TWI777870B - Tabs and Nonaqueous Electrolyte Devices - Google Patents

Abstract

An object of the present invention is to secure high adhesion between the lead terminal and the film portion. The tab of the present invention is used in a laminated non-aqueous electrolyte device in which at least an electrolytic solution or a solid electrolyte is enclosed in a laminated material, and includes a lead terminal having a terminal main body formed of a metal material and a surface covering the terminal main body a film; and a pair of film parts, which are in close contact with the lead terminals and the laminate material from both sides to seal the laminate material, and an adhesive layer using acid-modified polyolefin as a base resin is provided on the lead terminal side of the film part , the film contains the same components as the base resin of the adhesive layer, and the film is a surface-treated film containing water-soluble zirconium salt and water-soluble or water-dispersible acrylic resin. One square meter is set from 0.8 to 300 mg, the acid value of the solid content in the water-soluble or water-dispersible acrylic resin is set from 150 to 740 mgKOH/g, and the hydroxyl value of the solid content is set from 24 to 240, and the solid content is based on mass Each square meter becomes from 1.0 to 600 mg.

Description

Tabs and Nonaqueous Electrolyte Devices

The present invention relates to the technical field of a tab with a film portion in close contact with a lead terminal and a non-aqueous electrolyte device provided with the tab.

In the non-aqueous electrolyte device, for example, there are lithium ion batteries, lithium ion capacitors, and the like. Lithium ion batteries have the function of charging or discharging by moving lithium ions between the positive electrode and the negative electrode. The lithium ion capacitor has a positive electrode provided with an electric double layer and a negative electrode using a carbon-based material that can absorb lithium ions. The function of charging or discharging.

Such non-aqueous electrolyte devices include, for example, a laminate type in which an electrode and an electrolytic solution or a solid electrolyte are enclosed in a pouch-shaped laminate which is used as a vehicle-mounted battery, a storage battery, or the like. In the laminated non-aqueous electrolyte device, power output is performed by tabs, one end of the tab is connected to an electrode disposed inside the laminate, and the other end is exposed to the outside of the laminate and is connected to an external device. Connect the busbars of the terminals, etc.

The tab has a lead terminal and a film portion, the lead terminal is used for outputting electric power, the film portion is in close contact with the lead terminal and the laminated material to seal the laminated material, and is used for insulating the lead terminal and the laminated material. A terminal formed by covering the surface of a terminal main body formed of a metal material with a film. In the non-aqueous electrolyte device, the laminate is sealed by thermocompression bonding of the membrane portions of the tabs.

In order to ensure good performance of the non-aqueous electrolyte device, such tabs are required to have high sealing properties of the laminate, high insulation between the lead terminals and the laminate, long-term resistance to electrolytic solutions, etc., and the lead terminals and the membrane portion good adhesion, good solderability to electrodes of lead terminals, etc. In addition, in the lead terminal of the tab, since the rust resistance of the terminal body needs to be ensured by the coating, the coating needs to have high corrosion resistance.

Therefore, in the conventional non-aqueous electrolyte device, various proposals have been made in order to satisfy the requirements for the lead terminals as described above (for example, refer to Patent Document 1 and Patent Document 2).

In the tab described in Patent Document 1, the coating of the lead terminal is formed into a composite coating layer by coating a treatment liquid containing a resin component containing polyacrylic acid and a metal salt, whereby in consideration of environmental pollution, a chromium-free coating is used. The alloy is surface-treated to form a coating with excellent resistance to hydrogen fluoride acid to improve corrosion resistance.

In the tab described in Patent Document 2, the coating of the lead terminal is formed into a composite coating layer by spraying a treatment liquid containing a resin component containing polyacrylic acid and polyacrylamide and a metal salt. Considering the problem of environmental pollution, the use of The chromium-free alloy is surface-treated to form a coating with excellent resistance to hydrogen fluoride acid to improve corrosion resistance.

[Patent Document 1] Japanese Patent Laid-Open No. 2006-128096 [Patent Document 2] Japanese Patent Laid-Open No. 2011-81992

In the lead terminal of the tab, in addition to ensuring high corrosion resistance in the film as described above, it is also necessary to ensure high adhesion between the lead terminal and the film portion.

By ensuring high adhesion between the lead terminal and the film portion, there is no gap between the lead terminal and the film portion to prevent leakage of liquids such as electrolytes enclosed in the laminate material, so that the sealing property can be ensured, and the Ensure good performance of non-aqueous electrolyte devices.

Therefore, an object of the present invention is to have high adhesion between the lead terminal and the film portion, and to ensure long-term resistance to an electrolytic solution or the like.

First, the tab of the present invention is used in a laminate-type non-aqueous electrolyte device in which at least an electrolytic solution or a solid electrolyte is enclosed in a laminate material, and the tab includes a lead terminal having a terminal main body formed of a metal material and a a film covering the surface of the terminal main body; and a pair of film portions, which are in close contact with the lead terminals from both sides and the laminate material to seal the laminate material, and a pair of film portions are provided on the lead terminal side of the film portion. The modified polyolefin is used as the adhesive layer of the base resin. The above-mentioned film contains the same components as the base resin of the above-mentioned adhesive layer. The above-mentioned film is a surface-treated film containing a water-soluble zirconium salt and a water-soluble or water-dispersible acrylic resin. Prepared as follows: the zirconium in the aforementioned water-soluble zirconium salt is set from 0.8 to 300 mg per square meter on a mass basis, the acid value of the solid content in the aforementioned water-soluble or water-dispersible acrylic resin is set from 150 to 740 mgKOH/g, and the solid The component hydroxyl value is set to be from 24 to 240, and the solid content is set to be from 1.0 to 600 mg per square meter on a mass basis.

Thereby, the acid-modified adhesive layer of the polyolefin which is the base resin is in close contact with the coating film of the lead terminal containing the same components as the acid-modified portion of the base resin of the adhesive layer from both sides. In addition, the corrosion resistance of the film is improved, and the affinity of the film to the adhesive layer is improved.

Second, in the above-mentioned tab of the present invention, it is preferable that the aforementioned adhesive layer uses acrylic-modified polypropylene or polyethylene as the base resin.

Thereby, the adhesive layer has the same acrylic component as the film.

Thirdly, in the above-mentioned tab of the present invention, it is preferable to provide a second adhesive layer on the laminate material side of the film portion, and the second adhesive layer is formed with a base resin of the same material as the laminate material.

Thereby, the affinity of the 2nd adhesive layer and a laminated material improves.

Fourth, in the above-mentioned tab of the present invention, it is preferable that the second adhesive layer is made of polypropylene or polyethylene as the base resin.

Thereby, it is formed of a material having high affinity with the laminate material. In addition, in the case of polypropylene, the second adhesive layer is formed of a material that does not easily permeate water.

Fifth, the non-aqueous electrolyte device of the present invention is a laminate-type non-aqueous electrolyte device in which at least an electrolytic solution or a solid electrolyte is sealed inside a laminate material and tabs are provided, wherein the tabs are provided with lead terminals, which are made of metal. A terminal main body formed of material and a film covering the surface of the terminal main body; and a pair of film portions that are in close contact with the lead terminals from both sides and the laminate material to seal the laminate material, and the lead in the film portion The terminal side is provided with an adhesive layer with acid-modified polyolefin as the base resin, the film contains the same components as the base resin of the adhesive layer, and the film contains a water-soluble zirconium salt and a water-soluble or water-dispersible acrylic resin. Surface treatment film, the film is prepared such that zirconium in the water-soluble zirconium salt is set from 0.8 to 300 mg per square meter on a mass basis, and the acid value of the solid content in the water-soluble or water-dispersible acrylic resin is set from 150 to 740 mgKOH/g and the hydroxyl value of solid content are set from 24 to 240, and solid content is set to be from 1.0 to 600 mg per square meter on a mass basis.

Thereby, in the tab, the acid-modified adhesive layer of the polyolefin as the base resin is in close contact with the coating film of the lead terminal including the same component as the acid-modified portion of the base resin of the adhesive layer from both sides. In addition, the corrosion resistance of the film is improved, and the affinity of the film to the adhesive layer is improved. [Inventive effect]

According to the present invention, since the acid-modified adhesive layer of the polyolefin serving as the base resin is adhered from both sides to the film of the lead terminal containing the same components as the acid-modified portion of the base resin of the adhesive layer, the adhesive layer of the film portion and the The affinity of the coating film of the lead terminal is improved, the lead terminal and the film have high adhesion, and long-term resistance to an electrolytic solution and the like can be ensured.

Hereinafter, the form of the tab and the non-aqueous electrolyte device for carrying out the present invention will be described with reference to the drawings.

<Schematic structure of non-aqueous electrolyte device> First, as an example of a laminated non-aqueous electrolyte device using tabs, a schematic configuration of a lithium ion battery will be described (see FIGS. 1 and 2 ).

In addition, the scope of application of the non-aqueous electrolyte device of the present invention is not limited to lithium ion batteries, and the present invention can also be applied to other non-aqueous electrolyte devices such as laminated lithium ion capacitors.

The non-aqueous electrolyte device has a laminate in which an electrolyte solution and the like are sealed, and tabs partially protruding from the laminate. left and right directions.

However, the directions of front, back, up, down, left, and right shown below are for convenience of description, and the implementation of the present invention is not limited to these directions.

The non-aqueous electrolyte device 100 includes a pouch-shaped laminate 101 , each part enclosed in the laminate 101 , and tabs 1 and 1 partially protruding from the laminate 101 (see FIG. 1 ).

The laminated material 101 has a cylindrical shape in which the upper end portion is formed as the sealing portion 102 . The laminated material 101 has, for example, a three-layer structure, and an outer surface layer 101a and an inner surface layer 101b formed of a resin material are laminated on both sides of the metal layer 101c (see FIG. 2 ). As the outer surface layer 101a, for example, polyethylene terephthalate is used, as the inner surface layer 101b, for example, polypropylene or polyethylene, and as the metal layer 101c, for example, aluminum is used.

The electrolyte solution 103 is enclosed in the laminated material 101, and the positive electrode 104, the negative electrode 105, and the separator 106 are arrange|positioned. The positive electrode 104 and the negative electrode 105 are immersed in the electrolyte 103 , and the space where the positive electrode 104 is arranged and the space where the negative electrode 105 is arranged are separated by a separator 106 . As the positive electrode 104, for example, aluminum is used, and as the negative electrode 105, for example, nickel, copper, or an alloy thereof is used. In addition, a solid electrolyte may be used instead of the electrolytic solution 103 .

＜Structure of the polar ear＞ Next, the structure of the tab 1 will be described (see FIGS. 2 and 3 ). In addition, a pair of tabs 1 is provided, one tab 1 connected to the positive electrode 104 functions as a positive electrode in the non-aqueous electrolyte device 100 , and the other tab 1 connected to the negative electrode 105 functions as a negative electrode in the non-aqueous electrolyte device 100 . effect.

The tab 1 is composed of a thin plate-shaped lead terminal 2 and a pair of film portions 3 and 3 which are closely attached to the lead terminal 2 from both sides. The tab 1 is in a state in which a part of the outer peripheral surface is in close contact with the sealing part 102 , and the upper end side part protrudes upward from the laminate 101 .

The lead terminal 2 is formed in a thin plate shape whose thickness is, for example, from 50 μm to 1000 μm. The lower end portion of the lead terminal 2 serves as the electrode connection portion 2a, and is connected to the positive electrode 104 or the negative electrode 105 by, for example, welding or the like. The upper end portion of the lead terminal 2 is an external terminal portion 2b exposed from the laminate 101 to the outside, and is connected to a connection terminal (bus bar) of an external device, not shown, by welding or the like, for example.

The lead terminal 2 is constituted by covering the surface of the terminal main body 4 formed of a metal material with a film 5 . The terminal body 4 is formed of, for example, nickel or aluminum or copper or stainless steel. The coating 5 uses, for example, an acrylic copolymer as a base resin, and is formed as a composite coating of the acrylic copolymer and a zirconium salt.

By containing the zirconium salt in the film 5, good electrical conductivity is ensured, high conductivity and high solderability between the electrode connecting portion 2a and the positive electrode 104 or the negative electrode 105 are ensured, and the connection between the external terminal portion 2b and external equipment is ensured High conductivity and high solderability of terminals.

Specifically, the film 5 is a surface-treated film containing a water-soluble zirconium salt and a water-soluble or water-dispersible acrylic resin, and the film is prepared such that the zirconium in the water-soluble zirconium salt is set from 0.8 to 300 mg, the acid value of the solid content in the water-soluble or water-dispersible acrylic resin is set from 150 to 740 mgKOH/g, and the hydroxyl value of the solid content is set from 24 to 240, and the solid content is set from 1.0 to 1.0 to 600mg. The film 5 adjusted in this way is applied to the surface of the metal material (lead terminal 2 ) to be the terminal, and is heated and dried to form a surface-treated film.

The coating method of the surface treatment agent may be performed so that each component of the coating film 5 to be formed falls within the above-mentioned range, and is not particularly limited. For example, a roll coating method, a bar coating method, a spraying treatment method, a dipping treatment method, or the like can be used.

The heating method of the surface treating agent is not particularly limited, and examples thereof include oven drying, a method of forced circulation by hot air, and the like. The conditions of heat drying can be set to, for example, 40 to 200° C. for 2 to 60 seconds.

The film parts 3 and 3 are in close contact with the lead terminals 2 from both sides and are also in close contact with the inner surface of the sealing part 102 of the laminated material 101 to seal the laminated material 101, and have an electrolyte solution 103 that can prevent encapsulation in the laminated material 101, etc. of liquid leakage. In addition, the film portions 3 and 3 are interposed between the lead terminals 2 and the laminate material 101 , and also have a role of ensuring insulation between the lead terminals 2 and the laminate material 101 .

The film portions 3 and 3 are formed in a shape extending in a direction perpendicular to the lead terminal 2 , and are in close contact with both surfaces in the thickness direction of the lead terminal 2 from both sides. Therefore, the film portions 3 and 3 are in close contact with the coating film 5 of the lead terminal 2 from both sides. The thickness of the film portion 3 is, for example, 50 μm to 150 μm, and the central portion in the longitudinal direction is in close contact with the lead terminal 2 .

The film portion 3 has, for example, a three-layer structure, and the first adhesive layer 6 and the second adhesive layer 7 are laminated on both sides of the intermediate layer 8 . However, as long as the membrane portion 3 has a structure of two or more layers, the number of layers is arbitrary.

The thickness of the first adhesive layer 6 is, for example, 25 μm to 100 μm. The first adhesive layer 6 is located on the lead terminal 2 side, and is formed of acid-modified polyolefin as a resin, and the base resin is modified with, for example, acrylic. Moreover, the 1st adhesive layer 6 uses polypropylene or polyethylene as a polyolefin, for example. Therefore, the first adhesive layer 6 uses, for example, acrylic-modified polypropylene or acrylic-modified polyethylene as a base resin.

As described above, since the first adhesive layer 6 uses acrylic-modified polypropylene or acrylic-modified polyethylene as the base resin, it is configured to contain carboxylic acid, which is the same component as the acrylic copolymer as the base resin of the film 5 . In addition, in the first adhesive layer 6 , the base resin may be modified with maleic acid, for example, to be maleic acid-modified polypropylene or maleic acid-modified polyethylene, and in this case, the base resin of the film 5 may be used. On the other hand, using a resin containing a carboxylic acid, it is desirable to include the same components in the first adhesive layer 6 and the film 5 . Moreover, as the base resin of the film 5, a maleic acid copolymer, a maleic anhydride modified polyethylene, or the like can be used in addition to a resin containing a carboxylic acid.

The second adhesive layer 7 has a thickness of, for example, 25 μm to 100 μm, and is located on the opposite side of the first adhesive layer 6 via the intermediate layer 8 . The second adhesive layer 7 is formed of the same material as the first adhesive layer 6 , and as the base resin, for example, acrylic-modified polypropylene or acrylic-modified polyethylene is used. Moreover, like the 1st adhesive layer 6, in the 2nd adhesive layer 7, the base resin may be modified|denatured with maleic acid, and may be made into maleic-acid-modified polypropylene or maleic-acid-modified polyethylene.

In this way, since polypropylene or polyethylene is used as the base resin for the second adhesive layer 7 , the base resin is made the same material as the inner surface layer 101 b of the laminate material 101 .

The intermediate layer 8 is laminated between the first adhesive layer 6 and the second adhesive layer 7 , and has a thickness of, for example, 50 μm. The intermediate layer 8 is cross-linked with a base resin, and as the base resin, for example, polypropylene or polyethylene is used.

The film portion 3 is in close contact with the lead terminal 2 and the sealing portion 102 of the laminate 101 by thermocompression, but as described above, the base resin of the intermediate layer 8 via the film portion 3 is made of cross-linked polypropylene or cross-linked In polyethylene, the heat resistance of the film portion 3 is improved, and the deformation or breakage of the film portion 3 is suppressed. Therefore, it is possible to ensure a stable close contact state of the film portion 3 to the lead terminal 2 and the sealing portion 102 , and to ensure high insulation between the lead terminal 2 and the laminate material 101 .

In addition, since the base resin of the film portion 3 is polypropylene or polyethylene, which is a polyolefin-based resin that does not easily penetrate moisture, moisture permeation in the film portion 3 is less likely to occur, and generation of hydrofluoric acid inside the package is suppressed. As a result, peeling due to corrosion is less likely to occur between the film portion and the lead terminals, and penetration of the electrolyte solution 103 and the like is less likely to occur, and high functionality of the non-aqueous electrolyte device 100 can be ensured.

<Test results about adhesion> Hereinafter, the test result regarding the measurement of the adhesiveness of the adhesive state of a coating film and a 1st adhesive layer is demonstrated (refer FIG. 4).

According to the presence or absence of the film and the presence or absence of acid modification in the film part, four kinds of materials were tested for adhesion. The film used a material containing acrylic resin and zirconium salt, and the film part used a material whose base resin was acrylic modified polypropylene. . In addition, in the tabs that functioned as the positive electrode and the tabs that functioned as the negative electrode, tests were performed on the above-mentioned four materials, respectively. Aluminum was used as the terminal body in the positive electrode, and an alloy of nickel and copper was used as the terminal body in the negative electrode.

In the test, a "standard test" serving as a standard and an "actual measurement test" for measuring the adhesiveness with respect to the standard test were performed.

About the above-mentioned four kinds of tabs, a reference test was performed by stretching the film portion and peeling it off from the lead terminal. The peeling angle was set to 180 degrees, and the peeling speed was set to 5 mm/min.

On the other hand, in the actual measurement test, as an accelerated test, 1000 ppm of water was added to the electrolyte solution for lithium ion batteries, and this was prepared as an immersion solution for each tab. In the immersion solution thus produced, by adding water to the electrolytic solution to generate hydrogen fluoride acid, the film is in a state where the film is easily peeled off from the film portion.

The actual measurement test was performed by immersing the above-mentioned four types of tabs in the immersion liquid for a constant time, stretching the film portion after immersion, and peeling it off from the lead terminal. The peeling angle and peeling speed were the same as those of the reference test, the temperature of the immersion liquid was set to 85 degrees, and the immersion time of each tab in the immersion liquid was set to 336 hours.

Each test was performed by the method as described above, and the ratio of the results of the peel strength of the film portion in the standard test and the peel strength in the actual measurement test was calculated as the adhesion residual rate.

"○", "△" and "×" in Fig. 4 indicate the size of the residual adhesion rate, "○" indicates that the residual adhesion rate is 70% or more, and "△" indicates that the residual adhesion rate is 60% or more and less than 70% , "×" indicates that the residual rate of close contact is less than 60%.

As shown in FIG. 4 , when the film containing the acrylic resin and the zirconium salt was not formed on the lead terminal, regardless of whether the base resin of the film portion was acid-modified, a low rate of adhesion residue rate of less than 60% was obtained.

On the other hand, when a film containing an acrylic resin and a zirconium salt was formed on the lead terminal, the result that the adhesion residual ratio was 60% or more was obtained, especially when the film was formed on the lead terminal and the base resin of the film portion was modified with acrylic acid. In this case, a high rate result of the adhesion residual rate of 70% or more was obtained.

From the above measurement results, when the film containing the acrylic resin and the zirconium salt was formed on the lead terminal, high adhesion between the film of the lead terminal and the first adhesive layer of the film portion was confirmed. In addition, when a film containing an acrylic resin and a zirconium salt was formed on the lead terminal and the base resin of the film portion was modified with acrylic acid, it was confirmed that a higher level of contact between the film portion of the lead terminal and the first adhesive layer of the film portion could be ensured. of tightness.

＜Summary＞ As described above, in the tab 1 and the non-aqueous electrolyte device 100 including the tab 1, the first adhesive layer 6 using acid-modified polyolefin as a base resin is provided on the lead terminal 2 side of the film portion 3, and the film 5 includes It has the same composition as the base resin of the first adhesive layer 6 .

Therefore, the acid-modified first adhesive layer 6 of the polyolefin as the base resin is in close contact with the coating 5 of the lead terminal 2 containing the same component as the acid-modified portion of the base resin of the first adhesive layer 6 from both sides. The affinity between the first adhesive layer 6 of the film portion 3 and the coating film 5 of the lead terminal 2 is improved, and the lead terminal 2 and the film portion 3 have high adhesion, and long-term resistance to electrolytes and the like can be ensured. Thereby, liquid leakage such as the electrolyte solution 103 enclosed in the laminate 101 is prevented without creating a gap between the lead terminal 2 and the film portion 3 , and sealing performance is ensured, thereby ensuring good performance of the non-aqueous electrolyte device 100 .

In addition, the film 5 is a surface-treated film containing a water-soluble zirconium salt and a water-soluble or water-dispersible acrylic resin, and the film is prepared so that the zirconium in the water-soluble zirconium salt is set from 0.8 to 300 mg per square meter on a mass basis, The acid value of solid content in the water-soluble or water-dispersible acrylic resin is 150 to 740 mgKOH/g, the hydroxyl value of solid content is 24 to 240, and the solid content is 1.0 to 600 mg per square meter on a mass basis.

Accordingly, the corrosion resistance of the coating film 5 is improved, and the affinity of the coating film 5 to the first adhesive layer 6 is improved, so that the rust resistance of the terminal body 4 can be improved due to the improvement of the corrosion resistance of the coating film 5, and it is possible to ensure High adhesion between the lead terminal 2 and the film portion 3 .

Furthermore, by using acrylic-modified polypropylene or polyethylene as the base resin of the first adhesive layer 6, the first adhesive layer 6 has the same acrylic component as the film 5, so that the film portion 3 can be formed at low cost. , and high adhesion between the lead terminal 2 and the film portion 3 can be ensured.

In addition, the second adhesive layer 7 in which the base resin of the same material as the laminate 101 is formed is provided on the laminate material 101 side of the film portion 3 .

Therefore, the affinity between the second adhesive layer 7 and the laminate material 101 is improved, and high adhesiveness between the film portion 3 and the laminate material 101 can be ensured.

In addition, since the second adhesive layer 7 uses polypropylene or polyethylene as the base resin, it is formed of a material having high affinity with the laminate material 101 , so that the high functionality of the non-aqueous electrolyte device 100 can be ensured. High adhesion between the film portion 3 and the laminate material 101 is ensured. In addition, when the base resin of the second adhesive layer 7 is polypropylene, in particular, since the second adhesive layer 7 is formed of a material that does not easily permeate moisture, it is possible to ensure a more secure connection between the film portion 3 and the laminate material 101. High adhesion.

＜Other＞ The above shows an example in which the tabs 1, 1 connected to the positive electrode 104 or the negative electrode 105 both protrude in the same direction (upward) from the laminate 101, but in the non-aqueous electrolyte device 100, the tabs connected to the positive electrode 104 or the negative electrode 105 are shown. The tabs 1 , 1 may also protrude in opposite directions from the laminate 101 .

100: Nonaqueous Electrolyte Device 101: Laminates 103: Electrolyte 1: pole ear 2: lead terminal 3: Membrane 4: Terminal body 5: film 6: The first adhesive layer 7: Second Adhesion Layer

Fig. 1 is a front view of a non-aqueous electrolyte device showing an embodiment of the present invention together with Figs. 2 to 4 . [Fig. 2] is a cross-sectional view taken along line II-II of Fig. 1. [Fig. [Fig. 3] A front view of the tie tab. 4] It is a figure which shows the measurement result regarding the adhesiveness of the coating film of a lead terminal and the 1st adhesive layer of a film part.

1: pole ear 2: lead terminal 2a: Electrode connection part 2b: External terminal part 3: Membrane 4: Terminal body 5: film 6: The first adhesive layer 7: Second Adhesion Layer 8: middle layer 100: Nonaqueous Electrolyte Device 101: Laminates 101a: outer surface layer 101b: inner surface layer 101c: Metal Layer 102: Sealing part 103: Electrolyte 104: positive pole 105: negative pole 106: Divider

Claims (5)

A tab for use in a laminated non-aqueous electrolyte device in which at least an electrolytic solution or a solid electrolyte is sealed inside a laminate, the tab comprising: A lead terminal having a terminal body formed of a metal material and a coating covering the surface of the terminal body; and A pair of film portions are in close contact with the lead terminals from both sides and in close contact with the laminate material to seal the laminate material, On the lead terminal side of the film portion, an adhesive layer with acid-modified polyolefin as a base resin is provided, The coating film contains the same components as the base resin of the adhesive layer, The aforementioned film is a surface treatment film containing water-soluble zirconium salt and water-soluble or water-dispersible acrylic resin, The aforementioned film is prepared as follows: the zirconium in the aforementioned water-soluble zirconium salt is set from 0.8 to 300 mg per square meter on a mass basis, The acid value of the solid content in the water-soluble or water-dispersible acrylic resin is from 150 to 740 mgKOH/g, the hydroxyl value of the solid content is set from 24 to 240, and the solid content is from 1.0 to 600 mg per square meter on a mass basis . An ear as claimed in claim 1, wherein The aforementioned adhesive layer uses acrylic-modified polypropylene or polyethylene as the base resin. An ear as claimed in claim 1 or claim 2, wherein A second adhesive layer is provided on the laminate material side of the film portion, and a base resin of the same material as the laminate material is formed on the second adhesive layer. An ear as claimed in claim 3, wherein The said 2nd adhesive layer uses polypropylene or polyethylene as a base resin. A non-aqueous electrolyte device, which is a laminated non-aqueous electrolyte device in which at least an electrolyte or a solid electrolyte is sealed inside a laminate material and tabs are provided, The aforementioned tabs have: A lead terminal having a terminal body formed of a metal material and a coating covering the surface of the terminal body; and A pair of film portions are in close contact with the lead terminals from both sides and in close contact with the laminate material to seal the laminate material, On the lead terminal side of the film portion, an adhesive layer with acid-modified polyolefin as a base resin is provided, The coating film contains the same components as the base resin of the adhesive layer, The aforementioned film is a surface treatment film containing water-soluble zirconium salt and water-soluble or water-dispersible acrylic resin, The aforementioned film is prepared as follows: the zirconium in the aforementioned water-soluble zirconium salt is set from 0.8 to 300 mg per square meter on a mass basis, The acid value of the solid content in the aforementioned water-soluble or water-dispersible acrylic resin is set to be from 150 to 740 mgKOH/g, and the hydroxyl value of the solid content is set to be from 24 to 240, and the solid content is set to be from 1.0 to 600 mg per square meter on a mass basis .

Images