KR102414434B1 - Electrochemical device and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an electrochemical device capable of charging and discharging electric energy by an electrochemical reaction and a method for manufacturing the same. More specifically, the present invention relates to an electrochemical device that does not require a separate terminal and a method for continuously producing the same.

Description

Electrochemical device and manufacturing method thereof

The present invention relates to an electrochemical device capable of charging and discharging electric energy by an electrochemical reaction and a method for manufacturing the same. More specifically, the present invention relates to an electrochemical device that does not require a separate terminal and a method for continuously producing the same.

Energy-related technologies are being actively researched as the industry related to portable electronic devices expands according to the recent development of communication technology and semiconductor manufacturing technology, and the demand for the development of alternative energy to prepare for the depletion of fossil fuels and to preserve the environment is rapidly increasing. . Among these energy-related technologies, a battery, which is a representative energy storage device, is at the center.

Among batteries, a lithium primary battery has a higher voltage and higher energy density than a conventional aqueous-based battery, so it is easy to reduce the size and weight and is widely applied. Such lithium primary batteries are mainly used as a main power source or a backup power source for portable electronic devices. Another battery, a lithium secondary battery, is an energy storage device capable of charging and discharging using an electrode material having excellent reversibility.

Lithium secondary batteries are being manufactured in various shapes according to their applications. For example, the lithium secondary battery is packaged and manufactured in a cylindrical shape, a prismatic shape, and a pouch shape. Here, since the pouch-type secondary battery can be lightweight, related technologies are being continuously developed. In general, a pouch-type lithium secondary battery accommodates an electrode assembly in a pouch case having a space for accommodating the electrode assembly, and then seals the pouch case to form a bare cell, and the pouch is placed in the bare cell. It can be manufactured by attaching accessories such as a protective circuit module to form a pouch core pack.

However, such a pouch-type lithium secondary battery also becomes a factor limiting the shape and size of a lithium secondary battery in terms of packaging, and since the conventional pouch-type lithium secondary battery includes an electrode tab, in order to manufacture a single lithium secondary battery, each The lithium secondary battery must be packaged and manufactured, and there are problems in that it is difficult to manufacture, productivity is lowered, and it is difficult to apply to various electronic products.

Republic of Korea Patent Publication No. 10-2008-0034369 (2008.04.21)

As devised to solve the above-described problems, an object of the present invention is to provide a method of manufacturing an electrochemical device having the effect of reducing mass production and production costs by continuously manufacturing an electrode assembly and packaging process. is to provide

Another object of the present invention is to provide an electrochemical device that does not require a separate terminal unit and a method for manufacturing the same by directly connecting a metal current collector constituting the outermost layer of an electrode assembly and a metal layer constituting a package body to be electrically connected.

In addition, the present invention is to provide an electrochemical device and a method for manufacturing the same that can be manufactured in various shapes such as round, semi-circular, triangular, square, and star-shaped without restrictions on the design of the battery without the need for a terminal part, so that the design of the battery can be autonomous do.

In addition, the present invention uses a package having a plurality of cell areas, which is supplied continuously, and is manufactured by laminating by heat to form a plurality of cell areas in one electrochemical energy device, thereby providing a plurality of battery cells. can be continuously formed, and by dividing them, an electrochemical device having a plurality of battery cell regions can be manufactured at once or a plurality of battery cells can be manufactured, and the multiple battery cells can be electrically connected in series or parallel. An object of the present invention is to provide an electrochemical device and a method for manufacturing the same.

In addition, an object of the present invention is to provide an electrochemical device that can be applied to a flexible device because it has flexibility by using an electrode assembly that can be manufactured by a printing method, and can be applied to a curved surface rather than a flat surface.

Another object of the present invention is to provide an electrochemical device in which the thickness of each layer and the number of layers can be easily controlled.

One aspect of the present invention for achieving the above object is

It includes an electrode assembly accommodated in a space in which the upper sheet and the lower sheet are integrally formed to face each other,

The upper sheet and the lower sheet include a metal layer,

At least one of the upper sheet and the lower sheet includes a sealing layer on the edge of the metal layer,

The present invention relates to an electrochemical device in which current collectors of the positive and negative electrodes of the electrode assembly are in close contact with the metal layers of the upper and lower sheets and are electrically connected.

In one aspect of the electrochemical device of the present invention, the electrode assembly and the metal layer of the upper sheet and the lower sheet may be to further include a bonding portion in at least any one or more portions of the contact portion.

In one aspect of the electrochemical device of the present invention, any one or more layers selected from a conductive adhesive layer, a conductive adhesive layer and a conductive paste layer, etc. are further included between the electrode assembly and any one or more metal layers selected from the lower sheet and the upper sheet. may be doing

In one aspect of the electrochemical device of the present invention, any one or more selected from the upper sheet and the lower sheet may further include an insulating layer on an outermost layer, and a portion of the insulating layer may be open.

In one aspect of the electrochemical device of the present invention, the sealing layer may be made of a polymer material that can be fused by heat.

In one aspect of the electrochemical device of the present invention, the sealing layer may include one or more layers made of a heat-resistant material between layers made of a polymer material that can be fused by heat.

In one aspect of the electrochemical device of the present invention, an adhesive layer may be further included on the sealing layer.

In one aspect of the electrochemical device of the present invention, the sealing layer may be formed along the periphery of the electrode assembly at the edge except for the portion where the electrode assembly is located.

In one aspect of the electrochemical device of the present invention, the electrode assembly includes a positive electrode and a negative electrode, and at least one of the positive electrode and the negative electrode includes a gel polymer electrolyte including a cross-linked polymer matrix, a solvent, and a dissociable salt. can

In one aspect of the electrochemical device of the present invention, the positive electrode includes: i) an electrode-electrolyte composite coated with a gel polymer electrolyte on a current collector, ii) an active material layer comprising an electrode active material and a binder on the current collector, An electrode-electrolyte composite comprising an electrode-electrolyte composite coated with a gel polymer electrolyte on the active material layer, and iii) an electrode-electrolyte composite comprising a composite active material layer comprising an electrode active material, a crosslinked polymer matrix, a solvent and a dissociable salt on a current collector become,

The negative electrode may be an electrode made of only a current collector and one selected from i) to iii).

In one aspect of the electrochemical device of the present invention, the positive electrode may be selected from ii) and iii), and the negative electrode may be made of only a current collector or selected from i).

In one aspect of the electrochemical device of the present invention, the active material layer and the composite active material layer may further include a conductive material.

In one aspect of the electrochemical device of the present invention, the anode and the cathode may have substantially coincident edges.

In one aspect of the electrochemical device of the present invention, at least one separator may be further included between the anode and the cathode, and the separator may have substantially identical edges to the anode and the cathode.

In one aspect of the electrochemical device of the present invention, the separator may include a gel polymer electrolyte including a cross-linked polymer matrix, a solvent, and a dissociable salt.

In one aspect of the electrochemical device of the present invention, the electrode assembly includes a first gel polymer electrolyte in the positive electrode, and a second gel polymer electrolyte in the negative electrode, wherein the first gel polymer electrolyte and the second gel polymer electrolyte are They may be different from each other.

In one aspect of the electrochemical device of the present invention, the difference in solubility parameter between the first gel polymer electrolyte and the second gel polymer electrolyte may be 0.1 MPa ^1/2 or more.

In one aspect of the electrochemical device of the present invention, the energy level difference between the first gel polymer electrolyte and the second gel polymer electrolyte may be 0.01 eV or more.

In one aspect of the electrochemical device of the present invention, the first gel polymer electrolyte and the second gel polymer electrolyte may further include any one or two or more additives selected from inorganic particles and flame retardants.

In one aspect of the electrochemical device of the present invention, the first gel polymer electrolyte further comprises any one selected from succinonitrile and sebaconitrile or a mixture thereof, an anode heating inhibitor,

The second gel polymer electrolyte may further include a SEI layer stabilizer, which is any one selected from vinylene carbonate, ethylene fluoride carbonate, and catechol carbonate, or a mixture thereof.

In one aspect of the electrochemical device of the present invention, the cross-linked polymer matrix may further include a linear polymer to have a semi-interpenetrating network (semi-IPN) structure.

In one aspect of the electrochemical device of the present invention, the positive electrode current collector and the negative electrode current collector are each selectively in the form of a thin film, a mesh, or a thin film or a mesh type current collector on one or both sides of a conductive substrate to be laminated to form an integrated structure and It may be selected from the group consisting of metal-mesh composites.

In one aspect of the electrochemical device of the present invention, in the electrochemical device, one or two or more of the electrode assemblies may be stacked.

In one aspect of the electrochemical device of the present invention, the electrode assembly may include one or more bipolar electrodes.

In one aspect of the electrochemical device of the present invention, the sealing layer further includes a plurality of partition barriers so that a plurality of grooves in which the sealing layer is not formed are formed,

A plurality of electrode assemblies may be included in a space in which the upper sheet and the lower sheet are integrated to face each other to provide a plurality of cell regions.

In one aspect of the electrochemical device of the present invention, the electrochemical device may be a primary battery or a secondary battery capable of an electrochemical reaction.

In one aspect of the electrochemical device of the present invention, the electrochemical device is a lithium primary battery, a lithium secondary battery, a lithium-sulfur battery, a lithium-air battery, a sodium battery, an aluminum battery, a magnesium battery, a calcium battery, a zinc battery, zinc -air batteries, sodium-air batteries, aluminum-air batteries, magnesium-air batteries, calcium-air batteries, super capacitors, dye-sensitized solar cells, fuel cells, lead storage batteries, nickel cadmium batteries, nickel hydrogen storage batteries and alkaline batteries, etc. It may be selected from the group consisting of.

In addition, another aspect of the present invention is a lower sheet comprising a metal layer and a sealing layer forming a barrier rib pattern including a circumferential barrier rib on one surface of the metal layer and a partition barrier rib defining a space for accommodating an electrode assembly inside the circumferential barrier rib supply,

Laminating an electrode assembly in a space for accommodating the electrode assembly of the lower sheet,

The present invention relates to a method for manufacturing an electrochemical device that is continuously manufactured, including the step of supplying and laminating an upper sheet including a metal layer.

In one aspect of the method of manufacturing an electrochemical device of the present invention, during the lamination, the positive electrode current collector and the negative electrode current collector of the electrode assembly may be laminated so as to be in close contact with the metal layer of the upper sheet and the metal layer of the lower sheet, respectively.

In one aspect of the method for manufacturing an electrochemical device of the present invention, after the lamination, the metal layer of the lower sheet and the upper sheet and the electrode assembly are welded or soldered to form a junction by welding or soldering may be further included.

In one aspect of the method for manufacturing an electrochemical device of the present invention, the method may further include applying at least one selected from a conductive adhesive, a conductive adhesive and a conductive paste on the metal layer of the lower sheet and the upper sheet.

In one aspect of the method for manufacturing an electrochemical device of the present invention, after the lamination, the step of cutting the portion sealed by the sealing layer may be further included.

The present invention can continuously produce a plurality of electrochemical devices, thereby greatly improving productivity. That is, it is possible to manufacture the electrode assembly by the printing method, and since a package having a plurality of continuously supplied cell regions is used, continuous mass production is possible.

In addition, since a plurality of electrode assemblies can be stacked or an electrode assembly using a bipolar electrode can be used, there is an effect that an electrochemical device that can be easily changed according to use can be manufactured.

In addition, the divided electrochemical devices can be easily connected in series or in parallel, so that they can be applied to various electronic products.

In addition, since the metal layer of the package and the current collector of the electrode assembly are in close contact with each other and are electrically connected in all parts, a separate terminal part is not required, which simplifies the production process, and the part sealed between the sealing layers is cut to form a battery cell. When dividing, it is possible to manufacture a desired number of battery cells connected in parallel by cutting them at a desired part, so there is an effect that a battery of a desired capacity can be efficiently manufactured.

In addition, by forming a junction portion through a method such as welding or soldering at the portion where the metal layer of the package and the current collector of the electrode assembly are in close contact with each other, it is possible to manufacture a battery with reduced contact resistance and further improved electrical performance. In addition, it is possible to provide a battery with improved charging and discharging efficiency and improved impact characteristics.

1 shows a cross-section of an electrochemical device according to an embodiment of the present invention.
Figure 2 is a perspective view showing an aspect of the lower sheet and the upper sheet of the present invention.
3 is a cross-sectional view illustrating an electrochemical device according to an embodiment of the present invention.
4 is a cross-sectional view showing an electrochemical device according to an embodiment of the present invention.
5 is a cross-sectional view showing an electrochemical device according to an embodiment of the present invention.
6 is a cross-sectional view showing an electrochemical device according to an embodiment of the present invention.
7 is a cross-sectional view showing an embodiment of the lower sheet and the upper sheet of the present invention.
8 is a cross-sectional view showing an embodiment of the lower sheet and the upper sheet of the present invention.
9 is a cross-sectional view showing an embodiment of the lower sheet and the upper sheet of the present invention.
10 is a perspective view showing an embodiment of the lower sheet and the upper sheet of the present invention.
11 is a cross-sectional view showing an embodiment of the electrode assembly of the present invention.
12 is a cross-sectional view showing an embodiment of the electrode assembly of the present invention.
13 is a cross-sectional view showing an embodiment of the electrode assembly of the present invention.
14 is a cross-sectional view showing an embodiment of the electrode assembly of the present invention.
15 is a cross-sectional view showing an embodiment of the electrode assembly of the present invention.
16 is a cross-sectional view schematically illustrating a method of manufacturing an electrode assembly according to an embodiment of the present invention.
17 is a perspective view schematically illustrating a method of manufacturing an electrode assembly of the present invention.
18 is a cross-sectional view showing an embodiment of the electrode assembly of the present invention.
19 is a cross-sectional view schematically illustrating a method of manufacturing an electrode assembly according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail through embodiments or examples including the accompanying drawings. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

[Electrochemical device]

First, the electrochemical device of the present invention will be described in detail with reference to the drawings.

1 and 18 are cross-sectional views of an electrochemical device according to an embodiment of the present invention, and FIG. 2 is a perspective view showing an embodiment of a lower sheet and an upper sheet of the present invention.

1 shows that the lower sheet 200 and the upper sheet 300, which are packages, include metal layers 201 and 301, and the lower sheet 200 and the upper sheet 300 include sealing layers 202 and 302, respectively. 18 shows that the lower sheet 200 and the upper sheet 300, which are packages, include metal layers 201 and 301, and a sealing layer is formed on any one of the lower sheet 200 and the upper sheet 300. It shows an aspect in the case of including. 18 illustrates a case in which the sealing layer 202 is optionally included in the lower sheet, but is not limited thereto, and may be included in the upper sheet.

Hereinafter, the package will be described with reference to the same aspect as in FIG. 1 including the sealing layers 202 and 302 on the lower sheet 200 and the upper sheet 300, respectively, but this is only an example for a detailed description. it is not going to be

1 and 2, the electrochemical device 1000 of the present invention is composed of an electrode assembly 100 and a package covering the surface thereof. The package includes a lower sheet 200 and an upper sheet 300 . In addition, the lower sheet 200 and the upper sheet 300 have the metal layers 201 and 301 and the sealing layers 202 and 302 formed on the edges of the metal layer, and the sealing layer is not formed inside the sealing layer. grooves 213 and 313 .

The metal layer and the sealing layer of the lower sheet 200 and the upper sheet 300 may be made of the same material, and different materials may be used. A specific aspect of the package will be described in more detail with reference to FIGS. 7 to 10 .

As shown in FIG. 1 , the electrode assembly 100 is accommodated in a space in which the sealing layers 202 and 302 of the upper sheet 300 and the lower sheet 200 are integrated to face each other. Alternatively, as shown in FIG. 18 , the upper sheet 300 including the metal layer 301 and the lower sheet 200 including the metal layer 201 and the sealing layer 202 face each other to form an electrode assembly in a space formed integrally. (100) is accepted.

The space in which the electrode assembly 100 is accommodated may be the same as the size of the electrode assembly 100 or may be larger than the electrode assembly 100 . The free space created by the space in which the electrode assembly 100 is accommodated is larger than that of the electrode assembly 100 acts as a buffer space for internal pressure increase caused by gases that may occur during use of the electrochemical device, thereby making the electrochemical device It can contribute to improving the durability and safety of

The sealing layer may be made of a polymer material that can be fused and sealed by heat, and more specifically, may be made of a thermoplastic resin. Alternatively, a layer made of a polymer material capable of fusion by heat and a layer made of a heat-resistant material may be alternately stacked one or more layers, and the heat-resistant material may be made of a heat-resistant resin or metal.

In the electrochemical device according to an aspect of the present invention, all sides of the electrode assembly may be sealed by a sealing layer. In addition, although not specifically shown, the electrode assembly 100 includes a positive electrode and a negative electrode, and the positive electrode and the negative electrode may be one in which the positive electrode and the negative electrode are separated by a separator or a gel polymer electrolyte layer. In addition, the positive electrode current collector and the negative electrode current collector constituting the outermost layer of the electrode assembly are in close contact with the metal layer of the upper sheet and the metal layer of the lower sheet, respectively, and are electrically connected.

In addition, since all parts of the cell are electrically connectable as described above, there is no limitation in the shape of the battery cell, and a terminal part is not required. However, since the terminal part may be formed if necessary, this is not excluded.

In addition, it can be manufactured continuously, and can be manufactured by cutting the desired number of cells in consideration of the required capacity of the battery cell. A specific aspect of the electrode assembly 100 will be described in more detail with reference to FIGS. 11 to 15 .

The electrochemical device of the present invention has an advantage in that it is easy to manufacture and use because it does not form a separate terminal part as shown in FIGS. 1 and 18 . In addition, as shown in FIGS. 1 and 18 , the positive electrode current collector and the negative electrode current collector constituting the outermost portion of the electrode assembly 100 are in close contact with the metal layer 301 of the upper sheet and the metal layer 201 of the lower sheet, respectively. The thickness W1 of the assembly may be the same as the thickness of the sealing layers 202 and 302 or may be thicker than the thickness of the sealing layers.

3 is a cross-sectional view of an electrochemical device according to another embodiment of the present invention. As shown in FIG. 3, the electrochemical device 1000 of the present invention has a portion in which the metal layer 301 of the upper sheet 300 and the metal layer 201 of the lower sheet 200 and the electrode assembly 100 are in close contact ( W2) may be to further include the junction part 400 in part or all. Since contact resistance may be reduced by forming the junction, electrical performance may be further improved, charge/discharge efficiency may be improved, and output characteristics may be further improved. The junction 400 may be formed in the portion W2 where the metal layer and the current collector of the electrode assembly are in close contact, and may be formed only in a portion or all, but formed only in a portion in terms of ease of manufacture. can The joint 400 may be formed by welding, soldering, etc., but is not limited thereto. The welding may be formed in a spot or stripe shape by methods such as resistance welding, ultrasonic welding, and laser welding, but is not limited thereto. In addition, in the case of performing the soldering, the soldering paste may be further included inside the metal layers 201 and 301 , that is, on a portion to which the electrode assembly is in close contact.

4 is a cross-sectional view of an electrochemical device according to another embodiment of the present invention. As shown in FIG. 4, the electrochemical device 1000 of the present invention has a portion in which the metal layer 301 of the upper sheet 300 and the metal layer 201 of the lower sheet 200 and the electrode assembly 100 are in close contact ( W2) may further include any one or more conductive layers 203 and 303 selected from a conductive adhesive layer, a conductive adhesive layer, and a conductive paste layer. The conductive adhesive layer, the conductive pressure-sensitive adhesive layer and the conductive paste layer are not limited as long as they are commonly used in the field, and the metal layer of the upper sheet and the metal layer of the lower sheet, and the electrode assembly can be in better contact with each other, and the electricity is more You can make it work well. In addition, although not shown, the junction part 400 may be further included as shown in FIG. 3 if necessary.

5 is a cross-sectional view of an electrochemical device according to another embodiment of the present invention. 5, the electrochemical device 1000 of the present invention has an insulating layer 304 on the outer surface of any one or more metal layers 201 and 301 selected from the upper sheet 300 and the lower sheet 200, respectively. , 204) may be further included. By further including an insulating layer, it is possible to protect the electrode assembly from external substances from the outside of the metal layer, and to electrically insulate it from the outside. At this time, as shown in FIG. 5 , the insulating layers 204 and 304 may include grooves 205 and 305 in which the insulating layer is not formed because a part thereof is opened. The grooves 205 and 305 may be formed in any part W3 of the upper sheet 300 and the lower sheet 200 so that electricity can pass through them. can send. In this case, a separate terminal may be further included, but may be performed without a separate terminal.

In one aspect of the present invention, the insulating layers 204 and 304 may be used without limitation as long as they are materials having electrical insulating properties, and if it is possible to protect the electrode assembly from external materials from the outside of the metal layer, and to electrically insulate from the outside It can be used without limitation. Specifically, for example, polyethylene, polypropylene, casted polypropylene (CPP), polystyrene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyamide, cellulose resin, polyimide resin, etc. may be used. , but is not limited thereto. In addition, one layer or two or more layers may be laminated. In addition, although not shown, the junction part 400 may be further included as shown in FIG. 3 if necessary.

6 is a cross-sectional view of an electrochemical device according to another embodiment of the present invention. As shown in FIG. 6 , the electrochemical device 1000 of the present invention has an adhesive layer on at least one selected from the sealing layer 302 of the upper sheet 300 and the sealing layer 202 of the lower sheet 200 . (206, 306) may be further included. As described in FIG. 1 , the sealing layers 202 and 302 may be made of a polymer material that can be fused and sealed by heat, so that the sealing layers 202 and 302 are melted by thermal compression using a heating plate or a heating roller, etc. It may be sealed, but it may be to form separate adhesive layers 206 and 306 to further improve adhesion. The adhesive used at this time is not limited as long as it is conventionally used in the relevant field, and any adhesive having excellent adhesion to the polymer material used for the sealing layer and chemical stability with the electrode assembly may be used without limitation. Specifically, for example, an acrylic adhesive, an epoxy adhesive, and a cellulose adhesive may be used, but the present invention is not limited thereto. In addition, although not shown, the junction part 400 may be further included as shown in FIG. 3 if necessary.

In one aspect of the present invention, the electrochemical device may be a primary battery or a secondary battery capable of electrochemical reaction.

More specifically, lithium primary battery, lithium secondary battery, lithium-sulfur battery, lithium-air battery, sodium battery, aluminum battery, magnesium battery, calcium battery, sodium-air battery, aluminum-air battery, magnesium-air battery, calcium - It may be an air battery, a super capacitor, a dye-sensitized solar cell, a fuel cell, a lead storage battery, a nickel cadmium battery, a nickel hydrogen storage battery, and an alkaline battery, but is not limited thereto.

[Upper seat and lower seat]

Next, the upper sheet and the lower sheet of the present invention will be described in more detail. In one aspect of the present invention, the lower sheet 200 and the upper sheet 300 may be made of the same material, and more specifically, the lamination configuration thereof is as follows. The topsheet and bottomsheet are more specifically illustrated in Figures 2 and 7-10. Since the lower sheet and the upper sheet may have the same configuration, FIGS. 2 and 7 to 10 are illustrated based on the lower sheet 200 for convenience, and the numbers in parentheses indicate the signs of the upper sheet 300 . In addition, FIGS. 2 and 7 to 9 show a lower sheet and an upper sheet included in one electrochemical device manufactured by cutting, and FIG. 10 is a method for manufacturing a plurality of battery cells in the manufacturing method of the present invention. It shows an example of the lower sheet and the upper sheet continuously supplied from the roll.

As shown in FIG. 2 , the lower sheet 200 and the upper sheet 300 include metal layers 201 and 301 , sealing layers 202 and 302 formed on edges of the metal layer, and the sealing layer inside the sealing layer. It may include grooves 213 and 313 in which no layers are formed. The grooves 213 and 313 in which the sealing layer is not formed are for accommodating the electrode assembly 100, and the shape of the groove may be formed along the periphery of the electrode assembly. In addition, the size of the cross-sectional area of the grooves 213 and 313 may be the same as or larger than the size of the electrode assembly 100 .

In one aspect of the present invention, since the metal layers 201 and 301 form the packaging body of the electrochemical device, it is preferable that the metal layer is a material capable of preventing the inflow of gas, moisture, etc. and mechanical strength. It is not particularly limited as long as it is a metal that can be used in the art, but specifically, for example, aluminum, copper, stainless, nickel, nickel-plated iron, or a clad metal in which two or more alloys of these metals and two or more metals are laminated ( clad metal) and the like. In the case of double aluminum, it is preferable because it is light in weight, has excellent mechanical strength, and has excellent stability with respect to the electrochemical properties of the electrode assembly and the electrolyte, but is not limited thereto. The thickness of the metal layer is not limited, but may be 0.1 to 200 μm, more specifically 1 to 100 μm, in view of workability and penetration of moisture when forming the joint.

In one aspect of the present invention, the sealing layer may be used without limitation as long as it is a material that can be melted and sealed by heat, and a material having excellent adhesion to the metal layer may be more preferable. Specifically, for example, polyethylene, polypropylene, casted polypropylene (CPP), maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, poly Vylidene chloride, polyamide, cellulose resin, and a resin prepared by compounding two or more of these materials may be used, but the present invention is not limited thereto. In addition, one layer or two or more layers may be laminated.

When the thickness of the sealing layer is too thin or the sealing temperature is too high, the sealing layers 202 and 302 become too thin or melted in the process of sealing by applying heat to the sealing part, so that the metal layers 201 and 301 are mutually exclusive. It may stick and cause a short. Therefore, as shown in FIG. 7, the sealing layer of the present invention further includes a layer 215 made of a heat-resistant material, thereby preventing a short circuit from occurring in the sealing process and sufficiently functioning as a spacer. . More specifically, the sealing layer may include one or more layers 215 made of a heat-resistant material between the layers 214 made of a polymer material that can be fused by heat. That is, it may be laminated in the same order as a heat-sealable polymer material/heat-resistant material/heat-sealable polymer material. The number and thickness of the laminations are not limited. The heat-resistant material may be made of a metal such as aluminum or a heat-resistant resin such as nylon, polyethylene terephthalate, polyphenylene sulfide, polypropylene, polyimide, and polyamideimide, but is not limited thereto. The thickness of the heat-resistant material is preferably thinner than the thickness (W1) of the entire sealing portion.

7 to 9 are cross-sectional views showing other aspects of the lower sheet and the upper sheet of the present invention.

As shown in FIG. 7 , at least one of the lower sheet 200 and the upper sheet 300 includes metal layers 201 and 301 and sealing layers 202 and 302 formed on edges of the metal layer and the sealing layer. Inside the grooves 213 and 313 in which the sealing layer is not formed, the grooves 213 and 313 have at least one conductive layer 203 selected from a conductive adhesive layer, a conductive adhesive layer, and a conductive paste layer. 303) may be formed. The conductive adhesive layers 203 and 303 are to further improve the adhesion between the electrode assembly and the metal layer to further improve the electrical connection. The conductive adhesive layer, the conductive adhesive layer and the conductive paste layer may be used without limitation as long as they are conventionally used in the relevant field. The thickness of any one or more layers selected from the conductive adhesive layer, the conductive pressure-sensitive adhesive layer and the conductive paste layer is not particularly limited, but may be, for example, 0.1 to 10 μm.

More specifically, the conductive adhesive may be formed of a mixture of metal powder, a conductive material, and a binder. That is, metal powders, such as silver, zinc, copper; conductive materials such as carbon-based particles such as metal fibers, carbon powders, carbon fibers, and carbon nanotubes; And acrylic resin, epoxy resin, urethane resin, cellulose resin, adhesive polyolefin resin, specifically, maleic anhydride-grafted polyolefin, acrylic acid-grafted polyolefin, such as a polymer material such as a mixture of a binder can be used. . The size of the metal powder and carbon powder used may be in the range of 10 nm to 10 μm. The diameter of the metal fiber and the carbon fiber may be 10 nm to 10 μm or less, and the length may be 10 μm to 30 mm, but is not limited thereto.

In addition, as described above, the sealing parts 202 and 302 of the present invention further include a layer 215 made of a heat-resistant material to prevent a short circuit from occurring in the process of sealing and to function as a spacer sufficiently. can

As shown in FIG. 8 , the lower sheet 200 and the upper sheet 300 include metal layers 201 and 301 , sealing layers 202 and 302 formed on edges of the metal layer, and the sealing layer inside the sealing layer. It may include a groove 213 in which a layer is not formed, and further include insulating layers 204 and 304 on the opposite surface on which the sealing layer is formed. In this case, a portion of the insulating layer may be opened and include grooves 205 and 305 in which the insulating layer is not formed. The grooves 205 and 305 may be formed in any one or more selected from the upper sheet 300 and the lower sheet 200, and may be formed in a portion. Electricity may be transmitted to the outside through the grooves 205 and 305 . In one aspect of the present invention, the insulating layer may be used without limitation as long as it is a material having electrical insulating properties, and if it can protect the electrode assembly from external materials from the outside of the metal layer and electrically insulate from the outside, it can be used without limitation. have. Specifically, for example, polyethylene, polypropylene, casted polypropylene (CPP), polystyrene, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyamide, and cellulose resin may be used, However, the present invention is not limited thereto. In addition, one layer or two or more layers may be laminated.

In addition, the thickness of the insulating layer is not limited, and specifically, for example, may be 0.1 to 50 μm.

As shown in FIG. 9 , the lower sheet 200 and the upper sheet 300 have metal layers 201 and 301 and sealing layers 202 and 302 formed on edges of the metal layer, and the sealing layer inside the sealing layer. It may include grooves 213 and 313 in which no layers are formed, and further include adhesive layers 206 and 306 on top of the sealing layers 202 and 302 . The sealing layers 202 and 302 may be made of a polymer material that can be fused and sealed by heat, or may include one or more layers made of a heat-resistant material between layers made of a polymer material that can be fused and sealed by heat. In addition, the sealing layers 202 and 302 may be melted and sealed by thermal compression using a heating plate or a heating roller, but may be to form separate adhesive layers 206 and 306 to further improve adhesion. The adhesive used at this time is not limited as long as it is conventionally used in the relevant field, and any adhesive having excellent adhesion to the polymer material used for the sealing layer and chemical stability with the electrode assembly may be used without limitation. Specifically, for example, an acrylic resin, a urethane-based resin, an epoxy-based resin, etc. may be used, but the present invention is not limited thereto.

10 is a perspective view illustrating an embodiment of a lower sheet and an upper sheet continuously supplied from a roll in order to manufacture a plurality of electrochemical devices in the present invention. As shown in FIG. 10 , the metal layers 201 and 301 and the peripheral partition walls 211 and 311 on one surface of the metal layer, and spaces 213 and 313 for accommodating the electrode assembly inside the peripheral partition wall partition dividing The barrier ribs 212 and 312 may include sealing layers 202 and 302 forming a barrier rib pattern. FIG. 10 is an aspect to show that a plurality of spaces for accommodating the electrode assembly are formed, and is illustrated as having four spaces for convenience, but is not limited thereto. In addition, as shown in FIG. 1 or FIG. 17, the number of battery cells is cut as needed to form an electrochemical device composed of one battery cell ( FIGS. 1 and 18 ) or an electrochemical device composed of a plurality of battery cells ( FIG. 17 ). can be manufactured. In this case, the thickness W4 of the partition partition walls 212 and 312 may be thicker than the thickness W5 of the peripheral partition walls 211 and 311 to facilitate cutting. That is, it may be the electrochemical device 1000 composed of one battery cell, or the electrochemical device 2000 to which a plurality of battery cells are connected.

[Electrode assembly]

In one aspect of the present invention, when the electrode assembly is a set including a positive electrode and a negative electrode, one or more sets may be stacked. It may also include one or more gel polymer electrolyte layers or one or more separators between the positive electrode and the negative electrode. Alternatively, it may include a bipolar type electrode in which a positive electrode and a negative electrode are formed on both sides on one current collector.

In one aspect of the present invention, the electrode assembly includes a positive electrode and a negative electrode, and at least one of the positive electrode and the negative electrode includes a gel polymer electrolyte including a cross-linked polymer matrix, a solvent, and a dissociable salt to form an electrode-electrolyte complex it could be That is, in the electrode assembly of the present invention, it is possible to inject a liquid electrolyte in a state in which the positive electrode, the separator and the negative electrode are stacked, but preferably by applying a gel polymer electrolyte composition to any one or more selected from the positive electrode and the negative electrode, the positive electrode It may be made of a composite or an anode-electrolyte composite, and since it can be manufactured by coating in this way, it has a characteristic that can be continuously manufactured.

In addition, in the electrode assembly of one aspect of the present invention, the positive electrode and the negative electrode may have substantially identical edges. The term “substantially” means that the error range is within ±10 μm. That is, the substantially coincident edge means that the edges are completely coincident or that the error range is within ±10 μm.

Also, in one aspect of the present invention, the electrode assembly further includes at least one separator between the positive electrode and the negative electrode, and the separator may have edges substantially coincident with the positive electrode and the negative electrode. In addition, when a separator is included between the positive electrode and the negative electrode as described above, the separator may include a liquid electrolyte or a gel polymer electrolyte.

The electrode assembly according to an aspect of the present invention can manufacture a positive electrode and a negative electrode by a coating method, and since the electrode assembly can be manufactured by a method such as punching in a state in which the positive electrode, the separator and the negative electrode are stacked, the positive electrode, the separator and the The size of the negative electrode may be substantially the same. Specifically, in a state in which the positive electrode and the separator are laminated, the gel polymer electrolyte composition is applied and cured to include the gel polymer electrolyte in the positive electrode and the separator, and the negative electrode is laminated thereto. Since it is manufactured using

<Anode>

In one aspect of the present invention, the positive electrode may be formed in various aspects, for example, an electrode made of only a current collector, an electrode coated with an active material layer including a positive electrode active material and a binder on the current collector, and a positive electrode on the current collector It may be selected from composite electrodes coated with a composite active material layer including an active material, a crosslinked polymer matrix, and a liquid electrolyte. More preferably, from the viewpoint of improving the conductivity of ions, the positive electrode may include a liquid electrolyte or a gel polymer electrolyte. In the case of an electrode including the active material layer, a liquid electrolyte or a gel polymer electrolyte is applied on the active material layer to partially or completely impregnate or to be included in the surface layer. In addition, when the cross-linked polymer matrix is formed, adhesion and interfacial adhesion with the gel polymer electrolyte layer can be further improved, so it is preferable, but not limited thereto.

More specifically, for example, the positive electrode includes i) an electrode-electrolyte composite coated with a gel polymer electrolyte on a current collector, ii) an active material layer including an electrode active material and a binder on the current collector, and on the active material layer An electrode-electrolyte composite coated with a gel polymer electrolyte, and iii) an electrode-electrolyte composite comprising a composite active material layer comprising an electrode active material, a cross-linked polymer matrix, a solvent and a dissociable salt on a current collector, and iv) above iii) It may be selected from an electrode-electrolyte composite in which a gel polymer electrolyte is applied on a composite active material layer of

More preferably, the positive electrode may be selected from ii) and iii).

The current collector is not limited as long as it is a substrate having excellent conductivity used in the relevant technical field, and may be made of one including any one selected from a conductive metal, a conductive metal oxide, and the like. In addition, the current collector may be in a form in which the entire substrate is made of a conductive material, or a conductive metal, a conductive metal oxide, a conductive polymer, or the like is coated on one or both surfaces of the insulating substrate. In addition, the current collector may be made of a flexible substrate, and can be easily bent to provide a flexible electronic device. In addition, it may be made of a material having a restoring force that returns to the original shape after bending. In addition, the current collector may be selected from the group consisting of a thin film form, a mesh form, an integrated form in which a thin film or mesh type current collector is laminated on one or both sides of a conductive substrate, and a metal-mesh composite. The metal-mesh composite is integrated by heat-compressing a thin-film metal and a mesh-shaped metal or polymer material, so that a metal thin film is inserted between the holes of the mesh and integrated so that the metal thin film does not break or crack even when bent. do. As described above, when the metal-mesh composite is used, it is more preferable to prevent cracks from occurring in the current collector during bending of the battery or during charging and discharging, but is not limited thereto. More specifically, for example, the current collector may be made of aluminum, stainless steel, copper, nickel, iron, lithium, cobalt, titanium, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and a composite thereof. , but is not limited thereto.

Aspect ii) of the positive electrode of the present invention may be one in which an active material layer is coated by applying a positive electrode active material composition including a positive electrode active material and a binder on a current collector. In addition, by applying a composition for forming a gel polymer electrolyte on the active material layer, the active material layer may be partially or completely coated by being impregnated into the inside of the active material layer, or may be coated on the surface to form a gel polymer electrolyte. More specifically, by coating a gel polymer electrolyte composition comprising a crosslinkable monomer and derivative thereof, an initiator and a liquid electrolyte on a positive electrode, and crosslinking it by applying ultraviolet radiation or heat to crosslink it, the liquid electrolyte and the like are uniformly distributed in the network structure of the crosslinked polymer matrix. It may be distributed, and the evaporation process of the solvent may be unnecessary. In addition, the crosslinked polymer matrix may have a semi-interpenetrating network (semi-IPN) structure by further including a linear polymer. A detailed description of the gel polymer electrolyte will be described in more detail below.

The current collector is the same as described above, and the positive electrode active material composition may be directly coated and dried on a current collector such as aluminum to form a positive electrode plate having a positive electrode active material layer formed thereon. At this time, the coating may be coated by not only coating methods such as bar coating, spin coating, slot die coating, dip coating, etc., but also printing methods such as inkjet printing, gravure printing, gravure offset, aerosol printing, stencil printing and screen printing.

Alternatively, the positive electrode active material composition may be cast on a separate support, and then a film obtained by peeling from the support may be laminated on the current collector to prepare a positive electrode having a positive electrode active material layer. The thickness of the positive electrode active material layer is not limited, but may be 0.01 to 500 μm, more specifically, 1 to 200 μm, but is not limited thereto.

The cathode active material composition is not limited, but may include a cathode active material, a binder, and a solvent, and may further include a conductive material.

The positive active material may be used without limitation as long as it is commonly used in the art. Specifically, for a lithium primary battery or a secondary battery, a compound capable of reversible intercalation and deintercalation of lithium (a lithiated intercalation compound) may be used. The positive active material of the present invention may be in the form of a powder.

Specifically, at least one of a complex oxide of lithium and a metal consisting of any one or a combination of two or more selected from cobalt, manganese, nickel, and the like may be used. Although not limited, as a specific example, a compound represented by any one of the following formulas may be used. Li _a A _1-b R _b D ₂ (wherein 0.90 ≤ a ≤ 1.8 and 0 ≤ b ≤ 0.5); Li _a E _1-b R _b O _2-c D _c (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, and 0 ≤ c ≤ 0.05); LiE _2-b R _b O _4-c D _c (wherein 0 ≤ b ≤ 0.5 and 0 ≤ c ≤ 0.05); Li _a Ni _1-bc Co _b R _c D _α (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α ≤ 2); Li _a Ni _1-bc Co _b R _c O _2-α Z _α (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α <2); Li _a Ni _1-bc Co _b R _c O _2-α Z ₂ (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α <2); Li _a Ni _1-bc Mn _b R _c D _α (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α ≤ 2); Li _a Ni _1-bc Mn _b R _c O _2-α Z _α (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α <2); Li _a Ni _1-bc Mn _b R _c O _2-α Z ₂ (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α <2); Li _a Ni _b E _c G _d O ₂ (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5 and 0.001 ≤ d ≤ 0.1); Li _a Ni _b Co _c Mn _d G _e O ₂ (wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.5 and 0.001 ≤ e ≤ 0.1); Li _a NiG _b O ₂ (wherein 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); Li _a CoG _b O ₂ (wherein 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); Li _a MnG _b O ₂ (wherein 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); Li _a Mn ₂ G _b O ₄ (in the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); QO ₂ ; QS ₂ ; LiQS ₂ ; V ₂ O ₅ ; LiV ₂ O ₅ ; LiTO ₂ ; LiNiVO ₄ ; Li _(3-f) J ₂ (PO ₄ ) ₃ (0 ≤ f ≤ 2); Li _(3-f) Fe ₂ (PO ₄ ) ₃ (0 ≤ f ≤ 2); and LiFePO ₄ .

In the above formula, A is Ni, Co, Mn, or a combination thereof; R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P or a combination thereof; E is Co, Mn, or a combination thereof; Z is F, S, P or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V or a combination thereof; Q is Ti, Mo, Mn, or a combination thereof; T is Cr, V, Fe, Sc, Y or a combination thereof; J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

Of course, a compound having a coating layer on the surface of the compound may be used, or a mixture of the compound and a compound having a coating layer may be used. The coating layer is a coating element compound, and may include oxide, hydroxide, oxyhydroxide of the coating element, oxycarbonate of the coating element, or hydroxycarbonate of the coating element. The compound constituting these coating layers may be amorphous or crystalline. As the coating element included in the coating layer, Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof may be used. In the coating layer forming process, any coating method may be used as long as it can be coated by a method that does not adversely affect the physical properties of the positive electrode active material by using these elements in the compound, for example, spray coating, dipping, etc. Since it is a content that can be well understood by those engaged in the field, a detailed description will be omitted.

Although not limited, the positive active material may be included in an amount of 20 to 99% by weight, more preferably 30 to 95% by weight of the total weight of the composition. In addition, the average particle diameter may be 0.001 to 50 ㎛, more preferably 0.01 to 20 ㎛, but is not limited thereto.

The binder serves to adhere the positive active material particles well to each other and also to fix the positive active material to the current collector. It can be used without limitation as long as it is conventionally used in the relevant field, and representative examples include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, and ethylene oxide. Polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc. Alternatively, two or more types may be mixed and used, but the present invention is not limited thereto. Although not limited, the content of the binder may be 0.1 to 20% by weight, more preferably 1 to 10% by weight of the total weight. In the above range, an amount sufficient to act as a binder is not limited thereto.

The solvent may be any one or a mixed solvent of two or more selected from N-methyl pyrrolidone, acetone, and water, but is not limited thereto, and can be used as long as it is commonly used in the art. The content of the solvent is not limited, and may be used without limitation as long as the amount is sufficient to be applied on the positive electrode current collector in a slurry state.

In addition, the positive electrode active material composition may further include a conductive material.

The conductive material is used to impart conductivity to the electrode, and may be used without limitation as long as it does not cause a chemical change in the configured battery and is an electronically conductive material. Specifically, for example, natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon nanotubes, carbon-based materials such as carbon fibers; Metal-based substances, such as metal powders, such as copper, nickel, aluminum, and silver, or a metal fiber; conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material including a mixture thereof may be used, and may be used alone or in combination of two or more.

The content of the conductive material may include 0.1 to 20% by weight, more specifically 0.5 to 10% by weight, and more specifically 1 to 5% by weight of the cathode active material composition, but is not limited thereto. In addition, the average particle diameter of the conductive material may be 0.001 ~ 1000 ㎛, more specifically 0.01 ~ 100 ㎛, but is not limited thereto.

The gel polymer electrolyte composition may be coated on a positive electrode by a printing method such as roll-to-roll printing, inkjet printing, gravure printing, gravure offset, aerosol printing, and screen printing to enable continuous production. The gel polymer electrolyte may be one in which a crosslinkable monomer and a derivative thereof are photocrosslinked or thermally crosslinked by an initiator to form a crosslinked polymer matrix. By crosslinking, the mechanical strength and structural stability of the gel polymer electrolyte layer are improved, and when combined with the positive electrode of the above-described embodiment, the structural stability of the interface between the gel polymer electrolyte layer and the positive electrode can be further improved.

The gel polymer electrolyte composition preferably has a viscosity suitable for the printing process, and specifically, for example, a viscosity measured using a Brookfield viscometer at 25° C. is 0.1 to 10,000,000 cps, more preferably 1.0 to 1,000,000 cps, more preferably It may be from 1.0 to 100,000 cps, and it is preferable because it is a viscosity suitable for application to the printing process in the above range, but is not limited thereto.

The gel polymer electrolyte composition may include 1 to 50% by weight, specifically 2 to 40% by weight of a crosslinkable monomer and a derivative thereof, among 100% by weight of the total composition, but is not limited thereto. The initiator may be 0.01 to 50% by weight, specifically 0.01 to 20% by weight, more specifically 0.1 to 10% by weight, but is not limited thereto. The liquid electrolyte may be included in an amount of 1 to 95% by weight, specifically 1 to 90% by weight, more specifically 2 to 80% by weight, but is not limited thereto.

The crosslinkable monomer may be a monomer having two or more functional groups or a mixture of a monomer having two or more functional groups and a monomer having one functional group, and any monomer capable of photocrosslinking or thermal crosslinking may be used without limitation. .

Specifically, as the monomer having two or more functional groups, for example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane ethoxylate It may be any one or a mixture of two or more selected from triacrylate, trimethylolpropane ethoxylate trimethacrylate, bisphenol ethoxylate diacrylate, bisphenol ethoxylate dimethacrylate, and the like.

In addition, as the monomer having one functional group, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethylene glycol methyl ether acrylate, ethylene glycol methyl ether methacrylate, acrylo It may be any one or a mixture of two or more selected from nitrile, vinyl acetate, vinyl chloride and vinyl fluoride.

As the initiator, any photoinitiator or thermal initiator commonly used in the art may be used without limitation.

The liquid electrolyte may include a dissociable salt and a solvent.

The dissociable salt is not limited, but specifically, for example, lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluoroantimonate (LiSbF ₆ ), lithium hexafluoroacetate (LiAsF ₆ ), lithium difluoromethanesulfonate (LiC ₄ F ₉ SO ₃ ), lithium perchlorate (LiClO ₄ ), lithium aluminate (LiAlO ₂ ), lithium tetrachloroaluminate (LiAlCl ₄ ), lithium chloride (LiCl) , lithium iodide (LiI), lithium bisoxalatoborate (LiB(C ₂ O ₄ ) ₂ ), lithium trifluoromethanesulfonylimide (LiN(C _x F _2x+1 SO ₂ )(C _y F _{2y+ 1} SO ₂ ) (where x and y are natural numbers) and derivatives thereof may be any one or a mixture of two or more. The concentration of the dissociable salt is 0.1 to 10.0 M, more specifically 1 to 5 M may be, but is not limited thereto.

The solvent is any one or a mixture of two or more selected from organic solvents such as carbonate-based solvents, nitrile-based solvents, ester-based solvents, ether-based solvents, ketone-based solvents, glyme-based solvents, alcohol-based solvents and aprotic solvents, and water. may be using

In addition, the crosslinked polymer matrix of the gel polymer electrolyte may have a semi-interpenetrating network (semi-IPN) structure by further including a linear polymer. In this case, the positive electrode-electrolyte assembly has excellent flexibility, and exhibits strong resistance to stress such as bending when used as a battery, so that the battery can be driven normally without performance degradation. Therefore, application to a flexible battery or the like may be more advantageous.

The linear polymer may be used without limitation as long as it is easily mixed with the crosslinkable monomer and can be impregnated with a liquid electrolyte. Specifically, for example, polyvinylidene fluoride (Poly (vinylidene fluoride), PVdF), polyvinylidene fluoride hexafluoropropylene (Poy (vinylidene fluoride)-co-hexafluoropropylene, PVdF-co-HFP), polymethyl Any one selected from methacrylate (Polymethylmethacryalte, PMMA), polystyrene (PS), polyvinylacetate (PVA), polyacrylonitrile (PAN) and polyethylene oxide (PEO) or the like It may be a combination of two or more, but is not necessarily limited thereto.

The linear polymer may be included in an amount of 1 to 90 wt% based on the weight of the crosslinked polymer matrix. Specifically, it may be included in an amount of 1 to 80% by weight, 1 to 70% by weight, 1 to 60% by weight, 1 to 50% by weight, 1 to 40% by weight, 1 to 30% by weight. That is, when the polymer matrix has a semi-interpenetrating network (semi-IPN) structure, the crosslinkable polymer and the linear polymer may be included in a weight ratio of 99: 1 to 10: 90. When the linear polymer is included in the above range, the crosslinked polymer matrix may secure flexibility while maintaining appropriate mechanical strength. Accordingly, when applied to a flexible battery, stable battery performance can be realized even when the shape is deformed by various external forces, and the risk of battery ignition, explosion, etc. that may be caused by the shape deformation of the battery can be suppressed.

In addition, the gel polymer electrolyte composition may further include inorganic particles if necessary. The inorganic particles may enable printing by controlling rheological properties such as viscosity of the gel polymer electrolyte composition. The inorganic particles may be used to improve ionic conductivity and mechanical strength of the electrolyte, and may be porous particles, but is not limited thereto. For example, metal oxides, carbon oxides, carbon-based materials, organic-inorganic composites, etc. may be used, and may be used alone or in combination of two or more. More specifically, for example, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO ₂ , SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , and SiC may be any one or a mixture of two or more selected. Although not limited, by using the inorganic particles, it is possible to improve the thermal stability of the electrochemical device because it has high affinity with the organic solvent and is also very thermally stable.

The average diameter of the inorganic particles is not limited, but may be 0.001 μm to 10 μm. Specifically, it may be 0.1 to 10 μm, more specifically 0.1 to 5 μm. When the average diameter of the inorganic particles satisfies the above range, excellent mechanical strength and stability of the electrochemical device can be realized.

The content of the inorganic particles in the gel polymer electrolyte composition may be 1 to 50% by weight, more specifically 5 to 40% by weight, and more specifically 10 to 30% by weight, and the above-described viscosity range of 0.1 to 10,000,000 cps, more preferably 1.0 ~ 1,000,000 cps, more preferably, may be used in an amount that satisfies 1.0 ~ 100,000 cps, but is not limited thereto.

Next, aspect iii) of the positive electrode of the present invention may be a composite electrode in which a composite active material layer including a positive electrode active material, a crosslinked polymer matrix, a solvent, and a dissociable salt is coated on a current collector. At this time, since the current collector and the positive electrode active material are the same as described above, further description is omitted.

The composite active material layer may be one in which a crosslinkable monomer and a derivative thereof are photocrosslinked or thermally crosslinked by an initiator to form a crosslinked polymer matrix.

Therefore, the composite active material layer is formed by coating a composite active material composition including a crosslinkable monomer and derivatives thereof, an initiator, a positive electrode active material, and a liquid electrolyte on a current collector, and crosslinking it by applying ultraviolet radiation or heat to crosslink the positive electrode in the network structure of the crosslinked polymer matrix. The active material, the liquid electrolyte, etc. may be uniformly distributed, and the evaporation process of the solvent may be unnecessary. At this time, the coating is coated not only by coating methods such as bar coating and spin coating, but also by printing methods such as roll-to-roll printing, inkjet printing, gravure printing, gravure offset, aerosol printing, stencil printing, and screen printing to enable continuous production. it could be

Alternatively, the composite active material composition may be cast on a separate support, and then a film obtained by peeling from the support may be laminated on the current collector to prepare a positive electrode having a composite active material layer. The thickness of the composite active material layer is not limited, but may be 0.01 to 500 μm, more specifically 0.1 to 200 μm, but is not limited thereto.

One aspect of the composite active material composition may be comprised of 1 to 50% by weight, specifically 1 to 40% by weight, more specifically 2 to 30% by weight of a crosslinkable monomer and derivatives thereof, among 100% by weight of the total, It is not limited. The initiator may be 0.01 to 50% by weight, specifically 0.01 to 20% by weight, more specifically 0.1 to 10% by weight, but is not limited thereto. The content of the positive active material may be 1 to 95% by weight, specifically 1 to 90% by weight, and more specifically 5 to 80% by weight, but is not limited thereto. The liquid electrolyte may be included in an amount of 1 to 95% by weight, specifically 1 to 90% by weight, more specifically 2 to 80% by weight, but is not limited thereto. In addition, a conductive material may be further included as needed, and the content of the conductive material may be included in an amount of 0.1 to 20% by weight, specifically 1 to 10% by weight, but is not limited thereto.

The crosslinkable monomer may be a monomer having two or more functional groups or a mixture of a monomer having two or more functional groups and a monomer having one functional group, and any monomer capable of photocrosslinking or thermal crosslinking may be used without limitation. .

Specifically, as the monomer having two or more functional groups, for example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane ethoxylate It may be any one or a mixture of two or more selected from triacrylate, trimethylolpropane ethoxylate trimethacrylate, bisphenol ethoxylate diacrylate, bisphenol ethoxylate dimethacrylate, and the like.

In addition, as the monomer having one functional group, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethylene glycol methyl ether acrylate, ethylene glycol methyl ether methacrylate, acrylo It may be any one or a mixture of two or more selected from nitrile, vinyl acetate, vinyl chloride and vinyl fluoride.

As the initiator, any photoinitiator or thermal initiator commonly used in the art may be used without limitation.

The liquid electrolyte may include a dissociable salt and a solvent, and may have the same or different composition from the liquid electrolyte used in the gel polymer electrolyte.

The dissociable salt is not limited, but specifically, for example, lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluoroantimonate (LiSbF ₆ ), lithium hexafluoroacetate (LiAsF ₆ ), lithium difluoromethanesulfonate (LiC ₄ F ₉ SO ₃ ), lithium perchlorate (LiClO ₄ ), lithium aluminate (LiAlO ₂ ), lithium tetrachloroaluminate (LiAlCl ₄ ), lithium chloride (LiCl) , lithium iodide (LiI), lithium bisoxalatoborate (LiB(C ₂ O ₄ ) ₂ ), lithium trifluoromethanesulfonylimide (LiN(C _x F _2x+1 SO ₂ )(C _y F _{2y+ 1} SO ₂ ) (where x and y are natural numbers) and derivatives thereof may be any one or a mixture of two or more. The concentration of the dissociable salt is 0.1 to 10.0 M, more specifically 1 to 5 M may be, but is not limited thereto.

The solvent is any one or a mixture of two or more selected from organic solvents such as carbonate-based solvents, nitrile-based solvents, ester-based solvents, ether-based solvents, ketone-based solvents, glyme-based solvents, alcohol-based solvents and aprotic solvents, and water. may be using

Examples of the carbonate-based solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate ( EC), propylene carbonate (PC), and butylene carbonate (BC) can be used.

The nitrile-based solvent may be acetonitrile (acetonitrile), succinonitrile (succinonitrile), adiponitrile (adiponitrile, sebaconitrile), and the like.

Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethylethyl acetate, and methylpropio. Nate (methylpropionate), ethylpropionate (ethylpropionate), γ-butyrolactone (γ-butylolactone), decanolide (decanolide), valerolactone (valerolactone), mevalonolactone (mevalonolactone), caprolactone (caprolactone) ) may be used.

As the ether-based solvent, dimethyl ether, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. may be used, and as the ketone-based solvent, cyclohexanone, etc. this can be used

As the glyme-based solvent, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like may be used.

Ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol-based solvent, and the aprotic solvent is R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group, a double bond nitriles such as nitriles (which may contain aromatic rings or ether bonds), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, and the like can be used.

The solvent may be used alone or in combination of one or more, and when one or more of the solvents are mixed and used, the mixing ratio can be appropriately adjusted according to the desired battery performance, which can be widely understood by those in the art. .

<Cathode>

In one aspect of the present invention, the negative electrode may be formed in various aspects, and specifically, for example, an electrode consisting of only a current collector, an electrode coated with an active material layer including a negative active material and a binder on the current collector, and a current collector The composite electrode may be selected from a composite electrode coated with a composite active material layer including an anode active material, a crosslinked polymer matrix, and a liquid electrolyte thereon. More preferably, it may include a liquid electrolyte or a gel polymer electrolyte from the viewpoint of improving the conductivity of ions.

More specifically, for example, an electrode comprising only a current collector, i) an electrode-electrolyte composite coated with a gel polymer electrolyte on the current collector, ii) an active material layer comprising an electrode active material and a binder on the current collector, An electrode-electrolyte complex coated with a gel polymer electrolyte on an active material layer, and iii) an electrode-electrolyte complex comprising a composite active material layer comprising an electrode active material, a crosslinked polymer matrix, a solvent and a dissociable salt on a current collector it could be

More preferably, the negative electrode may be an electrode made of only a current collector or i) an electrode-electrolyte composite in which a gel polymer electrolyte is applied on the current collector.

The gel polymer electrolyte is the same as described above for the positive electrode.

In the negative electrode of the present invention, the current collector may be selected from the group consisting of a thin film form, a mesh form, an integrated form by stacking a thin film or mesh type current collector on one or both sides of a conductive substrate, and a metal-mesh composite. . The metal-mesh composite is integrated with the metal in the form of a thin film and the metal or polymer material in the form of a mesh by heat compression. As described above, when the metal-mesh composite is used, it is more preferable to prevent cracks from occurring in the current collector during bending of the battery or during charging and discharging, but is not limited thereto. The material may be made of a metal or polymer such as lithium metal, aluminum, aluminum alloy, tin, tin alloy, zinc, zinc alloy, lithium aluminum alloy and other lithium metal alloy, or a composite thereof.

The negative electrode of the present invention may be one in which the current collector in the form of a thin film or mesh is used as it is, or a current collector in the form of a thin film, mesh, or metal-mesh composite is laminated on a conductive substrate and integrated.

In addition, the current collector may be used without limitation as long as it is a substrate having excellent conductivity used in the art. Specifically, for example, it may be made of one including any one selected from a conductive metal, a conductive metal oxide, and the like. In addition, the current collector may be in a form in which the entire substrate is made of a conductive material, or a conductive metal, a conductive metal oxide, a conductive polymer, or the like is coated on one or both surfaces of the insulating substrate. In addition, the current collector may be made of a flexible substrate, and can be easily bent to provide a flexible electronic device. In addition, it may be made of a material having a restoring force that returns to the original shape after bending. More specifically, for example, the current collector may include aluminum, zinc, silver, tin, tin oxide, stainless steel, copper, nickel, iron, lithium, cobalt, titanium, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and It may be made of a complex thereof, and the like, but is not limited thereto.

Aspect ii) of the negative electrode of the present invention may be one in which an active material layer is coated by applying a negative electrode active material composition comprising a negative electrode active material and a binder on a current collector, and a gel polymer electrolyte composition is applied on the active material layer to the active material layer It may be an electrode-electrolyte composite in which a gel polymer electrolyte is formed on any one or more selected from the inside and the surface by being partially or fully impregnated.

The current collector is as described above, and the negative electrode active material composition may be directly coated and dried on a current collector such as a metal thin film to form a negative electrode plate having a negative electrode active material layer formed thereon. At this time, the coating may be coated by not only coating methods such as bar coating, spin coating, slot die coating, dip coating, etc., but also printing methods such as inkjet printing, gravure printing, gravure offset, aerosol printing, stencil printing and screen printing.

Alternatively, the negative electrode active material composition may be cast on a separate support, and then a film obtained by peeling from the support is laminated on the current collector to prepare a negative electrode having a negative electrode active material layer. The thickness of the anode active material layer is not limited, but may be 0.01 to 500 µm, more specifically 0.1 to 200 µm, but is not limited thereto.

The negative active material composition is not limited, but may include an anode active material, a binder, and a solvent, and may further include a conductive material.

The negative active material may be used without limitation as long as it is commonly used in the art. Specifically, for a lithium primary battery or a secondary battery, a compound capable of reversible intercalation and deintercalation of lithium (a lithiated intercalation compound) may be used. The negative active material of the present invention may be in the form of a powder.

More specifically, for example, it may be any one or a mixture of two or more selected from a metal alloyable with lithium, a transition metal oxide, a non-transition metal oxide, and a carbon-based material.

As the metal alloyable with lithium, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn may be used, However, the present invention is not limited thereto.

The transition metal oxide may be lithium titanium oxide, vanadium oxide, lithium vanadium oxide, or the like, and may be used alone or as a mixture of two or more thereof.

The non-transition metal oxide is Si, SiOx (0 < x < 2), Si-C composite, Si-Q alloy (wherein Q is an alkali metal, alkaline earth metal, group 13 to 16 element, transition metal, rare earth element, or these is a combination of, not Si), Sn, SnO2, Sn-C composite, Sn-R (wherein R is an alkali metal, alkaline earth metal, group 13 to 16 element, transition metal, rare earth element, or a combination thereof, Sn not) and the like. Specific elements of Q and R include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, It may be any one or a mixture of two or more selected from Sb, Bi, S, Se, Te and Po.

As the carbon-based material, any one or a mixture of two or more selected from crystalline carbon, amorphous carbon, and combinations thereof may be used. Examples of the crystalline carbon include graphite such as amorphous, plate-like, flake, spherical or fibrous natural graphite, artificial graphite, and the like, and examples of the amorphous carbon include soft carbon, hard carbon, mesophase pitch carbide, calcined coke and the like may be used, but is not limited thereto.

Although not limited, the negative active material may be included in an amount of 1 to 90% by weight, more preferably 5 to 80% by weight of the total weight of the composition. In addition, the average particle diameter may be 0.001 to 20 ㎛, more preferably 0.01 to 15 ㎛, but is not limited thereto.

The binder serves to adhere the negative active material particles well to each other and also to fix the negative active material to the current collector. It can be used without limitation as long as it is conventionally used in the relevant field, and representative examples include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, and ethylene oxide. Polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc. can be used. However, the present invention is not limited thereto.

The solvent may be any one or a mixed solvent of two or more selected from N-methyl pyrrolidone, acetone, and water, but is not limited thereto, and can be used as long as it is commonly used in the art.

In addition, the negative active material composition may further include a conductive material.

The conductive material is used to impart conductivity to the electrode, and any electronically conductive material can be used as long as it does not cause a chemical change in the battery configured, for example, natural graphite, artificial graphite, carbon black, acetylene black, ketjen black , carbon-based materials such as carbon fibers; Metal-based substances, such as metal powders, such as copper, nickel, aluminum, and silver, or a metal fiber; conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material including a mixture thereof may be used.

The content of the conductive material may be 1 to 90% by weight, more specifically 5 to 80% by weight of the anode active material composition, but is not limited thereto.

In addition, the average particle diameter of the conductive material may be 0.001 ~ 100 ㎛, more specifically 0.01 ~ 80 ㎛, but is not limited thereto.

Next, aspect iii) of the negative electrode of the present invention may be an electrode-electrolyte composite including a composite active material layer including a negative electrode active material, a crosslinked polymer matrix, and a liquid electrolyte on a current collector. At this time, since the current collector and the negative electrode active material are the same as described above, further description is omitted.

The crosslinked polymer matrix may be the same as or different from the polymer matrix used in the gel polymer electrolyte, but from the viewpoint of further improving adhesion and interfacial adhesion and further improving ionic conductivity, it is desirable to form the same polymer and crosslink density. desirable.

The composite active material layer may be one in which a crosslinkable monomer and a derivative thereof are photocrosslinked or thermally crosslinked by an initiator to form a crosslinked polymer matrix.

Accordingly, the composite active material layer is formed by coating a composite active material composition including a crosslinkable monomer and derivatives thereof, an initiator, a negative electrode active material, and a liquid electrolyte on a current collector, and crosslinking it by applying ultraviolet radiation or heat to crosslink it within the network structure of the matrix. The negative electrode active material, the liquid electrolyte, etc. may be uniformly distributed, and the evaporation process of the solvent may be unnecessary. At this time, the coating is coated by a printing method such as roll-to-roll printing, inkjet printing, gravure printing, gravure offset, aerosol printing and screen printing, as well as coating methods such as bar coating and spin coating, to enable continuous production. .

Alternatively, the composite active material composition may be cast on a separate support, and then a film obtained by peeling from the support may be laminated on the current collector to prepare a negative electrode having a composite active material layer. The thickness of the composite active material layer is not limited, but may be 0.01 to 500 μm, more specifically 0.1 to 200 μm, but is not limited thereto.

Since the composite active material composition is the same as the composition used for the positive electrode, a further description thereof will be omitted.

<Separator>

In one aspect of the present invention, the electrode assembly may further include one or more separators between the positive electrode and the negative electrode. The separator may be used from the viewpoint of improving mechanical strength, and may be impregnated with a liquid electrolyte to further improve ionic conductivity. Alternatively, a gel polymer electrolyte including a cross-linked polymer matrix, a solvent, and a dissociable salt may be included.

The separation membrane may be used without limitation as long as it is conventionally used in the relevant field. For example, it may be a woven fabric, a non-woven fabric, and a porous membrane. Also, they may be a multilayer film in which one layer or two or more are laminated. The material of the separator is not limited, but specifically, for example, polyethylene, polypropylene, polybutylene, polypentene, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polycarbonate, polyimide , polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene naphthalene, may be formed of any one or a mixture of two or more selected from the group consisting of copolymers thereof. In addition, the thickness is not limited, and may be in the range of 1 to 1000 μm, more specifically 10 to 800 μm, which is typically used in the art, but is not limited thereto.

In one aspect of the present invention, when the separator is included as described above, the electrode assembly may be prepared by placing the separator on the positive electrode, applying the gel polymer electrolyte composition, impregnating and curing, and laminating the negative electrode thereon. and is not limited thereto.

In one aspect of the present invention, the electrode assembly may include an electrolyte layer between the negative electrode and the positive electrode to prevent the positive electrode and the negative electrode from being electrically short-circuited. The electrolyte layer may be a gel polymer electrolyte layer. In addition, inorganic particles such as alumina and silica may be dispersed in the electrolyte layer to improve mechanical strength. In addition, the electrolyte layer may further include the above separator.

In one aspect of the present invention, the electrode assembly may have different electrolytes used for the positive electrode and the negative electrode. That is, any one or two or more of the components constituting the electrolyte layer may be different from each other or may have different contents.

In one aspect of the present invention, the electrode assembly may further include a gel polymer electrolyte layer having different compositions on the negative electrode and the positive electrode and facing each other. That is, it may include at least two or more heterogeneous gel polymer electrolytes having different compositions, and each gel polymer electrolyte may be integrated on the positive electrode and the negative electrode. The gel polymer electrolyte may not require a separate separator.

In one aspect of the present invention, the electrode assembly further comprises a first gel polymer electrolyte layer comprising a polymer matrix, a solvent, and a dissociable salt on the positive electrode, and a polymer matrix, the solvent and a dissociable salt on the negative electrode. A second gel polymer electrolyte layer is further included, wherein the first gel polymer electrolyte layer and the second gel polymer electrolyte layer have different compositions and may face each other.

The 'facing each other' includes directly facing each other in close contact, or facing spaced apart. In addition, 'different compositions' means that any one or two or more of the components constituting the first gel polymer electrolyte layer and the second gel polymer electrolyte layer are different in kind or different in content. More preferably, the composition may have different energy levels or different solubility parameters.

As such, by including at least two heterogeneous gel polymer electrolytes, the anode and the cathode have different chemical compositions to form a gel polymer electrolyte layer having different energy levels or solubility parameters, so that the liquid electrolyte components do not mix with each other. Therefore, it is possible to manufacture a battery having a heterogeneous electrolyte layer and to provide an electrochemical device having a wide range of potential windows. In addition, since the gel polymer electrolyte layer in contact with the positive electrode and the gel polymer electrolyte layer in contact with the negative electrode are separated without mixing with each other, different types of functional additives can be added, and when one type of existing electrolyte layer is used An electrochemical device having excellent oxidation/reduction stability can be provided, and performance such as lifespan characteristics of the electrochemical device can be improved.

More specifically, it is composed of an electrolyte having electrochemical properties optimized for each electrode (cathode and anode), and each electrolyte is physically and chemically bound by a polymer matrix to form a liquid electrolyte even when each gel polymer electrolyte layer is laminated with each other. It is possible to provide an electrochemical device in which components do not mix with each other. Specifically, the gel polymer electrolyte in contact with the negative electrode has a low reduction potential, and the gel polymer electrolyte in contact with the positive electrode uses a solid electrolyte with a high oxidation potential to have a wide potential window and suppress side reactions. It is possible to provide an electrochemical device that does not mix because the solubility parameters of the liver are different from each other. When manufactured in this way, an additional liquid electrolyte and a separator are not required, and by using a gel polymer electrolyte, an electrochemical device having better charge/discharge efficiency and lifespan characteristics of a battery can be provided compared to using a solid electrolyte. . In addition, it is possible to provide an electrochemical device with improved mechanical properties and stability against internal short circuit of the battery by further including a separator if necessary.

That is, one aspect of the electrode assembly of the present invention includes a positive electrode-electrolyte assembly coated with a first gel polymer electrolyte on a positive electrode, and a negative electrode-electrolyte assembly coated with a second gel polymer electrolyte on a negative electrode, wherein the first The gel polymer electrolyte and the second gel polymer electrolyte may have different compositions and may face each other.

In this case, the positive electrode and the negative electrode are each an electrode made of only a current collector, an electrode coated with an active material layer including an electrode active material and a binder on the current collector, and a composite active material comprising an electrode active material, a crosslinked polymer matrix, and a liquid electrolyte on the current collector It may be selected from the layer-coated composite electrode, as described above.

The positive electrode-electrolyte combination means that the positive electrode and the first gel polymer electrolyte layer are integrated. In this case, the first gel polymer electrolyte layer may be formed in one layer or in a form in which two or more layers are stacked, and the number of layers is not limited. In addition, being integrated means that they are superimposed on each other and physically bonded, and the first gel polymer electrolyte layer may be formed by coating on the positive electrode, and the coating solution is applied between the surface of the positive electrode and the pores by coating to make it more uniform and , can be closely formed.

The first gel polymer electrolyte layer is coated with a printing method such as roll-to-roll printing, inkjet printing, gravure printing, gravure offset, aerosol printing and screen printing on the positive electrode of the first gel polymer electrolyte composition to enable continuous production it could be The first gel polymer electrolyte layer may be one in which a crosslinkable monomer and a derivative thereof are photocrosslinked or thermally crosslinked by an initiator to form a crosslinked polymer matrix. By crosslinking, the mechanical strength and structural stability of the gel polymer electrolyte layer are improved, and when combined with the positive electrode of the above-described embodiment, the structural stability of the interface between the gel polymer electrolyte layer and the positive electrode can be further improved.

Therefore, the first gel polymer electrolyte layer is formed by coating a first gel polymer electrolyte composition comprising a crosslinkable monomer and derivative thereof, an initiator and a liquid electrolyte on a positive electrode, and crosslinking it by applying ultraviolet radiation or heat to form a crosslinked polymer matrix network structure. The liquid electrolyte and the like may be uniformly distributed therein, and the evaporation process of the solvent may be unnecessary. The first gel polymer electrolyte composition preferably has a viscosity suitable for the printing process, and specifically, for example, a viscosity measured using a Brookfield viscometer at 25° C. is 0.1 to 10,000,000 cps, more preferably 1.0 to 1,000,000 cps, More preferably, it may be from 1.0 to 100,000 cps, and since it is a viscosity suitable for application to a printing process in the above range, it is preferable, but is not limited thereto.

The first gel polymer electrolyte composition may include 1 to 50% by weight, specifically 2 to 40% by weight of a crosslinkable monomer and a derivative thereof, among 100% by weight of the total composition, but is not limited thereto. The initiator may be 0.01 to 50% by weight, specifically 0.01 to 20% by weight, more specifically 0.1 to 10% by weight, but is not limited thereto. The liquid electrolyte may be included in an amount of 1 to 95% by weight, specifically 1 to 90% by weight, more specifically 2 to 80% by weight, but is not limited thereto.

The types of the cross-linkable monomer and its derivatives, initiators, and liquid electrolytes are the same as those described above in the composite active material composition, and thus repeated descriptions will be omitted. In addition, the monomer used in the first gel polymer electrolyte composition may be of the same or different composition from the monomer used in the composite active material composition. More preferably, the adhesion may be further improved by using the same monomer.

In addition, the polymer matrix of the first gel polymer electrolyte layer may further include a linear polymer to have a semi-interpenetrating network (semi-IPN) structure. In this case, the first gel polymer electrolyte layer and the positive electrode-electrolyte combination have excellent flexibility, and when used as a battery, show strong resistance to stress such as bending, so that the battery can be driven normally without performance degradation. Therefore, it becomes possible to apply to a flexible battery or the like.

The linear polymer may be used without limitation as long as it is easily mixed with the crosslinkable monomer and can be impregnated with a liquid electrolyte. Specifically, for example, polyvinylidene fluoride (Poly (vinylidene fluoride), PVdF), polyvinylidene fluoride hexafluoropropylene (Poy (vinylidene fluoride)-co-hexafluoropropylene, PVdF-co-HFP), polymethyl Any one selected from methacrylate (Polymethylmethacryalte, PMMA), polystyrene (PS), polyvinylacetate (PVA), polyacrylonitrile (PAN) and polyethylene oxide (PEO) or the like It may be a combination of two or more, but is not necessarily limited thereto.

The linear polymer may be included in an amount of 1 to 90 wt% based on the weight of the crosslinked polymer matrix. Specifically, it may be included in an amount of 1 to 80% by weight, 1 to 70% by weight, 1 to 60% by weight, 1 to 50% by weight, 1 to 40% by weight, 1 to 30% by weight. That is, when the polymer matrix has a semi-interpenetrating network (semi-IPN) structure, the crosslinkable polymer and the linear polymer may be included in a weight ratio of 99: 1 to 10: 90. When the linear polymer is included in the above range, the crosslinked polymer matrix may secure flexibility while maintaining appropriate mechanical strength. Accordingly, when applied to a flexible battery, stable battery performance can be realized even when the shape is deformed by various external forces, and the risk of battery ignition, explosion, etc. that may be caused by the shape deformation of the battery can be suppressed.

In addition, the first gel polymer electrolyte composition may further include inorganic particles if necessary. The inorganic particles may be printed by controlling rheological properties such as viscosity of the first gel polymer electrolyte composition. The inorganic particles may be used to improve ionic conductivity and mechanical strength of the electrolyte, and may be porous particles, but is not limited thereto. For example, metal oxides, carbon oxides, carbon-based materials, organic-inorganic composites, etc. may be used, and may be used alone or in combination of two or more. More specifically, for example, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO ₂ , SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , and SiC may be any one or a mixture of two or more selected. Although not limited, by using the inorganic particles, it is possible to improve the thermal stability of the electrochemical device because it has high affinity with the organic solvent and is also very thermally stable.

The average diameter of the inorganic particles is not limited, but may be 0.001 μm to 10 μm. Specifically, it may be 0.1 to 10 μm, more specifically 0.1 to 5 μm. When the average diameter of the inorganic particles satisfies the above range, excellent mechanical strength and stability of the electrochemical device can be realized.

The content of the inorganic particles in the first gel polymer electrolyte composition may be 1 to 50% by weight, more specifically 5 to 40% by weight, more specifically 10 to 30% by weight, and the viscosity range described above 0.1 to 10,000,000 cps, more preferably 1.0 to 1,000,000 cps, more preferably, may be used in an amount that satisfies 1.0 to 100,000 cps, but is not limited thereto.

In addition, the first gel polymer electrolyte composition may further include a flame retardant if necessary, or a positive electrode heat inhibitor which is any one selected from succinonitrile and sebaconitrile or a mixture thereof. have. The content may be used in the range of 0.01 to 10% by weight, more specifically, 0.1 to 10% by weight of the first gel polymer electrolyte composition, but is not limited thereto.

The flame retardant may be used without limitation as long as it is a phosphate-based flame retardant commonly used in the relevant field, and the content thereof is in the range of 0.01 to 10% by weight of the first gel polymer electrolyte composition, more specifically 0.1 to 10% by weight. may be, but is not limited thereto.

The thickness of the first gel polymer electrolyte layer may be 0.01 μm to 500 μm. Specifically, it may be 5 to 100 μm. When the thickness of the first gel polymer electrolyte layer satisfies the above range, the performance of the electrochemical device may be improved while facilitating the manufacturing process, but is not limited thereto.

In addition, the first gel polymer electrolyte layer may have a gradient in which the crosslinking density decreases from the surface to the positive electrode. By forming a crosslinking density gradient, there is an effect that the charge/discharge cycle is further improved. In addition, when the crosslinking density is increased, the mechanical strength and structural stability are improved, but the ionic conductivity of the gel polymer electrolyte may be decreased due to the dense polymer structure. Not only stability but also ion conductivity can be solved.

In one aspect of the present invention, the first gel polymer electrolyte layer may have a multi-layer structure including two or more layers. More specifically, it may be a two-layer structure including a first layer and a second layer, or a three-layer structure, and the number of the layers is not limited.

In this case, the two or more layers may have the same or different compositions. More specifically, the first layer directly facing the positive electrode may have a gradient in which the crosslinking density or salt concentration is different from that of the second layer. Specifically, the second layer may have a higher crosslinking density or a higher salt concentration than the first layer. When the gradient is formed in this way, it is more preferable because the ionic conductivity can be further increased and side reactions can be suppressed.

In addition, if necessary, it may further include a separator between the two or more first gel polymer electrolyte layers.

In one aspect of the present invention, the negative electrode-electrolyte combination means that the negative electrode and the second gel polymer electrolyte layer are integrated. The negative electrode and the second gel polyelectrolyte layer may be separated, or a part or all of the second gel polyelectrolyte layer may be integrated into the negative electrode. In this case, the second gel polymer electrolyte layer may be formed in one layer or in a form in which two or more layers are stacked, and the number of layers is not limited. In addition, being integrated means that they are superimposed on each other and physically bonded, and the second gel polymer electrolyte layer may be formed by coating on the negative electrode, and the coating solution is applied between the negative electrode surface and the pores by coating to make it more uniform and , can be closely formed.

The second gel polymer electrolyte layer is coated with a printing method such as roll-to-roll printing, inkjet printing, gravure printing, gravure offset, aerosol printing and screen printing on the anode so that the second gel polymer electrolyte composition can be continuously produced. it could be

The second gel polymer electrolyte layer may be one in which a crosslinkable monomer and a derivative thereof are photocrosslinked or thermally crosslinked by an initiator to form a crosslinked polymer matrix. By crosslinking, the mechanical strength and structural stability of the gel polymer electrolyte layer are improved, and when combined with the negative electrode of the exemplified embodiment, the structural stability of the interface between the gel polymer electrolyte layer and the negative electrode is further improved.

Therefore, the second gel polymer electrolyte layer is formed by coating a second gel polymer electrolyte composition comprising a crosslinkable monomer and derivative thereof, an initiator and a liquid electrolyte on an anode, and crosslinking it by applying UV irradiation or heat to crosslink the network structure of the polymer matrix. The liquid electrolyte and the like may be uniformly distributed therein, and the evaporation process of the solvent may be unnecessary. The second gel polymer electrolyte composition preferably has a viscosity suitable for the printing process, and specifically, for example, a viscosity measured using a Brookfield viscometer at 25° C. is 0.1 to 10,000,000 cps, more preferably 1.0 to 1,000,000 cps, More preferably, it may be from 1.0 to 100,000, and a viscosity suitable for the printing process in the above range is preferable, but is not limited thereto.

The types and contents of the cross-linkable monomer and its derivatives, initiator, liquid electrolyte, and inorganic particles in the second gel polymer electrolyte composition are the same as those described above in the first gel polymer electrolyte composition, and thus additional descriptions will be omitted.

However, unlike the positive electrode, it may include a functional additive required for the negative electrode, and the second gel polymer electrolyte composition further includes a flame retardant if necessary, or any one selected from vinylene carbonate, ethylene fluoride carbonate, and catechol carbonate Or it may further include a SEI layer stabilizer that is a mixture thereof. Vinylene carbonate (VC) can be used to improve the charge/discharge life of the battery by forming a stable SEI layer during the initial charging process and suppressing the delamination of the carbon layer structure or direct reaction with the electrolyte. The content of the functional additive may be used in the range of 0.01 to 30% by weight, more specifically, 0.1 to 10% by weight of the first gel polymer electrolyte composition, but is not limited thereto.

The thickness of the second gel polymer electrolyte layer may be 0.01 μm to 500 μm. Specifically, it may be 1 to 100 μm, more preferably 5 to 50 μm. When the thickness of the second gel polymer electrolyte layer satisfies the above range, the performance of the electrochemical device can be improved while facilitating the manufacturing process, but is not limited thereto.

In addition, the second gel polymer electrolyte layer may have a gradient in which the crosslinking density decreases from the surface to the positive electrode.

In one aspect of the present invention, the second gel polymer electrolyte layer may have a multilayer structure including two or more layers. More specifically, it may have a two-layer structure or a three-layer structure, and the number of the layers is not limited.

In this case, the two or more layers may have the same or different compositions. More specifically, the first layer directly facing the negative electrode may have a gradient in which the crosslinking density or the salt concentration is different from that of the second layer facing the first layer. Specifically, the second layer may have a higher crosslinking density or a higher salt concentration than the first layer. When the gradient is formed in this way, it is more preferable because the ionic conductivity can be further increased and side reactions can be suppressed.

In addition, in the present invention, the first gel polymer electrolyte layer and the second gel polymer electrolyte layer are characterized in that they have different compositions.

More specifically, different types of crosslinked polymers are used, different types of organic solvents are used, different types of dissociable salts are used, or functional additives are added, or different compositions are used to have different energy levels. have. Accordingly, it is possible to provide a potential window of a wide range. More specifically, the first gel polymer electrolyte layer coupled to the positive electrode is formulated to have a high HOMO (Highest occupied molecular orbital) energy level, and the second gel polymer electrolyte layer coupled to the negative electrode has low LUMO (Lowest unoccupied molecular orbital) energy. By composing the composition to have a level, it is possible to provide a wide range of potential windows without side reactions.

More specifically, the following formulas 1 and 2 may be satisfied.

|C _e | < |CE _H | [Equation 1]

|A _e | < |AE _L | [Equation 2]

In Equations 1 and 2, C _e is the energy level of the positive electrode active material, A _e is the energy level of the negative electrode active material, CE _H is the energy level of the HOMO of the first gel polymer electrolyte layer, and AE _L is the second gel polymer electrolyte It is the energy level of the LUMO of the layer.

In addition, the energy level difference between the first gel polymer electrolyte layer and the second gel polymer electrolyte layer may be 0.01 eV or more. More specifically, it may be 0.01 to 7 eV.

The energy level of HOMO is the molecular orbital with the highest energy that electrons can participate in bonding, and the energy level of LUMO indicates the molecular orbital with the lowest energy in the non-bonding region of electrons. HOMO and LUMO energy levels can be calculated using any method based on quantum mechanics, and representative methods include density functional theory (DFT) and ab initio molecular orbital method.

The energy level may be changed according to the type of salt, the concentration of the salt, and the type of the solvent.

In addition, in order to prevent the liquid electrolyte used in the first gel polyelectrolyte layer and the second gel polyelectrolyte layer from being mixed with each other, the first gel polyelectrolyte layer and the second gel polyelectrolyte layer have different solubility parameters from each other. It is preferable to consist of a composition.

More specifically, the first gel polymer electrolyte layer and the second gel polymer electrolyte layer have a solubility parameter difference of 0.1 MPa ^1/2 or more, more specifically 0.1-20 MPa ^1/2 , more preferably 1-20 MPa ^{1/ 2} , more preferably 2 to 20 MPa ^1/2 difference.

The solubility parameter may vary depending on the organic solvent used in the liquid electrolyte.

As a selection criterion for indicating that the solubility parameters are incompatible with each other, Charles M. Hansen's book (Charles M. Hansen, "Hansen Solubility Parameters: A User's Handbook, 2nd Edition", 2nd Ed, CRC Press, 2007) described in It can be calculated according to the method.

From this point of view, the first gel polymer electrolyte layer may include a carbonate-based organic solvent as a solvent, and the second gel polymer electrolyte layer may include an ether-based organic solvent as an organic solvent. More specifically, the carbonate-based solvent is dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene It may be any one or a mixture of two or more selected from carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). More specifically, it may be any one or a mixture of two or more selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate.

The ether-based solvent may be any one or a mixture of two or more selected from dimethyl ether, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran.

In addition, the first gel polymer electrolyte layer and the second gel polymer electrolyte layer may have different salt concentrations, and at least one of the first gel polymer electrolyte layer and the second gel polymer electrolyte layer has a salt concentration of 2 mol or more. it could be More preferably, the salt concentration of the second gel polymer electrolyte layer laminated on the negative electrode is higher than the salt concentration of the first gel polymer electrolyte layer, and more specifically, the salt concentration of the first gel polymer electrolyte layer is 0.1 to 2.5 mol. , the salt concentration of the second gel polymer electrolyte layer may be 2 moles or more, more specifically 3 to 10 moles. When the salt concentration of the second gel polymer electrolyte layer is high, the reduction potential is lowered, so that the energy level difference between the first gel polymer electrolyte layer and the second gel polymer electrolyte layer may become wider. In addition, as the concentration of the salt increases, the cohesive energy increases, which may increase the difference in solubility parameters between the first gel polymer electrolyte layer and the second gel polymer electrolyte layer.

In this case, even when the first gel polymer electrolyte and the second gel polymer electrolyte use the same solvent and the same salt and only the concentration of the salt is different, the energy level or solubility parameter may be different.

In a liquid electrolyte containing 1 mole of salt, which is generally used, there are many solvent molecules in a free state that do not participate in solvation, and solvent molecules that do not participate in solvation are easily decomposed electrochemically, so that the life of the battery resulting in deterioration of properties. On the other hand, since the present invention uses a high-concentration liquid electrolyte of 2 moles or more, the salt concentration is high, so that most solvents participate in solvation, and there are hardly any free-state solvent molecules that do not participate in solvation. Accordingly, it is possible to improve the lifespan characteristics of the battery.

Hereinafter, an aspect of the electrode assembly 100 of the present invention will be described in more detail with reference to FIGS. 11 to 15 . 11 to 15 illustrate one embodiment of the electrode assembly of the present invention, but is not limited thereto.

First, an aspect in which the positive electrode and the negative electrode, which are one aspect of the electrode assembly of the present invention, are set as one set will be described in more detail with reference to FIG. 11 . 11, the electrode assembly 100 of the present invention is a negative electrode 20 comprising a positive electrode 10 and a negative electrode collector 21 in which a positive electrode active material layer 12 is laminated on a positive electrode current collector 11. ), and may include an electrolyte layer 50 between the positive electrode and the negative electrode. The positive electrode current collector 11 and the negative electrode current collector 21 are the same as described above, and the positive electrode active material layer 12 includes an active material layer or a positive electrode active material including a positive electrode active material and a binder, a crosslinked polymer matrix, and a liquid electrolyte. It may be made of a composite active material layer.

In addition, as described above, the first gel polymer electrolyte layer may be laminated on the positive electrode, or may be partially or fully impregnated and integrated, and the second gel polymer electrolyte layer may be laminated on the negative electrode.

The electrolyte layer 50 may be a liquid electrolyte or a gel polymer electrolyte layer, but is not limited thereto. Also, although not shown, one or more separators may be further included in any one or both selected between the electrolyte layer 50 and the negative electrode 20 and between the electrolyte layer 50 and the positive electrode 10 .

As shown in FIG. 12 , the electrode assembly 100 of the present invention includes a positive electrode 10 in which a positive electrode active material layer 12 is laminated on a positive electrode current collector 11 , and a negative electrode 20 comprising a negative current collector 21 . ) and the separation membrane 30 may be included. The positive electrode current collector 11, the negative electrode current collector 21, and the separator 30 are the same as described above, and the positive electrode active material layer 12 is an active material layer or a positive electrode active material including a positive electrode active material and a binder, and a cross-linked polymer matrix. and a composite active material layer including a liquid electrolyte. In addition, as described above, the first gel polymer electrolyte layer may be laminated on the positive electrode, or may be partially or fully impregnated and integrated, and the second gel polymer electrolyte layer may be laminated on the negative electrode.

Also, although not shown, the separator may be impregnated with an electrolyte. The electrolyte may be a liquid electrolyte or a gel polymer electrolyte, but is not limited thereto.

As shown in FIG. 13 , the electrode assembly 100 of the present invention has a positive electrode 10 in which a positive electrode active material layer 12 is stacked on a positive electrode current collector 11 and a negative electrode active material layer on the negative current collector 21 . 22 includes the stacked negative electrode 20 , and may include an electrolyte layer 50 between the positive electrode and the negative electrode. The positive electrode current collector 11 and the negative electrode current collector 21 are the same as described above, and the positive electrode active material layer 12 and the negative electrode active material layer 22 are an active material layer or positive electrode active material including a positive electrode active material and a binder, crosslinking It may be made of a composite active material layer including a polymer matrix and a liquid electrolyte. In addition, as described above on the positive electrode, the first gel polymer electrolyte layer is laminated, or partially or fully impregnated and integrated, and the second gel polymer electrolyte layer is laminated, partially or fully impregnated on the negative electrode. It may be unified.

The electrolyte layer 50 may be a liquid electrolyte or a gel polymer electrolyte layer, but is not limited thereto. In addition, although not shown, one or more separators may be further included in any one or both selected between the electrolyte layer 50 and the negative electrode 20 and between the electrolyte layer 50 and the positive electrode 10 .

As shown in FIG. 14 , the electrode assembly 100 of the present invention includes a positive electrode 10 in which a positive electrode active material layer 12 is laminated on a positive electrode current collector 11 , and a negative electrode active material layer on the negative electrode current collector 21 . 22 may include the stacked negative electrode 20 and the separator 30 . The positive electrode current collector 11, the negative electrode current collector 21, and the separator 30 are as described above, and the positive electrode active material layer 12 and the negative electrode active material layer 22 are active material layers including a positive electrode active material and a binder. Alternatively, it may be composed of a composite active material layer including a positive electrode active material, a crosslinked polymer matrix, and a liquid electrolyte.

In addition, as described above on the positive electrode, the first gel polymer electrolyte layer is laminated, or partially or fully impregnated and integrated, and the second gel polymer electrolyte layer is laminated, partially or fully impregnated on the negative electrode. It may be unified.

Also, although not shown, the separator may be impregnated with an electrolyte. The electrolyte may be a liquid electrolyte or a gel polymer electrolyte, but is not limited thereto.

As shown in FIG. 15 , the electrode assembly 100 of the present invention includes a positive electrode 10 in which a positive electrode active material layer 12 is stacked on a positive electrode current collector 11 , and a negative electrode active material layer on a bipolar current collector 41 . (42) and a bipolar electrode 40 on which the positive electrode active material layer 43 is laminated, and a negative electrode 20 in which the negative electrode active material layer 22 is laminated on the negative electrode current collector 21, between the positive electrode and the bipolar electrode and The electrolyte layer 50 may be included between the negative electrode and the bipolar electrode. Also, although not shown, one or more separators may be further included between the positive active material layer 12 and the negative active material layer 42 and between the positive active material layer 43 and the negative active material layer 22 . The separator may be impregnated with an electrolyte. The electrolyte may be a liquid electrolyte or a gel polymer electrolyte, but is not limited thereto. In addition, one or more bipolar electrodes may be stacked, and the number is not limited. The positive electrode current collector 11 , the negative electrode current collector 21 , and the bipolar current collector 41 are the same as the current collector described above, and the positive electrode active material layers 12 and 43 and the negative electrode active material layers 22 and 42 are the positive electrode current collectors. An active material layer including an active material and a binder or a composite active material layer including a positive active material, a crosslinked polymer matrix, and a liquid electrolyte may be used.

In addition, as described above on the positive electrode, the first gel polymer electrolyte layer is laminated, or partially or fully impregnated and integrated, and the second gel polymer electrolyte layer is laminated, partially or fully impregnated on the negative electrode. It may be unified.

The electrolyte layer 50 may be a liquid electrolyte or a gel polymer electrolyte layer, but is not limited thereto. Also, although not shown, between the electrolyte layer 50 and the negative electrode 20, between the electrolyte layer 50 and the bipolar electrode 40, between the electrolyte layer 50 and the positive electrode 10, and the electrolyte layer 50 and one or more separators may be further included in any one or two or more selected between the bipolar electrode 40 and the bipolar electrode 40 .

[Manufacturing method]

Hereinafter, a method for manufacturing the electrochemical device of the present invention will be described in detail. The manufacturing method of the present invention has the advantage that a plurality of battery cells can be continuously manufactured at the same time, and a single electrochemical device as shown in FIGS. 1 to 6 can be easily manufactured by cutting. In addition, as shown in FIG. 17 , there is an advantage in that an electrochemical device having a plurality of cell regions can be easily manufactured.

As shown in FIGS. 10, 16 and 19 , a metal layer 201 and a peripheral partition 211 on one surface of the metal layer, and a space 213 for accommodating an electrode assembly inside the peripheral partition partition partitioning The lower sheet 200 including the sealing layer 202 forming the barrier rib pattern including the barrier ribs 212 is supplied, and the electrode assembly 100 is provided in the space 213 for accommodating the electrode assembly of the lower sheet 200 . ), supplying the upper sheet 300 having the same configuration as the lower sheet 200 or the upper sheet 300 including a metal layer without a sealing layer as shown in FIG. 19, and laminating to be sealed.

In this case, the electrode assembly 100 may have the same size as the positive electrode and the negative electrode, the separator, and the electrolyte. The same size means that the edges are substantially congruent, as described above. Also, in the electrode assembly 100, the size of the separator may be greater than or equal to the size of the negative electrode, and the size of the positive electrode may be equal to or smaller than the size of the negative electrode.

In one aspect of the present invention, the electrode assembly may be manufactured by punching in a state in which the positive electrode, the separator and the negative electrode continuously supplied from each roller are stacked, and the positive electrode, the separator and the negative electrode have substantially the same size. can More specifically, in a state in which the positive electrode and the separator are laminated, the gel polymer electrolyte composition is applied, impregnated and cured, the negative electrode is laminated, and the electrode assembly of a certain shape is manufactured by punching in the laminated state.

In addition, in one aspect of the present invention, the lower sheet and the upper sheet may be continuously supplied from the respective rollers, and the lamination may be using a conventional heating and pressing means 500 such as a heating plate or a heating roller. By the heating and pressure, the polymer material of the sealing layer is melted and adhered to each other and sealed, and the metal layer of the lower sheet and the metal layer of the upper sheet are in close contact with the current collector, which is the outermost layer of the electrode assembly, so that they can be electrically connected. The temperature and pressure at the time of heating and pressing are preferably a temperature higher than or equal to the melting point of the polymer material used for the sealing layer, and is not limited because it may vary depending on the type of the polymer material.

At this time, although not shown, if necessary, the step of applying any one or more selected from a conductive adhesive, a conductive adhesive and a conductive paste on the metal layer corresponding to the space 213 for accommodating the electrode assembly of the upper sheet and the lower sheet is further performed. may include. In addition, it may further include the step of applying an adhesive on the upper portion of the sealing layer if necessary.

Next, after being laminated past the heating and pressing means 500, the welding or soldering step using a welding means 401 to weld or solder a portion where the metal layer of the lower sheet and the upper sheet and the electrode assembly are in close contact with each other is included in the joint ( 400) may be formed. The welding may be formed in a spot or stripe shape by methods such as resistance welding, ultrasonic welding, and laser welding, but is not limited thereto. In the case of the soldering, a soldering paste may be further included in a portion where the metal layer and the electrode assembly are in close contact.

Next, including the step of cutting the portion sealed by the sealing layer using the cutting means 600 , as shown in FIGS. 1 to 6 , the electrochemical device 1000 including one battery cell may be manufactured. Also, as shown in FIG. 17 , an electrochemical device 2000 in which a plurality of battery cells are connected in parallel may be manufactured. At this time, the method for cutting is not limited as long as it is conventionally used in the relevant field, and specifically, for example, it may be made by laser cutting, mold punching, die cutting, etc. and is not limited.

The present invention is not limited to the above-described embodiments, and the scope of application is varied, and anyone with ordinary knowledge in the field to which the present invention pertains without departing from the gist of the present invention as claimed in the claims It goes without saying that various modifications are possible.

1000: electrochemical device
100: electrode assembly
10: positive electrode
20: cathode
11: positive electrode current collector
12: positive electrode active material layer
21: negative electrode current collector
22: anode active material layer
30: separator
40: bipolar electrode
41: bipolar current collector
42: anode active material layer
43: positive electrode active material layer
50: electrolyte layer
200: lower seat
300: upper seat
201, 301: metal layer
202, 302: sealing layer
203, 303: conductive layer
213, 313: grooves in which a sealing layer is not formed
304, 204: insulating layer
205, 305: grooves in which an insulating layer is not formed
206, 306: adhesive layer
211, 311: perimeter bulkhead
211, 212, 311, 312: partition bulkhead
213, 313: space for accommodating the electrode assembly
214: heat-sealable polymer material layer
215: heat-resistant material layer
400: junction
500: heating and pressing means
401: welding means
600: cutting means

Claims (32)

It is accommodated in a space in which the upper sheet and the lower sheet are integrated to face each other, and includes an electrode assembly including an anode, a cathode, and at least one separator between the anode and the cathode,
The upper sheet and the lower sheet include a metal layer,
At least one of the upper sheet and the lower sheet includes a sealing layer on the edge of the metal layer,
The current collector of the positive electrode and the current collector of the negative electrode of the electrode assembly are in close contact with the metal layer of the upper sheet and the metal layer of the lower sheet and are electrically connected,
In the electrode assembly, the size of the negative electrode and the separator are the same, and the size of the current collector and the active material layer of each electrode in the positive electrode and the negative electrode are the same, the electrochemical device. The method of claim 1,
The electrochemical device further comprising a bonding portion in at least any one portion of the portion in which the electrode assembly and the metal layer of the upper sheet and the lower sheet are in close contact. The method of claim 1,
The electrochemical device further comprising any one or more conductive layers selected from a conductive adhesive layer, a conductive adhesive layer, and a conductive paste layer between the electrode assembly and any one or more metal layers selected from the lower sheet and the upper sheet. The method of claim 1,
Any one or more selected from the upper sheet and the lower sheet further includes an insulating layer on an outermost layer, and a portion of the insulating layer is open. The method of claim 1,
The sealing layer is an electrochemical device made of a polymer material that can be fused by heat. The method of claim 1,
The sealing layer is an electrochemical device comprising one or more layers made of a heat-resistant material between layers made of a polymer material that can be fused by heat. The method of claim 1,
The electrochemical device further comprising an adhesive layer on the sealing layer. The method of claim 1,
The sealing layer is an electrochemical device that is formed along the periphery of the electrode assembly at the edge except for the portion where the electrode assembly is located. The method of claim 1,
Any one or more selected from the upper sheet and the lower sheet further includes an insulating layer on the outermost layer, and a part of the insulating layer is open,
At least one of the positive electrode and the negative electrode is an electrochemical device comprising a gel polymer electrolyte comprising a cross-linked polymer matrix, a solvent, and a dissociable salt. 10. The method of claim 9,
The positive electrode includes ii) an electrode-electrolyte composite comprising an active material layer including an electrode active material and a binder on a current collector, a gel polymer electrolyte is applied on the active material layer, and iii) an electrode active material, a cross-linked polymer on the current collector an electrode-electrolyte complex comprising a composite active material layer comprising a matrix, a solvent, and a dissociable salt;
The cathode is an electrochemical device selected from ii) to iii).
delete 11. The method of claim 10,
The active material layer and the composite active material layer is an electrochemical device that further comprises a conductive material. delete The method of claim 1,
The separator is an electrochemical device that substantially coincides with the edges of the anode and the cathode. The method of claim 1,
The separator is an electrochemical device comprising a gel polymer electrolyte comprising a cross-linked polymer matrix, a solvent, and a dissociable salt. 10. The method of claim 9,
The electrode assembly includes a first gel polymer electrolyte in the positive electrode, and a second gel polymer electrolyte in the negative electrode, wherein the first gel polymer electrolyte and the second gel polymer electrolyte are different from each other. 17. The method of claim 16,
The first gel polyelectrolyte and the second gel polyelectrolyte have a solubility parameter difference of 0.1 MPa ^1/2 or more. 17. The method of claim 16,
The first gel polymer electrolyte and the second gel polymer electrolyte have an energy level difference of 0.01 eV or more. 17. The method of claim 16,
The first gel polymer electrolyte and the second gel polymer electrolyte may further include any one or two or more additives selected from inorganic particles and flame retardants. 17. The method of claim 16,
The first gel polymer electrolyte further comprises a positive electrode heat inhibitor which is any one selected from succinonitrile and sebaconitrile or a mixture thereof,
The second gel polymer electrolyte is an electrochemical device further comprising an SEI layer stabilizer, which is any one selected from vinylene carbonate, ethylene fluoride carbonate, and catechol carbonate, or a mixture thereof. 10. The method of claim 9,
The crosslinked polymer matrix is an electrochemical device that further includes a linear polymer and has a semi-interpenetrating network (semi-IPN) structure. The method of claim 1,
The current collector of the positive electrode and the current collector of the negative electrode are each selectively selected from the group consisting of a thin film form, a mesh form, an integrated form by stacking a thin film or mesh type current collector on one or both sides of a conductive substrate, and a metal-mesh composite An electrochemical device that becomes The method of claim 1,
The electrochemical device is an electrochemical device in which one or two or more of the electrode assemblies are stacked. The method of claim 1,
The electrode assembly is an electrochemical device further comprising one or more bipolar electrodes. The method of claim 1,
The sealing layer further includes a plurality of partition barrier ribs so that a plurality of grooves in which the sealing layer is not formed are formed,
An electrochemical device having a plurality of cell regions by including a plurality of electrode assemblies in a space in which the upper sheet and the lower sheet are integrated to face each other. The method of claim 1,
The electrochemical device is an electrochemical device that is a primary battery or a secondary battery capable of an electrochemical reaction. 27. The method of claim 26,
The electrochemical device is a lithium primary battery, lithium secondary battery, lithium-sulfur battery, lithium-air battery, sodium battery, aluminum battery, magnesium battery, calcium battery, zinc battery, zinc-air battery, sodium-air battery, aluminum- An electrochemical device selected from the group consisting of an air battery, a magnesium-air battery, a calcium-air battery, a super capacitor, a dye-sensitized solar cell, a fuel cell, a lead storage battery, a nickel cadmium battery, a nickel hydrogen storage battery, and an alkaline battery. A lower sheet comprising a metal layer and a sealing layer forming a barrier rib pattern including a circumferential barrier rib on one surface of the metal layer and a partition barrier rib defining a space for accommodating an electrode assembly inside the circumferential barrier rib,
A space for accommodating the electrode assembly of the lower sheet includes an anode, a cathode, and at least one separator positioned between the anode and the cathode, the cathode and the separator have the same size, and in the electrodes of the anode and the cathode An electrode assembly having the same size as the current collector and the active material layer of each electrode is stacked,
A method of manufacturing an electrochemical device that is continuously manufactured, including the step of supplying and laminating an upper sheet including a metal layer. 29. The method of claim 28,
The electrode assembly is a method of manufacturing an electrochemical device manufactured by punching in a state in which the positive electrode, the separator and the negative electrode are stacked. 29. The method of claim 28,
After the lamination, the method of manufacturing an electrochemical device further comprising the step of forming a junction by welding or soldering a portion in which the metal layer of the lower sheet and the upper sheet and the electrode assembly are in close contact. 29. The method of claim 28,
The method of manufacturing an electrochemical device further comprising the step of applying at least one selected from a conductive adhesive, a conductive adhesive and a conductive paste on the metal layer of the lower sheet and the upper sheet. 29. The method of claim 28,
After the lamination, the method of manufacturing an electrochemical device further comprising the step of cutting the sealed portion by the sealing layer.

Images