1]Mutual citations and related applications
[2]This application claims the benefit of priority based on dated Korea Patent Application No. 10-2018-0004212 years 01 January 2018, and all information disclosed in the literature of the Korea patent application are included as part of the specification.
[3]Art
[4]The present invention relates to the pouch film and relates to a method of manufacturing the same, and more particularly, the flexibility of the pouch, both the water resistance and the excellent property in the electrolytic solution and a method of manufacturing the pouch film.
BACKGROUND
[5]
In general, the kind of the secondary batteries include nickel-cadmium batteries, nickel hydrogen batteries, lithium ion batteries and lithium ion polymer batteries. Such secondary batteries digital camera, P-DVD, MP3P, cell phone, PDA, Portable Game Device, Power Tool and E-bike, etc. of small products, as well as development of large products and surplus that high power is required, such as electric cars or hybrid cars It is applied to the electric power storage device and the back-up power storage for storing power and renewable energy have been used.
[6]
This secondary battery according to the material of the case for accommodating the electrode assembly, it is classified as such a pouch type (Pouch Type) and the can-type (Can Type). The pouch type (Pouch Type) accommodates an electrode assembly in a pouch made of a polymer material of the soft. Then, the can-type (Can Type) accommodates an electrode assembly in a case made of a material such as metal or plastic.
[7]
Generally include the pouch, the gas barrier layer (Gas Barrier Layer), a surface protection layer (Surface Protection Layer) and sealant layer (Sealant Layer). The gas barrier layer comprises a metal intended to block the gas access, and is mainly used a thin film of aluminum (Al Foil). The surface protective layer is located on the outermost layer to be for protecting an electrode assembly from the friction and collision with the outside, and is used by a polymer such as nylon (Nylon) resin or PET having a mainly wear resistance and high heat resistance. And the sealant layer is located in the innermost layer in contact with the electrode assembly and direct, and is mainly used by a polymer such as polypropylene (PP).
[8]
In recent years, while increasing the interest in flexible (Flexible) electronic devices, research on the flexible secondary battery is also being actively conducted. However, the pouch of a conventional secondary battery, there is a problem that the lower the flexibility, you can perform a turn-bending cut or damaged. To solve this problem, a technique of forming the gas barrier layer, by depositing the metal particles has been proposed. However, since the air gap is generated between the deposition of the metal particles is decreased water resistance, there is a problem that the water and other foreign matter easily penetrate. In particular, the injected electrolyte solution therein to penetrate between the metal particles, there is a problem that the gas barrier layer is corroded and damaged.
Detailed Description of the Invention
SUMMARY
[9]
The problem to be solved by the present invention is that all of the flexibility, water resistance and resistance to liquid electrolyte of the pouch provides excellent pouch film and a process for producing the same.
[10]
An object of the present invention are not limited to the problem mentioned above, another problem that is not mentioned will be understood clearly to those skilled in the art from the following description.
Problem solving means
[11]
The method comprising the pouch film producing method according to an embodiment of the present invention for solving the above-mentioned problem is coated with an adhesive on one surface of the first polymer layer; Depositing the metal particles on said adhesive coating; By sintering by applying heat and pressure to the deposited metal particles to form a gas barrier layer; And a step of depositing a second polymer layer on the surface of the gas barrier layer.
[12]
In addition, the first polymer layer, a surface protection layer which is located on the outermost layer, wherein the second polymer layer, the sealant layer may be positioned on the innermost layer.
[13]
In addition, the first polymer layer, a sealant layer positioned at the innermost layer, the second polymer layer may be a layer surface protection which is located in the outermost layer.
[14]
In addition, the metal particles may include aluminum.
[15]
In addition, the metal particles may be less than the more than 0.01 μm 15 μm diameter.
[16]
Further, in the step of forming the gas barrier layer, the heat may be, the temperature is 50 ℃ to 200 ℃.
[17]
Further, in the step of forming the gas barrier layer, and the pressure, it may be a size of 50 MPa to 1000MPa.
[18]
Also, the pressure may be, for size 100 MPa to 500 MPa.
[19]
Pouch film according to an embodiment of the present invention for solving the aforementioned problems is the first polymer layer; An adhesive layer disposed on one surface of said first polymer layer; It is formed on the adhesive layer, a gas barrier layer comprising a sintered body of metal particles; And a second polymer layer to be laminated on one surface of the gas barrier layer.
[20]
In addition, the first polymer layer, a surface protection layer which is located on the outermost layer, wherein the second polymer layer, the sealant layer may be positioned on the innermost layer.
[21]
In addition, the first polymer layer, a sealant layer positioned at the innermost layer, the second polymer layer may be a layer surface protection which is located in the outermost layer.
[22]
In addition, the gas barrier layer may be less than a thickness of more than 0.01 μm 15 μm.
[23]
In addition, the first polymer layer or the second polymeric layer is a sealant layer which is located in the innermost layer, the adhesive strength between the sealant layer and the gas barrier layer measured after from 85 ℃ impregnated with the electrolytic solution for 24 hours from 3 to 4.5 N / 15mm can be.
[24]
In addition, the pouch film, and a water vapor transmission rate (WVTR) measured at a temperature of 38 ℃, 100% relative humidity conditions × 10 7 -3 to 10 × 9 -3 g / m 2 may be a · day.
[25]
A secondary battery according to an embodiment of the present invention for solving the above problems includes a battery case made of a pouch film.
[26]
More specific details of the invention are included in the following description and drawings.
Effects of the Invention
[27]
According to embodiments of the present invention has at least the following effects.
[28]
It can improve flexibility, water resistance and resistance to the electrolyte of the pouch.
[29]
In addition, it is possible to produce a reduced thickness of the pouch.
[30]
Effect according to the present invention is not limited by the details illustrated in the above, and is more diverse effects are included in the present specification.
Brief Description of the Drawings
[31]
1 is an assembly view of the pouch type secondary battery according to an embodiment of the present invention.
[32]
Figure 2 is a perspective view of a pouch type secondary battery of FIG manufacturing is complete.
[33]
3 is a cross-sectional view of a conventional secondary battery, a pouch film.
[34]
Figure 4 is a flow chart showing a method of manufacturing a secondary battery, a pouch film according to one embodiment of the present invention.
[35]
Figure 5 is a cross-sectional view showing a state that in order to prepare a secondary battery pouch film according to one embodiment of the present invention, depositing the metal particles on the surface protective layer.
[36]
Figure 6 is a SEM photograph showing a state after the deposition of the metal particles in FIG.
[37]
7 is a SEM photograph showing a state after sintering the metal particles.
[38]
8 is a cross-sectional view showing a state of forming the gas barrier layer by sintering the deposited the metal particles.
[39]
Figure 9 is a cross-sectional view of a secondary battery, a pouch film according to one embodiment of the present invention prepared by laminating a sealant layer to the gas barrier layer in Fig.
[40]
10 is a flow chart showing a method of manufacturing a secondary battery, a pouch film according to another embodiment of the present invention.
[41]
11 is a cross-sectional view showing a state that in order to prepare a secondary battery pouch film according to another embodiment of the present invention, the deposition of metal particles in the sealant layer.
[42]
12 is a cross-sectional view showing a state of forming the gas barrier layer by sintering the metal particles by the deposition in Fig.
[43]
13 is a cross-sectional view of the pouch film prepared by laminating a sealant layer rather than a sintering the deposited metal particles.
Mode for the Invention
[44]
Methods of accomplishing the advantages and features of the present invention and reference to the embodiments that are described later in detail in conjunction with the accompanying drawings will be apparent. However, the invention is not limited to the embodiments set forth herein may be embodied in many different forms, but the present embodiments, and the disclosure of the present invention to complete, and ordinary skill in the art is furnished the chair in order to fully convey the concept of the invention to have, the present invention will only be defined by the appended claims. Like reference numerals throughout the specification refer to like elements.
[45]
Unless otherwise defined, all terms used herein (including technical and scientific terms) could be used as a means that can be commonly understood by one of ordinary skill in the art to which this invention belongs. Another term that is defined in a general dictionary used are obviously not to be construed as ideal or excessively unless otherwise defined.
[46]
As used herein, the term is intended to illustrate the embodiments are not intended to limit the invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the text. As used herein "(comprising) comprising," "it includes (comprises)" and / or do not preclude the presence or addition of one or more other components in addition to the components mentioned.
[47]
With reference to the accompanying drawings will be described a preferred embodiment of the present invention;
[48]
1 is an assembly of the pouch type secondary battery 1 according to one embodiment of the invention, Figure 2 is a perspective view of a pouch type secondary battery 1 of Figure 1 produced is complete.
[49]
To generally prepare a lithium secondary battery (1), the first applied to a mixture of the electrode active material and a binder and a plasticizer slurry on the positive electrode collector and the negative electrode current collector to prepare a positive electrode and the negative electrode, and the amount of this separator (Separator) side by laminating the electrode to form an assembly (10). And accommodating the electrode assembly 10 into the battery case 13 and the sealing after injection of an electrolyte solution.
[50]
The electrode assembly 10 comprises an electrode tab (Electrode Tab, 11), as shown in FIG. An electrode tab 11 are respectively connected to the positive and negative electrodes of the electrode assembly 10, to protrude to the outside of the electrode assembly 10, is the path that the electron to move between the inside and the outside of the electrode assembly 10 . Electrode collector of the electrode assembly 10 is composed of a terminal portion that is not coated with the slurry section and the slurry is applied, that is plain. And the electrode tab 11 may be formed by connecting a separate conductive member formed by parts of solid foundation or a coated portion by ultrasonic welding or the like. The electrode tab 11 may be projected in the direction to each other, from one side of the electrode assembly 10, but may also be side-by-side protruding in the same direction, not limited to this, as shown in FIG.
[51]
An electrode tab 11, the electrode lead (Lead Electrode, 12) of the electrode assembly 10 is connected to the spot (Spot) welding or the like. Then, the part of the electrode lead 12 is surrounded by a surrounding insulating portion 14. Insulating portion 14 is to be limited to the sealed portion where the upper pouch 131 and a lower pouch 132 of the battery case 13, the welded location, thereby adhering the electrode lead 12 to the battery case 13. And, it prevents the electricity generated from the electrode assembly 10 flows into the battery case 13 via the electrode lead 12, and maintains sealing of the battery case 13. Thus, such insulation portion 14 is made of non-conductive with a non-conducting electricity is impervious well. Roneun generally insulating portion 14, it facilitates attachment to the electrode lead 12, and one using a lot of relatively thin insulating tape is thick, there may be isolated a electrode lead 12 is not limited to be used for various members have.
[52]
Lead electrode 12 may extend in the same direction with each other according to the positions of formation of the positive electrode tab 111 and the negative electrode tab 112 and may extend in opposite directions. A cathode lead 121 and anode lead 122 is a material that may be different from each other. That is, the positive electrode lead 121 is the same aluminum (Al) material body and the positive electrode collector, a negative electrode lead 122 may be of the same copper (Cu) material or a nickel (Ni) with the coated copper material and the negative electrode collector. And a portion of the electrode lead 12 projecting to the outside of the battery case 13 is a terminal portion and is connected to the external terminal and electrically.
[53]
The pouch type secondary battery (1) the battery case 13 in accordance with one embodiment of the present invention is a pouch made of a flexible material. Or less, the battery case 13 is described to be a pouch. And the battery case 13 is accommodated in a portion, that is, the electrode assembly 10 so that the terminal portion is exposed in the electrode lead 12 and the sealing. And such battery case 13 comprises a pouch top 131 and the pouch bottom 132, as shown in FIG. The so that the lower pouch 132 has a receiving space 133 that accommodates the electrode assembly 10 is provided, the upper pouch 131 being separated to the outside of the electrode assembly 10. The battery case 13 It covers the receiving space 133 at the top. At this time, also the accommodation space in the upper pouch 131 is formed, as shown in Figure 1, it is also possible to accommodate the electrode assembly 10 from the top. Upper pouch 131 and the pouch bottom 132 may be variously produced, such as to be produced is a separated from each other, but can be manufactured separately, are connected to each other one side is not limited to this, as shown in FIG.
[54]
When the electrode lead 12 connected to the electrode tab 11 of the electrode assembly 10 is, formed on the insulation portion 14 on a portion of the electrode lead 12, a receive provided in the lower pouch 132, space 133, the electrode assembly 10 is accommodated, the top pouch 131 that covers the receiving space 133 at the top. Then, when an electrolyte solution is injected therein and the sealing portion formed on an upper rim of the pouch 131 and the pouch bottom 132 seal, the secondary cell 1 is produced as shown in Figure 2.
[55]
3 is a cross-sectional view of a conventional secondary battery, a pouch film (20a).
[56]
In general, the electrode assembly 10, a battery case 13 for receiving, as shown in Figure 3, the first polymer layer, a gas barrier layer (Gas Barrier Layer, 21a) and a the second polymer layer are laminated in this order It is produced by stretching the film pouches (20a). And, among the first and the second polymer layer, a polymer layer disposed on the outermost layer is a polymer layer disposed on the surface protective layer (Surface Protection Layer, 22), the innermost layer is a sealant layer (Sealant Layer, 23). The "first" and "second" are merely indicate that the two building a configuration different from each other, it is not intended to secure the title.
[57]
A gas barrier layer (21a) is secured to the mechanical strength of the battery case 13, and block the entry of such secondary battery, an external gas or moisture, and prevent leakage of the electrolyte. In general, the gas barrier layer (21a) comprises a metal and has been mainly used aluminum (Al). Aluminum it is possible to ensure complementary and heat dissipation properties, such as for the electrochemical properties of the electrolyte and the weight, yet can ensure the mechanical strength over a predetermined level of light and the electrode assembly 10.
[58]
In recent years, while increasing the interest in flexible (Flexible) electronic devices, research on the flexible secondary battery is also being actively conducted. However, conventionally, a thin metal film (Metal Foil), especially aluminum (Al Foil) to produce the gas barrier layer (21a) was used as illustrated in FIG. When manufactured the gas barrier layer (21a) in such a thin aluminum film, there is a problem that there is a limit to the flexibility of the pouch, when performing several bending cut or broken. In addition, there is a current technology can not be made thinner than the thickness of the aluminum film 15 μm, to further increase the flexibility of the pouch limits.
[59]
In the present invention, the gas barrier layer 21, the metal by sintering prepared by the metal particle 210 is not a thin film was deposited on the first polymer layer, to improve the flexibility, water resistance and resistance to liquid electrolyte of the pouch It was.
[60]
Specifically, the secondary battery pouch film (20) depositing step, the metal particles 210 on the outer coating adhesive for applying an adhesive to one surface of the first polymer layer, the deposited said metal particles according to the present invention by sintering by applying heat and pressure to 210 to form a gas barrier layer (21); And it can be prepared according to the method for producing the gas-barrier pouch, including the step of depositing a second polymer layer on one surface of the layer 21 is loaded.
[61]
According to one embodiment of the invention, the first polymer layer may be a surface protective layer 22 which is located on the outermost layer, wherein the second polymer layer is a sealant layer 23 which is located in the innermost layer. And it may be, according to another embodiment of the invention, the first polymer layer and the sealant layer 23 located at the innermost layer, a surface protection layer 22 for the second polymer layer is located on the outermost layer.
[62]
Figure 4 is a flow chart showing a method of manufacturing a secondary battery, a pouch film 20 in accordance with one embodiment of the present invention.
[63]
The steps illustrated in the following, the flow chart of Figure 4 will be described with reference to Figures 5-9.
[64]
Figure 5 is a cross-sectional view showing a state that a secondary battery pouch deposition film 20 of metal particles 210, the surface protection layer 22 for the production of according to an embodiment of the present invention.
[65]
First depositing a first adhesive layer by applying an adhesive to one surface of a polymer layer (not shown) is formed, and (S401), the metal particles 210 on the coating the adhesive (S402). In accordance with one embodiment of the present invention, wherein the first polymer layer may be a surface protective layer 22 which is located on the outermost layer as shown in Fig.
[66]
The surface protective layer 22 is made of a polymer located in the outermost layer while protecting the secondary battery 1 from the collision and friction with the outside, thereby electrically insulated from the electrode assembly 10 from the outside. Wherein the outermost layer as is, the direction opposite to the direction in which the gas barrier layer, based on the 21 electrode assembly 10 is located, refers to a direction toward the outside. The surface protective layer 22 are polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polyvinyl chloride, acrylic polymer, poly-acrylonitrile, polyimide, polyamide, cellulose, aramid, nylon, polyester, para from phenylene benzo-bis-oxazole, polyarylate, Teflon, and the group consisting of glass fiber may be made of one or more materials selected. In particular, a polymer such as nylon (Nylon) resin or polyethylene terephthalate (PET) mainly has a wear resistance and high heat resistance is used. And the surface protective layer 22 is of a single layer structure made of one material, or may have a composite film structure in which two or more materials formed done in each layer.
[67]
Metal particles 210 of aluminum (Al), iron (Fe), molybdenum (Mo), stainless steel (Stainless), chromium (Cr), manganese (Mn) and nickel (Ni) formed of one or more materials selected from the group consisting of can. In particular, the aluminum can be ensured and heat dissipation properties, such as complement to the electrochemical properties of the electrolyte and the weight, yet can ensure the mechanical strength over a predetermined level of light and the electrode assembly 10 as described above. Thus, the metal particles 210 preferably comprises aluminum (Al). In addition, in order to uniformly deposit the metal particles 210, the diameter of the metal particle 210 is less than 0.01 μm 15 μm, preferably 0.01 to 10 μm. If the diameter of the metal particles 210 is larger than 15 μm, there is a problem, so large voids occurring between the particles of the metal (210). The metal particle 210 is less than 0.01 μm diameter has the problem that is difficult to manufacture the manufacturing cost rises.
[68]
When the deposition of these metal particles 210, may be deposited with a mixture of binders. Such binders include polyethylene (Polyethylene, PE), a polypropylene (Polypropylene, PP), stearic acid (Stearic Acid, SA), polyethylene glycol (Polyethylene Glycol PEG), polyacetal (Polyacetal, PA), paraffin wax (Paraffin Wax, PW from the group consisting of a) and Cavanaugh wax (Carnauba wax, CW) can be made of one or more materials selected.
[69]
A method of depositing the metal particles 210, rotating electrode method (Rotating Electrode Method), rotating disc method (Rotating Disc Method), water atom speech (Water Atomization Method), steam atom speech (Gas Atomization Method), Plasma Atomic there are a variety of methods, such as speech (Plasma Atomization method), the spark discharge method (spark Erosion). In particular, the use of 0.01 if to 10 μm, moisture atom speech (Water Atomization Method), Plasma Atomic speech (Plasma Atomization Method), the spark discharge method (Spark Erosion) the diameter of the metal particles 210 as described above desirable. However, if the present invention to deposit the metal particles 210 on the surface of the first polymer layer, it can be used a variety of deposition methods is not limited.
[70]
Further, Figure 5, is shown to directly deposited after the metal particle 210 is coated with an adhesive on one surface of the first polymer layer, that is, the surface protection layer 22 but, rather, according to an embodiment of the present invention are not limited to may be at least one after the separate layer is further laminated, and coated metallic particles 210, the adhesive on one surface of the surface protective layer 22 is deposited. Wherein a separate layer may include another polymer, synthetic rubber, or metal or the like.
[71]
Figure 6 is a SEM photograph showing a state after the deposition of metal particles 210 is illustrated in FIG.
[72]
As it is shown in FIG. 6, when the deposited metal particles 210, may be found between the deposition of the metal particles 210 hayeoteum the generation gap. Thus, if the voids between the metal particles 210, through the air gap tends to be the water or electrolyte penetration, which results can be a gas barrier layer 21 is damaged or corroded.
[73]
To solve this problem, according to one embodiment of the present invention, performs a process of further sintering (Sintering) not only to the deposition of the metal particles (210) (S403). Sintering is, when compression of the powder or particles being heated to a temperature of melting point or less, a phenomenon that the powder or particle integrity that is in close contact with each other melt. A method of sintering the metal particles 210, the normal sintering method, reaction sintering method, pressure sintering method, a constant pressure sintering method, gas pressure sintering, the deposited metal particles 210 in which the re-sintering, the impact compression sintering or the like, the present invention If you can sinter, you can use a variety of sintering methods without limitation.
[74]
The size of the column temperature and the pressure to be applied to carry out the sintering, but can vary depending on the material of the metal particles 210, the proper sintering temperature is from 50 ℃ to 200 ℃, preferably from 100 ℃ to 150 ℃. Then, the proper sintering pressure is 50 MPa to 1000 MPa, preferably 100 MPa to 500 MPa. If the temperature is not performed properly if the sintering is less than 50 ℃, if exceeding 200 ℃, it has a surface protection layer 22 may be damaged. Further, if the pressure is below 50 Mpa, does not remove the air gap between the metal particles 210, the density percentage (Fractional Density) is reduced, if the pressure is greater than 1000 Mpa, the surface protective layer 22 is damaged can.
[75]
Figure 7 is a cross-sectional view showing a state of forming the metal particles 210, and the SEM photograph is shown, even when 8 sintering the deposited metal particles 210, the gas barrier layer (21) showing a state after sintering shown It is.
[76]
As it is shown in Figure 7, when performing the sintering process, the voids between the metal particles 210 are removed, and the particles are brought into close contact with each other. Thus, a gas barrier layer 21 of the pouch film 20 in accordance with one embodiment of the present invention as shown in Figure 8 may be formed with a sintered body.
[77]
Figure 9 is a cross-sectional view of a secondary battery, a pouch film 20 in accordance with one embodiment of the present invention prepared by laminating a sealant layer 23 on the gas barrier layer 21 in FIG.
[78]
And laminating the formed one side or the second polymer layer coated with an adhesive on one surface, and the sealant layer 23 of the gas barrier layer (21) (S404). According to one embodiment of the invention, wherein the second polymer layer may be a sealant layer (23) which is located in, the innermost layer as shown in FIG. Then, the manufacture of the pouch film 20 in accordance with one embodiment of the present invention is completed.
[79]
Sealant layer 23 is made of a polymer located in the innermost layer in contact directly with the electrode assembly 10. Pouch-shaped battery case 13 has a pouch film (20a) of the multilayer structure as described above, when using a punch, such as molding drawing (Drawing), it is part of the stretching is produced, forming a receiving space of the blind (133) . Then, when such containing space 133, the electrode assembly 10 is housed inside the inject an electrolytic solution. After contacting with each other the upper pouch 131 and the pouch bottom 132, when the thermo-compression bonding to the sealing part between the sealant layer 23 by being a battery case 13 is sealed. At this time, the sealant layer 23 is so brought into contact directly with the electrode assembly 10 should have an insulation property, to have a corrosion resistance, so also in contact with the electrolyte. In addition, completely seal the inside so to block the material flow between the inside and the outside, should have a high sealability. That is, between the sealant layer 23, the adhesive sealing portion to have a high thermal bonding strength. Typically, this sealant layer 23 include polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polyvinyl chloride, acrylic polymer, poly-acrylonitrile, polyimide, polyamide, cellulose, aramid, nylon, polyester, from p-phenylene-benzo-bis-oxazole, polyarylate, Teflon, and the group consisting of glass fiber may be made of one or more materials selected. In particular, mainly used is a polyolefin-based resin such as polypropylene (PP) or polyethylene (PE). Polypropylene (PP) are excellent in chemical properties such as mechanical properties and corrosion resistance, such as tensile strength, rigidity, surface hardness, abrasion resistance, heat resistance, and to prepare the sealant layer 23 is mainly used. Furthermore, New lead-free polypropylene (Polypropylene Cated) or polypropylene-butylene-may be composed of an ethylene terpolymer. Further, the sealant layer 23, has a single layer structure made of one material, or may have a composite film structure in which two or more materials formed done in each layer.
[80]
9 is a second polymeric layer, that is, although the sealant layer 23 are shown to be directly laminated on one surface of the gas barrier layer 21, it is not limited according to the embodiment of the present invention to this, the gas barrier layer 21 or it may be a sealant layer 23 is laminated on the one side and then the at least one separate layer further laminated. That is, the surface protective layer 22 and between the gas barrier layer 21, or between the gas barrier layer 21 and the sealant layer 23, a separate layer is further included, the pouch film (20) is four It may be formed in more layers. Wherein a separate layer may include another polymer, synthetic rubber, or metal or the like.
[81]
10 is a flow chart showing a method of manufacturing a secondary battery, a pouch film 20 according to another embodiment of the present invention.
[82]
According to one embodiment of the invention, the gas barrier layer 21 was formed by sintering after the metal particles 210 deposited on one surface of the surface protective layer 22. However, the secondary battery pouch film 20 according to another embodiment of the present invention, the gas through a sintering process after depositing the metal particles 210 on one side of the surface protection layer 22, the sealant layer 23, non- the barrier layer 21 is prepared.
[83]
It will be described below with reference to Figs. 11 to 13 the steps illustrated in the flowchart of Fig.
[84]
11 is a cross-sectional view showing a state that in order to prepare a secondary battery pouch film 20 according to another embodiment of the present invention, the deposited metal particles 210 on the sealant layer (23).
[85]
To prepare the film pouch (20), the first deposited one after (S801), the metal particles 210 is coated with an adhesive on one surface of the first polymer layer (S802). In accordance with another embodiment of the present invention, wherein the first polymer layer may be a sealant layer (23) which is located in, the innermost layer as shown in FIG. When the deposition of these metal particles 210, may be deposited with a mixture of binders. Hereinafter, content and redundant information on the film pouch 20 in accordance with one embodiment of the present invention will not be described. However, this is not only intended for convenience of description is intended to limit the scope.
[86]
12 is a cross-sectional view showing a state of forming the gas barrier layer 21 by sintering metal particles 210 deposited in the above Fig.
[87]
In accordance with another embodiment of the invention, performs a process of sintering (Sintering) to the deposited metal particles (210) (S803). By this sintering the metal particles 210, the void between the metal particles 210 are removed, the particles may be brought into close contact with each other. Thereby, the gas barrier layer 21 of the pouch film 20 according to another embodiment of the present invention may be formed, including the sintered body.
[88]
So formed is coated with an adhesive on one surface of the gas barrier layer 21 or the second polymeric layer, and depositing a second polymer layer (S804). In accordance with another embodiment of the invention, wherein the second polymer layer may be a surface protective layer 22 which is located in, the outermost layer as shown in FIG. Then, the manufacture of the pouch film 20 according to another embodiment of the present invention as shown in Figure 9 is completed.
[89]
[90]
Pouch film 20 of the present invention manufactured through the above method, the first polymer layer; An adhesive layer disposed on one surface of said first polymer layer; The adhesive gas barrier layer 21 which comprises a sintered body is formed on the layer, the metal particles 210; And a second polymer layer to be laminated on one surface of the gas barrier layer (21). The first polymer layer, adhesive layer, gas barrier layer 21, and the specific specifications of the second polymer layer are the same as described above, the detailed description thereof will be omitted.
[91]
Pouch film 20 of the present invention after the deposition of metal particles (210) produced by sintering this, a gas barrier layer, so it is possible to form the thickness of the gas barrier layer thinner than the conventional film of the pouch. Specifically, in the present invention, the gas barrier layer 21 may be a thickness of less than 0.01 μm 15 μm, preferably 1 to 14 μm. And when the thickness of the gas barrier layer to satisfy the above-described range, it is possible to implement a high degree of flexibility.
[92]
In addition, the pouch film 20 according to the present invention, the gas barrier layer 21 because it contains a sintered body sintered and then depositing the metal particles 210, but a gap exists between the metal particles 210, waterproof, low permeability of the electrolyte in the electrolytic solution or water, and the castle is excellent.
[93]
Specifically, the pouch film 20 of the present invention, the adhesive strength between the sealant layer 23 and the gas barrier layer 21, measured after from 85 ℃ impregnated with the electrolytic solution for 24 hours, from 3 to 4.5 N / 15mm, preferably it may be 3.1 to 3.9 N / 15mm.
[94]
In addition, the pouch film according to the present invention, the water vapor transmission rate (WVTR) was measured at 38 ℃, 100% relative humidity conditions × 10 7 -3 to 10 × 9 -3 g / m 2 · day, preferably from 8 × 10 -3 to 10 × 8.5 -3 g / m 2 may be a · day.
[95]
[96]
Preparation Example 1
[97]
Polyethylene terephthalate (PET) coated with an adhesive on one surface of a surface protection layer made of, and the aluminum (Al) having a diameter of 0.1 to 10 μm of metal particles, deposited by plasma enhanced atomic speech (Plasma Atomization Method). By that then, while maintaining the temperature of 150 ℃ and pressure 200 MPa, using a pressure sintering method, sintering of the metal particles to form a gas barrier layer. The gas barrier layer thickness, when formed was determined to be 10 μm. And then applying an adhesive on one surface of the gas barrier layer, and laminating a sealant layer made of polypropylene (PP), to prepare a pouch film.
[98]
[99]
Comparative Production Example 1
[100]
Applying an adhesive to one surface of the surface protective layer made of a polyethylene terephthalate (PET), and depositing a thin film of aluminum (Al Foil) having a thickness of 15 μm on the adhesive of one side of the surface protection layer, and the adhesive on the thin film of aluminum It was applied by laminating a sealant layer made of polypropylene (PP), to prepare a pouch film that has the structure shown in Fig.
[101]
[102]
Comparative Production Example 2
[103]
After evaporation of metal particles to prepare a pouch film in the same manner as in Example 1, except that it did not perform the sintering process. The pouch film has a structure shown in FIG. 13 as prepared above.
[104]
[105]
Preparative Example 1 and Comparative Example was measured by the production method 1 to the to the physical properties of the pouch film made by the second measurement results are shown in Table 1 below.
[106]
[107]
How to measure physical properties
[108]
1. Flexibility (Flexibility)
[109]
Flexibility (Flexibility) was measured by performing a bending test (Bending Test), as follows: First, Preparation Example 1, Comparative Production Example 1 and Comparative then cut to Preparation Example 2 The size of each of the pouch film 15 mm × 150 mm manufactured by, and folding endurance tester (MIT folding endurance tester) both the one side of the pouch film fixed to the upper jig and, to secure the other end to the lower fixing jig (0.1mm curvature R, load 250 g of the tip). Then, the same was repeated bending of the pouch film with a speed of ± 90˚ angle, 175 cpm. After repeating this bending is irradiated with LED light to each of the pouch film and measure the bending number of times just before the occurrence of pin holes (Pinhole).
[110]
[111]
2. My Castle electrolyte
[112]
Preparation Example 1, Comparative Preparation 1 and Comparative Preparation Example 2, each cut into the same size of 25 mm × 100 mm The prepared pouch film, and 125ml day jenbyeong (Nalgene Bottle) electrolytic solution 80 ml (lithium salt in LiPF6 1 M, and ethylene carbonate (EC): ethyl methyl carbonate (EMC): the housing was prepared by dissolving at a rate of 4) and the pouch film, and sealing the opening with paraffin: dimethyl carbonate (DMC), respectively 3:03. The day jenbyeong then sealed with aluminum packaging and stored at 85 ℃ for 24 hours, taken out of the pouch film was removed after the water rinse in water completely. And it was cut by 5 mm to the width of the pouch film from the both sides to prepare a sample of a size of 15 mm × 100 mm. Then, out of the sheath to the surface protective layer of the sample is stripped to cut and hold the sample in either pulling the exposed portion of the sealant layer by repeating the bending to the gas barrier layer. The fixing a peel sealant layer to embellish the upper jig of a universal testing machine (Universal Testing Machine, UTM) and the remaining portion is then secured to the then attached to a glass slide using a double-faced tape, the lower jig. Then, the peeling rate of 50 mm / min, the grip gap (grip gap) 80 mm, test distance (test distance) there is a sealant layer and a gas barrier layer peeled 30 mm conditions and measuring the force required, the power to the adhesion strength It was evaluated.
[113]
[114]
3. The water vapor transmission rate (WVRT)
[115]
After cutting the Production Example 1, Comparative Production Example 1 and Comparative pouch films each prepared in Preparation Example 2 to a size of 108 mm × 108 mm, it was mounted on the inside of the water vapor transmission rate tester. Then, the pouch film surface, the water vapor was introduced to the other side, the dry nitrogen gas that does not contain water vapor. In this case, the two space so that the gas flowing into the both surfaces of the film pouches are mixed and the gas inlet are respectively were isolated from each other. On the other hand, the temperature throughout the experiment was 38 ℃, the humidity was set and maintained at 100% RH. And the amount of water vapor was measured at the one side a for 24 hours, introducing a dry nitrogen gas by using the humidity sensor. The amount of such water vapor divided by the area of ​​said one surface, and deriving an amount per unit area passing through the pouch film for 24 hours, water vapor, it was evaluated as WVRT.
[116]
[117]
TABLE 1
Preparation Example 1 Comparative Production Example 1 Comparative Production Example 2
Flexibility [times] 170 30 200
Adhesive strength [N / 15mm] 3.3 6.2 Not measured
WVTR[g/m2·day] 8.06 ×10-3 9.6 ×10-4 1.2 ×10-2

[118]
[119]
As shown in Table 1, Preparation 1 of the pouch film did not do damage caused by performing a bending test up to 170 times, Comparative Production Example 1 of the pouch film is 30 times, the comparison of Preparation 2 pouch film the damage did not occur up to 200 times. Thus, the embodiment of Example 1 the pouch film, compared it can be seen that the fact that the very excellent flexibility than the pouch film of Production Example 1.
[120]
In addition, the pouch film of Preparation Example 1, the adhesive strength was 3.3 N / 15 mm, compared to pouch film of Preparation Example 1 was measured, the adhesive strength to 6.2 N / 15 mm. However, comparing the measurement was not pouch film of Preparation Example 2 is a gas barrier layer corroded by the electrolyte solution. Accordingly, it can be seen that that of Preparation Example 1 the pouch film, in the electrolytic solution is significantly better than the comparative film pouch of Preparation 2.
[121]
Further, the Production Example 1 of the pouch film is water vapor transmission rate (WVTR) is 10 × 8.06 -3 g / m 2 · day were, Comparative Production Example 1 of a pouch film × 10 9.6 -4 g / m 2 · day, Comparative Preparation 2 of the pouch film is 10 × 1.2 -2 g / m 2 was determined to be · day. Accordingly, it can be seen that that of Preparation Example 1 the pouch is also very water-resistant film is superior to the pouch film of the Comparative Preparation 2. , There is simply a matter of the case where only the deposition without the sintered metal particles, compared to the voids between the metal particles of the pouch film of Preparation Example 2 caused too much to penetrate easily the electrolyte and water as described above. However, the pouch film of Production Example 1 can improve the water resistance and resistance to electrolytic solution by reducing the gap between the gas barrier layer to sinter the metal particles.
[122]
Through this, the pouch film according to one embodiment of the present invention, it is understood the fact that compared with the conventional film pouches, both excellent in flexibility, water resistance and resistance to liquid electrolyte of the pouch.
[123]
One of ordinary skill in the art will appreciate that the present invention without changing departing from the scope and spirit be embodied in other specific forms. Thus the embodiments described above are only to be understood as illustrative and non-restrictive in every respect. The scope of the invention is represented by the claims below rather than the foregoing description, it should be construed that various embodiments derived from the meaning and scope of the appended claims and their equivalents within the scope of the invention concept.

Claims

[Claim 1]Applying an adhesive to one surface of the first polymer layer; Depositing the metal particles on said adhesive coating; By sintering by applying heat and pressure to the deposited metal particles to form a gas barrier layer; And the pouch film production method comprising the step of depositing a second polymer layer on the surface of the gas barrier layer.
[Claim 2]
The method of claim 1 wherein the first polymer layer, a surface protection layer which is located on the outermost layer, wherein the second polymer layer, the sealant layer located at the innermost layer, the pouch film production method.
[Claim 3]
The method of claim 1 wherein the first polymer layer, a sealant layer positioned at the innermost layer, the second polymer layer is a surface protective layer which is located on the outermost layer of a pouch film production method.
[Claim 4]
The method of claim 1, wherein the metal particles, containing aluminum, method of producing the pouch film.
[Claim 5]
The method of claim 1, wherein the metal particles have a diameter of less than 0.01 μm 15 μm, the pouch film production method.
[Claim 6]
The method of claim 1, wherein in the step of forming the gas barrier layer, the heat, the temperature is 50 ℃ to 200 ℃, pouch film production method.
[Claim 7]
The method of claim 1, wherein in the step of forming the gas barrier layer, the pressure, the pouch film production method size is 50 MPa to 1000 MPa.
[Claim 8]
A first polymer layer; An adhesive layer disposed on one surface of said first polymer layer; It is formed on the adhesive layer, a gas barrier layer comprising a sintered body of metal particles; And the pouch film comprising a second polymer layer to be laminated on one surface of the gas barrier layer.
[Claim 9]
The method of claim 8, wherein the first polymer layer, a surface protection layer which is located on the outermost layer, wherein the second polymer layer, the sealant layer located at the innermost layer, the pouch film.
[Claim 10]
The method of claim 8, wherein the first polymer layer, a sealant layer positioned at the innermost layer, the second polymer layer is a surface protective layer positioned on the outermost layer, the film pouch.
[Claim 11]
The method of claim 8, wherein the gas barrier layer is more than 0.01 μm is less than 15 μm, the thickness of the film pouch.
[Claim 12]
The method of claim 8, wherein the first polymer layer or the second polymeric layer is a sealant layer which is located in the innermost layer, the sealant layer was measured after impregnating the electrolytic solution for 24 hours at a temperature of 85 ℃ and the gas barrier layer the adhesive strength between the 3 to 4.5 N / 15mm, the pouch film.
[Claim 13]
The method of claim 8 wherein the water vapor transmission rate (WVTR) is measured at a temperature of 7 × 10 38 ℃, 100% relative humidity conditions -3 to 10 × 9 -3 g / m 2 · day of pouch film.
[Claim 14]
Claim secondary battery comprising a battery case made of a claim 8 pouch film.