KR101393534B1 - Electrode Assembly Having Novel Structure and Secondary Battery Using the Same - Google Patents

Abstract

The present invention relates to a positive electrode, a negative electrode, and a separator layer formed integrally with an anode and a cathode between the positive electrode and the negative electrode, wherein the separator layer comprises: (a) one or more two- phase electrolyte, and (b) at least one three-phase electrolyte comprising a liquid phase component, a solid phase component and a polymer matrix, wherein the polymer matrix of the separating layer comprises a positive electrode or a negative electrode, And the liquid component of the separation layer is partially introduced into the electrode during the manufacturing process of the electrode assembly.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a novel structure electrode assembly,

The present invention relates to a novel structure electrode assembly and a secondary battery using the same. More particularly, the present invention relates to a structure electrode assembly, and more particularly, Layered structure comprising at least one two-phase electrolyte consisting of a liquid phase component and a polymer matrix, and (b) at least one three-phase electrolyte consisting of a liquid phase component, a solid phase component and a polymer matrix Wherein the polymer matrix of the separation layer is coupled to the anode or cathode and the liquid component of the separation layer is partially introduced into the electrode during the fabrication of the electrode assembly.

As the price of energy sources increases due to exhaustion of fossil fuels and the interest of environmental pollution is amplified, demand for environmentally friendly alternative energy sources is an indispensable factor for future life. Various researches on power generation technologies such as nuclear power, solar power, wind power, and tidal power have been continuing, and electric power storage devices for more efficient use of such generated energy have also been attracting much attention. As such power storage devices, secondary batteries are mainly used. Especially, in the case of lithium secondary batteries, lithium secondary batteries have been mainly used for portable devices, and the demand for light weight, high voltage and capacity has increased, and electric vehicles or hybrid electric The use area for automobiles, power assisted power supply through gridization, etc. has been greatly expanded.

However, there are many problems to be solved for using a lithium secondary battery with a large capacity power source, and the most important task is improvement of energy density and safety. In addition, uniformity of wetting due to large-sized surface and reduction of process time are also the most important problems to be solved. Therefore, many researchers are spurring research on materials that can meet low cost while improving energy density, and are also making efforts to study materials to improve safety.

As a material for improving the energy density, a Ni-based material or a Mn-based material having a capacity higher than that of LiCoO ₂ that has been used previously is being studied. As a cathode, The material by Li alloy reaction is being studied.

In order to improve safety, a stable olivine-based cathode active material such as LiFePO ₄ or an anode active material such as Li ₄ Ti ₅ O ₁₂ and the like are being studied. However, such a material for improving safety has a fundamentally low energy density, and can not fundamentally solve the safety problem of the structure of the lithium secondary battery.

The safety of the secondary battery can be divided into internal safety and external safety, and subdivided into electrical safety, impact safety and thermal safety. These various safety problems commonly involve a temperature rise in the event of a problem, in which case shrinkage of the drawn membranes generally used will inevitably occur.

Therefore, many researchers have proposed all solid type batteries to solve the problem of safety, but they have various problems to replace commercialized batteries.

First, the currently used electrode active material has a solid form, and when a solid electrolyte or a polymer electrolyte is used, the contact surface with the active material for lithium migration becomes very small. As a result, even if the conductivity of the solid electrolyte or the polymer electrolyte itself is 10 ^-5 s / cm which is the liquid electrolyte level at present, the ion conductivity becomes very low. Second, for the above reasons, the ionic conductivity at the interface between the solid and the solid, or at the interface between the solid and the polymer, must be further lowered. Third, in order to constitute a battery, the binding force is important, and in the case of a solid electrolyte having high conductivity, a polymer binder is indispensably required, and the ion conductivity is further lowered. Fourth, to construct a cell, ion conductivity is not only required for the separation layer. In order to improve the ionic conductivity of the electrode, a material capable of improving the ionic conductivity is required for the positive electrode and the negative electrode active material. When the solid electrolyte or the polymer electrolyte is included as the electrode component, the capacity is decreased.

Accordingly, there is a high need for a structure of a battery which prevents a short circuit due to shrinkage of the separator and has excellent cell performance.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-described problems of the prior art and the technical problems required from the past.

The inventors of the present application developed an integrated electrode assembly using a separation layer having a multilayer structure including a specific two-phase electrolyte and a three-phase electrolyte after intensive research and various experiments The integral electrode assembly can prevent a short circuit due to the shrinkage of the separator, and the liquid component of the separator layer flows into the electrode during fabrication of the electrode assembly to improve the wetting characteristic of the electrode, The present invention has been completed.

Therefore, the electrode assembly according to the present invention is characterized in that the positive electrode, the negative electrode, and the separating layer positioned between the positive electrode and the negative electrode have an integral structure,

The separating layer comprises: (a) at least one two-phase electrolyte comprising a liquid phase component and a polymer matrix; and (b) at least one three-phase electrolyte comprising a liquid phase component and a solid phase component and a polymer matrix. Layer structure,

Wherein the polymer matrix of the separating layer is bonded to the anode or the cathode,

And the liquid component of the separation layer is partially introduced into the electrode during the fabrication of the electrode assembly.

According to the experiment of the present inventors, the instant of maximization of the danger within the secondary battery is a state where the energy is increased, and the short-circuit situation which may occur due to the separation of the membrane in the charged state includes (1) 2) charged positive and negative current collectors, 3) negative current collector and positive current collector, and 4) positive current collector and charged negative electrode.

As a result of testing all of the above conditions in the dry room of the charged electrode, it was confirmed that the most severe thermal runaway occurred in the contact between the charged anode and the anode current collector. As a result of intensive research, it was found that this is due to a rapid exothermic reaction of, for example, 4Al + 3O ₂ → 2Al ₂ O ₃ in Al-foil, which is a positive electrode current collector. In all cases where the actual battery exploded, Al-foil could not find its shape.

In the above experiment, thermal runaway occurs only when the charged cathode and the positive electrode collector are in contact with each other. However, the other three cases are not necessarily safe. In a battery, it is dangerous to contact any part of the anode and the cathode with each other.

On the other hand, since the polymer matrix and the solid-phase component are not shrunk at high temperature, the integrated electrode assembly according to the present invention can prevent the occurrence of an event such as explosion as in the above-described experiment, and is excellent in high-temperature safety.

In addition, since the liquid component flows into the electrode during the manufacturing process of the electrode assembly, for example, the lamination process, the electrode is impregnated so that the ion conductivity of the electrode is improved and the performance of the battery can be improved. In addition, as the electrolyte is uniformly wetted to the electrodes, electrode degeneration due to uneven penetration of the electrolytic solution, which is the greatest problem in the large-sized electrolytic solution, can be minimized. Therefore, the electrode assembly of the present invention may be defined as having, in relation to the state of the electrolytic solution, a part of the liquid component derived from the separating layer contained or embedded in the electrode. At this time, the amount of the liquid component contained in or embedded in the electrode derived from the separation layer is not particularly limited, and may be, for example, 10 to 90% based on the total amount of the liquid component contained in the entire electrode assembly.

The two-phase electrolyte includes an ionic salt, a liquid component that partially flows into the electrode from the separation layer during the fabrication of the electrode assembly to improve the ion conductivity of the electrode; And a polymer matrix having affinity for the liquid component and providing adhesion to the positive electrode and the negative electrode.

Also, the three-phase electrolyte may include a liquid phase component including an ionic salt and partially flowing into the electrode from the separation layer in the process of manufacturing the electrode assembly to improve the ion conductivity of the electrode. A solid phase component supporting the three-phase electrolyte of the separation layer between the anode and the cathode; And a polymer matrix having affinity for the liquid component and providing adhesion to the positive electrode and the negative electrode.

The liquid component of the separation layer may be partially introduced into the electrode by a pressurizing process. In the case of manufacturing the integrated battery with the above-described structure, it is preferable that the liquid phase component flows into the electrode by a separate pressing process because the separation layer carries the liquid phase component. In this case, the wettability of the electrode is improved, and the problem of ionic conductivity, which has been pointed out as a disadvantage of the conventional polymer battery, can be solved.

In the case of a multi-layered separating layer, it is possible to minimize the problems caused by polymer degradation in terms of performance while maintaining the advantages thereof, as compared with the case of using a three-phase electrolyte alone. can do.

The ratio of the liquid component to the polymer matrix in the entire composition of the separation layer may be 3: 7 to 9: 1 by weight. If the amount of the liquid phase component is too small, the wetting performance may be deteriorated to affect the performance of the battery. On the contrary, if the liquid phase content is too large, the fluidity of the material itself increases and the process becomes difficult.

The polymer constituting the polymer matrix in the present invention is not limited in its kind, but preferred examples include polymers selected from the group consisting of an oxide-based non-crosslinked polymer, a polar non-crosslinked polymer, and a crosslinked polymer having a three-dimensional network structure Lt; / RTI > More preferably, the polymer matrix may include both an oxide-based non-crosslinked polymer and a polar non-crosslinked polymer.

Non-limiting examples of the oxide-based non-crosslinked polymer include at least one selected from the group consisting of poly (ethylene oxide), poly (propylene oxide), poly (oxymethylene), and poly (dimethylsiloxane).

Examples of non-limiting examples of the polarity ratio polymer include polyacrylonitrile, poly (methyl methacrylate), poly (vinyl chloride), poly (vinylidene fluoride), poly (vinylidenefluoride-co-hexafluoropropylene) terephthalamide). < / RTI >

In the present invention, the crosslinked polymer constituting the polymer matrix may be a polymer of a monomer having two or more functional groups, or a copolymer of a monomer having two or more functional groups and a polar monomer having one functional group.

The monomer having two or more functional groups is not limited in its kind but is preferably trimethylolpropane ethoxylate triacrylate, polyethylene glycol dimethacrylate, But are not limited to, polyethylene glycol diacrylate, divinylbenzene, polyester dimethacrylate, divinyl ether, trimethylolpropane, trimethylolpropane trimethacrylate, and ethoxy And ethoxylated bisphenol dimethacrylate. The term " acrylate "

The polar monomer having one functional group is not particularly limited in its kind, but is preferably selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethylene glycol methyl ether acryl Acrylate, acrylonitrile, vinyl acetate, vinyl chloride, and vinyl fluoride, and the like.

In the present invention, the solid-phase component may be contained in an amount of 20 to 90% by weight based on the weight of the polymer matrix of the three-phase electrolyte. If the solid phase component is less than 20% by weight, the separation force of the separation layer is weak and short-circuiting may occur. If the solid phase component is more than 90% by weight, the amount of the liquid component may be decreased to reduce wetting performance.

The liquid component may be an electrolytic solution containing an ionic salt, as long as it can partially flow into the electrode to increase the ion conductivity of the electrode.

The ionic salt, for example, may be a salt of lithium, the lithium salt is _{LiCl, LiBr, LiI, LiClO 4} , LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, But may be at least one selected from the group consisting of LiSbF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ Nli, chloroborane lithium, lower aliphatic carboxylate lithium and lithium tetraphenylborate, It is not.

Wherein the electrolyte is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, gamma butyrolactone, sulfolane, methyl acetate and methyl propionate But it is not limited to these.

In one preferred embodiment, the solid phase component may be a solid compound that is not reactive with ion conductive ceramic and / or lithium ions, and more preferably, the solid compound is comprised of an oxide, nitride, and carbide that is not reactive with lithium ions May be one or more selected from the group.

Non-limiting examples of the oxide that is not reactive with lithium ions include at least one selected from the group consisting of MgO, TiO ₂ (Rutile) and Al ₂ O ₃ , but is not limited thereto.

The separating layer may be composed of two layers of a two-phase electrolyte and a three-phase electrolyte or three layers of a two-phase electrolyte / a three-phase electrolyte / a two-phase electrolyte. It can be composed of three layers, and various structures are possible.

In the electrode assembly of the present invention, the positive electrode is prepared, for example, by applying and drying a slurry prepared by adding a positive electrode mixture containing a positive electrode active material to a solvent such as NMP on a positive electrode collector, May further include a binder, a conductive material, a filler, a viscosity adjusting agent, and an adhesion promoter.

The cathode current collector generally has a thickness of 3 to 500 mu m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and may be formed of a material such as stainless steel, aluminum, nickel, titanium, sintered carbon, or a surface of aluminum or stainless steel Treated with carbon, nickel, titanium, silver or the like may be used. The positive electrode current collector may have fine unevenness formed on the surface thereof to increase the adhesive force of the positive electrode active material as in the case of the negative electrode current collector. Alternatively, the positive electrode current collector may have various properties such as a film, sheet, foil, net, porous body, Form is possible.

The cathode active material is a material capable of causing an electrochemical reaction. Examples of the lithium transition metal oxide include lithium cobalt oxide (LiCoO ₂ ) containing two or more transition metals and substituted with one or more transition metals, lithium Layered compounds such as nickel oxide (LiNiO ₂ ); Lithium manganese oxide substituted with one or more transition metals; Formula _{LiNi 1-y M y O 2} ( where, M = Co, Mn, Al , Cu, Fe, Mg, B, Cr, Zn or Ga and Lim, 0.01≤y≤0.7 include one or more elements of the element) A lithium nickel-based oxide represented by the following formula: _{Li 1 + z Ni 1/3 Co 1/3} Mn 1/3 O 2, Li 1 + z Ni 0.4 Mn 0.4 Co 0.2 O 2 , such as _{Li 1 + z Ni b Mn c} Co 1- (b + c + d _{) M d O (2-e} ) A e ( where, -0.5≤z≤0.5, 0.1≤b≤0.8, 0.1≤c≤0.8, 0≤d≤0.2 , 0≤e≤0.2, b + c + d <1, M = Al, Mg, Cr, Ti, Si or Y, and A = F, P or Cl; lithium nickel cobalt manganese composite oxide; And the formula _{Li 1 + x M 1-y} M 'y PO 4-z X z ( wherein, M = a transition metal, preferably Fe, Mn, Co or Ni, M' = Al, Mg or Ti, X = F, S or N, and -0.5? X? +0.5, 0? Y? 0.5, and 0? Z? 0.1), but the present invention is not limited thereto.

Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), cellulose, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluorine rubber, various copolymers, high molecular weight polyolefins such as polyolefin, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, Vinyl alcohol, and the like.

The conductive material is not particularly limited as long as it has electrical conductivity without causing any chemical change in the battery, for example, graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used. Concrete examples of commercially available conductive materials include acetylene black series such as Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc.), Ketjenblack, EC (Armak Company), Vulcan XC-72 (Cabot Company), and Super P (Timcal).

The filler is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery, and examples thereof include olefin polymers such as polyethylene and polypropylene; Fibrous materials such as glass fibers and carbon fibers are used.

The viscosity modifier may be added up to 30% by weight based on the total weight of the negative electrode mixture as a component for adjusting the viscosity of the electrode mixture so that the mixing process of the electrode mixture and the coating process on the current collector may be easy. Examples of such viscosity modifiers include carboxymethylcellulose, polyvinylidene fluoride and the like, but are not limited thereto. In some cases, the above-described solvent may play a role as a viscosity adjusting agent.

The adhesion promoter may be added in an amount of 10% by weight or less based on the binder, for example, oxalic acid, adipic acid, Formic acid, acrylic acid derivatives, itaconic acid derivatives, and the like.

The negative electrode may be formed by applying a slurry prepared by adding a negative electrode active material containing a negative active material on a negative electrode current collector to a solvent such as NMP and drying the negative electrode active material. Fillers, viscosity modifiers, and adhesion promoters, and the like.

The negative electrode collector is generally made to have a thickness of 3 to 500 mu m. Such an anode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, and may be formed of a material such as copper, stainless steel, aluminum, nickel, titanium, fired carbon, surface of copper or stainless steel A surface treated with carbon, nickel, titanium, silver or the like, an aluminum-cadmium alloy, or the like can be used. The current collector may have fine irregularities on the surface thereof to increase the adhesive force of the negative electrode active material, and various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric are possible.

Examples of the negative electrode active material include carbon and graphite materials such as natural graphite, artificial graphite, expanded graphite, carbon fiber, non-graphitizable carbon, carbon black, carbon nanotube, fullerene and activated carbon; Metals such as Al, Si, Sn, Ag, Bi, Mg, Zn, In, Ge, Pb, Pt, and Ti that can be alloyed with lithium and compounds containing these elements; Complexes of metals and their compounds and carbon and graphite materials; Lithium-containing nitrides, and the like. Among them, a carbon-based active material, a tin-based active material, a silicon-based active material, or a silicon-carbon based active material is more preferable, and these may be used singly or in combination of two or more.

The present invention also provides a method of manufacturing an integral electrode assembly,

(1) a process for preparing a mixture for a two- or three-phase electrolyte by uniformly mixing a linear polymer, a monomer component for a crosslinking polymer, a liquid component comprising an ionic salt, a polymerization initiator and optionally a solid phase component;

(2) coating the two-phase or three-phase mixture on one electrode;

(3) a step of forming a two-phase or three-phase electrolyte layer by performing a polymerization reaction by UV irradiation or application of heat;

(4) repeating steps (2) and (3) on the two-phase or three-phase electrolyte layer to form a separation layer comprising a plurality of electrolyte layers; And

(5) placing and pressing the corresponding electrode on the separation layer;

The present invention provides a method of manufacturing an integral electrode assembly.

A conventional method for manufacturing an electrode assembly is a method of manufacturing a mold for forming a space between an anode and a cathode, and injecting a polymer monomer mixture into the space and then polymerizing the mixture.

On the other hand, as in the present invention, the method of coating and polymerizing a predetermined material on one electrode can simplify the process, and the liquid component of the separation layer in the pressurizing step (step (5) The ion conductivity of the electrode can be improved by impregnating the electrode, which is preferable for improving the performance of the battery.

In addition, in the process (1) of the present invention, the linear polymer is mixed in the form of a polymer rather than a monomer, so that during the polymerization of the crosslinked polymer in the process (3), a part of the linear polymer penetrates into the gel of the crosslinked polymer Physical connection structure can be achieved.

The present invention also provides a lithium secondary battery including the integral electrode assembly, wherein the lithium secondary battery includes the integral electrode assembly and a non-aqueous electrolyte solution containing a lithium salt. In one preferred example, the lithium secondary battery does not include a separate lithium salt-containing non-aqueous electrolyte, or may contain only a small amount.

This is possible by partially inflowing the liquid component of the separation layer into the electrode by impregnation with the electrode in step (5) of the manufacturing method of the present invention. Considering that the electrode impregnation process is a bottleneck process in the battery manufacturing process, An excellent secondary battery can be provided.

The present invention also provides a middle- or large-sized battery module including the lithium secondary battery as a unit battery and a battery pack including the battery module. The battery pack may be used in various middle- or large-sized devices requiring high rate characteristics and high- For example, a power tool powered by an electric motor; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle (HEV), and a plug-in hybrid electric vehicle (PHEV); Electric motorcycle including E-bike, E-scooter; An electric golf cart, or the like, and may be used in a power storage system, but the present invention is not limited thereto.

As described above, the integral electrode assembly according to the present invention can prevent a short circuit due to the shrinkage of the separator, and the electrolyte is impregnated into the electrode during the manufacturing process, so that the problem of increasing the electrode non- And it has an advantage that not only the ion conductivity of the electrode can be improved but also the safety is improved and the long-term performance or preservation property of the battery is excellent.

1 is a schematic view showing a cross section of an integral electrode assembly according to one embodiment of the present invention;
2 is a graph showing the cycle characteristics of the secondary battery according to the first embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings, but the present invention is not limited by the scope of the present invention.

1 is a schematic cross-sectional view of an integral electrode assembly according to one embodiment of the present invention.

1, an electrode assembly 100 according to the present invention includes an anode 110, a cathode 120, a three-phase separation layer 130, and a two-phase separation layer 140. have. The positive electrode 110 has a structure in which positive electrode mixture materials 112 and 113 are coated on both sides of the positive electrode collector 111 and the separator layer is disposed between the positive electrode 110 and the negative electrode 120 consist of.

Hereinafter, the present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.

&Lt; Example 1 >

The negative electrode was prepared by adding graphite, PVdF, and carbon black to NMP to prepare a slurry, which was then applied to a copper foil and dried at about 130 ° C for 2 hours. The anode was prepared by adding LiNiMnCoO ₂ / LiMnO ₂ , PVdF, and carbon black to NMP, coating it on aluminum foil, and drying it at about 130 ° C for 2 hours.

The electrolyte layer of the two phases was prepared by uniformly dissolving the polymer together with acetone so that the composition ratio was as shown in Table 1 below.

The electrolyte layer of the three phases was prepared by preparing the mixture so as to have the composition ratio shown in Table 2, and adding 3 wt% of benzoin as an ultraviolet initiator to TMPEOTA.

<Table 1>

<Table 2>

Two phases of electrolyte were coated on the anode, and three electrolyte layers were coated thereon and irradiated with ultraviolet ray for 1 minute to prepare an electrolyte membrane by polymerization. The negative electrode was placed on the positive electrode coated with the thus prepared electrolyte layer, laminated, and inserted into the pouch to prepare a secondary battery.

&Lt; Comparative Example 1 &

An olefin-based porous separator was inserted between the positive electrode and the negative electrode according to Example 1, and a liquid electrolyte was further injected to prepare a secondary battery.

<Experimental Example 1>

The secondary battery prepared in Example 1 was evaluated for battery characteristics without any additional impregnation process.

The charge was maintained at a constant voltage (CV) of 4.2 V after the constant current (CC) was charged to 4.2 V at a current density of 0.1 C at the time of charging. When the current density reached 0.05 C, charging was terminated. The discharge was completed in the CC mode up to 2.5 V at a current density of 0.1 C at discharge. Charging and discharging were repeated 50 times under the same conditions.

The discharge profile of the secondary battery described above exhibited excellent discharge characteristics and capacity implementation rates even though no separate electrolyte was added and no separate impregnation process was performed. Also, the cycle life characteristics showed stable performance without fading as shown in the graph of FIG. Therefore, it was confirmed that the processability can be improved by shortening the wetting time of the electrolyte using the electrolyte layer coating.

<Experimental Example 2>

The secondary batteries prepared in Example 1 and Comparative Example 1 were evaluated for battery characteristics without any additional impregnation process. The discharge capacities shown in the first charge / discharge cycle are shown in Table 3 below.

<Table 3>

Referring to Table 3, the results of evaluating the charge and discharge characteristics of the batteries of Example 1 and Comparative Example 1 without the electrolyte impregnation process are shown. It can be seen that the battery of Example 1 exhibits a higher discharge capacity than the battery of Comparative Example 1 at an actual 1 ^st discharge capacity and that the capacity implementation rate is superior to the theoretical capacity (17 mAh).

Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (26)

The positive electrode, the negative electrode, and the separating layer positioned between the positive electrode and the negative electrode have an integral structure,
The separating layer comprises: (a) at least one two-phase electrolyte comprising a liquid phase component and a polymer matrix; and (b) at least one three-phase electrolyte comprising a liquid phase component and a solid phase component and a polymer matrix. Layer structure,
Wherein the polymer matrix of the separating layer is bonded to the anode or the cathode,
Wherein a part of the liquid phase component of the separation layer flows into the electrode during fabrication of the electrode assembly. The method according to claim 1, wherein the two-
A liquid component which contains an ionic salt and partially flows into the electrode from the separation layer in the process of manufacturing the electrode assembly to improve the ion conductivity of the electrode; And
A polymer matrix having affinity for the liquid component and providing adhesion to the positive and negative electrodes;
And the two-phase electrode assembly includes a first electrode and a second electrode. The method according to claim 1, wherein the three-
A liquid component which contains an ionic salt and partially flows into the electrode from the separation layer in the process of manufacturing the electrode assembly to improve the ion conductivity of the electrode;
A solid phase component supporting the three-phase electrolyte of the separation layer between the anode and the cathode; And
A polymer matrix having affinity for the liquid component and providing adhesion to the positive and negative electrodes;
And the three-phase electrode assembly includes a first electrode and a second electrode. The integrated electrode assembly according to claim 1, wherein a part of the liquid component of the separation layer flows into the electrode by a pressing process. The integrated electrode assembly according to claim 1, wherein the polymer matrix is at least one selected from the group consisting of an oxide-based non-crosslinked polymer, a polar non-crosslinked polymer, and a crosslinked polymer having a three-dimensional network structure. The integrated electrode assembly according to claim 5, wherein the oxide-based non-crosslinked polymer is at least one selected from the group consisting of poly (ethylene oxide), poly (propylene oxide), poly (oxymethylene), and poly (dimethylsiloxane). The method of claim 5, wherein the polar non-crosslinking polymer is selected from the group consisting of polyacrylonitrile, poly (methyl methacrylate), poly (vinyl chloride), poly (vinylidene fluoride), poly (vinylidenefluoride-co-hexafluoropropylene) and terephthalamide). 2. The integrated electrode assembly of claim 1, The integrated electrode assembly according to claim 5, wherein the crosslinked polymer is a copolymer of a monomer having two or more functional groups, or a copolymer of a monomer having two or more functional groups and a polar monomer having one functional group. The method of claim 8, wherein the monomer having two or more functional groups is selected from the group consisting of trimethylolpropane ethoxylate triacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate glycol diacrylate, divinylbenzene, polyester dimethacrylate, divinyl ether, trimethylolpropane, trimethylolpropane trimethacrylate, and ethoxylated bisphenol A dimethacrylate, Wherein the electrode assembly is at least one member selected from the group consisting of ethoxylated bis phenol dimethacrylate. The method of claim 8, wherein the polar monomer having one functional group is selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethylene glycol methyl ether acrylate, ethylene glycol methyl ether Wherein at least one member selected from the group consisting of acrylate, acrylate, acrylate, vinyl acetate, vinyl chloride, and vinyl fluoride is used. The integrated electrode assembly according to claim 1, wherein the liquid component is an electrolyte solution containing an ionic salt. 12. The integrated electrode assembly of claim 11, wherein the ionic salt is a lithium salt. The method of claim 12, wherein the lithium salt is _{LiCl, LiBr, LiI, LiClO 4} , LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, chloroborane lithium, lithium lower aliphatic carboxylate, lithium tetraphenylborate, and the like. 12. The method of claim 11, wherein the electrolyte is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, gamma butyrolactone, sulfolane, methyl acetate and methyl propionate Wherein the electrode assembly is at least one selected from the group consisting of: The integrated electrode assembly according to claim 1, wherein the solid phase component is a solid compound that is not reactive with ion conductive ceramic or lithium ion, or a solid compound that is not reactive with ceramic and lithium ion. 16. The integrated electrode assembly of claim 15, wherein the solid compound is at least one selected from the group consisting of oxides, nitrides, and carbides that are not reactive with lithium ions. The method of claim 16, wherein the oxide is not the lithium ion and reactivity integral electrode assembly, characterized in that at least one selected from the group consisting of MgO, TiO ₂ (Rutile) and Al ₂ O _3. The integrated electrode assembly according to claim 1, wherein the separation layer comprises two layers of a two-phase electrolyte and a three-phase electrolyte. The integrated electrode assembly according to claim 1, wherein the separation layer comprises three layers of a two-phase electrolyte / a three-phase electrolyte / a two-phase electrolyte. The integrated electrode assembly according to claim 1, wherein the separation layer comprises three layers of a three-phase electrolyte / a two-phase electrolyte / a three-phase electrolyte. A method of manufacturing an integral electrode assembly according to claim 1,
(1) a process for preparing a mixture for a two- or three-phase electrolyte by uniformly mixing a linear polymer, a monomer component for a crosslinking polymer, a liquid component comprising an ionic salt, a polymerization initiator and optionally a solid phase component;
(2) coating the two-phase or three-phase mixture on one electrode;
(3) a step of forming a two-phase or three-phase electrolyte layer by performing a polymerization reaction by UV irradiation or application of heat;
(4) repeating steps (2) and (3) on the two-phase or three-phase electrolyte layer to form a separation layer comprising a plurality of electrolyte layers; And
(5) placing and pressing the corresponding electrode on the separation layer;
Wherein the electrode assembly includes a first electrode and a second electrode. A lithium secondary battery comprising the integral electrode assembly according to any one of claims 1 to 20. A battery module comprising the lithium secondary battery according to claim 22 as a unit cell. A battery pack comprising the battery module according to claim 23. 25. The battery pack according to claim 24, wherein the battery pack is included as a power source for a middle- or large-sized device. 26. The battery pack of claim 25, wherein the middle- or large-sized device is an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a system for power storage.

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