact with the electrolyte, it requires electrolyte resistance, and insulation resistance etc. as well as thermal adhesiveness and formability.


Meanwhile, a heat sealing is to make the inner surfaces (sealant layer) of the cell pouch film face each other, and then apply heat to seal them, so as to make the cell pouch film into a cell pouch.


The reason why heat sealing of the cell pouch film is important is that if the sealing is poor or weak, the electrolyte may leak out and the battery will not function properly.


In particular, the reason for measuring sealing strength at high temperatures regarding the heat sealing is that batteries are subjected to high temperatures during use, and if the sealing strength is weak at high temperatures, the sealing may lead to a leakage during use, which in turn may lead to a battery explosion.


Such seal stability at high temperatures is required for medium-sized and large-sized batteries for automotive and ESS applications with high safety requirements, but it is not easy to achieve and maintain high sealing strength at high temperatures in the actual manufacturing of pouch films for medium-sized and large-sized secondary batteries.


SUMMARY

In exemplary embodiments of the present disclosure, there are provided, in one aspect, a cell pouch film wherein its sealing strength may be maintained or increased at high temperature, a method for preparing the same, a secondary battery using the same, and a method for manufacturing the secondary battery.


In exemplary embodiments of the present disclosure, there are provided, in another aspect, a cell pouch film wherein its sealing strength may be maintained or increased at high temperature, thereby having excellent high-temperature stability and preventing leakage of electrolyte and securing battery safety even during battery use in a high-temperature environment, a method for preparing the same, a secondary battery using the same, and a method for manufacturing the secondary battery.


In exemplary embodiments of the present disclosure, there is provided a cell pouch film, comprising at least an outer layer, a barrier layer, and a sealant layer structured in that order, wherein the sealant layer is formed by non-lamination extrusion on the barrier layer, wherein the sealant layer has a glass transition temperature (Tg) of −10° C. to −7° C., and wherein a crystallinity of the sealant layer, as measured by a method below, is 28% to 32%.


Crystallinity Measurement Method

Crystallinity of a sealant layer delaminated from a cell pouch film is measured using DSC equipment at a temperature range of −50° C. to 200° C., with a heating rate of 10° C./min and a cooling rate of −20° C./min.


A crystallinity value is expressed as a percentage where an enthalpy value (AH (J/g)) at a crystallization temperature (Tc) is divided by 100% crystallization enthalpy value of isopolypropylene (Iso-PP), which is 209 J/g.


According to an exemplary embodiment, a sealing strength of the cell pouch film in a TD direction when sealed at 180° C. for 2 seconds may be at least −5% at high temperature relative to ambient temperature.


According to an exemplary embodiment, a sealing strength of the cell pouch film in the TD direction when sealed at 200° C. for 2 seconds may be at least 1% at high temperature relative to ambient temperature.


According to an exemplary embodiment, a sealing strength of the cell pouch film in the TD direction when sealed at 220° C. for 2 seconds may be at least −5% at high temperature relative to ambient temperature.


According to an exemplary embodiment, a sealing strength of the cell pouch film in a MD direction when sealed at 180° C. for 2 seconds may be at least 1% at high temperature relative to ambient temperature.


According to an exemplary embodiment, a sealing strength of the cell pouch film in the MD direction when sealed at 200° C. for 2 seconds may be at least 10% at high temperature relative to ambient temperature.


According to an exemplary embodiment, a sealing strength of the cell pouch film in the MD direction when sealed at 220° C. for 2 seconds may be at least −5% at high temperature relative to ambient temperature.


According to an exemplary embodiment, an average value of an increase ratio of a high-temperature sealing strength of the cell pouch film in the TD direction of the following [Formula 1] for each case of sealing at 180° C. for 2 seconds, sealing at 200° C. for 2 seconds, and sealing at 220° C. for 2 seconds may be within a range of −1% to 20%.





[(high-temperature TD sealing strength−ambient temperature TD sealing strength)/ambient temperature TD sealing strength]×100  Formula 1:


According to an exemplary embodiment, an average value of an increase ratio of a high-temperature sealing strength of the cell pouch film in the MD direction of the following [Formula 2] for each case of sealing at 180° C. for 2 seconds, sealing at 200° C. for 2 seconds, and sealing at 220° C. for 2 seconds may be within the range of 5% to 25%.





[(high-temperature MD sealing strength−ambient temperature MD sealing strength)/ambient temperature MD sealing strength]×100  Formula 2:


According to an exemplary embodiment, a sum of <the high-temperature sealing strength of the cell pouch film in the TD direction minus the ambient temperature sealing strength of the cell pouch film in the TD direction> and <the high-temperature sealing strength of the cell pouch film in the MD direction minus the ambient temperature sealing strength of the cell pouch film in the MD direction> for each case of sealing at 180° C., 200° C., and 220° C. for 2 seconds may be within the range of −10 to 70 N/15 mm.


In addition, in exemplary embodiments of the present disclosure, provided is a method for preparing the aforementioned cell pouch film, comprising forming a sealant layer by extruding by non-lamination extrusion on a barrier layer, wherein the sealant layer has a glass transition temperature (Tg) of −10° C. to −7° C., and wherein a crystallinity of the sealant layer, as measured by a method below, is 28% to 32%.


Crystallinity Measurement Method

Crystallinity of a sealant layer delaminated from a cell pouch film is measured using DSC equipment at a temperature range of −50° C. to 200° C., with a heating rate of 10° C./min and a cooling rate of −20° C./min.


A crystallinity value is expressed as a percentage where an enthalpy value (AH (J/g)) at a crystallization temperature (Tc) is divided by 100% crystallization enthalpy value of isopolypropylene (Iso-PP), which is 209 J/g.


In addition, in exemplary embodiments of the present disclosure, provided is a secondary battery encased in the aforementioned cell pouch film.


According to an exemplary embodiment, the secondary battery may be for use in an electric vehicle or energy storage device.


In addition, in exemplary embodiments of the present disclosure, provided is a method for manufacturing a secondary battery, comprising encasing the secondary battery in the aforementioned cell pouch film.


In exemplary embodiments of the present disclosure, the sealing strength of a cell pouch film may be maintained or increased at high temperatures. Consequently, the cell pouch film can exhibit excellent high-temperature stability, preventing electrolyte leakage and reducing defects during battery usage in high-temperature environments, thereby ensuring battery safety.


These secondary battery pouch films are useful for medium-sized to large-sized secondary battery pouches for electric vehicles and energy storage devices that require safety, especially high-temperature safety.





BRIEF DESCRIPTION OF DRAWINGS

The above and other aspects, features and advantages of the disclosed exemplary embodiments will be more apparent from the following detailed description taken in conjunction with the accompanying drawings in which:



FIG. 1 is a schematic diagram illustrating a configuration of a cell pouch film prepared by extrusion lamination.



FIG. 2 is a schematic diagram illustrating a configuration of a cell pouch film prepared by a non-lamination extrusion method.





DETAILED DESCRIPTION

Exemplary embodiments are described more fully hereinafter. The invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the description, details of features and techniques may be omitted to more clearly disclose exemplary embodiments.


Term Definition

In this disclosure, when a secondary battery pouch film includes layer(s), the secondary battery pouch does not necessarily consist of only that layer, and additional layers may be included therein.


In this disclosure, being formed “on” a specific layer includes not only being formed directly on that layer, but also being formed after interposing another additional layer in between.


In this disclosure, Extrusion Coating (EC) layer in the sealant layers refers to a layer of an extruded resin, such as a polyolefin-based resin, preferably a polypropylene-based resin, serving as a bonding layer with the barrier layer (in the case of an extrusion lamination method) or serving as a sealing layer as well as a bonding layer with the barrier layer (in the case of a non-lamination extrusion method).


As used herein, maintaining or increasing of sealing strength at high temperature means that the increase ratio in the high-temperature sealing strength over the ambient temperature sealing strength, i.e., [(high-temperature sealing strength−ambient temperature sealing strength)/ambient temperature sealing strength]×100, is at least −5%. An increase ratio of −5% to 0% in the high-temperature sealing strength may be considered to mean that the sealing strength is maintained, even if it is a negative value.


Description of Exemplary Embodiments

Exemplary implementations of the present disclosure are described below.


When preparing a secondary battery pouch, there are three methods for manufacturing a sealant layer: non-lamination extrusion, extrusion lamination, and solvent-dry lamination (hereinafter, “SDL”).


The solvent dry lamination method is a method of bonding a barrier layer (metal layer) using a solvent-based adhesive on a polypropylene (PP) layer and drying the solvent-based adhesive, so that the sealant layer produced is composed of a polypropylene (PP) layer. The solvent-based adhesive may remain in the polypropylene (PP) layer after drying, but it is present in a thickness of about 4 μm or less and is insignificant, so its thickness may be neglected.


The extrusion lamination method is a method of extruding a polypropylene-based resin layer, preferably a polyolefin-based resin, preferably a polypropylene resin, which is mainly used as a sealing resin for a sealant layer, especially a cast polypropylene (CPP) resin layer, when bonding a barrier layer (metal layer). As a result, the sealant layer consists of an Extrusion Coating (EC) layer (mainly an extruded polypropylene layer) and a polypropylene (PP) layer resin, preferably a cast polypropylene (CPP) layer (or film) underneath (inward with respect to the pouch film) (see FIG. 1).


On the other hand, the non-lamination extrusion method is a method of forming a sealant layer during the manufacture of a cell pouch film by extruding (or co-extruding) a polyolefin-based resin, preferably a polypropylene-based resin, directly onto the barrier layer, instead of joining (laminating) the sealing resin layer or film such as a polypropylene-based resin with the barrier layer, as in the case of extrusion lamination or solvent dry lamination. As a result, the sealant layer consists of a layer by extrusion, e.g. a polypropylene layer by extrusion. Such a sealant layer by non-lamination extrusion may also be formed by co-extruding a first extruded layer and a second extruded layer.


The inventors of the present disclosure have found that when a sealant layer is formed by performing a non-lamination extrusion method, the glass transition temperature (Tg) of the sealant layer is −10° C. to −7° C., and the crystallinity of the sealant layer measured by the following method is controlled to 28% to 32%, the sealing strength may be maintained or increased under high-temperature conditions after being left for 10 minutes at 60° C., and thus the high-temperature stability is excellent, which may prevent leakage of electrolyte even during use of the battery in high-temperature environments and secure battery safety.


The high-temperature sealing strength property is an essential property for the safety of medium and large-sized batteries such as automotive batteries, and by performing a non-lamination extrusion method while controlling the glass transition temperature (Tg) of the sealant layer to −10° C.˜−7° C. and the crystallinity of the sealant layer measured by the following method to 28˜32%, the sealing strength may be surprisingly maintained or increased under high-temperature conditions (measured after 10 minutes at 60° C.).


According to an exemplary embodiment, the glass transition temperature (Tg) of the sealant layer may be −10° C.˜−7° C., preferably −9.5° C.˜−7° C., more preferably −9° C.˜−7° C. It may be seen that it is advantageous for high-temperature sealing strength when the sealant layer has a relatively high glass transition temperature (Tg). If the glass transition temperature (Tg) of the sealant layer is less than the above −10° C., the high-temperature sealing strength may be reduced, as may be seen from the data described below.


In a non-limiting example, the glass transition temperature (Tg) of the sealant layer may be at least −10° C., at least −9.5° C., at least −9º° C., at least −8.5° C., at least −8° C., or at least −7.5° C. Alternatively, it may be −7° C. or less, −7.5° C. or less, −8° C. or less, −8.5° C. or less, −9° C. or less, or −9.5° C. or less.


According to an exemplary embodiment, the crystallinity of the sealant layer may be 28-32%, preferably 28.5-31.5%, more preferably 29-30%. It may be seen that a relatively low crystallinity is advantageous in terms of the fluidity of the polymer, which is advantageous for sealing strength at high temperatures. If the crystallinity of the sealant layer is greater than the above 32%, the high-temperature sealing strength may be reduced, as may be seen from the data described below.


In a non-limiting example, the crystallinity of the sealant layer may be at least 28%, at least 28.5%, at least 29%, at least 29.5%, at least 30%, at least 30.5%, at least 31%, or at least 31.5%. Alternatively, it may be 32% or less, 31.5% or less, 31% or less, 30.5% or less, 30% or less, 29.5% or less, 29% or less, or 28.5% or less.


According to an exemplary embodiment, the aforementioned glass transition temperature (Tg) or crystallinity may vary depending on the type of resin used in the sealant layer, such as the commonly used polypropylene-based resin, as known in the art, and may be appropriately adjusted by a skilled person in the art, for example, by changing the content of the main polymer of the polypropylene-based resin (changing the homopolypropylene or block polypropylene polymer content) or by using low molecular weight additives such as rubber components.


According to an exemplary embodiment, the cell pouch film may have a sealing strength in the TD direction when sealed at 180° C. for 2 seconds that is at least −5%, such as within a range of −5% to 20%, or −3% to 15%, or −2% to 14%, at high temperature relative to ambient temperature.


According to an exemplary embodiment, the cell pouch film may have a sealing strength in the TD direction when sealed at 200° C. for 2 seconds that is at least 1%, such as within a range of 1% to 20%, or 2% to 15%, or 2% to 14%, at high temperature relative to ambient temperature.


According to an exemplary embodiment, the cell pouch film may have a sealing strength in the TD direction when sealed at 220° C. for 2 seconds that is at least −5%, such as within a range of −5% to 30%, or −3% to 29%, or −1% to 27%, at high temperature relative to ambient temperature.


According to an exemplary embodiment, the cell pouch film may have a sealing strength in the MD direction when sealed at 180° C. for 2 seconds that is at least 1%, such as within a range of 1% to 10%, or 3% to 8%, or 4% to 7%, at high temperature relative to ambient temperature.


According to an exemplary embodiment, the cell pouch film may have a sealing strength in the MD direction when sealed at 200° C. for 2 seconds that is at least 10%, such as within a range of 10% to 30%, or 15% to 25%, or 20% to 25%, at high temperature relative to ambient temperature.


According to an exemplary embodiment, the cell pouch film may have a sealing strength in the MD direction when sealed at 220° C. for 2 seconds that is at least −5%, such as within a range of −5% to 45%, or −4% to 40%, or −4% to 38%, at high temperature relative to ambient temperature.


According to an exemplary embodiment, the cell pouch film may be such that the average value of the increase ratio of the high-temperature sealing strength in the TD direction of the following [Formula 1] in each case of sealing at 180° C. for 2 seconds, sealing at 200° C. for 2 seconds, and sealing at 220° C. for 2 seconds is within the range of −1% to 20%, or −0.4% to 18.2%.





[(high-temperature TD sealing strength−ambient temperature TD sealing strength)/ambient temperature TD sealing strength]×100  Formula 1:


According to an exemplary embodiment, the cell pouch film may be such that the average value of the increase ratio of the high-temperature sealing strength in the MD direction of the following [Formula 2] in each case of sealing at 180° C. for 2 seconds, sealing at 200° C. for 2 seconds, and sealing at 220° C. for 2 seconds is within the range of 5% to 25%, or 7.6% to 21.5%.





[(high-temperature MD sealing strength−ambient temperature MD sealing strength)/ambient temperature MD sealing strength]×100  Formula 2:


According to an exemplary embodiment, the cell pouch film may be such that the sum of the high-temperature sealing strength in the TD direction minus the ambient temperature sealing strength in the TD direction and the high-temperature sealing strength in the MD direction minus the ambient temperature sealing strength in the MD direction in each case of sealing at 180° C., 200° C., and 220° C. for 2 seconds is within the range of −10 to 70 N/15 mm, or −6 to 67 N/15 mm.


According to an exemplary embodiment, the outer layer may be formed of nylon, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), a mixed layer of nylon and PET, and the like. In a non-limiting example, the outer layer may preferably be a PET film of 7 to 12 μm on the outermost side and a nylon film of 20 to 30 μm on the inner side.


According to an exemplary embodiment, the metal layer may be formed of a metal such as aluminum, SUS, or copper, and is moisture permeable and impact resistant.


According to an exemplary embodiment, the polypropylene (CPP) layer of the sealant layer may contain various additives (rubber, elastomer, slip agent, etc.) depending on the required properties.


According to an exemplary embodiment, the total thickness of the secondary battery pouch film may be, for example, 60 to 185 μm. In an exemplary embodiment, the secondary battery pouch film may be 153 μm or more or 113 μm or less.


According to an exemplary embodiment, the thickness of the metal layer, which is the barrier layer, may be, for example, 20 to 80 μm, preferably 40 to 60 μm.


According to an exemplary embodiment, the thickness of the sealant layer may be, for example, 20 to 80 μm.


A method for preparing a secondary battery pouch film according to exemplary embodiments of the present disclosure includes forming a sealant layer by extruding polypropylene resin on a barrier layer, wherein the glass transition temperature (Tg) of the sealant layer is between −10° C. and −7° C., and the crystallinity of the sealant layer measured by the method described above is between 28% and 32%.


Meanwhile, exemplary embodiments of the present disclosure provide a secondary battery encased with the aforementioned secondary battery pouch film. Such a secondary battery may be, for example, a lithium-ion battery, and in particular, a medium to large-scale secondary battery for an electric vehicle (EV) or energy storage system (ESS).


In addition, exemplary embodiments of the present disclosure provide a method for manufacturing a secondary battery including encasing the secondary battery with the aforementioned secondary cell pouch film as described above.


Exemplary embodiments of the present disclosure are described in more detail in the following examples. The embodiments disclosed herein are illustrated for purposes of illustration only, and embodiments of the present disclosure may be practiced in various forms and the scope of the present disclosure should not be construed as being limited to the embodiments described herein.


Experiment Method

In the Examples and Comparative Examples, the outer layer is composed of a PET and nylon composite layer, and the metal layer is aluminum foil.


The Examples are formed by extruding polypropylene onto a barrier layer (non-lamination extrusion method), while the Comparative Examples are prepared by extrusion-lamination method in which polypropylene is extruded on a polypropylene (PP) layer and bonded to the barrier layer. The thickness of the metal layer, the respective thicknesses of the extruded and PP layers of the sealant layer, and the glass transition temperature, enthalpy, and crystallinity of the sealant layer are shown in Table 1. The total thickness of the pouch film is shown in Table 3 below.












TABLE 1









Sealant layer


















Sealant layer
Extruded
PP
Ratio of






Al
thickness
layer
layer
layers
Tg
ΔH(J/g)
crystallinity



















Example 1
60
80
80
0
 0:80
 −8.68° C.
62.045
29.7%


Example 2
40
80
80
0
 0:80
 −8.29° C.
65.545
31.4%


Comparative
60
80
30
50
50:80
−13.41° C.
72.687
34.8%


Example 1


Comparative
40
80
30
50
50:80
−14.37° C.
70.229
33.6%


Example 2


Comparative
60
100
30
70
 70:100
−14.23° C.
72.479
34.7%


Example 3


Comparative
40
110
40
70
 70:110
−13.95° C.
71.245
33.9%


Example 4


Comparative
40
80
40
40
40:80
−11.89° C.
69.743
33.2%


Example 5


Comparative
60
80
40
40
40:80
−11.73° C.
69.395
33.4%


Example 6


Comparative
40
80
0
80
80:80
−14.31° C.
74.256
36.2%


Example 7









For the above Examples and Comparative Examples, sealing strength, defect (defective product) evaluation, and burst tests were performed as follows.


Preparation of Specimen

The specimen is prepared by cutting the cell pouch film to 200 mm across (MD) and 100 mm down (TD).


The specimen is heat sealed in the MD direction.


The sealing conditions are as follows.

    • (1) Sealing time: 2.0 seconds
    • (2) Sealing temperature: Each 180° C., 200° C., 220° C.
    • (3) Sealing pressure: 0.2 MPa


Measurement of Sealing Strength

The specimen prepared above is cut to a 15 mm width in the longitudinal (TD) direction, and both sides of the film are held in a universal testing machine (UTM) jig for 90 degree peeling (UTM equipment: AGS-X by SIMADZU).


Sealing strength is measured at ambient temperature and high-temperature conditions. The maximum strength is expressed as the sealing strength. The unit is N/15 mm.

    • (1) Ambient temperature conditions: Measurement speed (10 mpm)
    • (2) High-temperature conditions: The measurement is performed under the same conditions as the ambient temperature measurement above, but after being placed in a 60° C. heat chamber for 3 minutes. The heat chamber is a TCE-N300 from SIMADZU.


Measurement of Tg and Crystallinity

The sealant layer is delaminated from the aforementioned specimen (the sealant layer was delaminated from the specimen before measuring the sealing strength). For this purpose, the specimen is completely immersed in a solution of FLOIL (Remover 200) from KantoKasei. Once the sealant layer is removed from the specimen, it is wiped with a rag or cotton tissue, washed with ethanol, wiped again with cotton tissue, and dried at ambient temperature.


(1) Measurement Method of Tg

DSC250 equipment by TA is used. The conditions area measured down to the temperature range of −50° C.° C., with a heating rate of 10° C. and a cooling rate of −20° C.


The Tg value is calculated using an analysis program (TRIOS) at −50° C., which is the approximate Tg value range of polypropylene.


(2) Crystallinity Measurement Method

DSC250 equipment by TA is used, as the same as the Tg measurement method. The conditions are measured down to the temperature range of −50° C.° C., with a heating rate of 10° C. and a cooling rate of −20° C. The value of crystallinity is calculated by obtaining the enthalpy of Tc (Δ(J/g)) through the analysis program (TRIOS) and dividing it by the enthalpy of 100% crystallization of general isopolypropylene (Iso-PP), which is 209 J/g. The results are shown in [Table 2] below.













TABLE 2









Sealing strength
Sealing strength
Sealing strength



(180° C. 2.0 sec) (N/15 mm)
(200° C. 2.0 sec) (N/15 mm)
(220° C. 2.0 sec) (N/15 mm)




















High temp
High temp

High temp
High temp

High temp
High temp





(after leaving
sealing

(after leaving
sealing

(after leaving
sealing




Ambient
for 3 min at
strength
Ambient
for 3 min at
strength
Ambient
for 3 min at
strength



Direction
temp
60° C.)
increase (%)
temp
60° C.)
increase (%)
temp
60° C.)
increase (%)





















Example 1
MD
112.3
120.3
7.1%
90
107.7
19.7%
101.9
140.2
37.6%



TD
89.6
101.7
13.5%
100.8
114.9
14.0%
105.4
133.9
27.0%


Example 2
MD
99.9
103.8
3.9%
107.9
132.9
23.2%
113.5
108.8
−4.1%



TD
105.6
103.8
−1.7%
115.6
117.4
1.6%
124.6
123.2
−1.1%


Comparative
MD
104.3
59.4624
−43.0%
112.3
82.6736
−26.4%
113.7
94.9312
−16.5%


Example 1
TD
93.37
67.2212
−28.0%
118.9
82.478
−30.6%
123.4
102.186
−17.2%


Comparative
MD
88.61
63.7656
−28.0%
101.5
66.2432
−34.7%
101.3
75.8276
−25.2%


Example 2
TD
96.56
72.698
−24.7%
95.32
71.068
−25.4%
98.84
77.5228
−21.6%


Comparative
MD
100
89.0632
−11.0%
120.3
101.43
−15.7%
131.2
98.847
−24.7%


Example 3
TD
108.7
75.1104
−30.9%
105.3
92.9752
−11.7%
128.2
93.1708
−27.3%


Comparative
MD
93.76
80.6524
−14.0%
107.1
85.6076
−20.0%
123.4
93.7576
−24.0%


Example 4
TD
99.69
80.7176
−19.0%
103.3
81.5652
−21.0%
127
97.7348
−23.0%


Comparative
MD
103.8
86.1292
−17.0%
113.2
101.8424
−10.0%
114.3
101.619
−11.1%


Example 5
TD
102.5
90.1716
−12.0%
111
100.9948
−9.0%
113.3
101.748
−10.2%


Comparative
MD
105.7
91.932
−13.0%
116.2
103.4072
−11.0%
119.4
103.32
−13.5%


Example 6
TD
97.41
81.826
−16.0%
106.3
92.5188
−13.0%
111.6
101.5816
−9.0%


Comparative
MD
89.45
69.764
−22.0%
92.26
74.7192
−19.0%
94.47
77.4576
−18.0%


Example 7
TD
86.46
70.0248
−19.0%
90.37
76.8056
−15.0%
92.65
76.8708
−17.0%









As can be seen from [Table 1] and [Table 2] above, in the case of Examples 1 and 2, the sealant layer consists only of an extruded layer, while in the case of Comparative Examples 1, 2, and 3, the sealant layer consists of an extruded layer and a PP layer. In Table 2, it can be seen that the sealing strength increases and is maintained at high temperature (measured after 3 minutes at 60° C.) in the case of Examples 1 and 2, while the sealing strength decreases in the case of Comparative Examples 1 to 7. Therefore, it is confirmed that the case where the sealant layer consists only of an extruded layer is advantageous for high-temperature sealing strength.


Meanwhile, in Table 1, it can be seen that the Tg value is about −8° C. for Examples 1 and 2, and about −11° C. to −14° C. for the Comparative Examples. From Table 1 and Table 2, it can be seen that Examples 1 and 2 with higher Tg values increase or maintain sealing strength at high temperatures. Therefore, it can be seen that a relatively high Tg value of the sealant layer is advantageous for high-temperature sealing strength.


In addition, it can be seen from Table 1 that the crystallinity is 29.7% and 31.4% for Examples 1 and 2, and 33% or more for the Comparative Examples. As described above, it can be seen that a relatively low crystallinity is advantageous in terms of the fluidity of the polymer, and advantageous for sealing strength at high temperatures.


From the above, it is confirmed that a cell pouch film in which the sealant layer consists only of an extruded layer and has a certain glass transition temperature and crystallinity is advantageous for high-temperature sealing strength.


Evaluation of the Number of Defects Based on a Burst Test

To evaluate the reliability of high-temperature sealing, the number of defects after sealing is evaluated.


Specifically, the cell pouch film is foamed to 12 mm and then three-way sealed. The cell pouch is filled with red penetrant and water. The one remaining direction is sealed.


The sealing width is 2 mm, the time is 2 seconds, and the pressure is 0.2 MPa.


After heating in the 60° C. chamber as described above for one day, it is pressed with a pressure tester for 30 minutes at a constant pressure (pressure: 300 kgf).


For each of the 10 samples sealed at 180° C. for 2 seconds, 10 samples sealed at 200° C. for 2 seconds, and 10 samples sealed at 220° C. for 2 seconds described above, the number of defects (high-temperature defects) is obtained and summed, i.e., the number of defects (high-temperature defects) among a total of 30 samples of 10 samples at 180° C., 10 samples at 200° C., and 10 samples at 220° C. is determined. The criterion for defects is when the seal bursts, i.e., when red penetrant leaks out of the seal during pressing after sealing.


The average value of the increase rate of high-temperature sealing strength in the MD direction [((high temperature−ambient temperature)/ambient temperature)×100] for each case of sealing at 180° C. for 2 seconds, sealing at 200° C. for 2 seconds, and sealing at 220° C. for 2 seconds is shown in [Table 3], and the average value of the increase rate of high-temperature sealing strength in the TD direction [((high temperature−ambient temperature)/ambient temperature)×100] is shown in Table 4. [Table 5] lists the number of high-temperature defects.












TABLE 3








Average value of increase





rate(%) of high-temp



Thickness
Direction
sealing strength







Example 1
183
MD
  21.5%


Example 2
153
MD
   7.6%


Comparative
183
MD
−28.6%


example 1





Comparative
153
MD
−29.3%


example 2





Comparative
203
MD
−17.1%


example 3





Comparative
203
MD
−19.3%


example 4





Comparative
153
MD
−12.7%


example 5





Comparative
183
MD
−12.5%


example 6





Comparative
183
MD
−19.7%


example 7




















TABLE 4









Average value of






increase rate(%) of






high-temp sealing




Thickness
Direction
strength








Example 1
183
TD
  18.2%



Example 2
153
TD
 −0.4%



Comparative
183
TD
−25.3%



example 1






Comparative
153
TD
−23.9%



example 2






Comparative
203
TD
−23.3%



example 3






Comparative
203
TD
−21.0%



example 4






Comparative
153
TD
−10.4%



example 5






Comparative
183
TD
−12.7%



example 6






Comparative
183
TD
−17.0%



example 7




















TABLE 5








Average value of
Number of





increase rate(%) of
high-temp





high-temp sealing
defects




Direction
strength
(among 30)








Example 1
MD
  21.5%
 5/30




TD
  18.2%
 8/30



Example 2
MD
   7.6%
10/30




TD
 −0.4%
 8/30



Comparative
MD
−28.6%
28/30



example 1
TD
−25.3%
25/30



Comparative
MD
−29.3%
30/30



example 2
TD
−23.9%
30/30



Comparative
MD
−17.1%
21/30



example 3
TD
−23.3%
27/30



Comparative
MD
−19.3%
28/30



example 4
TD
−21.0%
27/30



Comparative
MD
−12.7%
22/30



example 5
TD
−10.4%
21/30



Comparative
MD
−12.5%
19/30



example 6
TD
−12.7%
24/30



Comparative
MD
−19.7%
30/30



example 7
TD
−17.0%
30/30









As can be seen from [Table 3] to [Table 5] above, the average value of the high-temperature sealing strength increase (%) of the sealing temperatures in the Examples is at least −0.4% (TD direction) and at least 7.6% (MD direction), and it can be seen that the Examples are particularly superior to the Comparative Examples, with less than 10 high-temperature failures.


Evaluation of Air Pressure after Burst Test (Pressurizing Test)


To evaluate the reliability of high-temperature sealing, the air pressure after burst test (pressuring test) is evaluated.


Specifically, the cell pouch film is foamed to 12 mm and then three-way sealed. The cell pouch is filled with red penetrant and water. The one remaining direction is sealed.


The sealing width is 2 mm, the time is 2 seconds, and the pressure is 0.2 MPa.


After heating in the 60° C. chamber for one day as described above, it is pressed with a pressure tester for 30 minutes at a constant pressure (pressure: 300 kgf). The penetrant is checked for leakage, and the air pressure of the sample with no penetrant leakage (OK) is evaluated.


[Table 6] shows the values of high-temperature sealing strength in the TD direction minus ambient temperature sealing strength in the TD direction (“TD high temperature−ambient temperature” in the left table below) and the high-temperature sealing strength in the MD direction minus the ambient temperature sealing strength in the MD direction (“MD high temperature−ambient temperature” in the right table below) for each case of sealing at 180° C., 200° C., and 220° C. for 2 seconds, and their sums [“TD high temperature−ambient temperature”+“high temperature−ambient temperature”]. [Table 7] shows the sum values and the air pressure according to the busrt test (pressuring test) (after one day in a 60° C. chamber.














TABLE 6









180° C. sealing

180° C. sealing
















TD
Ambient
High
TD High temp −
MD
Ambient
High
MD High temp −



N/15 mm
temperature
temperature
Ambient temp
N/15 mm
temperature
temperature
Ambient temp
Sum





Example 1
89.6
101.7
12.1
Example 1
112.3
120.3
8
20.1


Example 2
105.6
103.8
−1.8
Example 2
99.9
103.8
3.9
2.1


Comparative
93.3664
67.2212
−26.145
Comparative
104.32
59.4624
−44.858
−71.003


example 1



example 1


Comparative
96.5612
72.698
−23.863
Comparative
88.6068
63.7656
−24.841
−48.704


example 2



example 2


Comparative
108.688
75.1104
−33.578
Comparative
100.017
89.0632
−10.954
−44.532


example 3



example 3


Comparative
99.6908
80.7176
−18.973
Comparative
93.7576
80.6524
−13.105
−32.078


example 4



example 4


Comparative
102.494
90.1716
−12.323
Comparative
103.798
86.1292
−17.669
−29.992


example 5



example 5


Comparative
97.4088
81.826
−15.583
Comparative
105.689
91.932
−13.757
−29.34


example 6



example 6


Comparative
86.4552
70.0248
−16.43
Comparative
89.4544
69.764
−19.69
−36.121


example 7



example 7















200° C. sealing

200° C. sealing
















TD
Ambient
High
TD High temp −
MD
Ambient
High
MD High temp −



N/15 mm
temperature
temperature
Ambient temp
N/15 mm
temperature
temperature
Ambient temp
Sum





Example 1
100.8
114.9
14.1
Example 1
90
107.7
17.7
31.8


Example 2
115.6
117.4
1.8
Example 2
107.9
132.9
25
26.8


Comparative
118.925
82.478
−36.447
Comparative
112.274
82.6736
−29.601
−66.048


example 1



example 1


Comparative
95.3224
71.068
−24.254
Comparative
101.516
66.2432
−35.273
−59.528


example 2



example 2


Comparative
105.298
92.9752
−12.323
Comparative
120.294
101.43
−18.864
−31.187


example 3



example 3


Comparative
103.277
81.5652
−21.712
Comparative
107.058
85.6076
−21.451
−43.162


example 4



example 4


Comparative
111.036
100.995
−10.041
Comparative
113.187
101.842
−11.345
−21.386


example 5



example 5


Comparative
106.341
92.5188
−13.822
Comparative
116.186
103.407
−12.779
−26.602


example 6



example 6


Comparative
90.3672
76.8056
−13.562
Comparative
92.258
74.7192
−17.539
−31.1


example 7



example 7















220° C. sealing

220° C. sealing
















TD
Ambient
High
TD High temp −
MD
Ambient
High
MD High temp −



N/15 mm
temperature
temperature
Ambient temp
N/15 mm
temperature
temperature
Ambient temp
Sum





Example 1
105.4
133.9
28.5
Example 1
101.9
140.2
38.3
66.8


Example 2
124.6
123.2
−1.4
Example 2
113.5
108.8
−4.7
−6.1


Comparative
123.358
102.186
−21.172
Comparative
113.709
94.9312
−18.778
−39.95


example 1



example 1


Comparative
98.8432
77.5228
−21.32
Comparative
101.321
75.8276
−25.493
−46.814


example 2



example 2


Comparative
128.183
93.1708
−35.012
Comparative
131.248
98.847
−32.401
−67.413


example 3



example 3


Comparative
127.01
97.7348
−29.275
Comparative
123.358
93.7576
−29.601
−58.876


example 4



example 4


Comparative
113.252
101.748
−11.504
Comparative
114.296
101.691
−12.677
−24.181


example 5



example 5


Comparative
111.622
101.582
−10.041
Comparative
119.446
103.32
−16.126
−26.167


example 6



example 6


Comparative
92.6492
76.8708
−15.778
Comparative
94.4748
77.4576
−17.017
−32.796


example 7



example 7



















TABLE 7









180° C. sealing





(TD High temp −
Burst test




Ambient temp) +
(after leaving in




(MD high temp −
High temp 60° C.




Ambient temp)
chamber for one day)






Example 1
20.1
300 kgf



Example 2
2.1
300 kgf



Comparative
−71.003
200 kgf



example 1





Comparative
−48.704
200 kgf



example 2





Comparative
−44.532
200 kgf



example 3





Comparative
−32.078
200 kgf



example 4





Comparative
−29.992
260 kgf



example 5





Comparative
−29.34
260 kgf



example 6





Comparative
−36.121
200 kgf



example 7







200° C. sealing





(TD High temp −





Ambient temp) +





(MD high temp −





Ambient temp)






Example 1
31.8
300 kgf



Example 2
26.8
300 kgf



Comparative
−66.048
160 kgf



example 1





Comparative
−59.528
160 kgf



example 2





Comparative
−31.187
260 kgf



example 3





Comparative
−43.162
160 kgf



example 4





Comparative
−21.386
260 kgf



example 5





Comparative
−26.602
260 kgf



example 6





Comparative
−31.1
160 kgf



example 7







220° C. sealing





(TD High temp −





Ambient temp) +





(MD high temp −





Ambient temp)






Example 1
66.8
300 kgf



Example 2
−6.1
300 kgf



Comparative
−39.95
260 kgf



example 1





Comparative
−46.814
160 kgf



example 2





Comparative
−67.413
160 kgf



example 3





Comparative
−58.876
160 kgf



example 4





Comparative
−24.181
300 kgf



example 5





Comparative
−26.167
300 kgf



example 6





Comparative
−32.796
160 kgf



example 7









As shown in [Table 7], if the sum of the high-temperature sealing strength minus the ambient temperature sealing strength in the MD and TD directions is high, it can be seen that the three-way sealing (C-type sealing) during molding is good in both the MD and TD directions, and the sealing is well maintained at high external and internal pressures. This can improve battery safety.


While non-limiting and exemplary embodiments of the present disclosure have been described above, the technical idea of the present disclosure is not limited to the accompanying drawings or the above description. It will be apparent to a skilled person in the art that various modifications are possible without departing from the technical ideas of the present disclosure, and that such modifications fall within the scope of the claims of the present disclosure.


This invention relates to national research and development projects performed by Youlchon Chemical Co., Ltd. where the national research and development projects are of Material/Parts Package Type (Top Company) and named as ‘Development of a next-generation secondary battery pouch capable of realizing more than twice the high adhesive strength at 60° C.’, and periods of the projects are 2022 Sep. 1˜2022 Dec. 31 (assignment unique number is 1415181922, assignment number is 20022450) and 2023 Jan. 1˜2023 Dec. 31 (an assignment unique number is 1415185612 and an assignment number is 20022450).

Claims
  • 1. A cell pouch film, comprising at least an outer layer, a barrier layer, and a sealant layer structured in that order,wherein the sealant layer is formed by non-lamination extrusion on the barrier layer,wherein the sealant layer has a glass transition temperature (Tg) of −10° C. to −7° C., andwherein a crystallinity of the sealant layer, as measured by a method below, is 28% to 32%.
  • 2. The cell pouch film of claim 1, wherein a sealing strength in a TD direction when sealed at 180° C. for 2 seconds is at least −5% at high temperature relative to ambient temperature.
  • 3. The cell pouch film of claim 1, wherein the sealing strength in the TD direction when sealed at 200° C. for 2 seconds is at least 1% at high temperature relative to ambient temperature.
  • 4. The cell pouch film of claim 1, wherein the sealing strength in the TD direction when sealed at 220° C. for 2 seconds is at least −5% at high temperature relative to ambient temperature.
  • 5. The cell pouch film of claim 1, wherein the sealing strength in a MD direction when sealed at 180° C. for 2 seconds is at least 1% at high temperature relative to ambient temperature.
  • 6. The cell pouch film of claim 1, wherein the sealing strength in the MD direction when sealed at 200° C. for 2 seconds is at least 10% at high temperature relative to ambient temperature.
  • 7. The cell pouch film of claim 1, wherein the sealing strength in the MD direction when sealed at 220° C. for 2 seconds is at least −5% at high temperature relative to ambient temperature.
  • 8. The cell pouch film of claim 1, wherein an average value of an increase ratio of the high-temperature sealing strength in the TD direction of the Formula 1 in each case of sealing at 180° C. for 2 seconds, sealing at 200° C. for 2 seconds, and sealing at 220° C. for 2 seconds is within a range of −1% to 20%, wherein Formula 1 is [(high-temperature TD sealing strength−ambient temperature TD sealing strength)/ambient temperature TD sealing strength]×100.
  • 9. The cell pouch film of claim 1, wherein an average value of an increase ratio of the high-temperature sealing strength in the MD direction of Formula 2] in each case of sealing at 180° C. for 2 seconds, sealing at 200° C. for 2 seconds, and sealing at 220° C. for 2 seconds is within the range of 5% to 25% wherein Formula 2 is [(high-temperature MD sealing strength−ambient temperature MD sealing strength)/ambient temperature MD sealing strength]×100.
  • 10. The cell pouch film of claim 1, wherein a sum of the high-temperature sealing strength of the cell pouch film in the TD direction minus the ambient temperature sealing strength of the cell pouch film in the TD direction and the high-temperature sealing strength of the cell pouch film in the MD direction minus the ambient temperature sealing strength of the cell pouch film in the MD direction for each case of sealing at 180° C., 200° C., and 220° C. for 2 seconds is within the range of −10 to 70 N/15 mm.
  • 11. A method for preparing a cell pouch film, comprising forming a sealant layer by extruding by non-lamination extrusion on a barrier layer, wherein the sealant layer has a glass transition temperature (Tg) of −10° C. to −7° C., andwherein a crystallinity of the sealant layer, as measured by a method below, is 28% to 32%.
  • 12. A secondary battery, wherein the battery is encased with the cell pouch film of claim 1.
  • 13. The secondary battery of claim 12, wherein the secondary battery is for use in an electric vehicle or energy storage device.
  • 14. A method for manufacturing a secondary battery, comprising encasing the secondary battery with the cell pouch film of claim 1.
Priority Claims (1)
Number Date Country Kind
10-2022-0189862 Dec 2022 KR national