KR20200099822A - Electrochemical device and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an electrochemical device and a method for manufacturing the same. More particularly, the present invention relates to an electrochemical device and a method for manufacturing the same, wherein, in an electrode assembly comprising a positive electrode, a separator and a negative electrode, at least two of the positive electrode, the separator and the negative electrode comprise gel polymeric electrolytes, and the gel polymeric electrolytes have different types and contents of monomers constituting cross-linking polymer matrixes, and at least one of the first electrolyte, the second electrolyte and the third electrolyte has a different ion conductivity. As the electrochemical device of the present invention comprises an electrolyte having a different ion conductivity in at least one of the positive electrode, the separator, and the negative electrode, the optimized ion flow can be provided to each electrode and the separator, and accordingly, there are more advantageous effects in the lifespan characteristics and stability improvement of the electrochemical device.

Description

Electrochemical device and manufacturing method thereof TECHNICAL FIELD

The disclosure of the present invention relates to an electrochemical device and a method of manufacturing the same. More specifically, in the electrode assembly consisting of a positive electrode, a separator, and a negative electrode, at least two or more of the positive electrode, the separator, and the negative electrode are made of a gel polymer electrolyte, and the gel polymer electrolytes each have different types or contents of monomers constituting the crosslinked polymer matrix. And, at least one or more selected from the first electrolyte, the second electrolyte and the third electrolyte relates to an electrochemical device having different ionic conductivity and a method of manufacturing the same. Since the electrochemical device of the present invention includes an electrolyte having a different ionic conductivity in at least one of the anode, the separator, and the cathode, it is possible to provide an optimized ion flow for each electrode and separator, and accordingly, the life characteristics of the electrochemical device And there is a more advantageous effect in improving safety.

The secondary battery is manufactured by mounting an electrode assembly composed of a negative electrode, a positive electrode, and a separator in a metal can such as a cylindrical or rectangular shape or a pouch-shaped case of an aluminum laminate sheet, and injecting an electrolyte into the electrode assembly.

As the electrolyte for the secondary battery, a liquid electrolyte obtained by dissolving a salt in a non-aqueous organic solvent is mainly used. However, such a liquid electrolyte has a high possibility of volatilization of an organic solvent, and causes various problems such as deterioration of the electrode material and leakage, making it difficult to implement various types of electrochemical devices with high stability. .

In recent years, in order to improve the stability problem of such a liquid electrolyte, a gel polymer electrolyte or a solid polymer electrolyte has been developed without a concern of leakage.

In general, a method of manufacturing a battery to which a gel polymer electrolyte is applied is to mount an electrode assembly inside a can or pouch-type case, and then prepare a precursor solution capable of forming a gel polymer matrix including an electrolyte salt, an electrolyte solvent, and a crosslinked polymer. After injection in batches, it is prepared by gelling through a specific temperature and time treatment.

When the gel polymer electrolyte is introduced by such a conventional method, it takes a long time for gelation, and only one electrolyte matrix is inevitably formed on each electrode and separator. In addition, there is a difficulty in impregnating a gel polymer matrix precursor solution into an electrode assembly composed of a high-density electrode for high energy density that has been recently applied.

In addition, when a gel polymer electrolyte or a liquid electrolyte is injected at one time in the same manner as above, there may be a problem that the electrolyte is not evenly impregnated to the inside, or due to the difference in energy levels between the positive electrode and the negative electrode, the electrolyte is subject to oxidation or reduction reactions, respectively. Participation causes side reactions, and accordingly, there is a problem that battery performance is deteriorated.

In order to suppress the side reaction of the electrolyte, it is necessary to use an electrolyte suitable for each of the positive electrode and the negative electrode, but it was impossible to inject a liquid electrolyte or a gel polymer electrolyte.

Korean Patent Registration No. 10-0525278 (2005.10.25)

An aspect of the present invention is to solve the problem that the same electrolyte is formed in both the positive electrode, the negative electrode, and the separator as a liquid electrolyte or a gel polymer electrolyte is injected, and a side reaction occurs in the positive electrode and the negative electrode. Specifically, one aspect of the present invention is that at least two or more of the electrolytes among the positive electrode, the separator, and the negative electrode are formed of a gel polymer electrolyte that can be formed by coating, and the gel polymer electrolytes each have different types or contents of monomers constituting the crosslinked polymer matrix. Accordingly, since the crosslinking density is different, it is intended to provide an electrochemical device capable of further improving battery performance by solving problems due to side reactions and providing optimized ion flow and physical properties to each electrode and separator.

In addition, an aspect of the present invention is to provide an electrochemical device having more excellent charging/discharging efficiency, life characteristics, and battery safety because it is possible to form a gel polymer electrolyte having a crosslinking density suitable for each of a positive electrode, a separator, and a negative electrode.

In addition, an aspect of the present invention is to provide an electrochemical device that can simply form a gel polymer electrolyte by a method such as coating, printing, or application, can be continuously produced, and can be easily controlled in thickness.

In addition, one aspect of the present invention is flexible by including a gel polymer electrolyte in both the anode, the separator, and the cathode, so that it can be applied to a flexible device, and can be applied to a curved surface other than a flat surface, and a method such as cutting. It is intended to provide an electrochemical device that can freely form the shape of the battery because it can form the shape of the battery.

One aspect of the present invention for achieving the above object is a positive electrode-electrolyte assembly comprising a first electrolyte on the positive electrode,

A cathode-electrolyte assembly comprising a second electrolyte on the cathode, and

Including a separator-electrolyte assembly including a third electrolyte on the separator,

At least two or more selected from the first electrolyte, the second electrolyte, and the third electrolyte are a crosslinked polymer matrix, a solvent, and a gel polymer electrolyte containing a dissociable salt, and each of the gel polymer electrolytes is a type of monomer constituting the crosslinked polymer matrix. Or the content is different,

At least one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte provides an electrochemical device having different ionic conductivity.

Another aspect of the present invention is a) coating and curing a first gel polymer electrolyte composition on a positive electrode to prepare a positive electrode-electrolyte assembly including a first electrolyte, and coating and curing a second gel polymer electrolyte composition on the negative electrode. Thus preparing a cathode-electrolyte assembly including a second electrolyte;

b) manufacturing an electrode assembly by laminating the anode-electrolyte assembly, the separator, and the cathode-electrolyte assembly; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including, wherein the first electrolyte and the second electrolyte each have a different type or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the second electrolyte and the liquid electrolyte is different in ionic conductivity. It provides a method of manufacturing an electrochemical device.

Another aspect of the present invention is a) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the third gel polymer electrolyte composition on the separator. Thereby preparing a separator-electrolyte assembly including a third electrolyte;

b) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including,

The first electrolyte and the third electrolyte are each different in type or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the third electrolyte and the liquid electrolyte is different in ionic conductivity. Provides a method of manufacturing a device.

Another aspect of the present invention is a) coating and curing a second gel polymer electrolyte composition on a negative electrode to prepare a negative electrode-electrolyte assembly including a second electrolyte, and coating and curing a third gel polymer electrolyte composition on a separator. Thereby preparing a separator-electrolyte assembly including a third electrolyte;

b) manufacturing an electrode assembly by laminating the anode, the separator-electrolyte assembly, and the cathode electrolyte assembly; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including,

The second electrolyte and the third electrolyte are each different in type or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte and the liquid electrolyte is different in ionic conductivity. Provides a method of manufacturing a device.

Another aspect of the present invention is a) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the second gel polymer electrolyte composition on the negative electrode. Preparing a negative electrode-electrolyte assembly including a second electrolyte, and applying and curing a third gel polymer electrolyte composition on the separation membrane to prepare a separation membrane-electrolyte assembly including a third electrolyte; And

B) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly;

Including,

At least one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte differ in the type or content of the monomers constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte, and the liquid electrolyte It provides a method of manufacturing an electrochemical device that has different ionic conductivity.

The electrochemical device according to an aspect of the present invention may provide a gel polymer electrolyte having an optimized crosslinking density for each of the anode, the separator, and the cathode, and accordingly, the electrochemical device by controlling the ion flow optimized for each electrode and the separator. There is a more advantageous effect in improving the life characteristics and safety of the device.

In addition, the gel polymer electrolyte according to an aspect of the present invention is characterized by easy impregnation into a high-density electrode for high energy density with a porosity of 20% or less due to its inherent rheological properties having a viscosity that can be applied directly to the electrode. There is this.

In addition, by using a gel polymer electrolyte for at least one selected from the positive electrode, the separator and the negative electrode, not only coating processes such as bar coating, spin coating, slot die coating, dip coating and spray coating, but also roll-to-roll printing, inkjet printing, It can be applied in a printing process such as gravure printing, gravure offset, aerosol printing, stencil printing, and screen printing, and can be continuously manufactured, thereby improving productivity. In addition, the gel polymer electrolyte layer may be uniformly and closely contacted with the anode, the separator, or the cathode, and may be uniformly impregnated to the central portion.

In addition, since the gel polymer electrolyte layer can be formed by direct application to the electrode, the performance of the electrochemical device is improved by stabilizing the interface between the electrode and the gel polymer electrolyte layer. When applied to the flexible battery, the shape change due to various external forces It is possible to implement a stable battery performance, there is an effect of suppressing the risk that may be caused by the shape deformation of the battery.

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

In addition, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. The terms used in the description in the present invention are merely intended to effectively describe specific embodiments and are not intended to limit the present invention.

In addition, the singular form used in the specification and the appended claims may be intended to include the plural form unless otherwise indicated in the context.

In the present invention,'electrode assembly' means that the anode, the separator, and the cathode are stacked in a stacked or jelly roll state, and refers to a state before being sealed with a packaging material.

In the present invention, "electrochemical device" means a state in which the electrode assembly is sealed with a packaging material and can be used as a battery.

In the present invention, for convenience, the electrolyte formed on the positive electrode is expressed as the first electrolyte, the electrolyte formed on the negative electrode is the second electrolyte, and the electrolyte formed on the separator is expressed as a third electrolyte, but at least one of them is excluded. It may be the same electrolyte.

That is, specifically, for example, two of the first electrolyte, the second electrolyte, and the third electrolyte may be a gel polymer electrolyte, and the other may be a liquid electrolyte. In this case, the two gel polymer electrolytes may have different ionic conductivity, and one of the gel polymer electrolytes may have the same ionic conductivity as the liquid electrolyte. Specifically, the type or content of monomers constituting the crosslinked polymer matrix of the gel polymer electrolyte may be different from each other, and thus ionic conductivity may be different.

In addition, the two gel polymer electrolytes may have different ionic conductivity, and the liquid electrolyte may also have different ionic conductivity than the two gel polymer electrolytes. Specifically, the type or content of monomers constituting the crosslinked polymer matrix of the gel polymer electrolyte may be different from each other, and thus ionic conductivity may be different.

In addition, the two gel polymer electrolytes may have the same ionic conductivity and different ionic conductivity of the gel polymer electrolyte and the liquid electrolyte.

In the present invention, the “electrolyte assembly” means that an electrolyte is applied or impregnated onto an anode, a separator, or a cathode to be integrated. In this case, the electrolyte may be a gel polymer electrolyte or a liquid electrolyte, and at least two of the anode, the separator, and the cathode may be a gel polymer electrolyte.

In the present invention, "different ionic conductivity" means that the ionic conductivity differs by 0.1 mS/cm or more. A method of measuring ionic conductivity will be described in more detail in the following examples.

In the present invention, it can be confirmed through X-ray photoelectron analysis that'the type or content of the monomer is different'. Specifically, when an electrolyte having a different type or content of monomers is applied or impregnated, a charging/discharging current is applied to separate the anode, the cathode, and the separator from the electrode assembly in which the initial formation process has been completed, and each is subjected to an X-ray photoelectron analyzer (X- ray Photoelectron Spectroscopy, K-Alpha, Thermo Fisher), and from the energy of photoelectrons escaped by X-rays irradiated to the electrolyte, the presence of elements in the polymer matrix and the analysis of the chemical bonding state The type or content of monomers can be distinguished.

In addition, if necessary, it can be confirmed through infrared spectroscopy, inductively coupled plasma mass analysis, and time-of-flight secondary ion mass analysis. The measurement method thereof will be described in more detail in the following examples.

In addition, in the present invention, the'gel polymer electrolyte' may be formed by coating and curing a gel polymer electrolyte composition including a crosslinkable monomer, an initiator, a dissociable salt, and a solvent. The difference in the type or content of the monomer means that the type or content of the monomer used in the gel polymer electrolyte composition is different.

Specifically, one aspect of the present invention is a positive electrode-electrolyte assembly comprising a first electrolyte on the positive electrode,

A cathode-electrolyte assembly comprising a second electrolyte on the cathode, and

Including a separator-electrolyte assembly including a third electrolyte on the separator,

At least two or more selected from the first electrolyte, the second electrolyte, and the third electrolyte are a crosslinked polymer matrix, a solvent, and a gel polymer electrolyte containing a dissociable salt, and each of the gel polymer electrolytes is a type of monomer constituting the crosslinked polymer matrix. Or the content is different,

At least one selected from the first electrolyte, the second electrolyte, and the third electrolyte is an electrochemical device having different ionic conductivity.

In one aspect of the present invention, two selected from the first electrolyte, the second electrolyte and the third electrolyte are gel polymer electrolytes, and the gel polymer electrolyte may include a crosslinked polymer matrix, a solvent, and a dissociable salt. Specifically, for example, two selected from the first electrolyte, the second electrolyte, and the third electrolyte may be a gel polymer electrolyte, and the other may be a liquid electrolyte.

In this case, the ionic conductivity between the two gel polymer electrolytes is different, and the liquid electrolyte may have the same ionic conductivity as any one of the gel polymer electrolytes. That is, the gel polymer electrolyte may include a crosslinked polymer matrix, a solvent, and a dissociable salt, and the gel polymer electrolytes may have different types or contents of monomers constituting the crosslinked polymer matrix.

Alternatively, the ionic conductivity between the two gel polymer electrolytes may be different, and the liquid electrolyte may also have different ionic conductivity from the two gel polymer electrolytes. That is, the gel polymer electrolyte may include a crosslinked polymer matrix, a solvent, and a dissociable salt, and the gel polymer electrolytes may have different types or contents of monomers constituting the crosslinked polymer matrix.

Alternatively, the ionic conductivity between the two gel polymer electrolytes may be the same, and the ionic conductivity of the gel polymer electrolyte and the liquid electrolyte may be different.

In one aspect of the present invention, the first electrolyte, the second electrolyte, and the third electrolyte are all gel polymer electrolytes, and the gel polymer electrolyte includes a crosslinked polymer matrix, a solvent, and a dissociable salt, and at least one of the gel polymer electrolytes One or more may have different types or contents of monomers constituting the crosslinked polymer matrix.

Specifically, for example, the gel polymer electrolyte of any one of the first electrolyte, the second electrolyte, and the third electrolyte may be different from the other two gel polymer electrolytes in the type or content of monomers forming the crosslinked polymer matrix. Accordingly, the crosslinked polymer matrix may have different ionic conductivity.

In addition, the first electrolyte, the second electrolyte, and the third electrolyte may have different types or contents of monomers constituting the crosslinked polymer matrix. Accordingly, the crosslinked polymer matrix may have different ionic conductivity.

In one aspect of the present invention, the crosslinked polymer matrix may have a semi-interpenetrating network (semi-IPN) structure further including a linear polymer.

In one aspect of the present invention, at least one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte may have a difference in ionic conductivity of 0.1 mS/cm or more.

In one aspect of the present invention, at least any one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte may have a different slope obtained from the Arrhenius plot of the temperature at 20 ~ 80 °C and the ion conductivity. . Since the slope of the Arrhenius plot refers to the activation energy for ion migration of the polymer matrix in the electrolyte, it is possible to grasp the difference in the type and content of the monomer from the difference in the slope.

In one aspect of the present invention, the ionic conductivity IC ₁ of the first electrolyte and the ionic conductivity IC ₂ of the second electrolyte may satisfy Equation 1 below.

[Equation 1]

IC ₁ -IC ₂ ≥ 0.1 mS/cm

In this case, more specifically, the ionic conductivity IC ₃ of the third electrolyte is IC ₂ ≥ IC ₃ may be.

In an aspect of the present invention, the ionic conductivity IC ₁ of the first electrolyte, the ionic conductivity IC ₂ of the second electrolyte, and the ionic conductivity IC ₃ of the third electrolyte may satisfy Equations 2 and 3 below.

[Equation 2]

IC ₁ -IC ₃ ≥ 0.1 mS/cm

[Equation 3]

IC ₂ -IC ₃ ≥ 0.1 mS/cm

In this case, the ionic conductivity between the first electrolyte and the second electrolyte may be the following IC ₁ ≥ IC ₂ , and more specifically IC ₁ -IC ₂ ≥ 0.1 mS/cm, but is not limited thereto.

In one aspect of the present invention, the type of the monomer is any one or a mixture of two or more selected from the group consisting of acrylate-based monomers, acrylic acid-based monomers, sulfonic acid-based monomers, phosphoric acid-based monomers, perfluorine-based monomers, and acrylonitrile-based monomers. It can be.

In one aspect of the present invention, the acrylate-based monomer is polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane ethoxylate triacrylate , In trimethylolpropane ethoxylate trimethacrylate, bisphenol ethoxylate diacrylate and bisphenol ethoxylate dimethacrylate, beta carboxyethyl acrylate, 2,4,6-tribromophenyl acrylate Is any one or a mixture of two or more selected,

The acrylic acid-based monomer is any one or a mixture of two or more selected from acrylic acid, methacrylic acid, methyl acrylic acid, methyl methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid and 2-trifluoromethylacrylic acid,

The sulfonic acid-based monomer is from sulfonic acid, sodium styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate and 3-sulfopropyl methacrylate. Is any one or a mixture of two or more selected,

The phosphoric acid-based monomer is any one or a mixture of two or more selected from phosphoric acid, bis(2-methacryloxyethyl)phosphate, phosphoric acid-2-hydroxyethylacrylate ester, and 2-(methacryloxy)ethylphosphate ,

The perfluorine-based monomers are hexafluoroisopropyl methacrylate, 1,1,3-hexafluorobutyl methacrylate, 1,1,7-dodecafluoroheptyl methacrylate, 2,2,2-trifluoroethyl methacrylate Any one or a mixture of two or more selected from acrylate, 1,1,5-octafluoropentyl methacrylate, pentafluorophenyl acrylate and 2,2,2-trifluoroethyl acrylate,

The acrylonitrile-based monomer may be one selected from acrylonitrile, 1-cyanovinyl acetate, and 2-cyanoethyl acrylate, or a mixture of two or more.

In one aspect of the present invention, the content of the monomer may be different from 0.5% by weight or more.

In one aspect of the present invention, the positive electrode may include a positive electrode active material layer, the negative electrode may include a negative electrode active material layer, and the positive electrode active material layer and the negative electrode active material layer may include pores.

In one aspect of the present invention, the porosity of the positive active material layer may be 5 to 30 vol%, and the porosity of the negative active material layer may be 10 to 35 vol%.

In one aspect of the present invention, the porosity of the positive active material layer may be 10 to 20 vol%, and the porosity of the negative active material layer may be 15 to 25 vol%.

In one aspect of the present invention, the positive electrode may include a positive electrode active material layer, the negative electrode may include a lithium metal layer, and the positive electrode active material layer may include pores.

In one aspect of the present invention, the porosity of the positive active material layer may be 5 to 30% by volume.

In one aspect of the present invention, the porosity of the positive active material layer may be 10 to 20% by volume.

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

In one aspect 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, a zinc-air battery, Selected from the group consisting of sodium-air cells, aluminum-air cells, magnesium-air cells, calcium-air cells, super capacitors, dye-sensitized solar cells, fuel cells, lead storage batteries, nickel cadmium batteries, nickel hydrogen storage batteries, and alkaline batteries. It may be of one kind.

Another aspect of the present invention is a method of manufacturing an electrochemical device, and the first aspect is

a) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the second gel polymer electrolyte composition on the negative electrode to include a second electrolyte Preparing a cathode-electrolyte assembly;

b) manufacturing an electrode assembly by laminating the anode-electrolyte assembly, the separator, and the cathode-electrolyte assembly; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including, wherein the first electrolyte and the second electrolyte each have a different type or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the second electrolyte and the liquid electrolyte is different in ionic conductivity. will be.

Another aspect of the present invention is a method of manufacturing an electrochemical device, and the second aspect is

a) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the third gel polymer electrolyte composition on the separator to include a third electrolyte Preparing a separator-electrolyte assembly;

b) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including,

Each of the first electrolyte and the third electrolyte has a different kind or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the third electrolyte, and the liquid electrolyte has different ionic conductivity.

Another aspect of the present invention is a method of manufacturing an electrochemical device, and the third aspect is

a) coating and curing the second gel polymer electrolyte composition on the negative electrode to prepare a negative electrode-electrolyte assembly including the second electrolyte, and coating and curing the third gel polymer electrolyte composition on the separator to include a third electrolyte Preparing a separator-electrolyte assembly;

b) manufacturing an electrode assembly by laminating the anode, the separator-electrolyte assembly, and the cathode electrolyte assembly; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including,

The second electrolyte and the third electrolyte are each different in type or content of a monomer constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte, and the liquid electrolyte has different ionic conductivity.

In one aspect of the present invention, the first gel polymer electrolyte composition and the second gel polymer electrolyte composition may have different types or contents of monomers.

In one aspect of the present invention, step b) is

b-1) preparing an electrode assembly by laminating the positive electrode or positive electrode-electrolyte assembly, the separator or separator-electrolyte assembly, and the negative electrode or negative electrode-electrolyte assembly and cutting them into a predetermined shape; or

b-2) manufacturing an electrode assembly by cutting the anode or the anode-electrolyte assembly, the separator or the separator-electrolyte assembly, and the cathode or cathode-electrolyte assembly into a predetermined shape, respectively, and stacking them;

It may be selected from.

Another aspect of the present invention is a method of manufacturing an electrochemical device, and the second aspect is

A) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the second gel polymer electrolyte composition on the negative electrode to include a second electrolyte Preparing a cathode-electrolyte assembly, and applying and curing a third gel polymer electrolyte composition on the separation membrane to prepare a separation membrane-electrolyte assembly including a third electrolyte; And

B) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly;

Including,

At least one selected from the first electrolyte, the second electrolyte, and the third electrolyte is different in the type or content of the monomers constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte, and the liquid electrolyte Silver ion conductivity is different.

In one aspect, step b) is

B-1) laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly and then cutting them into a predetermined shape; or

B-2) cutting the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly into a predetermined shape and then laminating them;

It may be selected from.

In one aspect, after the step b), c) sealing the electrode assembly with a packaging material; may further include.

Hereinafter, an aspect of the present invention will be described in more detail.

First, an electrochemical device according to an aspect of the present invention will be described in more detail.

An electrochemical device according to an aspect of the present invention includes an anode-electrolyte assembly including a first electrolyte on an anode, a cathode-electrolyte assembly including a second electrolyte on a cathode, and a separator including a third electrolyte on the separation membrane. -It contains an electrolyte conjugate.

At this time, at least two or more selected from the first electrolyte, the second electrolyte, and the third electrolyte are gel polymer electrolytes, and at least one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte have different ionic conductivity. Do.

Specifically, in the first aspect of the electrochemical device of the present invention, two of the first electrolyte, the second electrolyte, and the third electrolyte are a crosslinked polymer matrix, a solvent, and a gel polymer electrolyte containing a dissociable salt, and the other is a solvent and It may be a liquid electrolyte containing a dissociable salt. In this case, the two gel polymer electrolytes may have the same ionic conductivity, and the gel polymer electrolyte and the liquid electrolyte may have different ionic conductivity. Alternatively, the two gel polymer electrolytes may have different ionic conductivity from each other, and any one of the two gel polymer electrolytes may have the same ionic conductivity as the liquid electrolyte. Alternatively, the two gel polymer electrolytes may have different ionic conductivity from each other, and the liquid electrolyte may also have different ionic conductivity from the two gel polymer electrolytes.

More specifically for the first aspect, for example, the first electrolyte and the second electrolyte may be a gel polymer electrolyte, and the third electrolyte may be a liquid electrolyte. In this case, the gel polymer electrolyte of the first electrolyte and the gel polymer electrolyte of the second electrolyte may have different ionic conductivity, and the liquid electrolyte of the third electrolyte may also have different ionic conductivity from the first and second electrolytes. .

Alternatively, the first electrolyte and the second electrolyte may be a gel polymer electrolyte, and the third electrolyte may be a liquid electrolyte. At this time, the gel polymer electrolyte of the first electrolyte and the gel polymer electrolyte of the second electrolyte have different ionic conductivity, and the liquid electrolyte of the third electrolyte has the same ionic conductivity as any one of the first electrolyte and the second electrolyte. Can be.

Alternatively, the first electrolyte and the second electrolyte may be a gel polymer electrolyte, and the third electrolyte may be a liquid electrolyte. In this case, the gel polymer electrolyte of the first electrolyte and the gel polymer electrolyte of the second electrolyte may have the same ionic conductivity, and the liquid electrolyte of the third electrolyte may have different ionic conductivity from the first and second electrolytes. .

In a second aspect of the electrochemical device of the present invention, the first electrolyte, the second electrolyte, and the third electrolyte are all gel polymer electrolytes, and at least one of them may have different ionic conductivity.

More specifically with respect to the second aspect, for example, the first electrolyte, the second electrolyte, and the third electrolyte are all gel polymer electrolytes, and the ionic conductivity of the first electrolyte is the ions of the second electrolyte and the third electrolyte. It may be different from conductivity.

Alternatively, the first electrolyte, the second electrolyte, and the third electrolyte may all be gel polymer electrolytes, and the ionic conductivity of the second electrolyte may be different from that of the first and third electrolytes.

Alternatively, the first electrolyte, the second electrolyte, and the third electrolyte may all be gel polymer electrolytes, and the ionic conductivity of the third electrolyte may be different from that of the first and second electrolytes.

Alternatively, the first electrolyte, the second electrolyte, and the third electrolyte may all be gel polymer electrolytes, and the ionic conductivity of the first electrolyte, the second electrolyte, and the third electrolyte may all be different.

The above first to second aspects are only described to specifically illustrate one aspect of the present invention, and the disclosure of the present invention is not limited to the first to second aspects, and the first to second aspects It is obvious that various changes can be made with reference to the mode.

The difference in ionic conductivity between the gel polymer electrolytes in the first to second embodiments is that the gel polymer electrolyte of the present invention can be applied and cured by a coating method to form a gel polymer electrolyte. In addition, the difference in ionic conductivity between the gel polymer electrolytes can be achieved by varying the type or content of the monomers constituting the crosslinked polymer matrix.

The content of the monomer may be different from 0.5% by weight or more.

In one aspect of the present invention, the first electrolyte, the second electrolyte, and the third electrolyte may be a gel polymer electrolyte or a liquid electrolyte, and two or more of them may be a gel polymer electrolyte.

In addition, at least one or more have different ionic conductivity, and more specifically, the difference in ionic conductivity may be 0.1 mS/cm or more. When the difference in ionic conductivity is 0.1 mS/cm or more, charging/discharging efficiency and battery life are increased, and high battery safety can be secured at the same time.

In addition, at least one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte have different characteristics in the slope obtained from the Arrhenius plot of the temperature at 20 ~ 80 ℃ and the ion conductivity. When the slope of the Arrhenius plot is different, charging/discharging efficiency and battery life may increase, and at the same time, high battery safety may be secured.

The liquid electrolyte is not limited as long as it is a liquid electrolyte commonly used in the field, and may specifically include, for example, a solvent and a dissociable salt.

In addition, the gel polymer electrolyte may specifically include, for example, a crosslinked polymer matrix, a solvent, and a dissociable salt. In the gel polymer electrolyte, the gel polymer electrolyte composition is not only coating methods such as bar coating, spin coating, slot die coating, dip coating and spray coating, but also inkjet printing, gravure printing, gravure offset, aerosol printing, stencil printing, and screen printing, etc. It may be applied by a printing method of to enable continuous production.

In the gel polymer electrolyte, a crosslinkable monomer and a derivative thereof may be photocrosslinked or thermally crosslinked by an initiator to form a crosslinked polymer matrix. Specifically, coating a gel polymer electrolyte composition containing a crosslinkable monomer and a derivative thereof, an initiator, a solvent, and a dissociable salt, and crosslinking by applying UV irradiation or heat to include a solvent and a dissociable salt in the network structure of the crosslinkable polymer matrix. The liquid electrolyte may be uniformly distributed, and the evaporation process of the solvent may be unnecessary.

The gel polymer electrolyte composition preferably has a viscosity suitable for the printing process, and specifically, the 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 Specifically, it may be 1.0 to 100,000 cps, and it is preferable because it is a viscosity suitable for applying to a 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, based on 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, and more specifically 0.1 to 10% by weight, but is not limited thereto. The liquid electrolyte in which the solvent and the dissociable salt are mixed may be included in an amount of 1 to 95% by weight, specifically 1 to 90% by weight, and more specifically 2 to 80% by weight, but is not limited thereto.

The crosslinkable monomer may be used by mixing a monomer having two or more functional groups or 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. . More specifically, it may be one or a mixture of two or more selected from the group consisting of acrylate-based monomers, acrylic acid-based monomers, sulfonic acid-based monomers, phosphoric acid-based monomers, perfluorine-based monomers, and acrylonitrile-based monomers.

Specifically, as a monomer having two or more functional groups, for example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane ethoxylate Triacrylate, trimethylolpropane ethoxylate trimethacrylate, bisphenol ethoxylate diacrylate, bisphenol ethoxylate dimethacrylate, acrylic acid, beta carboxyethyl acrylate, sodium styrene sulfonic acid, 2 -Acrylamide-2-methylpropanesulphonic acid, 2-sulfoethylmethacrylate, 3-sulfopropylacrylate, 3-sulfopropylmethacrylate, bis(2-methacryloxyethyl)phosphate, phosphoric acid 2-hydroxyethyl acrylate ester, 2- (methacryloxy) ethyl phosphate, 2-cyanoethyl acrylate, 2,4,6-tribromophenyl acrylate, pentafluorophenyl acrylate and 2,2, It may be any one or a mixture of two or more selected from 2-trifluoroethyl acrylate.

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, and acrylo Nitrile, vinyl acetate, vinyl chloride, vinyl fluoride, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, 2-trifluoromethylacrylic acid, sulfonic acid, phosphoric acid, hexafluoroisopropyl Methacrylate, 1,1,3-hexafluorobutyl methacrylate, 1,1,7-dodecafluorheptylmethacrylate, 2,2,2-trifluoroethylmethacrylate and 1,1,5- It may be any one or a mixture of two or more selected from octafluoropentyl methacrylate and the like.

More specifically, the monomer may be any one or a mixture of two or more selected from trimethylolpropane ethoxylate triacrylate, acrylamide-2-methylpropane sulphonic acid, and phosphoric acid 2-hydroxyethyl acrylate ester. I can.

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

The liquid electrolyte is meant to contain 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 bisoxalato borate (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, etc. The concentration of the dissociable salt may be 0.1 to 10.0 M, more specifically 1 to 5 M It may be, but is not limited thereto.

More specifically, the dissociable salt may be any one or a mixture of two or more selected from lithium hexafluorophosphate, lithium bisoxalato borate, lithium trifluoromethanesulfonylimide, and derivatives thereof.

The solvent is any one or two or more mixed solvents 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 to use.

The carbonate-based solvents 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), butylene carbonate (BC), and the like can be used.

As the nitrile-based solvent, acetonitrile, succinonitrile, adiponitrile, sebaconitrile, or the like may be used.

As the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethyl ethyl acetate, methyl propio Methylpropionate, ethylpropionate, γ-butylolactone, decanolide, valerolactone, mevalonolactone, caprolactone ), etc. may be used.

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

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

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

The solvent may be used alone or in combination of one or more, and the mixing ratio in the case of using one or more mixtures may be appropriately adjusted according to the desired battery performance, which may be widely understood by those engaged in the field. .

More specifically, the solvent is dimethyl carbonate, ethylene carbonate, propylene carbonate, methylpropyl carbonate, methylethyl carbonate, succinonitrile, 1,3-dioxolane, dimethylacetamide, sulfolane and tetraethylene glycol dimethyl ether, dimethoxyethane It may be any one selected from or a mixture of two or more.

In addition, the crosslinked polymer matrix may have a semi-interpenetrating network (semi-IPN) structure further including a linear polymer. In this case, it has excellent flexibility and shows strong resistance to stress such as bending when used as a battery, so that the battery can be operated normally without deteriorating performance. Therefore, it can be applied to a flexible battery.

The linear polymer may be easily mixed with the crosslinkable monomer and may be used without limitation as long as it is a polymer capable of impregnating 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), polyethylene oxide (PEO), etc. Or 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% by weight based on the weight of the crosslinked polymer matrix. Specifically, it may be included in 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-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 can secure flexibility while maintaining appropriate mechanical strength. Accordingly, when applied to a flexible battery, stable battery performance can be implemented even with shape deformation due to various external forces, and the risk of battery ignition and explosion that may be caused by shape deformation of the battery can be suppressed.

In addition, the gel polymer electrolyte composition may further include inorganic particles as needed. The inorganic particles may be printed 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 are 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, SiO2, Al2O3, TiO2, BaTiO3, Li2O, LiF, LiOH, Li3N, BaO, Na2O, Li2CO3, CaCO3, LiAlO2, SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, ZrO2, and It may be any one or a mixture of two or more selected from SiC. Although not limited, by using the inorganic particles, not only has high affinity with an organic solvent, but is also very stable thermally, thereby improving the thermal stability of the electrochemical device.

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 may be implemented.

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, more specifically 10 to 30% by weight, and the viscosity range described above 0.1 to It may be used in an amount satisfying 10,000,000 cps, more preferably 1.0 to 1,000,000 cps, more preferably 1.0 to 100,000 cps, but is not limited thereto.

(1) Anode-electrolyte combination

In one aspect of the present invention, the positive electrode means that a positive electrode active material layer is formed on a positive electrode current collector.

The positive electrode current collector is not limited as long as it is a substrate having excellent conductivity used in the art, and may be made of any one selected from conductive metals and conductive metal oxides. In addition, the current collector may have 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 sides of an insulating substrate. In addition, the current collector may be formed of a flexible substrate, and may be easily bent, thereby providing a flexible electronic device. In addition, it may be made of a material having a restoring force that is bent and returned to its original shape. More specifically, for example, the current collector may be made of aluminum, stainless steel, copper, nickel, iron, lithium, cobalt, titanium, nickel foam, copper foam, and a polymer substrate coated with a conductive metal, but is limited thereto. It is not.

The positive electrode active material layer may be formed of an active material layer including a positive electrode active material and a binder.

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.

Among the positive electrode active material layers, the active material layer may be formed by applying a positive electrode active material composition including a positive electrode active material, a binder, and a solvent. 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 positive electrode active material may be used without limitation as long as it is commonly used in the art. Specifically, for example, a lithium primary battery or a secondary battery, a compound capable of reversible intercalation and deintercalation of lithium (retiated intercalation compound) may be used. The positive electrode active material of the present invention may be in the form of a powder.

Specifically, one or more of a composite oxide of lithium and a metal composed of any one selected from cobalt, manganese, nickel, or a combination of two or more may be used. Although not limited, a specific example may be a compound represented by any one of the following formulas. LiaA1-bRbD2 (wherein 0.90≦a≦1.8 and 0≦b≦0.5); LiaE1-bRbO2-cDc (wherein, 0.90≦a≦1.8, 0≦b≦0.5, and 0≦c≦0.05); LiE2-bRbO4-cDc (wherein 0≦b≦0.5, 0≦c≦0.05); LiaNi1-b-cCobRcDα (wherein, 0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05, and 0<α≦2); LiaNi1-b-cCobRcO2-αZα (wherein, 0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2); LiaNi1-b-cCobRcO2-αZ2 (in the above formula, 0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2); LiaNi1-b-cMnbRcDα (wherein, 0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05, and 0<α≦2); LiaNi1-b-cMnbRcO2-αZα (wherein, 0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05 and 0<α<2); LiaNi1-b-cMnbRcO2-αZ2 (in the above formula, 0.90≦a≦1.8, 0≦b≦0.5, 0≦c≦0.05, and 0<α<2); LiaNibEcGdO2 (in the above formula, 0.90≦a≦1.8, 0≦b≦0.9, 0≦c≦0.5, and 0.001≦d≦0.1); LiaNibCocMndGeO2 (wherein, 0.90≦a≦1.8, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5, and 0.001≦e≦0.1.); LiaNiGbO2 (in the above formula, 0.90≦a≦1.8 and 0.001≦b≦0.1); LiaCoGbO2 (in the above formula, 0.90≦a≦1.8 and 0.001≦b≦0.1); LiaMnGbO2 (in the above formula, 0.90≦a≦1.8 and 0.001≦b≦0.1); LiaMn2GbO4 (in the above formula, 0.90≦a≦1.8 and 0.001≦b≦0.1); QO2;QS2;LiQS2;V2O5;LiV2O5;LiTO2;LiNiVO4;Li(3-f)J2(PO4)3(0≦f≦2); Li(3-f)Fe2(PO4)3 (0≦f≦2); And LiFePO4.

In the above formula, A is Ni, Co, Mn, or a combination thereof; R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, or combinations 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, one 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 may include, as a coating element compound, oxide, hydroxide of a coating element, oxyhydroxide of a coating element, oxycarbonate of a coating element, or hydroxycarbonate of a coating element. The compound constituting these coating layers may be amorphous or crystalline. As a 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. The coating layer forming process may use any coating method 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, immersion method, etc. Since the content can be well understood by those in the field, detailed descriptions will be omitted.

Although not limited, the positive electrode active material may include 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 ~ 50 ㎛, more preferably 0.01 ~ 20 ㎛, but is not limited thereto.

The binder serves to attach the positive electrode active material particles well to each other and also to fix the positive electrode active material to the current collector. If it is generally used in the field, it may be used without limitation, and representative examples include polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinylfluoride, and ethylene oxide. Including 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. The amount sufficient to serve as a binder in the above range, but is not limited thereto.

The solvent may be any one or two or more mixed solvents selected from N-methyl pyrrolidone, acetone, water, etc., but is not limited thereto, and any one commonly used in the art may be used. The content of the solvent is not limited, and may be used without limitation as long as it is an amount sufficient to be coated 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 does not cause chemical changes in the battery to be configured, and may be used without limitation as long as it is an electron conductive material. Specifically, for example, carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon nanotubes, and carbon fibers; Metal-based materials such as metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material containing 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 positive electrode active material composition, but is not limited thereto. In addition, the average particle diameter of the conductive material may be 0.001 to 1000 μm, more specifically 0.01 to 100 μm, but is not limited thereto.

In one aspect of the present invention, the positive electrode active material layer may include pores, and may have a porosity of 5 to 30% by volume, and more specifically 10 to 20% by volume, and limited thereto. It does not become. If the porosity is in the above range, when the liquid electrolyte or the gel polymer electrolyte is injected, there is a problem that the porosity is low and it is difficult to impregnate the central part of the battery. Even though the porosity is low, an evenly and uniformly impregnated electrolyte layer can be formed.

In one aspect of the present invention, the positive electrode-electrolyte combination means that the liquid electrolyte or the gel polymer electrolyte is laminated or impregnated on the positive electrode to be integrated. The impregnation means that some or all of them are penetrated and integrated.

When the first electrolyte in the positive electrode-electrolyte combination is a gel polymer electrolyte, the thickness of the gel polymer electrolyte layer may be 0.01 μm to 500 μm. Specifically, it may be 0.01 to 100 μm, but is not limited thereto. When the thickness of the gel polymer electrolyte layer satisfies the above range, it is possible to improve the performance of the electrochemical device and facilitate the manufacturing process.

(2) cathode-electrolyte combination

In one aspect of the present invention, the negative electrode may have various aspects, and specifically, for example, i) an electrode made of only a current collector, ii) an electrode coated with an active material layer including a negative active material and a binder on the current collector It may be selected from.

The negative electrode current collector may be in the form of a thin film or a mesh, and the material may be made of a metal such as lithium metal, lithium aluminum alloy, or other lithium metal alloy, or a polymer. The negative electrode of the present invention may be integrated by using the thin-film or mesh-type current collector as it is or by stacking the thin-film or mesh-type current collector on a conductive substrate.

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 any one selected from conductive metals and conductive metal oxides. In addition, the current collector may have 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 sides of an insulating substrate. In addition, the current collector may be formed of a flexible substrate, and may be easily bent, thereby providing a flexible electronic device. In addition, it may be made of a material having a restoring force that is bent and returned to its original shape. More specifically, for example, the current collector may be made of aluminum, stainless steel, copper, nickel, iron, lithium, cobalt, titanium, nickel foam, copper foam, and a polymer substrate coated with a conductive metal, but is limited thereto. It is not.

In the ii) aspect of the negative electrode of the present invention, an active material layer may be coated by applying a negative active material composition including a negative active material and a binder on a current collector. The current collector is as described above, and the negative electrode active material composition may be applied and dried directly on a current collector such as a metal thin film to form a negative electrode plate on which the negative active material layer is formed.

Alternatively, the negative electrode active material composition may be cast on a separate support, and then a film obtained by peeling off the support may be laminated on the current collector to prepare a negative electrode having a negative electrode active material layer. The thickness of the negative electrode 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 may include, but is not limited to, a negative 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 example, a lithium primary battery or a secondary battery, a compound capable of reversible intercalation and deintercalation of lithium (retiated intercalation compound) may be used. The negative active material of the present invention may be in a powder form.

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.

The metal alloyable with lithium may be Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn, etc. It is not limited thereto.

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

The non-transition metal oxide is Si, SiOx (0 <x <2), Si-C composite, Si-Q alloy (the 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 complex, Sn-R (wherein R is an alkali metal, alkaline earth metal, group 13-16 element, transition metal, rare earth element, or a combination thereof, Sn Not). 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, and calcined coke. And the like can be used, but is not limited thereto.

Although not limited, the negative active material may include 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 µm, more preferably 0.01 to 15 µm, but is not limited thereto.

The binder serves to attach the negative active material particles well to each other and to fix the negative active material to the current collector. If it is generally used in the field, it may be used without limitation, and representative examples include polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, and ethylene oxide. Included polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc. However, it is not limited thereto.

The solvent may be any one or two or more mixed solvents selected from N-methyl pyrrolidone, acetone, water, etc., but is not limited thereto, and any one commonly used in the art may be used.

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 chemical changes in the battery to be configured, such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black , Carbon-based materials such as carbon fiber; Metal-based materials such as metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material containing a mixture thereof may be used.

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

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

In one aspect of the present invention, the negative active material layer may include pores, and may have a porosity of 10 to 35 vol%, more specifically 15 to 25 vol%, and limited thereto. It does not become. If the porosity is in the above range, when the liquid electrolyte or the gel polymer electrolyte is injected, there is a problem that the porosity is low and it is difficult to impregnate the central part of the battery. Even though the porosity is low, an evenly and uniformly impregnated electrolyte layer can be formed.

In one aspect of the present invention, the negative electrode-electrolyte combination means that the liquid electrolyte or the gel polymer electrolyte is laminated or impregnated on the negative electrode to be integrated. The impregnation means that some or all of them are penetrated and integrated.

When the second electrolyte in the negative electrode-electrolyte combination is a gel polymer electrolyte, the thickness of the gel polymer electrolyte layer may be 0.01 μm to 500 μm. Specifically, it may be 0.01 to 100 μm, more preferably 0.01 to 50 μm, but is not limited thereto. When the thickness of the gel polymer electrolyte layer satisfies the above range, it is possible to improve the performance of the electrochemical device and facilitate the manufacturing process.

(3) Membrane-electrolyte combination

In one aspect of the present invention, the separator may be used without limitation as long as it is commonly used in the field. For example, it may be a woven fabric, a non-woven fabric, and a porous membrane. In addition, these may be one layer or a multilayer film in which two or more are stacked. 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, and a copolymer thereof may be formed of any one or a mixture of two or more selected from the group consisting of. 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, the separator-electrolyte combination means that the liquid electrolyte or the gel polymer electrolyte is laminated or impregnated on the separator to be integrated. The impregnation means that some or all of them are penetrated and integrated.

When the third electrolyte in the separator-electrolyte combination is a gel polymer electrolyte, the thickness of the gel polymer electrolyte layer may be 0.01 μm to 500 μm. Specifically, it may be 0.01 to 100 μm, but is not limited thereto. When the thickness of the gel polymer electrolyte layer satisfies the above range, it is possible to improve the performance of the electrochemical device and facilitate the manufacturing process.

(4) Electrochemical device

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.

(5) Manufacturing method of electrochemical device

Hereinafter, a method of manufacturing an electrochemical device according to an aspect of the present invention will be described in more detail.

As described above, the electrochemical device of the present invention may be manufactured in various aspects, of which several methods of manufacturing are specifically described, but these are only exemplified for specific explanation, but are not limited thereto. Do.

The first aspect of the method for manufacturing the electrochemical device of the present invention

a) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the second gel polymer electrolyte composition on the negative electrode to include a second electrolyte Preparing a cathode-electrolyte assembly;

b) manufacturing an electrode assembly by laminating the anode-electrolyte assembly, the separator, and the cathode-electrolyte assembly; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including,

The first electrolyte and the second electrolyte are each different in type or content of the monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the second electrolyte, and the liquid electrolyte has different ionic conductivity.

The second aspect of the method for manufacturing the electrochemical device of the present invention

a) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the third gel polymer electrolyte composition on the separator to include a third electrolyte Preparing a separator-electrolyte assembly;

b) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including,

Each of the first electrolyte and the third electrolyte has a different kind or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the third electrolyte, and the liquid electrolyte has different ionic conductivity.

The third aspect of the method for manufacturing the electrochemical device of the present invention

a) coating and curing the second gel polymer electrolyte composition on the negative electrode to prepare a negative electrode-electrolyte assembly including the second electrolyte, and coating and curing the third gel polymer electrolyte composition on the separator to include a third electrolyte Preparing a separator-electrolyte assembly;

b) manufacturing an electrode assembly by laminating the anode, the separator-electrolyte assembly, and the cathode electrolyte assembly; And

c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;

Including,

The second electrolyte and the third electrolyte are each different in type or content of a monomer constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte, and the liquid electrolyte has different ionic conductivity.

In one aspect of the present invention, step b) is

b-1) preparing an electrode assembly by laminating the positive electrode or positive electrode-electrolyte assembly, the separator or separator-electrolyte assembly, and the negative electrode or negative electrode-electrolyte assembly and cutting them into a predetermined shape; or

b-2) manufacturing an electrode assembly by cutting the anode or the anode-electrolyte assembly, the separator or the separator-electrolyte assembly, and the cathode or cathode-electrolyte assembly into a predetermined shape, respectively, and stacking them;

It may be selected from.

The fourth aspect of the method for manufacturing the electrochemical device of the present invention

A) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the second gel polymer electrolyte composition on the negative electrode to include a second electrolyte Preparing a cathode-electrolyte assembly, and applying and curing a third gel polymer electrolyte composition on the separation membrane to prepare a separation membrane-electrolyte assembly including a third electrolyte; And

B) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly;

Including,

At least one selected from the first electrolyte, the second electrolyte, and the third electrolyte is different in the type or content of the monomers constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte, and the liquid electrolyte Silver ion conductivity is different.

In one aspect, step b) is

B-1) laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly and then cutting them into a predetermined shape; or

B-2) cutting the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly into a predetermined shape and then laminating them;

It may be selected from.

In one aspect, after the step b), c) sealing the electrode assembly with a packaging material; may further include.

In one aspect of the manufacturing method of the present invention, the gel polymer electrolyte is not only a coating method such as bar coating, spin coating, slot die coating, dip coating, spray coating, etc., but also inkjet printing, gravure printing, gravure offset, aerosol printing, stencil It may be applied by a printing method such as printing and screen printing to enable continuous production.

More specifically, the liquid electrolyte may be uniformly distributed in the net structure of the crosslinked polymer matrix by applying a composition for polymerization of the gel polymer electrolyte and crosslinking by applying ultraviolet rays or heat, and the evaporation process of the solvent may be unnecessary. .

In addition, since the gel polymer electrolyte can be formed by the coating method, it can be formed by coating a separate electrolyte suitable for the characteristics of each electrode. In addition, since the gel polymer electrolyte can be formed by the coating method, the electrolyte can be formed evenly and uniformly on the electrode and the separator compared to the injection method. In addition, since the gel polymer electrolyte has a crosslinked structure, the degree of miscibility of the components in the gel polymer electrolyte with the liquid electrolyte is low even when used for a long period of time.

In one aspect of the present invention, the liquid electrolyte may be injected after sealing with a packaging material.

Since the composition for polymerization of the liquid electrolyte and the gel polymer electrolyte is the same as previously mentioned, a redundant description will be omitted.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for describing the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

1) Ionic conductivity

The ionic conductivity can be checked through the following calculation formula.

[Calculation 1]

IC ₁ = (τ _cathode ² × IC _cathode )/P _cathode

[Calculation 2]

IC ₂ = (τ _anode ² × IC _anode )/P _anode

[Calculation 3]

IC ₃ = (τ _separator ² × IC _separator )/P _separator

At this time, IC ₁ , IC ₂ , IC ₃ are the ionic conductivity of the _first , _second , and _third electrolytes, respectively, and IC _cathode , IC _anode , and IC _separator are a positive electrode-electrolyte combination, a negative electrode-electrolyte combination, It is the ionic conductivity of the membrane-electrolyte combination, τ _cathode , τ _anode , and τ _separator are the curvature of the anode, cathode, and separator, respectively, and P _cathode , P _anode , and P _separator are the porosities of the anode, cathode, and separator.

In order to calculate the ionic conductivity of the electrolyte, the porosity (% by volume) of the specimen may be measured using a mercury pressure porosity meter for each of the anode, the cathode, and the separator. A standard electrolyte with known ionic conductivity (in this patent, a liquid electrolyte in which 1 mol of LiPF ₆ is dissolved in a solvent mixed with 50% by volume of ethylene carbonate and 50% by volume of ethyl methyl carbonate was used as the standard electrolyte.) The ionic conductivity of the positive electrode-electrolyte combination, the negative electrode-electrolyte combination, and the separator-electrolyte combination may be measured, and the degree of curvature of the positive electrode, the negative electrode, and the separator may be calculated through the above calculation formula.

The ionic conductivity is measured by cutting a positive electrode-electrolyte assembly, a negative electrode-electrolyte assembly, and a separator-electrolyte assembly into a circle having a diameter of 18 mm, and preparing a coin cell 2032, respectively, according to temperature, using an AC impedance measurement method. I can. The ion conductivity measurement was performed in a frequency band of 1 MHz to 0.01 Hz using a VMP3 measuring device.

In the case of an electrochemical device containing any electrolyte, the seal is removed, the positive electrode-electrolyte assembly, the negative electrode-electrolyte assembly, and the separator-electrolyte combination are separated, and each combination is put in a dimethyl carbonate solvent and stored for 24 hours, and then acetone solvent And then stored in a dimethyl carbonate solvent for 24 hours, and then stored in a dimethyl carbonate solvent for 24 hours to remove the electrolyte in each of the conjugates, and then dried for 24 hours in a vacuum atmosphere (at this time, the positive and negative electrodes from which the electrolyte was removed is 130 degrees, and the separator is 60 It was dried at degrees temperature.) The positive electrode, the negative electrode, and the separator from which the electrolyte has been removed are calculated using the porosity and the standard electrolyte in the above-mentioned method, and the positive electrode-electrolyte combination, the negative electrode-electrolyte combination and the separator in the state before removing the electrolyte- By measuring the ionic conductivity of the electrolyte assembly, the ionic conductivity of the first electrolyte, the second electrolyte, and the third electrolyte can be measured through the above calculation formula.

Hereinafter, a Nyquist plot obtained by measuring the ionic conductivity of the positive electrode-electrolyte assembly, the negative electrode-electrolyte assembly, and the separator-electrolyte assembly will be described in detail. The positive electrode-electrolyte combination and the negative electrode-electrolyte combination are both an electron conductor and an ion conductor as a composite conductor, and the Nyquist plot for this shows the outline of a semicircle. In this case, the semicircle is divided into a resistance in a high frequency region (R ₁ ) and a resistance in a low frequency region (R ₂ ), and the resistance against ion conduction can be calculated through the following calculation formula.

[Equation 4]

R _ion = R ₂ -R ₁

The separator-electrolyte combination is an ion conductor and exhibits a vertically rising shape in a Nyquist plot, and an impedance resistance value along the horizontal axis indicates resistance to ion conduction. The ionic conductivity of the positive electrode-electrolyte assembly, the negative electrode-electrolyte assembly, and the separator-electrolyte assembly is a resistance value for ionic conduction obtained above and can be calculated through the following calculation formula.

[Equation 5]

IC = L/(R _ion × A)

In this case, L denotes the thickness of the specimen (thickness excluding the current collectors of the positive electrode and negative electrode and the thickness of the separator), and A denotes the area of the specimen.

2) Arrhenius plot slope

The slope of the Arrhenius plot shows the ionic conductivity data for each temperature obtained above in graphs, with the inverse 1/T of the temperature T(K) on the horizontal axis and the logarithmic ln(IC) of the ion conductivity on the vertical axis, respectively. The slope of the straight line at °C was determined.

3) viscosity

It was measured at 25°C using a Brookfield viscometer (Dv2TRV-cone&plate, CPA-52Z).

4) Battery performance evaluation

The lithium battery was initially charged/discharged at a current of 0.1 C (= 0.3 mA/㎠) in a voltage range of 3.0 to 4.2 V at room temperature (25℃), and under a current of 0.2 C (= 0.6 mA/㎠) The life characteristics of the lithium battery according to the number of charging/discharging were observed.

The initial discharge capacity is the discharge capacity in the first cycle (mAh/cm2). Initial charge/discharge efficiency is the ratio of charge capacity and discharge capacity in the first cycle. The capacity retention rate for the life characteristics was calculated by the following equation.

Capacity retention rate (%) = [200th cycle discharge capacity/first cycle discharge capacity] × 100

5) Porosity

For the positive and negative electrodes, the porosity (volume %) of the specimen was measured using a mercury intrusion porosimetry (equipment name: AutoPore IV 9500, equipment manufacturer: Micromeritics Instrument Corp.). In order to exclude the effect of the pores formed by the sample stacking, the porosity of the electrode was calculated under the conditions of a pressure range of 30 psia to 60000 psia.

6) Infrared spectral analysis

Each Fourier transform infrared spectroscopy (Fourier transform infrared spectroscopy, equipment name: 670-IR, equipment manufacturer: Varian) is performed by separating the anode, cathode and separator from the electrode assembly in the state where the initial formation process has been completed by applying charge/discharge current. Performed. It was confirmed that the peak intensity derived from the material properties of different monomers can be distinguished and judged from the absorption spectrum obtained by spectroscopy of the reflected light when irradiated with infrared rays.

7) X-ray photoelectron analysis

X-ray photoelectron analysis (X-ray Photoelectron Spectroscopy, equipment name: K-Alpha, equipment manufacturer: Thermo Fisher) by separating the positive electrode, negative electrode, and separator from the electrode assembly in the state where the charging/discharging current was applied and the initial formation process was completed. Was performed. From the energy of photoelectrons escaped by X-rays irradiated on the sample, the type of monomer or the content of the monomer can be distinguished according to the presence or absence of elements contained in different monomers and the analysis of the state of chemical bonding.

8) Inductively coupled plasma mass spectrometry

Inductively Coupled Plasma Mass Spectromerty, equipment name: ELAN DRC-II, equipment manufacturer: Perkin, by separating the positive electrode, negative electrode, and separator from the electrode assembly in which the initial formation process has been completed by applying a charging/discharging current. Elmer). By ionizing the monomers included in the sample and separating the ions using a mass spectrometer, it was confirmed that the types and contents of different monomers can be distinguished and judged.

9) Time-of-flight secondary ion mass analysis

Time-of-flight Secondary Ion Mass Spectrometry, equipment name: TOF-SIMS, by separating the anode, cathode, and separator from the electrode assembly in the state where the initial formation process is completed by applying charge/discharge current. 5, equipment manufacturer: ION TOF) was performed. Through mass analysis of secondary ions generated in the sample, it was confirmed that different types of monomers can be distinguished and determined.

10) Nail penetration test

Secondary batteries prepared according to Examples and Comparative Examples were prepared in a fully charged state under a voltage of 4.2V. After penetrating the center of the battery using a 2.5 mm diameter nail, it was observed whether there were changes in ignition or explosion. If there was no ignition or explosion after piercing the nail, it was evaluated as “passed”, and if there was an ignition or explosion during penetration, it was evaluated as “not passed”. At this time, the nail penetration speed was constant at 12 mm/min, and the results are summarized in Table 2 below.

11) Heat exposure test (Hot box test)

Secondary batteries prepared according to Examples and Comparative Examples were prepared in a fully charged state under a voltage of 4.2V. In the 150 ^o C Hot Box, parts, ignition, and explosions, etc. after 3 hours of storage were investigated and summarized in Table 2. It was evaluated as "passed" if it was maintained in a swollen form after 3 hours and there was no ignition or explosion, and "not passed" if there was an ignition or explosion after 3 hours.

[Example 1]

1) Preparation of positive electrode-electrolyte combination

95% by weight of lithium cobalt composite oxide (LiCoO ₂ ) having an average particle diameter of 5㎛ as a positive electrode active material, ₂ % by weight of Super-P having an average particle diameter of 40 nm as a conductive material, and 3% by weight of polyvinylidene fluoride as a binder as an organic solvent. A positive electrode active material composition (positive electrode mixture slurry) was prepared by adding N-methyl-2-pyrrolidone to a solid content of 50% by weight.

The positive electrode active material composition was applied to an aluminum thin film having a thickness of 20 μm using a doctor blade, dried at 120° C., rolled with a roll press, and coated with a 40 μm thick active material layer (porosity 15% by volume). Ready.

The first gel polymer electrolyte composition was coated on the active material layer of the prepared positive electrode using a doctor blade, and then crosslinked by irradiating ultraviolet rays at 2000 mW/cm ^-2 for 20 seconds, and the first gel polymer electrolyte layer was formed with a thickness of 41 μm. A positive electrode-electrolyte assembly was prepared.

The first gel polymer electrolyte composition was a mixture of 7.5% by weight of trimethylolpropane ethoxylate triacrylate, 0.1% by weight of hydroxy methyl phenyl propanone as a photoinitiator, and 92.4% by weight of a liquid electrolyte. As the liquid electrolyte, a liquid electrolyte in which 1 mol of LiPF6 was dissolved in propylene carbonate, a cyclic carbonate-based organic solvent with excellent electrochemical oxidation stability, was used. The viscosity of the first gel polymer electrolyte composition was 12 cps at 25°C.

2) Preparation of cathode-electrolyte combination

A negative electrode active material composition (cathode) by adding 96% by weight of natural graphite powder as an anode active material, 2% by weight of carbon black having an average particle diameter of 40 nm as a conductive material, 1% by weight of styrene-butadiene rubber and 1% by weight of carboxymethylcellulose as a binder. Mixture slurry) was prepared. The negative electrode active material composition was applied to a copper thin film having a thickness of 20 μm using a doctor blade, dried at 120° C., rolled with a roll press, and coated with an active material layer having a thickness of 40 μm (porosity: 20% by volume). Ready.

A second gel polymer electrolyte composition was coated on the active material layer of the prepared negative electrode using a doctor blade, and crosslinked by irradiating ultraviolet rays at 2000 mW/cm ^-2 for 20 seconds, and a second gel polymer electrolyte layer having a thickness of 41 μm was formed. A negative electrode-electrolyte assembly was prepared.

The second gel polymer electrolyte composition was a mixture of 7.5% by weight of trimethylolpropane ethoxylate triacrylate, 0.1% by weight of hydroxymethyl phenyl propanone as a photoinitiator, and 92.4% by weight of a liquid electrolyte. As the liquid electrolyte, a liquid electrolyte in which 4 mol of LiFSI was dissolved in a dimethoxyethane solvent was used. The viscosity of the first gel polymer electrolyte composition was 65 cps at 25°C.

3) Preparation of membrane-electrolyte combination

A 25 µm-thick polyolefin microporous membrane (Celgard 3501) was used as a separator.

A third gel polymer electrolyte composition was coated on the prepared separator using a doctor blade, and crosslinked by irradiating ultraviolet rays at 2000 mW/cm ^-2 for 20 seconds, and a 30 µm thick separator-electrolyte assembly with a third gel polymer electrolyte layer formed thereon. Was prepared.

In the third gel polymer electrolyte composition, 17.5 wt% of trimethylolpropane ethoxylate triacrylate, 0.1 wt% of hydroxy methyl phenyl propanone and 82.4 wt% of a liquid electrolyte were mixed as a photo initiator. As the liquid electrolyte, a liquid electrolyte in which 1 mol of LiPF ₆ was dissolved in ethylene carbonate/diethyl carbonate (1:1 volume ratio mixture), which is a linear carbonate-based mixed organic solvent with excellent wettability in the separator, was used. The viscosity of the third gel polymer electrolyte composition was 30 cps at 25°C.

4) Manufacture of lithium ion secondary battery

The positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly were stacked, and then punched to produce batteries (coin cells and pouch cells).

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Example 2]

In Example 1, the first gel polymer electrolyte composition and the third gel polymer electrolyte composition were the same, and trimethylolpropane ethoxylate triacrylate 12.5% by weight as the second gel polymer electrolyte composition, and hydroxy methyl phenyl as a photoinitiator. A battery (coin cell and pouch cell) was prepared in the same manner as in Example 1, except that 0.1% by weight of propanone and 87.4% by weight of a liquid electrolyte were mixed and used.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Example 3]

In Example 1, the first gel polymer electrolyte composition, the second gel polymer electrolyte composition, and the third gel polymer electrolyte composition were the same, except that acrylamide-2-methylpropane sulfonic acid was used as a monomer. A battery (coin cell and pouch cell) was manufactured in the same manner as in Example 1.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Example 4]

In Example 2, the first gel polymer electrolyte composition, the second gel polymer electrolyte composition, and the third gel polymer electrolyte composition were the same, except that acrylamide-2-methylpropane sulfonic acid was used as a monomer. A battery (coin cell and pouch cell) was manufactured in the same manner as in Example 1.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Example 5]

In Example 1, the first gel polymer electrolyte composition, the second gel polymer electrolyte composition, and the third gel polymer electrolyte composition were the same, except that phosphoric acid 2-hydroxyethyl acrylate ester was used as a monomer. A battery (coin cell and pouch cell) was manufactured in the same manner as in Example 1.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Example 6]

In Example 2, the first gel polymer electrolyte composition, the second gel polymer electrolyte composition, and the third gel polymer electrolyte composition were the same, except that phosphoric acid 2-hydroxyethyl acrylate ester was used as a monomer. A battery (coin cell and pouch cell) was manufactured in the same manner as in Example 1.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Comparative Example 1]

The positive electrode, the negative electrode, and the separator were the same as in Example 1, and the same gel polymer electrolyte was formed on the positive electrode, the negative electrode, and the separator, and the thickness was the same as that of Example 1.

The gel polymer electrolyte was crosslinked after application using a gel polymer electrolyte composition in which 3% by weight of trimethylolpropane ethoxylate triacrylate, 0.1% by weight of hydroxymethyl phenyl propanone as a photoinitiator, and 96.9% by weight of a liquid electrolyte were mixed. Except for that, a battery (coin cell and pouch cell) was manufactured in the same manner as in Example 1.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Comparative Example 2]

The positive electrode, the negative electrode, and the separator were the same as in Example 1, and the same gel polymer electrolyte was formed on the positive electrode, the negative electrode, and the separator, and the thickness was the same as that of Example 1.

The gel polymer electrolyte was crosslinked after application using a gel polymer electrolyte composition in which 7.5% by weight of trimethylolpropane ethoxylate triacrylate, 0.1% by weight of hydroxymethylphenyl propanone as a photoinitiator, and 92.4% by weight of a liquid electrolyte were mixed. Except for that, a battery (coin cell and pouch cell) was manufactured in the same manner as in Example 1.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Comparative Example 3]

The positive electrode, the negative electrode, and the separator were the same as in Example 1, and the same gel polymer electrolyte was formed on the positive electrode, the negative electrode, and the separator, and the thickness was the same as that of Example 1.

The gel polymer electrolyte was crosslinked after application using a gel polymer electrolyte composition in which 17.5% by weight of trimethylolpropane ethoxylate triacrylate, 0.1% by weight of hydroxymethylphenyl propanone as a photoinitiator, and 82.4% by weight of a liquid electrolyte were mixed. Except for that, a battery (coin cell and pouch cell) was manufactured in the same manner as in Example 1.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Comparative Example 4]

The positive electrode, the negative electrode, and the separator were the same as in Example 1, and a liquid electrolyte in which 1 mol of LiPF ₆ was dissolved in ethylene carbonate/dimethyl carbonate (1:1 volume ratio mixture) containing no monomer was injected into the battery (coin cell And a pouch cell) was prepared.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

[Comparative Example 5]

The positive electrode, the negative electrode, and the separator were the same as in Example 1, and a gel obtained by mixing 7.5% by weight of trimethylolpropane ethoxylate triacrylate, 0.1% by weight of hydroxymethyl phenyl propanone as a photoinitiator, and 92.4% by weight of a liquid electrolyte After injecting a polymer electrolyte, a battery (coin cell and pouch cell) was prepared by crosslinking.

Table 1 shows the results of observing the charge/discharge efficiency under the charge/discharge current rate of 0.1 C and the life characteristics under the charge/discharge current rate of 0.2 C with a coin cell.

The pouch cell was completely charged to 4.2V under a charging current rate of 0.1C, and then the results of the nail penetration experiment and the heat exposure experiment were evaluated and are shown in Table 2 below.

Charging/discharging efficiency (%) Capacity retention rate (%) IC ₁
(mS/cm) IC ₂
(mS/cm) IC ₃
(mS/cm) Example 1 99.7 97.2 4.51 4.2 2.5 Example 2 99.8 97.4 4.51 3.07 2.5 Example 3 98.8 97.7 4.65 4.45 2.6 Example 4 99.1 97.9 4.65 3.32 2.6 Example 5 99.2 98.1 4.61 4.41 2.58 Example 6 99.5 98.3 4.61 3.21 2.58 Comparative Example 1 Not measurable Not measurable 5.33 5.33 5.33 Comparative Example 2 Not measurable Not measurable 4.51 4.51 4.51 Comparative Example 3 Not measurable Not measurable 2.2 2.2 2.2 Comparative Example 4 94.8 87 7.5 7.5 7.5 Comparative Example 5 0.05 Not measurable 2~3 3~4 ~4

Nail penetration test result Heat exposure test result Example 1 Pass Pass Example 2 Pass Pass Example 3 Pass Pass Example 4 Pass Pass Example 5 Pass Pass Example 6 Pass Pass Comparative Example 1 Not passed Not passed Comparative Example 2 Not passed Not passed Comparative Example 3 Not passed Pass Comparative Example 4 Not passed Not passed Comparative Example 5 Not passed Not passed

As described above, in the present invention, specific matters and limited embodiments and drawings have been described, but this is provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is Those of ordinary skill in the relevant field can make various modifications and variations from this description.

Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later fall within the scope of the spirit of the present invention. .

Claims (25)

A positive electrode-electrolyte assembly comprising a first electrolyte on the positive electrode,
A cathode-electrolyte assembly comprising a second electrolyte on the cathode, and
Including a separator-electrolyte assembly including a third electrolyte on the separator,
At least two or more selected from the first electrolyte, the second electrolyte, and the third electrolyte are a crosslinked polymer matrix, a solvent, and a gel polymer electrolyte containing a dissociable salt, and each of the gel polymer electrolytes is a type of monomer constituting the crosslinked polymer matrix. Or the content is different,
At least one selected from the first electrolyte, the second electrolyte, and the third electrolyte is an electrochemical device that is different in ionic conductivity. The method of claim 1,
The first electrolyte, the second electrolyte, and the third electrolyte are all gel polymer electrolytes,
At least one of the gel polymer electrolytes is an electrochemical device in which the type or content of monomers forming the crosslinked polymer matrix is different. The method of claim 1,
The cross-linked polymer matrix further comprises a linear polymer to have a semi-interpenetrating network (semi-IPN) structure. The method of claim 1,
At least any one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte has an ionic conductivity difference of 0.1 mS/cm or more. The method of claim 1,
At least any one or more selected from the first electrolyte, the second electrolyte, and the third electrolyte have different slopes obtained from the Arrhenius plot of the temperature at 20 to 80 °C and the ion conductivity. The method of claim 1,
The ionic conductivity IC ₁ of the first electrolyte and the ionic conductivity IC ₂ of the second electrolyte satisfy Equation 1 below.
[Equation 1]
IC ₁ -IC ₂ ≥ 0.1 mS/cm The method of claim 1,
The ionic conductivity IC ₁ of the first electrolyte, the ionic conductivity IC ₂ of the second electrolyte, and the ionic conductivity IC ₃ of the third electrolyte satisfy the following Equations 2 and 3.
[Equation 2]
IC ₁ -IC ₃ ≥ 0.1 mS/cm
[Equation 3]
IC ₂ -IC ₃ ≥ 0.1 mS/cm The method of claim 1,
The type of the monomer is any one selected from the group consisting of an acrylate-based monomer, an acrylic acid-based monomer, a sulfonic acid-based monomer, a phosphoric acid-based monomer, a perfluorine-based monomer, and an acrylonitrile-based monomer, or a mixture of two or more electrochemical devices. The method of claim 8,
The acrylate monomers are polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane ethoxylate Any one or two or more selected from trimethacrylate, bisphenol ethoxylate diacrylate and bisphenol ethoxylate dimethacrylate, beta carboxyethyl acrylate, 2,4,6-tribromophenyl acrylate Is a mixture,
The acrylic acid-based monomer is any one or a mixture of two or more selected from acrylic acid, methacrylic acid, methyl acrylic acid, methyl methacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid and 2-trifluoromethylacrylic acid,
The sulfonic acid-based monomer is from sulfonic acid, sodium styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate and 3-sulfopropyl methacrylate. Is any one or a mixture of two or more selected,
The phosphoric acid-based monomer is any one or a mixture of two or more selected from phosphoric acid, bis(2-methacryloxyethyl)phosphate, phosphoric acid-2-hydroxyethylacrylate ester, and 2-(methacryloxy)ethylphosphate ,
The perfluorine-based monomers are hexafluoroisopropyl methacrylate, 1,1,3-hexafluorobutyl methacrylate, 1,1,7-dodecafluorheptyl methacrylate, 2,2,2-trifluoroethyl methacrylate Any one or a mixture of two or more selected from acrylate, 1,1,5-octafluoropentyl methacrylate, pentafluorophenyl acrylate and 2,2,2-trifluoroethyl acrylate,
The acrylonitrile-based monomer is an electrochemical device that is any one or a mixture of two or more selected from acrylonitrile, 1-cyanovinyl acetate, and 2-cyanoethyl acrylate. The method of claim 1,
The content of the monomer is an electrochemical device that is different from 0.5% by weight or more. The method of claim 1,
The positive electrode includes a positive electrode active material layer, the negative electrode includes a negative electrode active material layer, and the positive electrode active material layer and the negative electrode active material layer include pores. The method of claim 11,
An electrochemical device in which a porosity of the positive active material layer is 5 to 30 vol%, and a porosity of the negative active material layer is 10 to 35 vol%. The method of claim 12,
The electrochemical device in which the porosity of the positive active material layer is 10 to 20 vol%, and the porosity of the negative active material layer is 15 to 25 vol%. The method of claim 1,
The positive electrode includes a positive electrode active material layer, the negative electrode is a lithium metal layer, and the positive electrode active material layer is an electrochemical device including pores. The method of claim 14,
The electrochemical device in which the porosity of the positive active material layer is 5 to 30% by volume. The method of claim 15,
The electrochemical device in which the porosity of the positive active material layer is 10 to 20% by volume. The method of claim 1,
The electrochemical device is an electrochemical device which is a primary or secondary battery capable of an electrochemical reaction. The method of claim 1,
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 that is one kind selected from the group consisting of an air cell, a magnesium-air cell, a calcium-air cell, 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) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the second gel polymer electrolyte composition on the negative electrode to include a second electrolyte Preparing a cathode-electrolyte assembly;
b) manufacturing an electrode assembly by laminating the anode-electrolyte assembly, the separator, and the cathode-electrolyte assembly; And
c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;
Including,
The first electrolyte and the second electrolyte are each different in type or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the second electrolyte, and the liquid electrolyte is different in ionic conductivity. Device manufacturing method. a) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the third gel polymer electrolyte composition on the separator to include a third electrolyte Preparing a separator-electrolyte assembly;
b) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode; And
c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;
Including,
The first electrolyte and the third electrolyte are each different in type or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the first electrolyte, the third electrolyte and the liquid electrolyte is different in ionic conductivity. Device manufacturing method. a) coating and curing the second gel polymer electrolyte composition on the negative electrode to prepare a negative electrode-electrolyte assembly including the second electrolyte, and coating and curing the third gel polymer electrolyte composition on the separator to include a third electrolyte Preparing a separator-electrolyte assembly;
b) manufacturing an electrode assembly by laminating the anode, the separator-electrolyte assembly, and the cathode electrolyte assembly; And
c) sealing the electrode assembly with a packaging material and then injecting a liquid electrolyte;
Including,
The second electrolyte and the third electrolyte are each different in type or content of monomers constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte and the liquid electrolyte is different in ionic conductivity. Device manufacturing method. The method according to any one of claims 19 to 21,
Step b)
b-1) preparing an electrode assembly by laminating the positive electrode or positive electrode-electrolyte assembly, the separator or separator-electrolyte assembly, and the negative electrode or negative electrode-electrolyte assembly and cutting them into a predetermined shape; or
b-2) manufacturing an electrode assembly by cutting the anode or anode-electrolyte assembly, the separator or separator-electrolyte assembly, and the cathode or cathode-electrolyte assembly into a predetermined shape, respectively, and stacking them;
Method of manufacturing an electrochemical device that is selected from. A) coating and curing the first gel polymer electrolyte composition on the positive electrode to prepare a positive electrode-electrolyte assembly including the first electrolyte, and coating and curing the second gel polymer electrolyte composition on the negative electrode to include a second electrolyte Preparing a negative electrode-electrolyte assembly, and coating and curing a third gel polymer electrolyte composition on the separation membrane to prepare a separation membrane-electrolyte assembly including a third electrolyte; And
B) manufacturing an electrode assembly by laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly;
Including,
At least one selected from the first electrolyte, the second electrolyte, and the third electrolyte is different in the type or content of the monomers constituting the crosslinked polymer matrix, and at least one selected from the second electrolyte, the third electrolyte, and the liquid electrolyte The method of manufacturing an electrochemical device in which the silver ion conductivity is different. The method of claim 23,
Step b) is
B-1) laminating the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly and then cutting them into a predetermined shape; or
B-2) cutting the positive electrode-electrolyte assembly, the separator-electrolyte assembly, and the negative electrode-electrolyte assembly into a predetermined shape and then laminating them;
Method of manufacturing an electrochemical device that is selected from. The method of claim 23,
After the step b), c) sealing the electrode assembly with a packaging material; the method of manufacturing an electrochemical device further comprising.