KR102286725B1 - Lithium secondary battery electrode with electron conductivity difference and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a lithium secondary battery electrode having a difference in electronic conductivity and a manufacturing method thereof, and an aspect of the present invention includes: a lower layer including a metal material; an intermediate layer formed on the lower layer and including a metal material and a polymer material; and an upper layer formed on the intermediate layer and including a polymer material and an inorganic material.

Description

Lithium secondary battery electrode having a difference in electronic conductivity and manufacturing method thereof

The present invention relates to a lithium secondary battery electrode having a difference in electronic conductivity and a method for manufacturing the same.

With the recent increase in market demand for IT electronic devices such as smartphones, tablet PCs, and high-performance notebook PCs, as part of measures against global warming and resource depletion, large-capacity power storage such as electric vehicles and smart grids As the demand for devices has greatly increased, the demand for electrochemical devices including secondary batteries is rapidly increasing.

Among them, a lithium secondary battery is an electrochemical device receiving the most attention due to its excellent cycle life and high energy density, and various studies are being conducted to meet the demand for high output and high capacity.

In a lithium secondary battery, lithium metal has a very high capacity and a low reduction potential, and thus has been spotlighted as an anode material for a lithium secondary battery.

However, the conventional lithium metal has a problem in that lithium dendrites grow due to non-uniform lithium deposition and cause a short circuit, as well as forming dead lithium that does not contribute to capacity. In addition, there was a disadvantage in that the thickness of the electrode was increased by using thick lithium with an excessive lithium source.

In order to overcome this, studies have been conducted to introduce a host layer capable of uniform deposition of lithium ions, but lithium ions are deposited on the conductive layer when the conductive host layer is introduced. showed

The present invention is to solve the above problems, and an object of the present invention is to provide a lithium secondary battery electrode capable of suppressing the growth of lithium dendrites by uniformly depositing lithium ions from the bottom, and a method for manufacturing the same.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention, the lower layer comprising a metal material; an intermediate layer formed on the lower layer and including a metal material and a polymer material; and an upper layer formed on the intermediate layer and including a polymer material and an inorganic material.

According to an embodiment, the metal material may include any one or more selected from the group consisting of metal nanowires, metal nanoparticles, and metal nanomesh.

According to one embodiment, the metal material is copper (Cu), nickel (Ni), zinc (Zn), platinum (Pt), gold (Au), silver (Ag), aluminum (Al), tungsten (W) , and may include any one or more selected from the group consisting of tin (Sn).

According to one embodiment, the polymer material is, cellulose (cellulose), cellulose (cellulose) derivative, polyurethane (polyuretan), polyurethane copolymer, cellulose acetate (celluloseacetate), acetate butyrate (acetate butylate), polymethyl meta Acrylate (polymethyl methacrylate, PMMA), polymethyl acrylate (PMA), polyacrylic copolymer, polyvinyl acetate copolymer, polyvinylacetate (PVAc), polyvinylpyrrolidone (PVP) , polyvinyl alcohol (PVA), polyfurfuryl alcohol (PPFA), polystyrene (PS), polystyrene copolymer, polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene oxide copolymer, polypropylene oxide Copolymer, polycarbonate (PC), polyvinyl chloride (PVC), polycaprolactone, polyvinyl fluoride, polyvinylidene fluoride copolymer, containing any one or more selected from the group consisting of polyamide and polyimide it could be

According to an embodiment, the polymer material may include polymer nanofibers.

According to an embodiment, the polymer material may be one in which one or more functional groups selected from the group consisting of a hydroxyl group, an acrylate group, an ester group, an ether group, and an amine group are introduced.

According to one embodiment, the inorganic material is, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO ₂ , _{SrTiO 3} , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ and SiC may be included.

According to an embodiment, the intermediate layer may include 0.1 parts by weight to 100 parts by weight of the polymer material based on 100 parts by weight of the metal material.

According to an embodiment, the upper layer may include 1 part by weight to 100 parts by weight of the inorganic material based on 100 parts by weight of the polymer material.

According to an embodiment, the thickness of the intermediate layer may be 1 μm to 30 μm.

According to an embodiment, in the order of the lower layer, the middle layer, and the upper layer, the electron conductivity may be gradually decreased.

Another aspect of the present invention comprises the steps of forming a lower layer by filtering a metal solution containing a metal material under reduced pressure; preparing an intermediate layer composition by mixing the metal solution and a polymer dispersion in which the polymer material is dispersed; on the lower layer, filtering the intermediate layer composition under reduced pressure to form an intermediate layer; preparing an upper layer composition by mixing the polymer dispersion and an inorganic material; and on the intermediate layer, filtering the upper layer composition under reduced pressure to form an upper layer.

According to an embodiment, forming the upper layer; Thereafter, the step of heat-treating; may further include.

According to an embodiment, the heat treatment may be performed at a temperature of 100° C. to 500° C. for 1 hour to 5 hours.

According to an embodiment, the concentration of the metal solution may be 1 mg/ml to 10 mg/ml.

According to one embodiment, the weight ratio of the metal solution and the polymer dispersion may be 10: 1 to 30: 1.

Another aspect of the present invention includes the lithium secondary battery electrode or the lithium secondary battery electrode manufactured by the manufacturing method as a negative electrode, and the negative electrode is that lithium ions are uniformly deposited from the lower layer, a lithium secondary battery provides

The lithium secondary battery electrode according to the present invention includes a multilayer having a difference in electronic conductivity so that lithium ions are sequentially deposited from a layer having high electronic conductivity to a layer having low electronic conductivity, so that lithium ions can be uniformly and stably deposited from the bottom There is an effect of suppressing lithium dendrites.

In addition, the thickness of the electrode may be reduced compared to the case of using a conventional conductive host, and excellent mechanical properties are secured.

Furthermore, there is an effect that the volume expansion of the electrode is suppressed and structural deformation does not occur during charging and discharging.

In the method for manufacturing a lithium secondary battery electrode according to the present invention, by sequentially forming each layer having different electronic conductivity, various types of electrodes having different electronic conductivity can be manufactured, and the thickness of the electrode can be formed thin. can have an effect.

In the lithium secondary battery according to the present invention, the number of cycles is significantly increased, and battery performance is significantly improved.

1 is a schematic diagram and a lithium ion deposition form when an electrode according to an embodiment of the present invention is used.
2 is a schematic diagram and a lithium ion deposition form when an electrode formed of a copper foil is used.
3 is a schematic diagram and a lithium ion deposition form when an electrode formed of a copper mesh is used.
4 is a graph showing a change in voltage of a battery during charging and discharging of a lithium secondary electrode according to an embodiment of the present invention.
5 is an SEM photograph showing a cross section of a lithium secondary electrode according to a state of charge according to an embodiment of the present invention.
6 is a graph showing the voltage change according to the number of cycles in a lithium symmetric cell using an electrode, a copper foil electrode, and a copper mesh electrode using an electrode manufactured through an embodiment of the present invention, respectively.
7 is a view illustrating a change in specific capacity and coulombic efficiency according to the number of cycles in a lithium secondary battery using an electrode, a copper foil electrode, and a copper mesh electrode, respectively, manufactured according to an embodiment of the present invention; is a graph showing

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all modifications, equivalents and substitutes for the embodiments are included in the scope of the rights.

The terms used in the examples are used for description purposes only, and should not be construed as limiting. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In addition, in the description of the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description thereof will be omitted.

Hereinafter, the lithium secondary battery electrode of the present invention and a manufacturing method thereof will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these examples and drawings.

One aspect of the present invention, the lower layer comprising a metal material; an intermediate layer formed on the lower layer and including a metal material and a polymer material; and an upper layer formed on the intermediate layer and including a polymer material and an inorganic material.

The lithium secondary battery electrode according to the present invention includes a multilayer in which electrical conductivity is sequentially decreased, so that lithium ions are uniformly deposited and lithium dendrite growth is suppressed, and the deposited lithium ions are uniformly deposited from the top. It has a desorption effect.

According to an embodiment, the lower layer including the metal material may form a lower region of the lithium secondary battery electrode, may be a layer having the highest electronic conductivity, and may be a layer in which lithium ions are first deposited.

In the lithium secondary battery electrode according to the present invention, the electronic conductivity of the lower layer is the highest, and the electronic conductivity of the layers formed on the lower layer is sequentially lowered, so that lithium ions are uniformly deposited from the bottom.

According to an embodiment, the metal material may include any one or more selected from the group consisting of metal nanowires, metal nanoparticles, and metal nanomesh.

When metal nanowires, metal nanoparticles, or metal nanomesh is used as the metal material, the thickness of the electrode layer may be significantly reduced along with imparting electronic conductivity.

Preferably, the metal material may include metal nanowires.

According to an embodiment, the metal material may be a metal material having high electron conductivity, copper (Cu), nickel (Ni), zinc (Zn), platinum (Pt), gold (Au), silver (Ag) ), aluminum (Al), tungsten (W), and may include any one or more selected from the group consisting of tin (Sn).

For example, the metal material may include copper nanowires, thereby forming a lower layer in the form of a thin film having high electronic conductivity.

According to an embodiment, the intermediate layer is formed on the lower layer, and may include a metal material having electronic conductivity and a polymer material having no electronic conductivity, and may be a layer having lower electronic conductivity than the lower layer.

According to an embodiment, the intermediate layer may implement a layer having various electronic conductivity by different types and content ratios of the metal material and the polymer material, and may be formed in plurality on the lower layer.

When the intermediate layer is formed in plurality, the electronic conductivity of each layer may be sequentially decreased from the layer close to the lower layer to the layer close to the upper layer.

According to one embodiment, the polymer material is, cellulose (cellulose), cellulose (cellulose) derivative, polyurethane (polyuretan), polyurethane copolymer, cellulose acetate (celluloseacetate), acetate butyrate (acetate butylate), polymethyl meta Acrylate (polymethyl methacrylate, PMMA), polymethyl acrylate (PMA), polyacrylic copolymer, polyvinyl acetate copolymer, polyvinylacetate (PVAc), polyvinylpyrrolidone (PVP) , polyvinyl alcohol (PVA), polyfurfuryl alcohol (PPFA), polystyrene (PS), polystyrene copolymer, polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene oxide copolymer, polypropylene oxide Copolymer, polycarbonate (PC), polyvinyl chloride (PVC), polycaprolactone, polyvinyl fluoride, polyvinylidene fluoride copolymer, containing any one or more selected from the group consisting of polyamide and polyimide it could be Preferably, the polymer material may include nano-cellulose.

According to one embodiment, the polymer material may include polymer nanofibers, and the nanofibers are microfibers having a diameter expressed in nanometers, which may mean having a diameter of about several to several thousand nm. there is.

According to one embodiment, the polymer nanofiber may have a thickness of 1 μm to 5 μm.

The polymer nanofiber may have a uniform thickness and may have flexibility.

According to an embodiment, the polymer material may be a porous polymer material, and the porous material may improve the flexibility of the electrode, increase the energy density per volume or weight to realize high energy density, and expand the volume with dendrites. can be suppressed.

According to an embodiment, the polymer material may be one in which one or more functional groups selected from the group consisting of a hydroxyl group, an acrylate group, an ester group, an ether group, and an amine group are introduced.

The functional group is a functional group having a negative surface charge, and may increase the electrical attraction with lithium ions to increase the deposition rate of lithium ions and improve deposition uniformity.

According to an embodiment, the upper layer may be a layer formed on the intermediate layer, including a polymer material and an inorganic material, and having the lowest electronic conductivity or no electronic conductivity.

According to one embodiment, the inorganic material is, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO ₂ , _{SrTiO 3} , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ and SiC may be included.

According to one embodiment, the inorganic material may have the form of particles, wires, tubes, fibers, needles, and the like. The size of the inorganic material may be 1 nm to 1 μm, and the size may mean a particle size, diameter, length, thickness, etc. depending on the shape of the inorganic material.

In the upper layer, mechanical strength of the electrode surface may be improved by including the inorganic material, and flexibility of the electrode may be improved by including a polymer material.

According to an embodiment, the intermediate layer may include 0.1 parts by weight to 100 parts by weight of the polymer material based on 100 parts by weight of the metal material.

Preferably, with respect to 100 parts by weight of the metal material, 1 part by weight to 100 parts by weight of the polymer material may be included, and more preferably, 1 weight part of the polymer material with respect to 100 parts by weight of the metal material. It may be included in parts by weight to 10 parts by weight.

If, based on the metal material, the polymer material is included in less than the above range, the difference in electron conductivity with the lower layer is insignificant, so that the effect of uniformly depositing lithium ions from the bottom may not be realized.

On the other hand, when the polymer material is included in excess of the above range, the difference in electron conductivity with the upper layer is insignificant, so that the effect of uniformly depositing lithium ions from the bottom may not be realized.

According to an embodiment, the upper layer may include 1 part by weight to 100 parts by weight of the inorganic material based on 100 parts by weight of the polymer material.

Preferably, with respect to 100 parts by weight of the polymer material, 1 to 10 parts by weight of the inorganic material may be included, and more preferably, 3 parts by weight to 3 parts by weight of the inorganic material based on 100 parts by weight of the polymer material. It may be included in 8 parts by weight.

If, based on the polymer material, the inorganic material is included below the above range, mechanical properties of the lithium secondary battery electrode may be reduced, and when included in excess of the above range, the flexibility of the lithium secondary battery electrode may be reduced. there is.

According to an embodiment, the thickness of the intermediate layer may be 1 μm to 30 μm.

Preferably, the thickness of the intermediate layer may be 5 μm to 30 μm, and more preferably, 5 μm to 20 μm.

If the thickness of the intermediate layer is less than the above range, the capacity of the battery may be reduced, and if it exceeds the above range, the thickness of the electrode may be improved.

According to an embodiment, in the order of the lower layer, the middle layer, and the upper layer, the electron conductivity may be gradually decreased.

Specifically, the lower layer may have the highest electronic conductivity, the upper layer may have the lowest electronic conductivity, and the intermediate layer may have lower electronic conductivity than the lower layer and higher than the upper layer.

The difference in the electron conductivity may be constant, may increase or decrease at a constant rate, or may vary non-constantly.

According to one embodiment, the lower layer, the middle layer, and the upper layer, each, may exist in plurality, and when there is a plurality, the electronic conductivity of each layer may be the same or have a difference.

Also, when there are a plurality of them, the electron conductivity may be gradually decreased from the lower layer to the upper layer.

According to an embodiment, each of the lower layer, the intermediate layer, and the upper layer may be present in plurality, and when present in plurality, each layer may include a different composition or component.

According to an embodiment of the present invention, the lithium secondary battery electrode may be a lithium secondary battery negative electrode.

According to an embodiment, the lithium secondary battery electrode may include: a lower layer; middle layer; and an upper layer; from the lower layer to the upper layer, the electronic conductivity of each layer may be sequentially decreased.

Another aspect of the present invention comprises the steps of forming a lower layer by filtering a metal solution containing a metal material under reduced pressure; preparing an intermediate layer composition by mixing the metal solution and a polymer dispersion in which the polymer material is dispersed; on the lower layer, filtering the intermediate layer composition under reduced pressure to form an intermediate layer; preparing an upper layer composition by mixing the polymer dispersion and an inorganic material; and on the intermediate layer, filtering the upper layer composition under reduced pressure to form an upper layer.

According to one embodiment, the forming of the lower layer is a step of forming the lower layer by filtering the metal solution containing the metal material under reduced pressure.

According to one embodiment, the metal solution can form a film in the form of a gel by solidifying a filtrate that has fallen through reduced pressure filtration, and is filtered and dispersed under reduced pressure on a substrate or substrate, or applied on a substrate or substrate and hardened Thus, it is possible to form a film in the form of a gel.

The metal solution may be a solution in which a metal material is added to a solvent, and a hydrazine additive may be mixed therein.

The additive may be used to prevent oxidation of the metal material in the metal solution.

As the solvent, water, alcohol or isopropyl alcohol (IPA) can be used, and preferably isopropyl alcohol can be used.

According to an embodiment, the intermediate layer composition is a mixture for preparing the intermediate layer formed on the lower layer, and may be prepared by mixing the metal solution and the polymer dispersion in which the polymer material is dispersed.

The polymer dispersion is a solution in which the polymer material is dispersed in a solvent, and water, alcohol, etc. may be used as the solvent, and preferably, a polymer water dispersion may be used.

According to an embodiment, the forming of the intermediate layer is a step of forming the intermediate layer by filtering the intermediate layer composition under reduced pressure on the formed lower layer.

According to one embodiment, the intermediate layer composition can form a film in the form of a gel on the lower layer, that is, by falling off and solidifying on the surface of the lower layer through reduced pressure filtration, and is applied and hardened after filtration under reduced pressure to form a film in the form of a gel can do.

According to an embodiment, after forming the intermediate layer, heat treatment may be performed.

According to an embodiment, the upper layer composition may be prepared by mixing the polymer dispersion and the inorganic material, and the inorganic material may be mixed in the form of an inorganic material dispersion in which the inorganic material is dispersed in a solvent. The upper layer composition may include isopropyl alcohol.

According to an embodiment, the forming of the upper layer is a step of forming the upper layer by filtering the upper layer composition under reduced pressure on the formed intermediate layer.

According to one embodiment, the upper layer composition can form a film in the form of a gel on the intermediate layer, that is, by falling off and solidifying on the surface of the intermediate layer through reduced pressure filtration, and is applied and hardened after filtration under reduced pressure to form a film in the form of a gel can do.

According to an embodiment, forming the upper layer; Thereafter, the step of freeze-drying; may further include.

Through the freeze-drying, it is possible to secure a pore structure in the film laminated as a lower layer, an intermediate layer, and an upper layer.

According to an embodiment, forming the upper layer; Thereafter, the step of heat-treating; may further include.

The heat treatment may include: freeze-drying; may proceed later.

Through the heat treatment, the conductivity of the metal material in the lower layer and the intermediate layer may be improved.

According to an embodiment, the heat treatment may be performed at a temperature of 100° C. to 500° C. for 1 hour to 5 hours.

Preferably, the heat treatment may be performed at a temperature of 200 °C to 300 °C for 2 hours to 4 hours.

The heat treatment may be performed under an inert atmosphere.

According to an embodiment, the concentration of the metal solution may be 1 mg/ml to 10 mg/ml.

According to one embodiment, the weight ratio of the metal solution and the polymer dispersion liquid may be 10: 1 to 100: 1.

According to one embodiment, the metal solution may include a hydrazine additive.

Another aspect of the present invention includes the lithium secondary battery electrode or the lithium secondary battery electrode manufactured by the manufacturing method as a negative electrode, and the negative electrode is that lithium ions are uniformly deposited from the lower layer, a lithium secondary battery provides

In the lithium secondary battery electrode according to the present invention, volume expansion of the electrode is suppressed during charging and discharging, and structural deformation does not occur.

In addition, in the lithium secondary battery according to the present invention, the number of cycles is significantly increased, and battery performance is significantly improved.

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples.

However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

< Example >

Copper metal nanowires were mixed with isopropyl alcohol (IPA) at a concentration of 5 mg/mL, and hydrazine (0.5 wt%) was added to prepare a copper metal solution.

The prepared copper metal solution was filtered under reduced pressure to form a lowermost layer.

The copper metal solution (5 mg/mL) and the nano-cellulose water dispersion (5 wt%) were mixed in a weight ratio of 100: 1, and filtered under reduced pressure on the formed copper metal nanowire film to form an intermediate layer.

Next, silica particles were mixed with a nano cellulose water dispersion (5 wt%) and isopropyl alcohol, and filtered under reduced pressure on the intermediate layer to prepare an uppermost layer. At this time, the silica particles were mixed in an amount of 5 parts by weight based on 100 parts by weight of the nano-cellulose.

The laminated gel film was dried under reduced pressure sequentially by filtration under reduced pressure, and heat treatment was performed at 230 ° C for about 3 hours to improve the conductivity of copper metal nanowires (H ₂ /Ar, 5%/95%) multi-layer negative electrode. was prepared.

< Experimental example 1> Lithium deposition type comparison

The lithium ion deposition form after cycling was compared and observed in the lithium secondary battery using the electrode, the copper foil electrode, and the copper mesh electrode, respectively, prepared in the above Examples.

1 is a schematic diagram and a lithium ion deposition form when an electrode according to an embodiment of the present invention is used.

2 is a schematic diagram and a lithium ion deposition form when an electrode formed of a copper foil is used.

3 is a schematic diagram and a lithium ion deposition form when an electrode formed of a copper mesh is used.

1 to 3, while lithium ions are uniformly deposited in the electrode according to the present invention, lithium ions are non-uniformly deposited in the copper foil electrode and the copper mesh electrode. In particular, in the case of the copper foil electrode, lithium ions are most It can be seen that the deposition is non-uniform.

Through this, it can be seen that, in the electrode according to the present invention, lithium ions are uniformly deposited from the lower layer having the highest electrical conductivity, thereby forming a stable lithium-based negative electrode.

< Experimental example 2> Lithium deposition morphology observe

Using the electrode prepared in Example, for each state of charge (depth of discharge, DOC), Li Plating / Stripping Morphology was observed through SEM.

4 is a graph showing a change in voltage of a battery during charging and discharging of a lithium secondary electrode according to an embodiment of the present invention.

Referring to FIG. 4 , it can be seen that, in the lithium secondary electrode according to the present invention, a change in battery voltage does not occur significantly during charging and discharging.

5 is an SEM photograph showing a cross section of a lithium secondary electrode according to a state of charge according to an embodiment of the present invention.

Referring to FIG. 5 , in the electrode according to the present invention, it can be confirmed that lithium ions are uniformly deposited sequentially from the bottom as Li plating proceeds, and it can be confirmed that the lithium ions deposited while Li Stripping proceeds are desorbed from the top. In addition, it can be confirmed that volume expansion is suppressed and structural deformation does not occur during charging and discharging.

< Experimental example 3> Performance evaluation of lithium secondary batteries

The voltage and capacity of the lithium ion battery after cycling were measured in the lithium secondary battery using the electrode, the copper foil electrode, and the copper mesh electrode, respectively, prepared through the above Examples.

6 is a graph showing the voltage change according to the number of cycles in a lithium symmetric cell using an electrode, a copper foil electrode, and a copper mesh electrode using an electrode manufactured through an embodiment of the present invention, respectively.

Referring to FIG. 6 , in the case of the battery using the electrode manufactured according to the embodiment of the present invention, it can be seen that the number of cycles is significantly increased compared to the battery using the copper foil electrode and the copper mesh electrode.

7 is a view illustrating a change in specific capacity and coulombic efficiency according to the number of cycles in a lithium secondary battery using an electrode, a copper foil electrode, and a copper mesh electrode, respectively, manufactured according to an embodiment of the present invention; is a graph showing

Referring to FIG. 7 , in the case of a battery using an electrode manufactured according to an embodiment of the present invention, unlike a battery using a copper foil electrode, the battery capacity does not decrease even if the number of cycles is increased, and a 100% coulombic efficiency is obtained. It can be confirmed that the battery performance does not deteriorate.

As described above, although the embodiments have been described with reference to the limited drawings, those skilled in the art may apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (17)

a lower layer comprising a metallic material;
an intermediate layer formed on the lower layer and including a metal material and a polymer material; and
an upper layer formed on the intermediate layer and comprising a polymer material and an inorganic material;
The polymer material is a polymer material that does not have electronic conductivity,
The lower layer, the intermediate layer and the upper layer are to include a porous structure,
In the order of the lower layer, the intermediate layer and the upper layer, the electronic conductivity gradually decreases,
In the order of the lower layer, the middle layer and the upper layer, lithium ions are deposited,
Anode for lithium metal batteries.
According to claim 1,
The metal material will include any one or more selected from the group consisting of metal nanowires, metal nanoparticles, and metal nanomesh,
Anode for lithium metal batteries.
According to claim 1,
The metal material may include copper (Cu), nickel (Ni), zinc (Zn), platinum (Pt), gold (Au), silver (Ag), aluminum (Al), tungsten (W), and tin (Sn). Which comprises any one or more selected from the group consisting of
Anode for lithium metal batteries.
According to claim 1,
The polymer material is cellulose, cellulose derivatives, polyurethane, polyurethane copolymer, cellulose acetate, acetate butylate, polymethyl methacrylate, PMMA), polymethyl acrylate (PMA), polyacrylic copolymer, polyvinyl acetate copolymer, polyvinylacetate (PVAc), polyvinylpyrrolidone (PVP), polyvinyl alcohol (polymethyl alcohol, PVA), polyfurfuryl alcohol (PPFA), polystyrene (PS), polystyrene copolymer, polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene oxide copolymer, polypropylene oxide copolymer, polycarbonate (PC) ), polyvinyl chloride (PVC), polycaprolactone, polyvinyl fluoride, polyvinylidene fluoride copolymer, polyamide and polyimide comprising any one or more selected from the group consisting of,
Anode for lithium metal batteries.
According to claim 1,
The polymer material will include a polymer nanofiber,
Anode for lithium metal batteries.
According to claim 1,
The polymer material is one or more functional groups selected from the group consisting of a hydroxyl group, an acrylate group, an ester group, an ether group and an amine group is introduced,
Anode for lithium metal batteries.
According to claim 1,
The inorganic material is, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO ₂ , _{SrTiO 3} , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ and that comprising any one or more selected from the group consisting of SiC,
Anode for lithium metal batteries.
According to claim 1,
The intermediate layer, based on 100 parts by weight of the metal material, the polymer material is included in an amount of 0.1 to 100 parts by weight,
Anode for lithium metal batteries.
According to claim 1,
The upper layer, with respect to 100 parts by weight of the polymer material, comprising 1 part by weight to 100 parts by weight of the inorganic material,
Anode for lithium metal batteries.
According to claim 1,
The intermediate layer has a thickness of 1 μm to 30 μm,
Anode for lithium metal batteries.
delete filtering the metal solution containing the metal material under reduced pressure to form a lower layer;
preparing an intermediate layer composition by mixing the metal solution and a polymer dispersion in which the polymer material is dispersed;
on the lower layer, filtering the intermediate layer composition under reduced pressure to form an intermediate layer; and
preparing an upper layer composition by mixing the polymer dispersion and an inorganic material;
forming an upper layer on the intermediate layer by filtering the upper layer composition under reduced pressure; and
Including; depositing lithium ions in the order of the lower layer, the intermediate layer, and the upper layer;
The polymer material is a polymer material that does not have electronic conductivity,
The lower layer, the intermediate layer and the upper layer are to include a porous structure,
In the order of the lower layer, the middle layer and the upper layer, the electronic conductivity gradually decreases,
A method of manufacturing a negative electrode for a lithium metal battery.
13. The method of claim 12,
forming the upper layer; Thereafter, the step of heat-treating; which will further include
A method of manufacturing a negative electrode for a lithium metal battery.
14. The method of claim 13,
The heat treatment, which is carried out for 1 hour to 5 hours at a temperature of 100 ℃ to 500 ℃,
A method of manufacturing a negative electrode for a lithium metal battery.
13. The method of claim 12,
The concentration of the metal solution will be 1 mg / ml to 10 mg / ml
A method of manufacturing a negative electrode for a lithium metal battery.
13. The method of claim 12,
In the intermediate layer composition, the weight ratio of the metal solution and the polymer dispersion is 10: 1 to 30: 1,
A method of manufacturing a negative electrode for a lithium metal battery.
A negative electrode for a lithium metal battery of claim 1 or comprising a negative electrode for a lithium metal battery prepared by the method of claim 12,
lithium secondary battery.

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