KR20130116420A - Anode assembly for li secondary battery and method of fabricating the same - Google Patents

Abstract

PURPOSE: A negative electrode assembly is provided to improve charging speed and charging efficiency by performing the oxidation and the reduction reaction of lithium in electrolyte in which the mobility of the lithium is big. CONSTITUTION: A negative electrode assembly (100A) includes a conductive network layer (10) with conductive wires (10W) including pores (10P), forming a three-dimension, and contacting other network layers by being extended to two different directions. Lithium passes through the pores, and deposited on the conductive wires when a battery is charged, and the lithium is ionized and separated from the conductive wires when the battery is discharged. The deposition and the separation of the lithium is repeated by the charging and the discharging of the battery.

Description

Anode assembly for Li secondary battery and method of fabricating the same}

The present invention relates to a secondary battery technology, and more particularly, to a negative electrode assembly for a lithium secondary battery and a manufacturing method thereof.

Recently, the demand for secondary batteries such as lithium batteries, lithium ion batteries, and lithium ion polymer batteries has been greatly increased. A secondary battery is a battery which can be charged and discharged by using an electrode material having excellent reversibility, and is a nickel-hydrogen (Ni-MH) battery, a lithium (Li) battery, a lithium ion (Li-ion) battery, etc. according to a positive electrode and a negative electrode active material. It can be divided into. Such secondary batteries are increasingly being applied as a power source for smart devices such as smart phones, portable computers, and electronic devices such as electronic paper, or vehicles such as bicycles and electric vehicles.

Secondary batteries using lithium or a compound thereof as a negative electrode active material have high voltage and high energy density and have been the subject of many studies. In the secondary battery using the lithium or a compound thereof as a negative electrode active material, chemical reactions due to charging and discharging and natural chemical reactions occur constantly, and thus, lithium dendrite, which is an undesirable crystalline protrusion in the metallic lithium anode, may be formed. have.

When the dendritic lithium is formed inside the secondary battery, the pores of the separator may be blocked, and thus the movement of the ionic material may be blocked. As a result, the charging and discharging efficiency of the battery may be reduced, thereby reducing the life of the secondary battery. In addition, when the dendritic lithium is excessively grown, the dendritic lithium may penetrate the separator to short-circuit the positive and negative electrodes of the secondary battery.

Accordingly, the technical problem to be solved by the present invention is to provide a negative electrode assembly with improved charging and discharging efficiency and lifespan.

In addition, another technical problem to be solved by the present invention is to provide a method for producing a negative electrode assembly having the above advantages.

The negative electrode assembly according to an embodiment of the present invention for solving the above technical problem, extends in at least two different directions to be in contact with each other, the conductive wire to form a three-dimensional solid with pores formed from the surface to the inside And a conductive network layer including the conductive network layer, wherein lithium is electrodeposited on the conductive wires through the pores when the battery is charged, and the lithium electrodeposited on the conductive wires is ionized and detached when the battery is discharged. As the battery is charged and discharged, electrodeposition and detachment of the lithium are repeated.

In some embodiments, the conductive network layer may have a nonwoven structure. Further, in another embodiment, the conductive network layer may have a lattice structure. In addition, at least a portion of the conductive network layer may have an increased porosity in the direction of the anode facing the cathode assembly in the conductive network layer.

In some embodiments, the conductive wires may comprise any one or combination of stainless steel, nickel, titanium, tantalum, copper, gold, platinum, ruthenium, silver or alloys thereof. Alternatively, the conductive wires may include a lithium compound.

In some embodiments, the negative electrode assembly may further comprise a lithium source comprising any one or a combination of lithium and lithium compounds provided in the pores of the conductive network layer or bonded onto the surface of the conductive network layer. have. The lithium source provided in the pores of the conductive network layer may have a powder form. In addition, the lithium source bonded on the surface of the conductive network layer may be a gap containing metal foil.

In some embodiments, a current collecting tab or lead wire may be coupled to the conductive network layer. The cathode assembly may further include a binder layer on the surface of the conductive network layer for adhesion with an adjacent layer, wherein the binder layer may include linear binders. In this case, the adjacent layer may include any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane.

In another embodiment, the negative electrode assembly may further include linear binders mixed with the conductive wires in the conductive network layer. In this case, the negative electrode assembly may further include an adjacent layer adhered to the conductive network layer, and the adjacent layer includes any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane. can do.

According to another aspect of the present invention, there is provided a method of manufacturing a negative electrode assembly, which extends in at least two different directions to be in contact with each other, and has a three-dimensional shape with pores formed therein from a surface thereof. Providing a conductive network layer comprising conductive wires to form; Providing an adjacent layer adhered to the conductive network layer; Providing a binder layer comprising linear binders between the adjacent layer and the conductive network layer; And compressing the conductive network layer and the adjacent layer.

According to another aspect of the present invention, there is provided a method of manufacturing a negative electrode assembly, which extends in at least two different directions to be in contact with each other, and has a three-dimensional shape having pores formed therein from a surface thereof. Providing a conductive network layer comprising conductive wires and linear binders mixed with the conductive wires; Providing an adjacent layer adhered to the conductive network layer; And compressing the conductive network layer and the adjacent layer.

In these embodiments, the adjacent layer may include any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane. In addition, in the pressing step, the step of heating the binder layer may be further performed.

According to an embodiment of the present invention, there is provided a conductive network layer including conductive wires having conductive pores formed from the surface to form a three-dimensional solid, and the charging and discharging of the battery causes the pores on the conductive wires. By repeatedly performing the electrodeposition and desorption of the elapsed lithium ions, the oxidation and reduction reaction of lithium occurs in the electrolyte having a high mobility of lithium, it is possible to improve the charging rate and charging efficiency. In addition, the conductive network layer randomly provides a linear reaction site in the three-dimensional space from the standpoint of lithium ions penetrated therein, so that lithium electrodeposited on the surface of the conductive wires is ordered in any particular direction. It is possible to provide a negative electrode assembly which cannot grow freely, thereby suppressing orderly growth of lithium such as dendritic growth.

According to another embodiment of the present invention, since the negative electrode assembly can be manufactured by only linear contact or point contact using linear binders, there is provided a method of manufacturing a negative electrode assembly that provides excellent mechanical adhesion without increasing the internal resistance of the negative electrode. Can be. In addition, according to an embodiment of the present invention, since the performance of the linear binder can be expressed by pressing and heating without an organic solvent, there is no performance deterioration due to the drying process and impurities due to the organic solvent, environmentally friendly with less environmental load The manufacturing process of a negative electrode assembly can be obtained.

1A is a perspective view of a negative electrode assembly according to an embodiment of the present invention, FIG. 1B is a cross-sectional view taken along line II ′ of FIG. 1A, and FIG. 1C is a partially enlarged view illustrating conductive wires of the negative electrode assembly.
2A is a perspective view of a negative electrode assembly according to another embodiment of the present invention, and FIG. 2B is a cross-sectional view taken along the line II ′ of FIG. 2A.
3A is a perspective view of a negative electrode assembly according to still another embodiment of the present invention, and FIG. 3B is a cross-sectional view taken along the line II ′ of FIG. 3A.
4A and 4B are exploded views and cross-sectional views taken along the line II-II 'of the conductive wires inside the conductive network layer for explaining the lithium reduction reaction of the negative electrode assembly according to the embodiment of the present invention. Scanning electron micrograph image of the conductive wires analyzed after the charge is completed after 100 charge and discharge.
FIG. 5A is an enlarged view of conductive wires inside a conductive network layer for explaining lithium oxidation reaction of a negative electrode assembly according to an exemplary embodiment of the present invention, and FIG. 5B is a part of a negative electrode assembly analyzed after discharge is completed after 100 charge / discharge cycles. Scanning electron micrograph image of.
6A and 6B are perspective views illustrating cathode assemblies according to still other embodiments of the present invention, respectively.
7A and 7B are perspective views illustrating negative electrode assemblies according to still other embodiments of the present invention, respectively.
8A and 8B are perspective views illustrating a method of manufacturing a negative electrode assembly according to various embodiments of the present disclosure.
9A is a perspective view illustrating a method of manufacturing a negative electrode assembly according to still another embodiment of the present invention, and FIG. 9B is a partially enlarged view of the manufactured conductive network layer.
10 is a view showing a lithium secondary battery having a negative electrode assembly according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The embodiments of the present invention are described in order to more fully explain the present invention to those skilled in the art, and the following embodiments may be modified into various other forms, It is not limited to the embodiment. Rather, these embodiments are provided so that this disclosure will be more faithful and complete, and will fully convey the scope of the invention to those skilled in the art.

In addition, in the following drawings, the thickness or size of each layer is exaggerated for convenience and clarity of description, the same reference numerals in the drawings refer to the same elements. As used herein, the term "and / or" includes any and all combinations of any of the listed items.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an," and "the" include singular forms unless the context clearly dictates otherwise. Also, " comprise "and / or" comprising "when used herein should be interpreted as specifying the presence of stated shapes, numbers, steps, operations, elements, elements, and / And does not preclude the presence or addition of one or more other features, integers, operations, elements, elements, and / or groups.

The metal fibers disclosed herein are formed by maintaining a metal or alloy in a molten state in a vessel, by quenching and solidifying the molten metal in the atmosphere through an injection hole of the vessel using a pressurization device such as a compressed gas or a piston. It can be made or produced by a condensed drawing method, and is an integral metal fiber body that extends continuously with a substantially uniform thickness over a full length range of substantially 1 cm or more. The metal fibers have the heat resistance, plasticity, and electrical conductivity that the metal has, while at the same time having the advantages of fiber-specific weaving and nonwoven processing. The present invention relates to features and advantages of applying such metal fiber advantages to the electrode structure of a cell. However, the above-described manufacturing process is illustrative only and the present invention is not limited by this manufacturing process. By controlling the number, size, and / or emergence of the injected molten metal, the thickness, uniformity, structure such as nonwoven fabric and aspect ratio of the metal fibers can be controlled.

The term 'separation membrane' as used herein includes a separator generally used in a liquid electrolyte battery using a liquid electrolyte having a small affinity with the separator. In addition, the "separation membrane" used herein includes an intrinsic solid electrolyte membrane and / or a gel solid electrolyte membrane in which the electrolyte is strongly bound to the separation membrane, and the electrolyte and the separation membrane are recognized as the same. Therefore, the term separation membrane used herein should be interpreted to include all of them, unless it is clearly distinguished from the solid electrolyte membrane and the gel solid electrolyte membrane.

FIG. 1A is a perspective view of a negative electrode assembly 100A according to an embodiment of the present invention, FIG. 1B is a cross-sectional view taken along line II ′ of FIG. 1A, and FIG. 1C is conductive wires of the negative electrode assembly 100A. A partial enlarged view showing 10w.

1A and 1B, the cathode assembly 100A may include a conductive network layer 10 made of conductive wires 10W. The conductive wires 10W of the conductive network layer 10 extend in at least two different directions to contact each other, and have a three-dimensional solid shape with pores 10P formed therein from the surface of the conductive network layer 10. Can be formed. The pore 10P may penetrate the electrolyte as described below, and may provide a movement path of lithium ions due to charging and discharging of the battery.

The conductive wires 10W may be metal fibers. In another embodiment, the conductive wires 10W may have a conductive surface provided with a metal layer coated on a polymer core wire or carbon fiber. As such, when the conductive wires 10W are formed using a light polymer core wire or carbon fiber, the weight of the conductive wires 10W may be reduced, and thus an energy density of the battery may be expected to increase.

In yet another embodiment, the conductive wires 10W are formed between lithium and alloying other than metals, metalloids, nonmetals or combinations thereof that are alloyable and dealloying with lithium as the lithium source. It may be formed of a lithium compound. This will be described later.

Preferably, the conductive wires 10W are the metal fibers which can be easily manufactured and are electrochemically inert at low operating potentials, the metal fibers being any of stainless steel, nickel, titanium and copper or alloys thereof. It may include one or a combination thereof. Other examples of the metal fibers may be noble metals such as gold, platinum, ruthenium and silver or alloys thereof.

There may be a plurality of conductive wires 10W segmented to have a predetermined length. These may have a nonwoven structure within three-dimensional solids, as shown in FIGS. 1A and 1B. The conductive wires 10W can be segmented to have a length of about 2 cm to 8 cm, and because they are formed by bending or tangling and contacting or joining each other, they have pores 10P therein and because of their fibrous properties. It may have flexibility.

In some embodiments, the conductive wires 10W may have a thickness in the range of 0.1 μm to 200 μm. When the thickness of the conductive wires 10W is 0.1 μm or less, it is difficult to manufacture the metallic conductive wires 10W through a process such as drawing or injection, and the conductive wires for forming a conductive network as described below ( 10W) can be difficult to handle for artificial arrangements. When the thickness of the conductive wires 10W is 200 μm or more, the surface area per volume of the conductive wires 10W may be reduced, making it difficult to obtain an improvement in battery performance due to the increase in the surface area, and the energy density may be reduced. have.

Preferably, the conductive wires 10W may have a thickness of 0.1 μm to 20 μm, and may have a surface area density to obtain excellent processability and high energy density within this range. The surface area density is defined as the ratio of the surface area / volume per unit length of the conductive wires 10W (eg 4 / diameter if it has a circular cross section), in the thickness range, the surface area density of the conductive wires 10W. ^{May be} 2 × 10 ⁵ (1 / m) to 4 × 10 ⁷ (1 / m).

In some embodiments, one surface of the conductive network layer 10 may further be provided with a lead wire 100W for electrical connection between the current collector tab 100T and an internal battery electrode (not shown). Although not shown, the lead wire 100W may be the conductive wires 10W extending outwards or may be directly coupled by soldering to the conductive wires 10W without the current collector tab 100T.

In some embodiments, negative electrode assembly 100A may include a lithium source for cell reaction. The lithium source may be granulated powder 20P including any one or a combination of lithium and lithium compounds provided in the pores 10P of the conductive network layer 10, as shown in FIG. 1C. have. Preferably, the lithium source may be pure lithium powder. The lithium compound is, for example, a lithium compound between lithium, which can be alloyed and de-alloyed, and a metal other than the lithium, a metalloid, a nonmetal, or a combination thereof, for example lithium and silicon And compounds of germanium, tin, lead, antimony, bismuth, zinc, aluminum, iron, cadmium and sulfur. However, the foregoing lithium source materials are exemplary and the present invention is not limited thereto. For example, a known lithium-containing compound used as a conventional anode active material may be used.

The lithium source, which is provided in powder form, is provided before use of the battery, and may gradually lose some or all of its amount as the battery is charged and discharged. In this case, other metal elements constituting the lithium source may serve as the conductive material in the conductive network layer 10.

In some embodiments, a conductive material (not shown) may be further added into the pores 10P of the conductive network layer 10 as needed. The conductive material may be, for example, a fine carbon such as carbon black, acetylene black, ketjen black and ultra fine graphite particles, a nano metal particle paste, or a ratio such as an indium tin oxide paste or a carbon nanotube. It may be a nanostructure having a large surface area and low resistance. In the negative electrode assembly according to the present embodiment, since the conductive wires 100W having a fine size may play the same role as the conductive material, there is an advantage of suppressing an increase in manufacturing cost due to the addition of the conductive material. .

In addition, the negative electrode assembly may further comprise a suitable binder (also called a binder, not shown). The binder may be, for example, polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyacrylic resin, derivatives thereof, or a combination thereof. In another embodiment, the binder is carboxy methyl cellulose (CMC), polybutadiene (polybutadiene), polyisoprene, polybutyl acrylate (polybutyl acrylate), polybutyl methacrylate (polybutyl methacrylate) used in the form of a slurry ), Polyhydroxyethyl methacrylate, polyacrylamide, polyisobutylene, isobutylene-isoprene rubber, vinylidene fluoride-hexafluoro Propylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene (PTFE), styrene Butylbutadiene rubber (SBR), butyl acrylate-styrene copolymer, Butyl acrylate-acrylic nitrile copolymer, butyl acrylate-acrylic nitrile-glycidyl methacrylate copolymer, isobutylene-styrene Various polymer systems such as homopolymers, condensation polymers, copolymers and block polymers such as isobutylene-styrene copolymers, ethylene-propylene-diene copolymers (EPDM), derivatives thereof or combinations thereof It may be a material. However, these materials are illustrative, and the present invention is not limited thereto. For example, the binder may be another olefin polymer, an acrylic polymer, a diene polymer, a silicon-containing polymer, a vinyl polymer, a fluorine-containing polymer, a thermosetting elastomer, a natural rubber, a latex, a polypeptide, a protein, or a combination thereof. If necessary, the binder may be a conductive polymer-based material, petroleum pitch, or coal tar. Preferably, the binder may be a polymer material having an easy binding process and excellent binding force for preparing a linear binder, as described below. This will be described later in more detail with reference to FIGS. 9A and 9B.

According to this embodiment, since both of the main surface (10U, 10B) of the electrode assembly (100A) can be made of both the coming and going of the lithium, so that the separation between the separator, and the anode (not shown) facing each other, respectively, Since two anodes can share one cathode assembly, there is an advantage of providing a battery having a high energy density to thickness. However, this is exemplary, and a current collector layer (see 100L in FIG. 3A) may be coupled to one of the main surfaces 10U and 10B of the electrode assembly 100A, and the collector may be disposed on the first main surface 10B side. When the entire layer 100T is coupled, the separator and the anode may be sequentially disposed on the second main surface 10U.

2A is a perspective view of a negative electrode assembly 100B according to another embodiment of the present invention, and FIG. 2B is a cross-sectional view taken along the line II ′ of FIG. 2A. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.

2A and 2B, the negative electrode assembly 100B of FIG. 1A includes a lithium-containing metal foil 20L including any one or a combination of lithium and a lithium compound as a lithium source. 100A). Preferably, the lithium containing metal foil 20L may be pure lithium foil. Unlike the powdered lithium source, the plate-shaped lithium-containing metal foil 20L can not only increase the lithium content, but also can eliminate the space occupied by the lithium powder as compared to the case of applying the powdered lithium source. In addition, the porosity of the conductive network layer can be further reduced, thereby increasing the linear density of the conductive wires in the conductive network layer, thereby further increasing the surface area of the battery reaction. Extending the surface area of the cell reaction has the advantage of improving the charge and discharge rate and efficiency of the battery.

The lithium alloy is a compound between a metal, a metalloid, a nonmetal, or a combination thereof and lithium, which is capable of alloying and dealloying with lithium as described above, for example, silicon, germanium, tin, Lead, antimony, bismuth, zinc, aluminum, iron, cadmium, sulfur, or any combination thereof, or a compound comprising lithium. However, these materials are illustrative, and the present invention is not limited thereto. For example, a known lithium-containing compound used as a conventional anode active material may be used.

The lithium-containing metal foil 20L may be bonded on one main surface of the conductive network layer 10. For example, the lithium-containing metal foil 20L may be formed on an opposite surface of the conductive network layer 10 opposite the anode (not shown), for example, the first main surface of the conductive network layer 10 (see 10B in FIG. 1A). ) May be combined. The lithium-containing metal foil 20L may gradually lose some or all of its amount during the charging and discharging process of the battery. The remaining foil of the lithium foil or the lithium compound may thus function as a current collector. However, in the embodiment of the present invention, since the conductive wires 10W itself can function as a current collector in three-dimensional solid, this current collector function of the foil is not essential.

In the embodiment shown in FIG. 2A, the current collector tab 100T is coupled to the side of the conductive network layer 10, but this is illustrative, and the current collector tab 100T is attached to the lithium-containing metal foil 20L. ) And the lead wire 100W, or only the wire 100W may be combined. In some embodiments, another conductive network layer is also bonded to the other main surface of the lithium-containing metal foil 20L to which the conductive network layer 10 is bonded, so that both main surfaces of the negative electrode assembly 100B may be utilized as the negative electrode. have.

3A is a perspective view of a negative electrode assembly 100C according to another embodiment of the present invention, and FIG. 3B is a cross-sectional view taken along the line II ′ of FIG. 3A. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.

3A and 3B, the electrode assembly 100C may further include a current collector layer 100L together with the conductive network layer 10 and the lithium-containing metal foil 20L. May be coupled to current collector layer 100L. Current collector layer 100T may be a suitable metal layer, such as copper or aluminum.

As another example, although not shown, a lithium-containing powder (see 20P in FIG. 1C) may be added instead of the lithium-containing metal foil 20L as the lithium source, and in this case, the current collector layer 100L may be a conductive network layer ( 10) may be coupled directly.

4A and 4B are exploded views and cross-sectional views taken along the line II-II 'of the conductive wires inside the conductive network layer for explaining the lithium reduction reaction of the negative electrode assembly according to the embodiment of the present invention. Scanning electron micrograph image of the conductive wires analyzed after the charge is completed after 100 charge and discharge.

Conductive wires 10W of the negative electrode assembly provide a reaction site for the reduction reaction of lithium. During charging of the battery, lithium ions moving from the positive electrode to the negative electrode assembly through the electrolyte may be transferred from the surface of the conductive network layer 10 to the interior through the pores 10P of the conductive network layer 10. Lithium ions delivered to the interior of the conductive network layer 10 are in close proximity to the conductive wires that provide a linear reaction site disposed three-dimensionally within the conductive network layer, and on any surface of the conductive wire selected therefrom. It will be electrodeposited as shown in 4a and 4b. From among the conductive wires adjacent to the lithium ions, it is arbitrary and spatially non-directional in which conductive wires lithium ions are electrodeposited. Therefore, lithium electrodeposited on the surface of the conductive wires does not grow in any particular direction in the inner space of the conductive network layer, whereby dendritic growth of lithium in the conductive network can be suppressed.

As an example, using a stainless wire of about 8 μm in diameter (see the scale in FIG. 5B), a conductive network layer having a nonwoven structure is fabricated using a fiber process such as entanglement, and the current collector tab is subjected to a conventional soldering process. Was bonded to the conductive network layer. Pure lithium powder was used as a lithium source, the lithium powder was filled in the conductive network layer, and an electrolyte layer and an anode were sequentially stacked on the conductive network layer to form a cell, and the electrical characteristics thereof were evaluated. 4C is a photographic image obtained by cutting and then finally charging the cell after 100 times of charging and discharging of the cell. It can be seen that lithium was evenly deposited on the surfaces of the stainless wires to form the lithium film layer CL in FIG. 4B. The fiber diameter was thickened to about 12 to 14 μm, and the lithium film layer CL has a thickness of about 2 μm to 3 μm.

In some embodiments of the present invention, the volume of the lithium coating layer formed during charging may be larger than the volume of the conductive wire therein. In general, an active material that reversibly reacts with lithium according to the alloying and dealloing mechanism or the intercalation and deintercalation mechanism is bulkier than lithium. Accordingly, the volume occupied by the active material in the electrode is generally larger than the occupied volume of lithium participating in the battery reaction. However, in some embodiments of the present invention, the volume of conductive wires occupying in the negative electrode assembly may be smaller than that of lithium participating in the reaction, so that when using conventional active materials based on the same lithium volume, There is an advantage that can reduce the size of the negative electrode assembly.

Reduction of lithium in the electrode assembly, since electrodeposition to conductive wires has a thermodynamically stable energy state compared to lithiation reactions such as alloying or intercalation that occurs in negative active materials such as lithium compounds during charging. The reaction predominantly occurs on the conductive wires. 4C supports this fact, in the case where a lithium containing alloy is used as the lithium source, the reduction reaction of lithium occurs selectively or dominantly on the conductive wire, and the lithium containing alloy powder may gradually disappear.

Although the Example mentioned above is a case where lithium powder is used as a lithium source, it is the same also when the lithium containing foil or the lithium compound containing conductive wire is used as a lithium source. For example, in the case where conductive wires are formed of a lithium compound as a lithium source, lithium provided to the outside by de-alloing during discharge may be reduced by lithium by conductive wire when charging, and the reduction of lithium is conductive Although it may be performed first through a lithiation reaction such as alloying on the surface of the wires, the reduction of the lithium is completed through a continuous process in which lithium is electrodeposited on the conductive wire once a microalloy layer is formed.

Thus, according to an embodiment of the present invention, the mobility of lithium is not caused by charging of the battery, i.e., by the lithium insertion and lithium alloying reaction involving lithium diffusion in the layered structure, in the conductive network layer. Can be predominantly or selectively made by an electrodeposition process in a large electrolyte, so that the charging speed can be increased and the charging efficiency can be improved.

Referring again to FIG. 4C, dendritic growth due to reduction of lithium does not appear in the conductive network layer. This means that the conductive wires arranged three-dimensionally in the conductive network layer randomly provide linear reaction sites in the three-dimensional space from the standpoint of lithium ions penetrating into the conductive network layer. Lithium electrodeposited on the surface of the field cannot grow in any particular direction in the inner space of the conductive network layer. As a result, according to the embodiment of the present invention, orderly growth of lithium such as dendritic growth in the conductive network layer can be suppressed. If dendritic growth of lithium occurs in the conductive network layer, the growth of the lithium resin body may be terminated when the lithium resin body grows and reaches another conductive wire adjacent to the conductive wire with the lithium resin body attached thereto. The dendritic growth of lithium may not be sustained outside the conductive network layer, for example, beyond the separator.

5A is an enlarged view of conductive wires inside a conductive network layer for explaining a lithium oxidation reaction of a negative electrode assembly according to an embodiment of the present invention, and 5B is a scan of conductive wires analyzed after discharge is completed after 100 charge / discharge cycles. An electron micrograph image.

As described above with reference to FIGS. 4A to 4C, the lithium film layer CL electrodeposited on the conductive network layer during charging of the battery may be ionized during discharge of the battery and detached from the surface of the conductive wires. Referring to FIG. 5A, when the battery is discharged, the lithium film layer CL may be detached to expose the surfaces of the conductive wires 10W again.

Referring to FIG. 5B, when charging and discharging is performed 100 times or more, and the battery is completely discharged by connecting an external load to the battery, the lithium film layer CL may disappear and the surfaces of the stainless wires of the conductive network layer may be exposed. According to an embodiment of the present invention, the electrolyte may be evenly impregnated into the conductive network layer by the pores of the conductive network layer, whereby lithium electrodeposited on the conductive wires is uniformly oxidized over the entire volume of the conductive network layer. It can be seen that the excessive consumption of lithium ions does not appear. As such, upon completion of the oxidation process of lithium, the thickness of the conductive wires is reduced.

According to the embodiment of the present invention, since the standard electrode potential (0.0 V) of lithium metal can be used as electromotive force without the problem of internal short circuit of the battery due to dendritic growth of lithium, the capacity of the battery Close to the capacity, it is possible to maximize the energy density. In addition, since irreversibility of the negative electrode, such as excessive consumption of lithium, does not appear upon reduction of lithium, it may also contribute to improving the capacity of the battery by increasing the reversible capacity of the positive electrode.

In addition, compared with the conventional negative electrode assembly formed by slurry coating a negative electrode active material on the negative electrode current collector layer, according to an embodiment of the present invention, the movement of lithium ions because the pores in the conductive network layer provides a passage for lithium ions Since the figure is not limited by the conductive network layer and is substantially determined by the separator or the electrolyte membrane, the mobility of lithium ions can be significantly improved as compared with the conventional negative electrode assembly. Accordingly, according to the embodiment of the present invention, the efficiency of charging and discharging the secondary battery can be improved.

In addition, the conductive network layer may undergo a volume change of the conductive wires as lithium is electrodeposited and detached on the conductive wires as the battery is charged and discharged. However, despite the volume change of the conductive wires, the volume change of the entire conductive network layer can be mitigated by the pores in the conductive network layer. As a result, according to the embodiment of the present invention, the mechanical stability of the battery package can be secured. Although the features and advantages of the above embodiments are described for stainless wires, conductive wires of other materials could also be applied, as long as the cell reaction could occur by lithium electrodeposition and desorption.

6A and 6B are perspective views illustrating cathode assemblies 100D and 100E, respectively, in accordance with yet other embodiments of the present invention. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.

Referring to FIG. 6A, the conductive network layer 10 of the negative electrode assembly 100D may include a conductive network layer 10 having a pore 10P therein and forming a three-dimensional shape. The conductive network layer 10 may have a lattice structure formed by conductive wires 10W_1 and 10W_2 that extend in parallel and cross each other. The lattice structure is provided by stacking two or more, for example, first and second sub network layers 10_1 and 10_2 made of conductive wires 10w to form a three-dimensional solid, and such a sub network layer 10_1. , The pores 10P may be provided therein by lamination of 10_2.

As described above, the negative electrode assembly 100D may further include a lithium source. As shown in FIG. 6A, the lithium source may be a lithium-containing metal foil 20L. In some embodiments, the conductive network layer 10 may extend from the contact surface of the lithium containing metal foil 20L to the backside to surround the lithium containing metal foil 20l. The conductive wires 10W_1 and 10W_2 may surround the lithium-containing metal foil 20L as one fiber body at least partially extending integrally. In some embodiments, as shown in FIG. 6A, only a portion of the conductive network layer 10, only the first sub network layer 10_1, surrounds the lithium containing metal foil 20l, and the second sub network layer 10_2 is It may be stacked on the first sub network layer 10_1.

In another embodiment, the lithium source comprises a compound of lithium including metals, metalloids, and nonmetallic elements capable of dealloying lithium, together with or in place of the lithium-containing metal foil 20L. It may be provided in the form of powder or as pure lithium powder in the pores of the conductive network layer 10 or by forming the conductive wires 10 with these lithium compounds.

The lithium source provided as described above may be partially or totally dissipated according to the use of the battery, while the oxidation and reduction reaction of lithium according to the charging and discharging of the battery occurs predominantly by electrodeposition and detachment of the conductive wires. In this case, other metal elements of the lithium compound constituting the lithium source may serve as the conductive material in the conductive network layer 10.

In another embodiment, referring to FIG. 6B, the cathode assembly 100E may include a conductive network layer 10 that forms a three-dimensional conformation of another structure. The conductive network layer 10 may have a lattice structure formed by woven conductive wires 10W_1 and 10W_2. The woven structure is provided by stacking two or more, for example, first and second sub-network layers 10_1 and 10_2 made of conductive wires 10W to form a three-dimensional solid, or one continuous conductive network. It may be provided by winding up layers so as to have pores therein.

As described above, the negative electrode assembly 100E may further include a lithium source, and the lithium source shown in FIG. 6B is a lithium containing metal foil 20l. However, this is exemplary, and the lithium source may be provided in the pores of the conductive network layer 10 in powder form, together with or in place of the lithium containing metal foil 20l, the source in powder form It may be a pure lithium powder or a lithium compound powder including a lithium compound including lithium and other metals, metalloids, and nonmetallic elements other than lithium and lithium capable of de-alloying lithium. In addition, the lithium source may be provided by forming the conductive wires 10 with the above-described lithium compound.

The conductive wires 10W of the cathode assemblies 100D, 100E can be manufactured to have the lattice configuration shown in FIGS. 6A and 6B due to the fibrous properties. This configuration has a relatively regular arrangement as compared to the conductive wires 10W having the nonwoven structure of FIGS. 1A to 5B, but the three-dimensional three-dimensional structure is made through the pores of the conductive network layer 10 during charging of the battery. From the standpoint of lithium ions moving inside, the three-dimensional linear reduction sites can be random, so that dendritic growth of lithium can be suppressed. As another example of the conductive network, it may have a knitted structure, a multilayer fabric structure that can be obtained through a general fiber process.

7A and 7B are perspective views illustrating cathode assemblies 100F and 100G, respectively, according to still other embodiments of the present invention. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.

7A and 7B, the conductive network layers 10 of the cathode assemblies 100F and 100G form a three-dimensional solid state in which the porosity is increased in the anode direction. In some embodiments, subconductive network layers having different porosities may be stacked to provide varying porosities. For example, as illustrated in FIG. 7A, a nonwoven fabric having a second porosity greater than the first porosity in the anode direction is formed on the first sub conductive network layer 10_1 of the nonwoven fabric having the first porosity. It may be provided by stacking two sub conductive network layers 10_2. Similarly, as shown in FIG. 7B, the lattice structure having the second porosity greater than the first porosity in the anode direction on the first sub-conductive network layer 10_1 having the first porosity is formed. It may be provided by stacking two sub conductive network layers 10_2.

The porosity of the sub conductive network layers 10_2 can be controlled by adjusting the density of the conductive wires. For example, when the first sub conductive network layer 10_1 and the second sub conductive network layer 10_2 have the same volume, the density of the conductive wires of the second sub conductive network layer 10_2 is equal to the first sub conductive network layer 10_1. It may be less than the density of the conductive wires of the conductive network layer 10_1. Accordingly, the size of the pores 10P_1 and 10P_2 increases in the conductive network layer 10 toward the anode direction.

In the above-described embodiment, the nonwoven structure and the lattice structure are disclosed respectively, but this is exemplary, and the inside of the conductive network layer is a subconductive network layer of a nonwoven structure having a small porosity and the surface of the lattice subconductive network having a large porosity. It may be a layer. In addition, the embodiment of the present invention is not limited to stacking sub conductive network layers having different porosities so as to form a conductive network layer in which the porosity is thus changed. For example, in the conductive network layer of the nonwoven fabric structure, the conductive wire layers are randomly deployed at high density, the conductive wires are randomly deployed at low density thereon, and then an integrated conductive network layer having porosity is changed through a process such as entanglement. The conductive network layer may be formed through another spinning fiber process.

Although the illustrated embodiments disclose that the porosity increases from the inside of the conductive network layer to the surface of the anode direction, the portion of the conductive network layer 10 bonded to the lithium-containing metal foil 20l and the surface of the anode direction. The part has a relatively large porosity, the middle part has a small porosity, and toward the anode side, the structure which has a big porosity, a small porosity, and a big porosity is also possible.

As such, when the porosity of the anode side surface portion of the conductive network layer 10 is increased compared to the inside, lithium ions transferred from the anode side to the cathode assembly through the electrolyte easily pass through the surface of the conductive network layer 10, Electrodeposition and desorption of lithium ions can occur more dominantly in interiors with smaller porosity than on three-dimensional surfaces. Accordingly, uniformity of electrodeposition and desorption of lithium ions over the entire volume of the conductive network layer 10 may be improved, or electrodeposition and desorption of lithium ions may be induced locally only in the conductive network layer 10.

8A and 8B are perspective views illustrating a method of manufacturing the negative electrode assemblies 100H and 100I according to various embodiments of the present disclosure. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.

8A and 8B, the negative electrode assemblies 100H and 100I may include linear binders 30W. The linear binders 30W may be polymer fibers fibrillated from a suitable polymer material by a fiberization process such as melt spinning and / or thermal stretching process. The polymer fibers may be long filaments, short filaments, staples, multifilaments, monofilaments or composites thereof, but the present invention is not limited thereto. The polymer material may be, for example, polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), or polyacrylic resin. In another embodiment, the polymer material is carboxy methyl cellulose (CMC), polybutadiene, polyisoprene, polybutyl acrylate, polybutyl acrylate, polybutyl methacrylate, which are applied in the form of a conventional slurry. (polybutyl methacrylate), polyhydroxyethyl methacrylate, polyacrylamide, polyisobutylene, isobutylene-isoprene rubber, vinylidene fluoride- Hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene (PTFE) ), Styrenebutadiene rubber (SBR), butyl acrylate-styrene copolymer (butyl acrylate-sty butyl copolymer, butyl acrylate-acrylic nitrile copolymer, butyl acrylate-acryllic nitrile-glycidyl methacrylate copolymer, isobutyl acrylate-acrylic nitrile copolymer Homogeneous polymers such as isobutylene-styrene copolymers, ethylene-propylene-diene copolymers (EPDM), derivatives thereof or combinations thereof, condensation polymers, copolymers and block polymers; Various polymer-based materials such as; Or polymer material which is another olefin polymer, acrylic polymer, diene polymer, silicone-containing polymer, vinyl polymer, fluorine-containing polymer, thermosetting elastomer, natural rubber, latex, polypeptide, protein, or a combination thereof. It may be prepared by fiber. If desired, the linear binders 30W may be a conductive polymeric material, petroleum pitch or coal tar.

The linear binders 30 may be used to bond the conductive network layer 10 onto adjacent layers such as lithium-containing metal foils, current collector layers, another conductive network layer, separators or solid electrolyte membranes. 8A and 8B illustrate the lithium containing metal foil 20l and the current collector layer 100L, respectively.

Since the linear binders 30W are a dry material, they are formed in a regular lattice pattern as shown in FIG. 8A or randomly developed as shown in FIG. 8B, on the adjacent base layer, so that the binder layers 30A and 30B are formed. ) Can be formed. In this case, the linear binders 30W may be developed in one or several layers. The manner of deployment of such linear binders 30W is exemplary only, and the present invention is not limited thereto. For example, the linear binders 30W may have a woven structure, a coarse nonwoven structure, or other woven structure, such as a line pattern, polygonal pattern, or knit without the intersection of the linear binders.

Thereafter, the conductive network layer 10 is provided on the binder layers 30A and 30B made of the linear binders 30W, and the adjacent layer is applied by applying pressure to the adjacent layers 20L and 100L and the conductive network layer 10. And a bond between the conductive network layer 10 can be obtained. In some embodiments, in addition to applying the input, heat may be applied to the linear binders 30W to induce melting of the linear binders 30, thereby thermally sealing the linear binders 30W. Heat for melting the linear binders 30W may be applied in a manner such as hot air, joule heating, or halogen lamp irradiation. The heating is carried out at a relatively low temperature, for example at 50 ° C. to 400 ° C., preferably at 150 ° C. to 300 ° C., in which the linear binders 30W can be melted, so that an economical manufacturing process is possible. Do.

When spraying or spin coating the above-described binder material between these interfaces to bond the conductive network layer on the adjacent layer, an insulating coating by the binder material may be formed between the adjacent layer and the conductive network layer. The insulating coating not only increases the internal resistance in the negative electrode assembly, but also can passivate reaction sites of the conductive wires in which oxidation and reduction reactions of lithium occur. However, according to the embodiment of the present invention, since the linear binders 30 can achieve the coupling between the adjacent layer and the conductive network layer only by line contact or point contact and not by surface contact, without increasing the internal resistance of the cathode. It can also provide good mechanical adhesion.

 In addition, according to an embodiment of the present invention, since the linear binders 30W may be fused by pressure and heating without an organic solvent such as carbonates, esters, and lactones, according to an embodiment of the present invention, the negative electrode structure May be carried out in a dry process. Accordingly, there is no drying process due to the organic solvent and performance deterioration due to impurities, and an environment-friendly manufacturing process with less environmental load can be obtained.

9A is a perspective view illustrating a method of manufacturing the negative electrode assembly 100J according to another embodiment of the present invention, and FIG. 9B is a partially enlarged view of the manufactured conductive network layer 10. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.

9A and 9B, the negative electrode assembly 100J may include linear binders 30W comprising a fibrous polymeric material, petroleum pitch or coal tar as described above. The negative electrode assembly 100J may be linear. The binders 30W are distinguished from the negative electrode assembly 100J of FIGS. 8A and 8B in that they are provided mixed with the conductive wires 10W in the conductive network layer 10. The linear binders 30W to be mixed may be randomly mixed with the conductive wires 10W and a nonwoven structure may be obtained through a process such as entanglement, or a regular structure such as a woven structure may be obtained through a fiber blending process. Such a manufacturing method is exemplary and the present invention is not limited thereto.

 The conductive network layer 10 may be adhered to the adjacent layer, for example, the lithium-containing metal foil 20L by the linear binders 30W, for which pressure and / or heat may be applied. Although the embodiment shown in FIGS. 9A and 9B discloses a cathode assembly 100J with an adjacent layer added, there may be no adjacent layer. For example, when the lithium source is provided in the conductive network layer in powder form or, optionally, the conductive material is provided in the conductive network layer in powder form with the lithium source, the linear binders in the conductive network layer 10 ( 30W) may serve to bind the lithium source and the conductive material inside the conductive network layer.

In manufacturing terms, the conductive wires 10W and the linear binder 30W are mixed at a suitable mixing ratio, so that a conductive network layer of nonwoven structure can be produced. Thereafter, the negative electrode assembly 100J may be manufactured by invading the lithium source and / or the conductive material in the form of dried particles in the pores 10P of the conductive network layer, and heating and compressing the same. Thus, according to an embodiment of the present invention, since solvents such as water or organic solvents for slurry production are not used, the load on the environment is small and a separate process for removing the solvent after invading the particle composition in the conductive network layer is performed. Since the drying process is not necessary, the process can be simplified, productivity can be improved, and equipment can be simplified. In addition, when the solvent remains in the electrical active material, since the electrical active material may deteriorate, the mixing process using the solvent-free dry powder described above may improve the yield.

10 is a view showing a lithium secondary battery having a negative electrode assembly according to an embodiment of the present invention. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.

Referring to FIG. 10, the lithium secondary battery 1000 includes a case 300, a negative electrode assembly 100, a separator 500, and a positive electrode assembly 200. The case 300 accommodates the negative electrode assembly 100, the positive electrode assembly 200, and the separator 500 therein, and the negative electrode assembly 100 and the positive electrode are disposed inside the case 300 with the separator 500 interposed therebetween. Assembly 200 may be wound. In addition, an electrolyte may be provided between the negative electrode assembly 100 and the positive electrode assembly 200 inside the case 300 to serve as a medium through which the ions generated by ionization of the active material move. Pores in the conductive network layer 10 of the negative electrode assembly 100 may facilitate the impregnation of the electrolyte.

The electrolyte is a suitable aqueous electrolyte solution containing salts such as potassium hydroxide (KOH), potassium bromide (KBr), potassium chloride (KCL), zinc chloride (ZnCl ₂ ) and sulfuric acid (H ₂ SO ₄ ), or LiClO ₄ , LiPF _6, or the like. It may be a non-aqueous electrolyte such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate containing a lithium salt of the, and the moisture is absorbed by the electrodes (100, 200) and / or separator 500, the battery 1000 is completed Can be. Although not shown, a suitable battery management system for controlling stability and / or power supply characteristics during use of the battery 1000 may be further coupled to the battery 1000.

As described with reference to the above embodiments, despite the use of the pure lithium active material in the negative electrode assembly, in the conductive network layer 10 of the negative electrode assembly 100 in accordance with the charge and discharge action of the lithium secondary battery 1000 Lithium is uniformly electrodeposited and desorbed so that dendritic growth of lithium can be suppressed. As a result, a phenomenon in which the negative electrode assembly 100 and the positive electrode assembly 200 are short-circuited with each other by lithium in the battery is prevented, so that the stability of the lithium secondary battery 1000 may be improved.

Although the illustrated cell form discloses a cylindrical shape, this is exemplary, and because of the excellent processability and flexibility due to the fibrous properties of the negative electrode assembly, in addition to the winding type, it can be modified in three dimensions such as stacking, bending and winding up. It is possible to provide a flexible battery which can be attached to a known structure such as square, coin type and pouch type or directly to surfaces such as garments, bags and flexible displays. In addition, since the negative electrode assembly according to the embodiment of the present invention can not only obtain an output voltage due to the reduction potential of lithium but also improve the irreversibility of charge and discharge, a battery of high output, high capacity, and high efficiency can be obtained. It can be applied as a power source or medium and large battery for power storage.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It will be clear to those who have knowledge.

Claims (31)

A conductive network layer comprising conductive wires extending in at least two different directions and contacting each other and having three-dimensional solids with pores formed therein from the surface,
When the battery is charged, lithium is electrodeposited on the conductive wires through the pores, and when the battery is discharged, the lithium is ionized and desorbed on the conductive wires, and the battery is charged and discharged. Anode assembly in which the electrodeposition and desorption of the lithium is repeated. The method of claim 1,
And the conductive network layer has a nonwoven structure. The method of claim 1,
And the conductive network layer has a lattice structure. The method of claim 1,
At least a portion of the conductive network layer has an increased porosity in the direction of the anode opposite the cathode assembly within the conductive network layer. The method of claim 1,
And the conductive wires are metal fibers. The method of claim 5, wherein
And the metal fibers comprise any one or combination of stainless steel, nickel, titanium, tantalum, copper, gold, platinum, ruthenium, silver or alloys thereof. The method of claim 1,
The conductive wires as a lithium source, the negative electrode assembly comprising a lithium compound containing a metal, metalloid, non-metallic element other than lithium and lithium capable of de-alloying lithium. The method of claim 1,
The conductive wires are negative electrode assembly, characterized in that the composite core body having a conductive surface provided with a metal layer coated on a polymer core wire or carbon fiber. The method of claim 1,
Further comprising a lithium source provided in the pores of the conductive network layer or bonded onto a surface of the conductive network layer,
And the lithium source comprises any one or combination of lithium and a lithium compound comprising the lithium and at least one of metals, metalloids and base metals other than the lithium. The method of claim 9,
And the lithium source provided in the pores of the conductive network layer has a powder form. The method of claim 9,
And the lithium source bonded onto the surface of the conductive network layer is a lithium containing metal foil. The method of claim 1,
And a current collector tab or lead wire is coupled to the conductive network layer. The method of claim 1,
Further comprising a binder layer for adhesion to the adjacent layer on the surface of the conductive network layer,
And the binder layer comprises linear binders. The method of claim 13,
And the linear binders comprise a fibrous polymeric material. 15. The method of claim 14,
The polymer material is polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyacrylic resin, carboxymethyl cellulose (CMC), polybutadiene (polybutadiene), poly Isoprene, polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyisobutylene , Isobutylene-isoprene rubber, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile ), Polymethylmethacrylate, polytetrafluoroethylene (PTFE), styrenebutadiene rubber ( styrenebutadiene rubber (SBR), butyl acrylate-styrene copolymer, butyl acrylate-acryllic nitrile copolymer, butyl acrylate-acrylonitrile-glycidyl methacrylate Butyl acrylate-acrylic nitrile-glycidyl methacrylate copolymer, isobutylene-styrene copolymer, ethylene-propylene-diene copolymer (EPDM), derivatives thereof, or A negative electrode assembly comprising a combination of these. The method of claim 13,
And the adjacent layer includes any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane. The method of claim 1,
And linear binders mixed with the conductive wires in the conductive network layer. The method of claim 17,
And the linear binders comprise a fibrous polymeric material. The method of claim 18,
The polymer material is polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polyacrylic resin, carboxymethyl cellulose (CMC) , Polybutadiene, polyisoprene, polybutyl acrylate, polybutyl methacrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide , Polyisobutylene, isobutylene-isoprene rubber, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (polyvinylidene fluoride) ), Polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene ethylene: PTFE), styrenebutadiene rubber (SBR), butyl acrylate-styrene copolymer, butyl acrylate-acryllic nitrile copolymer, butyl acrylate Butyl acrylate-acrylic nitrile-glycidyl methacrylate copolymer, isobutylene-styrene copolymer, ethylene-propylene-diene copolymer copolymer: EPDM), a derivative thereof or a combination thereof. The method of claim 17,
Further comprising an adjacent layer adhered to the conductive network layer,
And the adjacent layer comprises any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, or an electrolyte membrane. Providing a conductive network layer comprising conductive wires extending in at least two different directions to be in contact with each other and having three-dimensional solids with pores formed therein from the surface;
Providing an adjacent layer adhered to the conductive network layer;
Providing a binder layer comprising linear binders between the adjacent layer and the conductive network layer; And
Compressing the conductive network layer and the adjacent layer. 22. The method of claim 21,
And the adjacent layer comprises any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane. 22. The method of claim 21,
And the linear binders are randomly developed or have a knit or woven structure. 22. The method of claim 21,
And the linear binders comprise a fibrous polymeric material. 25. The method of claim 24,
The polymer material is polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyacrylic resin, carboxymethyl cellulose (CMC), polybutadiene (polybutadiene), poly Isoprene, polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyisobutylene , Isobutylene-isoprene rubber, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile ), Polymethylmethacrylate, polytetrafluoroethylene (PTFE), styrenebutadiene rubber ( styrenebutadiene rubber (SBR), butyl acrylate-styrene copolymer, butyl acrylate-acryllic nitrile copolymer, butyl acrylate-acrylonitrile-glycidyl methacrylate Butyl acrylate-acrylic nitrile-glycidyl methacrylate copolymer, isobutylene-styrene copolymer, ethylene-propylene-diene copolymer (EPDM), derivatives thereof, or A negative electrode assembly comprising a combination of these. 22. The method of claim 21,
In the pressing step, the manufacturing method of the negative electrode assembly, further comprising the step of heating the binder layer. A conductive network layer comprising conductive wires extending in at least two different directions and contacting each other and having pores formed from the surface to form a three-dimensional shape, and linear binders mixed with the conductive wires; Providing;
Providing an adjacent layer adhered to the conductive network layer; And
Compressing the conductive network layer and the adjacent layer. The method of claim 27,
And the linear binders comprise a fibrous polymeric material. 29. The method of claim 28,
The polymer material is polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyacrylic resin, carboxymethyl cellulose (CMC), polybutadiene (polybutadiene), poly Isoprene, polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyisobutylene , Isobutylene-isoprene rubber, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile ), Polymethylmethacrylate, polytetrafluoroethylene (PTFE), styrenebutadiene rubber ( styrenebutadiene rubber (SBR), butyl acrylate-styrene copolymer, butyl acrylate-acryllic nitrile copolymer, butyl acrylate-acrylonitrile-glycidyl methacrylate Butyl acrylate-acrylic nitrile-glycidyl methacrylate copolymer, isobutylene-styrene copolymer, ethylene-propylene-diene copolymer (EPDM), derivatives thereof, or A negative electrode assembly comprising a combination of these. The method of claim 27,
And the adjacent layer comprises any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane. The method of claim 27,
In the pressing step, the manufacturing method of the negative electrode assembly, further comprising the step of heating the binder layer.

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