JP7066227B2 - Encapsulating film and tab leads and secondary batteries using it - Google Patents

Description

The present invention relates to a sealing film that is placed between a lead conductor connected to a positive electrode or a negative electrode and the exterior package and heat-sealed in a secondary battery covered with an exterior package. Further, the present invention relates to a tab lead using the sealing film. Further, the present invention relates to a secondary battery using the sealing film.

In recent years, the evolution of miniaturization and high functionality of mobile devices has been remarkable, and along with this, there is a strong demand for miniaturization and high capacity of batteries mounted on the devices. In the past, the shape of secondary batteries such as lithium-ion batteries was mainly tubular batteries represented by 18650 batteries, but square batteries were developed for the purpose of reducing dead space in equipment and extending the life. Was done. However, in order to further reduce the dead space and make it lighter, a pouch-type secondary battery using an exterior material in which a polyolefin film or a polyamide film and a metal foil are laminated has been developed as a new form of the secondary battery. .. Applications of this pouch-type secondary battery are being studied not only in mobile devices but also in other fields. For example, for storage batteries for electric vehicles (EVs) and energy storage systems (ESSs). It is also being put to practical use as a stationary storage battery.

In order to use such a pouch-type secondary battery safely, it is necessary to prevent the internal electrolyte from leaking when an abnormal reaction or temperature rise occurs inside the battery. Sufficient airtightness is required. In particular, the portion of the lead conductor drawn out from the electrode tends to have insufficient airtightness, and reliable sealing is required. On the other hand, if the temperature or pressure in the laminating operation is set too high for reliable sealing, the metal foil contained in the exterior material and the lead conductor may come into contact with each other to cause a short circuit. Therefore, various measures have been proposed, such as a method of sandwiching a sealing film between the exterior material and the lead conductor for heat sealing.

Patent Document 1 describes a laminated metal terminal-coated resin film for a secondary battery that covers a metal terminal connected to a positive electrode or a negative electrode of a secondary battery, wherein the resin film has a three-layer structure. When the intermediate layer of the above is used as a core layer and the other layers are used as a skin layer, the melt flow rate of at least one of the resins constituting the resin film is set to 0.1 to 2.5 g / 10 min, and the core layer and the skin are used. A resin film coated with a metal terminal for a secondary battery, in which the difference in melt flow rate from the layer is 5 to 30 g / 10 min, is described. Then, in the Example, an example in which acid-modified polypropylene having a melt flow rate of 10 to 15 g / 10 min was used for the skin layer and polypropylene having a melt flow rate of 0.7 to 1 g / 10 min was used for the core layer is described. ing. Therefore, it is said that the core layer can secure the insulating property and the skin layer can secure the wraparound property of the resin.

Patent Document 2 is a tab lead sealing material for sealing a tab lead of a laminated lithium ion secondary battery, and has a three-layer structure including a co-extruded laminated adhesive layer, an insulating layer, and a lead conductor adhesive layer. The laminated adhesive layer is made of a polypropylene resin having a melting point of 140 ° C. or lower and a load deflection temperature of 70 ° C. or higher, and the insulating layer is made of a polypropylene resin having a melting point of 145 ° C. or higher and a load deflection temperature of 100 ° C. or higher. As the lead conductor adhesive layer, a tab lead sealing material made of a polymer alloy of acid-modified polypropylene having a melting point of 140 ° C. or lower and a polypropylene-based resin is described. According to this, it is said that the difference in melting point between the insulating layer and the laminated layer can be increased to prevent the insulating layer from melting and flowing out in the heat sealing process, and as a result, the occurrence of a short circuit can be prevented. Further, it is said that by setting the deflection temperature under load of the insulating layer to 100 ° C. or higher, the amount of deformation due to pressurization during heat welding at the time of battery sealing can be reduced, and the occurrence of a short circuit can also be prevented.

In recent years, pouch-type lithium-ion secondary batteries have become larger in size for EV applications and ESS applications. In the heat sealing process of the exterior package when manufacturing such a large battery, the heat sealing process is performed with a larger amount of heat than the small battery, so that the risk of defects due to a short circuit is further increased. In addition, gas is generated inside the battery due to vaporization or decomposition of the electrolytic solution, and the internal pressure rises, which destroys the sealing film and causes a problem that the sealing property of the secondary battery cannot be maintained. Was there. The films and sealing materials described in Patent Documents 1 and 2 do not have sufficient performance to solve such a problem.

Japanese Unexamined Patent Publication No. 2014-132538 Japanese Unexamined Patent Publication No. 2014-225378

The present invention has been made to solve the above problems, and by sandwiching a sealing film between the lead conductor and the outer package and heat-sealing, the metal layer in the outer package and the lead conductor are separated from each other. To provide a secondary battery having excellent insulation and sealing properties, which can prevent a short circuit in the battery and prevent the sealed portion from being destroyed and leaking when the pressure inside the battery rises. The purpose. It is also an object of the present invention to provide a sealing film used for such a secondary battery and a tab lead using the same.

The subject is a sealing film that is placed between a lead conductor connected to a positive or negative electrode and the outer package and heat-sealed in a secondary battery covered with an outer package; the sealing film. Is a three-layer multi-layer sealing film in which a core layer and skin layers are formed on both sides thereof. The core layer has a melting point of 155 to 166 ° C. and a melt flow rate (MFR) of 0.5 to 5 g. The skin layer contains polypropylene having a melting point of 120 to 150 ° C. and a melt flow rate (MFR) of 1 to 40 g / 10 min, and the charpy strength of the core layer is 15 kJ / m. Provided is a sealing film having ² or more, the thickness of the sealing film is 30 to 300 μm, and the ratio of the thickness of the skin layer to the thickness of the core layer is 0.2 to 5. It will be solved by doing.

At this time, the core layer contains polypropylene having a melting point of 158 to 166 ° C. and a melt flow rate (MFR) of 1 to 3 g / 10 min, and the skin layer has a melting point of 128 to 150 ° C. It preferably contains polypropylene having a melt flow rate (MFR) of 1-7 g / 10 min.

At this time, it is also preferable that the polypropylene contained in at least one of the skin layers is modified with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an unsaturated epoxy compound. It is also preferable that the polypropylene contained in the core layer is a polypropylene block copolymer.

At this time, one layer of the skin layer is a metal adhesive layer that adheres to the lead conductor, the other layer is a package adhesive layer that adheres to the exterior package, and the polypropylene contained in the metal adhesive layer is: Polypropylene modified with unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or unsaturated epoxy compound, and the polypropylene contained in the package adhesive layer is unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or unsaturated epoxy. It is also preferable that it is polypropylene modified with a compound, or a polypropylene random copolymer.

It is preferable that the melting point of polypropylene contained in the package adhesive layer is higher than the melting point of polypropylene contained in the metal adhesive layer. It is also preferable that the polypropylene MFR contained in the metal adhesive layer is higher than either the polypropylene MFR contained in the core layer or the polypropylene MFR contained in the package adhesive layer.

The above problem is also solved by providing a tab lead in which both sides of a part of the lead conductor are coated with the sealing film.

Further, the above-mentioned problems include a power generation element including a positive electrode, a negative electrode, an electrolyte and a separator, an exterior package accommodating the power generation element and having a heat-sealed peripheral portion, and the exterior package connected to the positive electrode or the negative electrode. A secondary battery having a lead conductor drawn out and a sealing film disposed between the exterior package and the lead conductor and formed by heat sealing; the exterior package is at least a metal layer and a sealant resin. It is also solved by providing a secondary battery comprising a multilayer film including a layer and characterized in that the sealing film is the above-mentioned sealing film.

The sealing film of the present invention is excellent in insulating property and sealing property. Therefore, by sandwiching such a sealing film between the lead conductor of the secondary battery and the outer package and heat-sealing it, it is possible to prevent a short circuit between the metal layer and the lead conductor in the outer package. , It is possible to prevent the seal portion from being destroyed and leaking when the pressure inside the battery rises. This provides a secondary battery having excellent insulation and sealing properties, and a tab lead used in the manufacture thereof. In particular, even when the size of the secondary battery is increased, sufficient insulation and sealing properties can be exhibited.

It is sectional drawing of a multilayer film. It is a figure which showed the appearance of the secondary battery of this invention. It is sectional drawing of the heat seal part of the secondary battery of this invention. FIG. 2 is a cross-sectional view taken along the line XY in FIG. It is a figure which showed the measuring method of the spread ratio of the sealing film before and after a heat seal. It is a figure which showed the measuring method of the adhesive strength.

The present invention relates to a sealing film that is placed between a lead conductor connected to a positive electrode or a negative electrode and the exterior package and heat-sealed in a secondary battery covered with an exterior package. As shown in FIG. 1, the sealing film 20 of the present invention is a three-layered multilayer sealing film in which a core layer 21 and skin layers 22 and 23 are formed on both sides thereof.

FIG. 2 shows the appearance of the secondary battery 10 of the present invention using the sealing film 20. Further, FIG. 3 shows a cross-sectional view of a heat-sealed portion of the secondary battery 10 of the present invention. The secondary battery 10 of the present invention is connected to a power generation element including a positive electrode, a negative electrode, an electrolyte and a separator, an exterior package 40 accommodating the power generation element and having a peripheral portion heat-sealed, and the positive electrode or the negative electrode. It has a lead conductor 31 drawn out to the outside of the outer package 40, and a sealing film 20 arranged between the outer package 40 and the lead conductor 31 and heat-sealed. The exterior package 40 at this time is composed of a multilayer film including a metal layer 42 for preventing the permeation of oxygen and moisture and a sealant resin layer 41 for heat sealing, and may be sealed in a pouch shape. many. At this time, the sealing film 20 of the present invention is adopted in order to prevent a short circuit between the lead conductor 31 and the metal layer 42 in the exterior package 40 and to improve the sealing property between the lead conductor 31 and the exterior package 40. ..

As described in the background technology section, lithium-ion secondary batteries have become larger in recent years, and in that case, the heat-sealing process of the exterior package is performed with a larger amount of heat than a small battery. The risk of defects due to short circuits is even higher. Therefore, the sealing film is required to have a higher degree of insulation. As one of the measures to improve the insulation property, as described in Patent Documents 1 and 2, the sealing film has a three-layer structure of polypropylene, and the melting point of polypropylene in the core layer is higher than that in polypropylene in the skin layer. Measures to increase the melt viscosity and the deflection temperature under load have been proposed. As a result, the skin layer can be easily melted and flowed to enable thermal adhesion, while the core layer can withstand the pressure from above and below and maintain a sufficient thickness, and the insulating property is ensured.

When using a secondary battery, the pressure inside the secondary battery may rise when the temperature rises, the electrolytic solution decomposes and vaporizes, or an external force is applied. The present inventors have a problem that when the internal pressure of the secondary battery becomes extremely high, if the sealing film having a three-layer structure of polypropylene is used, the sealing film is destroyed and the electrolytic solution leaks out. I noticed that there are cases. Then, in order to clarify the cause, the cross-sectional shape of the adhesive portion of the sealing film was observed.

FIG. 4 shows a cross-sectional view taken along the line XY of FIG. 2 in the secondary battery having the configuration described in Comparative Example 1 of the present application. In FIG. 4, the left side is the heat-sealed portion and the right side is the inside of the battery. At this time, in the heat-sealed portion, the metal layer 42 in the exterior package 40 and the lead conductor 31 come close to each other, and the thickness of the sealant resin layer 41, the skin layers 22, and 23 is greatly reduced, but the core layer 21 is sufficiently thick. By keeping the above, the insulating property between the metal layer 42 and the lead conductor 31 is ensured. However, it was discovered that a partially protruding protrusion 5 was formed in the core layer 21 near the seal portion, and a notch 6 was formed beside the protrusion 5. This is because the low melting point polypropylene forming the sealant resin layer 41 and the skin layer 23 easily flows out, whereas the high melting point polypropylene forming the core layer 21 cannot easily flow and is plastically deformed. Inferred. Since it is considered that the notch 6 became a vulnerable point and the fracture proceeded, the present inventors tried using polypropylene having excellent impact resistance for the core layer 21, and found that a sealing film having excellent sealing property. It was found that 20 was obtained and the above problem was solved.

The sealing film of the present invention thus found is a three-layered multilayer sealing film in which a core layer and skin layers are formed on both sides thereof.
The core layer contains polypropylene having a melting point of 155 to 166 ° C. and a melt flow rate (MFR) of 0.5 to 5 g / 10 min.
The skin layer comprises polypropylene having a melting point of 120-150 ° C. and a melt flow rate (MFR) of 1-40 g / 10 min.
The Charpy strength of the core layer is 15 kJ / m ² or more, and the core layer has a Charpy strength of 15 kJ / m 2.
The sealing film has a thickness of 30 to 300 μm, and the ratio of the thickness of the skin layer to the thickness of the core layer is 0.2 to 5.

As described above, in the sealing film 20 of the present invention, the type of polypropylene is properly used for the core layer 21 and the skin layers 22 and 23. Polypropylene used here includes polypropylene homopolymers (H-PP), polypropylene random copolymers (R-PP) and polypropylene block copolymers (B-PP), which are commercially available from polypropylene manufacturers. Polypropylene homopolymer is obtained by polymerizing only propylene monomer, has a high melting point, and has a high elastic modulus. The polypropylene random copolymer is a random copolymerization of propylene with a small amount of other comonomer, and the comonomer is randomly incorporated into the polypropylene chain. Random copolymers have lower melting points and modulus of elasticity than homopolymers. Polypropylene block copolymers have a structure in which a chain of polypropylene homopolymers and a chain of polymers of a small amount of other comonomer are linked. Block copolymers have improved impact resistance while exhibiting melting points and elastic moduli close to homopolymers. Polypropylene homopolymers, polypropylene random copolymers and polypropylene block copolymers are commercially available, and although their chemical compositions are not specified, their melting points, melt flow rates, elastic moduli, charpy strength, etc. are shown in the catalog. It can be appropriately selected and used.

The greatest feature of the sealing film 20 of the present invention is that the core layer 21 contains polypropylene having a melting point of 155 to 166 ° C. and a melt flow rate (MFR) of 0.5 to 5 g / 10 min, and the core layer 21. Charpy strength is 15 kJ / m ² or more.

The melting point of polypropylene contained in the core layer 21 is 155 to 166 ° C. If the melting point is less than 155 ° C., the difference in melting point from polypropylene contained in the skin layers 22 and 23 becomes small, which is not preferable. Here, in the heat sealing step, the skin layers 22 and 23 are melted, and the skin layers 22 and 23 are heat-sealed with the lead conductor 31 and the exterior package 40. At this time, by setting the melting point of polypropylene contained in the core layer 21 to 155 ° C. or higher, the core layer 21 is less likely to flow than the skin layers 22 and 23 even when heated and pressurized in the heat sealing step. Therefore, a certain thickness can be secured as the core layer 21, and excellent insulating properties can be obtained. The melting point is preferably 158 ° C. or higher, more preferably 161 ° C. or higher, and even more preferably 163 ° C. or higher. On the other hand, the melting point is preferably 165 ° C. or lower. The melting point in the present specification means a melting peak temperature (° C.) measured at a heating rate of 10 ° C./min at the time of measuring 2nd Run using a differential scanning calorimeter (DSC). Here, when two or more melting peaks are observed, the temperature of the peak having the highest peak height with respect to the baseline is defined as the melting peak temperature (° C.) of polypropylene contained in the core layer 21. The same applies to the skin layers 22 and 23.

The MFR of polypropylene contained in the core layer 21 is 0.5 to 5 g / 10 min. If the MFR is less than 0.5 g / 10 min, the viscosity becomes too high and the sealing film 20 cannot be stably formed. The MFR is preferably 1 g / 10 min or more, more preferably 1.2 g / 10 min or more, and even more preferably 1.5 g / 10 min or more. On the other hand, when the MFR exceeds 5 g / 10 min, the fluidity of polypropylene becomes too high in the heat sealing step, the thickness of the core layer 21 in the sealed portion becomes thin, and excellent insulating properties cannot be obtained. The MFR is preferably 3 g / 10 min or less, more preferably 2.8 g / 10 min or less, further preferably 2.5 g / 10 min or less, and particularly preferably 2.0 g / 10 min or less. preferable. The MFR in the present specification is a value measured under a load of 230 ° C. and 2.16 kg according to JIS K 7210.

It is important that the Charpy strength of the core layer 21 is 15 kJ / m ² or more. By setting the Charpy strength of the core layer 21 to 15 kJ / m ² or more, it is possible to prevent the sealing film 20 from being destroyed starting from the vulnerabilities formed in the core layer 21. The Charpy intensity is preferably 20 kJ / m ² or more, more preferably 40 kJ / m ² or more, and even more preferably 60 kJ / m ² or more. On the other hand, the Charpy strength is usually 200 kJ / m ² or less.

The polypropylene contained in the core layer 21 is preferably a polypropylene block copolymer. Since the polypropylene contained in the core layer 21 is a polypropylene block copolymer, it is possible to effectively prevent the sealing film 20 from being destroyed starting from the weak point of the core layer 21. Here, polypropylene block copolymers are known to have a relatively high melting point and elastic modulus and high Charpy strength, and are often used for injection-molded products that require impact resistance. On the other hand, it is rarely used for flexible films because the extrudability is not always good. Moreover, only some of the grades have a Charpy strength of 15 kJ / m ² or more. Therefore, it is usual to select a polypropylene block copolymer that is rarely used for film molding, select a polypropylene block copolymer having a certain or higher Charpy strength, and use it for the core layer 21 of the sealing film 20 of the present invention. It goes beyond the design choices of.

In the sealing film 20 of the present invention, the skin layers 22 and 23 contain polypropylene having a melting point of 120 to 150 ° C. and a melt flow rate (MFR) of 1 to 40 g / 10 min.

The melting points of polypropylene contained in the skin layers 22 and 23 are 120 to 150 ° C. When the melting point is less than 120 ° C., the heat resistance to heat generation and external heat during use of the secondary battery 10 is lowered. The melting point is preferably 128 ° C. or higher, more preferably 130 ° C. or higher, and even more preferably 135 ° C. or higher. On the other hand, when the melting point exceeds 150 ° C., the difference in melting point from polypropylene contained in the core layer 21 becomes small, so that the core layer 21 also tends to melt in the heat sealing step, and excellent insulating properties cannot be obtained. The melting point is preferably 148 ° C. or lower, more preferably 146 ° C. or lower.

The MFR of polypropylene contained in the skin layers 22 and 23 is 1 to 40 g / 10 min. If the MFR is less than 1 g / 10 min, the viscosity becomes too high and the sealing film 20 cannot be stably formed. The MFR is preferably 1.5 g / 10 min or more, and more preferably 2 g / 10 min or more. On the other hand, when the MFR exceeds 40 g / 10 min, the difference from the polypropylene MFR contained in the core layer 21 becomes large, and in this case as well, the sealing film 20 cannot be stably formed, and the skin layer 22 and the skin layer 22 The mechanical strength of 23 is also reduced. The MFR is preferably 7 g / 10 min or less, more preferably 6.5 g / 10 min or less, and even more preferably 6 g / 10 min or less.

In the sealing film 20 of the present invention, the ratio of the polypropylene MFR _s contained in the skin layers 22 and 23 (MFR _s / MFR _c ) to the polypropylene MFR _c contained in the core layer 21 is 0.8 to 7. Is preferable. When the ratio (MFR _s / MFR _c ) is less than 0.8, the fluidity of polypropylene in the core layer 21 becomes too high in the heat sealing step, the thickness of the obtained core layer 21 becomes thin, and the insulating property deteriorates. There is a risk. The ratio (MFR _s / MFR _c ) is more preferably 1 or more, and even more preferably 1.5 or more. On the other hand, when the ratio (MFR _s / MFR _c ) exceeds 7, the viscosities of the skin layers 22 and 23 become too low, and the sealing film 20 may not be stably formed. The ratio (MFR _s / MFR _c ) is more preferably 6 or less, and even more preferably 4 or less.

It is preferable that the polypropylene contained in at least one of the skin layers 22 and 23 is modified with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an unsaturated epoxy compound. These modifications may be due to random copolymerization or block copolymerization, or may be graft modification.

In the present invention, it is preferable that one of the skin layers 22 and 23 is the metal adhesive layer 22 that adheres to the lead conductor 31, and the other layer is the package adhesive layer 23 that adheres to the exterior package 40. At this time, the polypropylene contained in the metal adhesive layer 22 is preferably polypropylene modified with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an unsaturated epoxy compound. By doing so, the adhesion with the lead conductor 31 can be improved. Above all, polypropylene is more preferably polypropylene modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.

The polypropylene contained in the metal adhesive layer 22 and the polypropylene contained in the package adhesive layer 23 may be the same type of polypropylene or different types of polypropylene. By using the same type of polypropylene, the metal adhesive layer 22 and the package adhesive layer 23 are no longer distinguished in the sealing film 20, so that it is not necessary to identify the front and back surfaces when performing the sealing work, and workability is improved. It is also possible to prevent the occurrence of defective products due to incorrect front and back surfaces.

On the other hand, when different types of polypropylene are used for the metal adhesive layer 22 and the package adhesive layer 23, the polypropylene contained in the metal adhesive layer 22 is modified with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an unsaturated epoxy compound. It is preferable that the polypropylene is polypropylene and the polypropylene contained in the package adhesive layer 23 is a polypropylene random copolymer which is not so modified. By doing so, it is possible to secure the adhesion with the lead conductor 21 while suppressing the manufacturing cost of the sealing film 20.

It is preferable that the melting point of polypropylene contained in the package adhesive layer 23 is higher than the melting point of polypropylene contained in the metal adhesive layer 22. In the heat sealing step, heat is applied from the outer package 40 side, but by making the melting point of polypropylene contained in the package adhesive layer 23 higher than the melting point of polypropylene contained in the metal adhesive layer 22, the heat is first generated. It is possible to prevent the polypropylene contained in the added package adhesive layer 23 from excessively flowing and spreading. In this case, the difference between the melting point of polypropylene contained in the package adhesive layer 23 and the melting point of polypropylene contained in the metal adhesive layer 22 is preferably 2 ° C. or higher.

Further, it is preferable that the polypropylene MFR contained in the metal adhesive layer 22 is higher than either the polypropylene MFR contained in the core layer 21 or the polypropylene MFR contained in the package adhesive layer 23. By doing so, the polypropylene contained in the metal adhesive layer 22 can be wrapped around the lead conductor 31 without a gap. The difference between the polypropylene MFR contained in the metal adhesive layer 22 and the polypropylene MFR contained in the core layer 21 and the polypropylene MFR contained in the package adhesive layer 23 is preferably 1 or more.

The core layer 21 or the skin layers 22 and 23 of the sealing film 20 of the present invention both contain polypropylene. The polypropylene content of each layer is usually 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. In addition to polypropylene, various additives that can be normally used, such as fillers and colorants, may be contained. Further, a resin other than polypropylene may be contained, but in that case, the content of the other resin is usually 20% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass. % Or less, preferably not substantially contained.

The thickness of the sealing film 20 is 30 to 300 μm. If the thickness of the sealing film 20 is less than 30 μm, it is not possible to sufficiently prevent a short circuit between the lead conductor 31 and the metal layer 42 in the exterior package 40. The thickness of the sealing film 20 is preferably 50 μm or more, more preferably 70 μm or more. On the other hand, if the thickness of the sealing film 20 exceeds 300 μm, the weight increases and the cost also increases. The thickness of the sealing film 20 is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less.

The ratio of the thicknesses of the skin layers 22 and 23 to the thickness of the core layer 21 is 0.2 to 5. When the ratio is less than 0.2, the adhesion of the sealing film 20 to the lead conductor 31 and the outer package 40 is lowered. The ratio is preferably 0.3 or more, and more preferably 0.5 or more. On the other hand, when the ratio exceeds 5, excellent insulating properties cannot be obtained. The ratio is preferably 4 or less, more preferably 3 or less. The thicknesses of the skin layers 22 and 23 referred to here are the thicknesses of the metal adhesive layer 22 and the package adhesive layer 23, respectively.

The lead conductor 31 used in the secondary battery of the present invention is a metal tape-shaped member connected to a positive electrode or a negative electrode, and can be charged and discharged through the lead conductor 31. Aluminum is mainly used as the lead conductor 31 connected to the positive electrode. Further, as the lead conductor 31 connected to the negative electrode, nickel or copper plated with nickel, or a clad material of copper and nickel is mainly used. In order to improve the corrosion resistance of these metal materials or to improve the adhesiveness with the sealing film 20, hexavalent chromate, trivalent chromate, zirconium-based or manganese-based surface treatment agent, or polyvinyl. It may be treated with an organic surface treatment agent containing alcohol or polyacrylic acid as a main component. The thickness of the lead conductor 31 is usually 0.05 to 1 mm, and the width is 2 to 100 mm.

The tab lead 30 used in the secondary battery 10 of the present invention is formed by covering both sides of a part of the lead conductor 31 with a sealing film 20. Since the sealing film 20 is heat-sealed to the lead conductor 31 in advance, the space between the lead conductor 31 and the sealing film 20 can be reliably sealed, and the positioning when the outer package 40 is heat-sealed can be determined. It will be easier. Since one end of the lead conductor 31 is connected to the positive electrode or the negative electrode and the other end is connected to the charging / discharging device, the intermediate portion thereof is covered with the sealing film 20. Then, the outer package 40 is heat-sealed at a position where it overlaps with the sealing film 20.

The exterior package 40 used in the secondary battery 10 of the present invention is made of a multilayer film including at least a metal layer 42 and a sealant resin layer 41. Preferably, it is preferable to further have the surface resin layer 43 on the outside of the metal layer 42. The surface resin layer 43 may be appropriately printed or the like, or the surface resin layer 43 may be composed of a plurality of resin layers. The total thickness of the outer package 40 is usually 50 to 500 μm.

The resin constituting the sealant resin layer 41 may be any resin that can be heat-sealed, and a thermoplastic resin is usually used. Preferably, polyolefin, especially polypropylene, is preferably used. The thickness of the sealant resin layer 41 is usually 30 to 200 μm. The resin constituting the surface resin layer 43 is not particularly limited, and a polyamide resin, a polyester resin, a polyolefin resin, a polystyrene resin, a thermoplastic polyimide resin, a phenoxy resin, an epoxy resin, an acetal resin, a fluororesin, or the like can be used depending on the application. Can be used. The thickness of the surface resin layer 43 is usually 30 to 400 μm. The metal constituting the metal layer 42 is not particularly limited, but aluminum is preferable in consideration of workability, flexibility, cost and the like. A metal foil having a thickness of 5 to 100 μm may be used, or a thin-film film having a thickness of 0.1 to 2 μm may be used.

In the secondary battery 10 of the present invention, the power generation element including the positive electrode, the negative electrode, the electrolyte and the separator is accommodated and sealed by heat-sealing the peripheral portion of the outer package. The type of the secondary battery 10 is not limited, but a lithium ion battery is suitable. A so-called pouch-shaped package in which two exterior packages 40 face each other to accommodate a power generation element is preferable.

As a method for manufacturing the tab lead 30, a method is adopted in which the sealing film 20 is arranged vertically at a predetermined position of the lead conductor 31 and the fused portion is heated and pressed from above and below. At this time, by not only heating from above and below but also heating the lead conductor 31 at the same time, excessive flow of the sealing film 20 can be suppressed, and fusion can be easily performed with a width substantially the same as the width of the sealing film 20. Become. Further, by arranging a cushioning material such as silicone rubber or a Teflon sheet between the press head and the lead conductor 31 at the time of pressurization, it is possible to improve the wraparound of the resin to the end of the lead conductor 31.

The exterior package 40 containing the power generation element is superposed on the portion of the tab lead 30 thus obtained covered with the sealing film 20, and the peripheral edge of the exterior package 40 is heated and pressed from both sides to heat and pressurize the secondary battery 10. To manufacture. When sealing the outer package 40 without manufacturing the tab lead 30 in advance, the lead conductor 31 and the sealing film 20 can be overlapped and heat-sealed at the same time.

The secondary battery 10 of the present invention thus obtained is a secondary battery 10 which can prevent a short circuit between the metal layer 42 and the lead conductor 31 in the outer package 40 and is excellent in sealing property and insulating property. It can be used particularly usefully in a large secondary battery or the like, which requires a high degree of reliability as the heat sealing conditions of the outer package 40 become strict.

Example 1
[Preparation of sealing film]
A three-layer coextruded film manufacturing apparatus equipped with three extruders was used to manufacture the sealing film 20. Polypropylene random copolymer pellets (R-PP) were put into one extruder for the outer layer (for the package adhesive layer 23), and acid-modified propylene random copolymer pellets (R-PP) were put into the other extruder for the outer layer (metal adhesive layer 22). A-PP) was added. Further, polypropylene block copolymer pellets (B-PP) were put into the extruder for the core layer 21. Coextrusion molding was performed by setting the extrusion temperature of the three extruders to 200 ° C. and the temperature of the multi-manifold type T-die to 220 ° C. In this way, a multi-layer film having a total thickness of 100 μm, in which the thickness of the package adhesive layer 23 is 20 μm, the thickness of the core layer 21 is 30 μm, and the thickness of the metal adhesive layer 22 is 50 μm, is obtained. It was cut to obtain a sealing film 20 having a size of 4 mm × 8 mm.

[Making tab leads]
An aluminum plate (A1050) having a thickness of 0.1 mm was slitted to prepare a lead conductor 31 having a length of 13 mm and a width of 4 mm. As shown in FIG. 5A, the lead conductor 31 was sandwiched between two sealing films 20, and the upper and lower portions thereof were sandwiched between 0.2 mm-thick silicone rubber sheets. At this time, the length A of the sealing film 20 was measured.

Then, it was heated and pressed at 170 ° C. for 5 seconds with a hot press to obtain a tab lead 30 whose both sides were covered with the sealing film 20. The obtained tab lead 30 is shown in FIG. 5 (b). The sealing films 20 were adhered to each other with a width of 4.1 mm on the outside of the lead conductor 31 having a width of 4 mm. Here, the length B was measured, and the spread ratio of the sealing film 20 was measured using the following formula. It can be said that the smaller this value is, the more excellent the insulating property of the secondary battery 10 can be obtained.
Spread rate (%): [((length B)-(length A)) / (length A)] × 100

[Measurement of adhesive strength]
As the exterior packaging material, a multilayer film laminated in the order of the polyamide layer 25 μm / aluminum foil 50 μm / polypropylene layer 25 μm from the outermost layer was used. This was cut into strips having a length of 100 mm and a width of 20 mm, and brought into contact with both sides of the sealing film 20 portion of the produced tab lead 30 (contact area: 3 mm × 8 mm). At this time, the two exterior package materials were arranged so that the polypropylene layer of the exterior package material was in contact with the sealing film 20. Subsequently, a sample was obtained by heating and pressurizing at a temperature of 180 ° C. and a pressure of 0.3 MPa for 5 seconds using a hot press having a width of 2 mm. Then, using the obtained sample, as shown in FIG. 6, the outer packaging material of the portion not fused with the sealing film 20 is sandwiched between chucks and pulled at a speed of 50 mm / min using a tensile tester. rice field. As a result, the force required for destruction was 2.7 kgf / 4 mm. It can be said that the greater the force required for this destruction, the more the secondary battery 10 having excellent sealing properties can be obtained. Moreover, when the fractured portion was observed with an optical microscope, the fracture was a cohesive fracture of the exterior package material (evaluation result A in Table 1). The results are summarized in Table 1.

Examples 2 to 6, Comparative Examples 1 to 4
As shown in Tables 1 and 2, a sealing film 20 was prepared and evaluated in the same manner as in Example 1 except that the types of polypropylene forming the package adhesive layer 23, the core layer 21 and the metal adhesive layer 22 were changed. .. Here, as shown in Table 1, two melting peaks (134 ° C and 104 ° C) of polypropylene contained in the package adhesive layer 23 of Example 5 were observed. Since the peak height at 134 ° C. was higher than the peak height at 104 ° C., 134 ° C. was set as the melting point of polypropylene contained in the package adhesive layer 23. The results are summarized in Tables 1 and 2. Here, when the fractured portion in the tensile test was the cohesive fracture of the sealing film 20, the evaluation result was B.

10 Rechargeable battery 20 Encapsulating film 21 Core layer 22 Skin layer (metal adhesive layer)
23 Skin layer (package adhesive layer)
30 Tab lead 31 Lead conductor 40 Exterior package 41 Sealant resin layer 42 Metal layer 43 Surface resin layer 5 Protrusion 6 Notch

Claims (9)

A sealing film that is placed between a lead conductor connected to a positive electrode or a negative electrode and the exterior package and heat-sealed in a secondary battery covered with an exterior package;
The sealing film is a three-layered multilayer sealing film in which a core layer and skin layers are formed on both sides thereof.
The core layer contains polypropylene having a melting point of 155 to 166 ° C. and a melt flow rate (MFR) of 0.5 to 5 g / 10 min.
The skin layer contains polypropylene having a melting point of 120-150 ° C. and a melt flow rate (MFR) of 1-7 g / 10 min.
The Charpy strength of the core layer is 15 kJ / m ² or more, and the core layer has a Charpy strength of 15 kJ / m 2.
A sealing film having a thickness of the sealing film of 30 to 300 μm and a ratio of the thickness of the skin layer to the thickness of the core layer of 0.2 to 5. The core layer contains polypropylene having a melting point of 158 to 166 ° C. and a melt flow rate (MFR) of 1 to 3 g / 10 min, and the skin layer has a melting point of 128 to 150 ° C. and a melt flow rate. The sealing film according to claim 1, which comprises polypropylene having an (MFR) of 1 to 7 g / 10 min. The sealing film according to claim 1 or 2, wherein the polypropylene contained in at least one of the skin layers is modified with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an unsaturated epoxy compound. The sealing film according to any one of claims 1 to 3, wherein the polypropylene contained in the core layer is a polypropylene block copolymer. One layer of the skin layer is a metal adhesive layer that adheres to the lead conductor, and the other layer is a package adhesive layer that adheres to the exterior package.
The polypropylene contained in the metal adhesive layer is polypropylene modified with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an unsaturated epoxy compound, and the polypropylene contained in the package adhesive layer is an unsaturated carboxylic acid. The sealing film according to claim 3 or 4, which is polypropylene modified with an unsaturated carboxylic acid anhydride or an unsaturated epoxy compound, or a polypropylene random copolymer. The sealing film according to claim 5, wherein the melting point of polypropylene contained in the package adhesive layer is higher than the melting point of polypropylene contained in the metal adhesive layer. The sealing film according to claim 5 or 6, wherein the polypropylene MFR contained in the metal adhesive layer is higher than any of the polypropylene MFR contained in the core layer and the polypropylene MFR contained in the package adhesive layer. A tab lead having both sides of a part of a lead conductor coated with the sealing film according to any one of claims 1 to 7. A power generation element including a positive electrode, a negative electrode, an electrolyte and a separator, an exterior package accommodating the power generation element and having a heat-sealed peripheral portion, and a lead conductor connected to the positive electrode or the negative electrode and pulled out to the outside of the exterior package. And a secondary battery having a sealing film disposed between the exterior package and the lead conductor and heat-sealed;
A secondary battery, wherein the exterior package is made of a multilayer film including at least a metal layer and a sealant resin layer, and the sealing film is the sealing film according to any one of claims 1 to 7.

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