KR20160062617A - Three-dimensional porous-structured current colletor, method of manufacturing the same, electrode including the same, method of manufacturing the same electrode, and electrochemical device including the same current colletor - Google Patents

Abstract

Disclosed are a three-dimensional porous-structured current collector, a method for manufacturing the current collector, an electrode including the current collector, a method for manufacturing the electrode, and an electrochemical device including the current collector. Provided is a three-dimensional porous-structured current collector, comprising a porous non-woven fabric including a plurality of polymer fibers, and a conductive material; wherein pores are formed among the polymer fibers included in the porous non-woven fabric, and the pores are filled with the conductive material; and also provided are a method for manufacturing the current collector, an electrode including the current collector, a method for manufacturing the electrode, and an electrochemical device including the current collector.

Description

TECHNICAL FIELD [0001] The present invention relates to a three-dimensional structure current collector, a method of manufacturing the same, an electrode including the same, a method of manufacturing the electrode, and an electrochemical device including the current collector , METHOD OF MANUFACTURING THE SAME ELECTRODE, AND ELECTROCHEMICAL DEVICE INCLUDING THE SAME CURRENT COLLETOR}

A three-dimensional structure current collector, a method of manufacturing the same, an electrode including the electrode, a method of manufacturing the electrode, and an electrochemical device including the current collector.

Recently, as the industries such as mobile electronic devices, electric vehicles, and smart grids are rapidly developing, there is an increasing demand for large-capacity, high-performance energy storage devices. In order to meet this demand, electrochemical devices There is a need for improvement measures.

In this connection, the capacity of an electrochemical device is expressed by an electrode, and such an electrode is generally made of a metal current collector and a mixture of an active material, a conductive agent, and a binder coated thereon. However, such a general electrode structure has a limitation in improving the capacity per volume and volume of the electrode.

Specifically, although a material widely used as a current collector is a metal, resistance is generated not only at the interface between the metal collector and the active material, but also causes the metal collector and the active material to desorb as the charge and discharge are repeated have. In addition, since the metal current collector has a large weight and a large volume in the electrode, it is one of the causes for decreasing the capacity per volume and volume per electrode.

In addition, it is necessary to improve the output characteristics of the electrochemical device by forming a uniform electronic conduction network in the current collector, but it is difficult to greatly improve the output characteristics of the electrochemical device only when the conductive material is included in the current collector.

In addition, since only the active material contributes substantially to the capacity and the energy density of the electrochemical device among the general electrode structures, there is a problem that the capacity per volume and volume of the electrode decreases as the conductive material and the binder are further included.

Therefore, in order to develop an electrochemical device having a high capacity and a high output characteristic, it is necessary to improve the capacity per volume and volume of the electrode. However, studies on the current collector and the electrode to solve the above- It is true.

The present inventors have developed a current collector having a structure capable of solving the above-mentioned problems and electrodes including the same. The details of this are as follows.

In one embodiment of the present invention, a porous nonwoven fabric comprising a plurality of polymer fibers; And a conductive material, wherein pores are formed between the plurality of polymer fibers contained in the porous nonwoven fabric, and the pores are filled with the conductive material.

In another embodiment of the present invention, a colloidal solution containing a conductive material is simultaneously radiated with a polymer solution to form an interconnected porous network by a plurality of polymer fibers serving as a support, A three-dimensional densified packing structure based on a material is formed and a method for manufacturing the three-dimensional structure current collector can be provided.

In another embodiment of the present invention, an electrode including the three-dimensional structure current collector and the active material layer coated on the surface thereof may be provided.

According to another embodiment of the present invention, there is provided a method of manufacturing the electrode by a series of steps of manufacturing a three-dimensional structure current collector by the above-described method and then forming an active material layer on the prepared three-dimensional structure electrode .

According to another embodiment of the present invention, an electrochemical device including the three-dimensional structure current collector can be provided.

In one embodiment of the present invention, a porous nonwoven fabric comprising a plurality of polymer fibers; And a conductive material, wherein pores are formed between the plurality of polymer fibers contained in the porous nonwoven fabric, and the pores are filled with the conductive material.

Specifically, the filled shape may be such that the conductive material covers the surface of the plurality of polymer fibers.

A detailed description of the three-dimensional structure current collector is as follows.

The ratio of the content of the porous nonwoven fabric and the conductive material in the three-dimensional structure current collector may be expressed as a weight ratio of the conductive material to the porous nonwoven fabric in the range of 5:95 to 95: 5.

The average diameter of the plurality of polymer fibers may be 0.001 to 1000 탆.

The average particle diameter of the conductive material may be 0.001 to 10 mu m.

The porosity of the three-dimensional structure current collector may be 5 to 95% by volume.

The thickness of the three-dimensional structure current collector may be 1 to 1000 mu m.

The porous nonwoven fabric may be at least one selected from the group consisting of polyethylene terephthalate, polyimide, polyamide, polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene, polyetherimide, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, Polyvinyl pyrrolidone, polyvinyl pyrrolidone, agarose, alginate, polyvinylidene hexafluoropropylene, polyurethane, nylon 6, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof, Lt; / RTI >

The conductive material may be selected from the group consisting of carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphen oxide, reduced graphene oxide, polypyrrole, poly 3,4- At least one selected from the group including polyaniline, derivatives thereof, and mixtures thereof.

In another embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: dissolving a polymer in a solvent to prepare a polymer solution; Dispersing a conductive material in a dispersion medium to produce a colloidal solution; Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber; And compressing the three-dimensional structural fibers to obtain a three-dimensional structural current collector, wherein the step of simultaneously spinning the polymer solution and the colloid solution to prepare a three-dimensional structural fiber comprises: Wherein the porous nonwoven fabric is filled with the conductive material between a plurality of polymer fibers contained in the porous nonwoven fabric.

Specifically, in the step of simultaneously spinning the polymer solution and the colloid solution to produce a three-dimensional structural fiber, the filled shape may be a form in which the conductive material covers the surface of the plurality of polymer fibers.

Meanwhile, the step of simultaneously spinning the polymer solution and the colloid solution to prepare a three-dimensional structural fiber will be described.

This can be any of the methods selected from the group including dual electrospinning, electrospray, double spray, and combinations thereof.

The spinning speed of the polymer solution may be 2 to 10 μl / min, and the spinning speed of the colloid solution may be 30 to 80 μl / min.

Further, the step of dissolving the polymer in a solvent to prepare a polymer solution is explained as follows.

The content of the polymer in the polymer solution may be 5 to 30% by weight based on the total weight of the polymer solution.

The polymer in the polymer solution may be at least one selected from the group consisting of carbon nanotubes, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, ≪ / RTI >

Wherein the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-Methylpyrrolidone, Lt; / RTI >

A step of dispersing a conductive material in a dispersion medium to prepare a colloidal solution is explained as follows.

The content of the conductive material in the colloidal solution may be 0.1 to 50% by weight based on the total weight of the colloidal solution.

The conductive material may be selected from the group consisting of carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphen oxide, reduced graphene oxide, polypyrrole, poly 3,4- At least one selected from the group including polyaniline, derivatives thereof, and mixtures thereof.

The dispersion medium may be selected from the group consisting of deionized water, iso-propylalcohol, buthalol, ethanol, hexanol, acetone, N, N-dimethylformamide, , N, N-dimethylacetamide, N, N-methylpyrrolidone, and combinations thereof.

The colloidal solution further comprises a dispersing agent, and the content of the dispersing agent in the colloid solution may be 0.001 to 10% by weight based on the total weight of the colloidal solution.

The dispersant may be at least one selected from the group consisting of polyvinylpyrrolidone, poly 3,4-ethylenedioxythiophene, and mixtures thereof.

Compressing the three-dimensional structural fibers to obtain a three-dimensional structure current collector; And firing the three-dimensional structure current collector, wherein the plurality of polymer fibers contained in the pre-firing three-dimensional structure current collector may be converted into a plurality of carbon nanofibers by the firing.

According to another embodiment of the present invention, there is provided a three dimensional structure collector; And an active material layer coated on a surface of the three-dimensional structure current collector, wherein the three-dimensional structure current collector comprises a plurality of polymer fibers; And a conductive material, wherein the conductive material is filled between a plurality of polymer fibers contained in the porous nonwoven fabric.

The active material contained in the active material layer includes a lithium metal oxide, a carbonaceous material, an oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), derivatives thereof, At least one selected from the group consisting of < RTI ID = 0.0 >

The weight per area of the electrode including the three-dimensional structure current collector may be 0.001 mg / cm ² to 1 g / cm ² .

The three-dimensional structure electrode may have a plurality of electrodes formed in a multilayer structure.

The weight per area of the electrode including the three-dimensional structure current collector may be 0.002 mg / cm ² to 10 g / cm ² .

According to another embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: dissolving a polymer in a solvent to prepare a polymer solution; Dispersing a conductive material in a dispersion medium to produce a colloidal solution; Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber; Compressing the three-dimensional structural fibers to obtain a three-dimensional structure current collector; And coating the active material slurry on the surface of the three-dimensional structure current collector to produce an electrode, wherein the step of simultaneously spinning the polymer solution and the colloid solution to prepare a three-dimensional structural fiber comprises: Wherein the porous nonwoven fabric is filled with the conductive material between a plurality of polymer fibers contained in the porous nonwoven fabric.

Coating an active material slurry on the surface of the three-dimensional structure current collector to produce an electrode; Thereafter, the electrode is compressed using a roll press; And drying the compressed electrode.

According to another embodiment of the present invention, cathode; A separator disposed between the anode and the cathode; Wherein at least one of the anode and the cathode comprises a three-dimensional structure current collector according to any one of the above-mentioned embodiments, and an active material layer coated on the surface of the three-dimensional structure current collector, And an electrochemical device.

The electrochemical device includes a group including a lithium secondary battery, a super capacitor, a lithium-sulfur battery, a sodium ion battery, a lithium-air battery, a zinc-air battery, an aluminum-air battery, and a magnesium ion battery It can be any one selected.

According to an embodiment of the present invention, it is possible to provide a three-dimensional structure current collector in which a uniform electronic conduction network is formed while using a light material and a content of an additive material is minimized.

According to another embodiment of the present invention, a method of manufacturing a three-dimensional structure current collector having excellent characteristics as described above can be provided by a simple method of simultaneously spraying two solutions.

According to another embodiment of the present invention, by using the three-dimensional structure current collector, it is possible to provide an electrode having an improved capacity per weight and volume.

According to another embodiment of the present invention, there is provided a method of manufacturing the electrode by a simple method of manufacturing a three-dimensional structure current collector by the method and then forming an active material layer on the surface of the three-dimensional structure current collector can do.

According to another embodiment of the present invention, by including the current collector, an electrochemical device having high capacity and high output characteristics can be provided.

FIG. 1 schematically shows a method of manufacturing a three-dimensional structure current collector according to another embodiment of the present invention, together with the structure of a three-dimensional structure current collector 100 according to an embodiment of the present invention.
FIG. 2 is a schematic view of a lithium secondary battery including a three-dimensional fiber structure current collector according to an embodiment of the present invention.
Figs. 3A and 3B show the results of observing the surface and cross-section of the current collector produced by Example 1 of the present invention by a scanning electron microscope (SEM), respectively.
Figures 4a and 4b illustrate. 1 is an external view of a current collector manufactured according to Example 1 of the present invention.
Fig. 5 shows the results obtained by measuring and comparing the respective electronic conductivities of the electrodes manufactured in Example 1 of the present invention.
6A is a graph showing the results of observing the discharge capacity per weight of the active material for the lithium secondary battery fabricated in Example 1 of the present invention and the lithium secondary battery fabricated in Comparative Example 1. FIG.
6B is a graph showing the results of observing the discharge capacity per electrode weight of the lithium secondary battery fabricated in Example 1 of the present invention and the lithium secondary battery fabricated in Comparative Example 1. FIG.
FIG. 7A is a graph showing the results of observing the discharge capacity per weight of the active material for the lithium secondary battery fabricated in Example 2 of the present invention and the lithium secondary battery fabricated in Comparative Example 2. FIG.
FIG. 7B is a graph showing the results of observing the discharge capacity per electrode weight of the lithium secondary battery fabricated in Example 2 of the present invention and the lithium secondary battery fabricated in Comparative Example 2. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise. Also, singular forms include plural forms unless the context clearly dictates otherwise.

FIG. 1 schematically shows a method of manufacturing a three-dimensional structure current collector according to another embodiment of the present invention, together with the structure of a three-dimensional structure current collector 100 according to an embodiment of the present invention. The following description will be made with reference to Fig. In this regard, like reference numerals refer to like elements throughout the specification.

In one embodiment of the present invention, a porous nonwoven fabric comprising a plurality of polymer fibers; And a conductive material, wherein pores are formed between the plurality of polymer fibers contained in the porous nonwoven fabric, and the pores are filled with the conductive material.

Referring to FIG. 1, the shape of the phase-structure structure current collector can be more clearly understood.

Specifically, the three-dimensional structure current collector 100 has a structure in which a plurality of polymer fibers 10 contained in the porous nonwoven fabric serve as a support, and the plurality of polymer fibers 10 are aggregated three-dimensionally irregularly and continuously Thereby forming a plurality of uneven spaces (that is, pores), and the conductive material 20 is filled between the pores to form a three-dimensional super lattice structure.

This corresponds to a collection of all three aspects of a lightweight collector, a good electron conduction network, and minimization of additive materials (such as binders).

Specifically, the porous nonwoven fabric, which is a light material, is used in place of the metal current collector, an interconnected porous network is formed by the fibers serving as the support, and the conductive material A uniform electron conduction network is formed.

In addition, even if a separate material (for example, a binder) is not included, the porous nonwoven fabric and the conductive material are not separated from each other in a state where the current collector is bent, and the three-dimensional superstructure is stably maintained .

When the current collector is applied to an electrode, the weight and capacity per unit volume of the electrode can be improved, ultimately contributing to the realization of an electrochemical device having a high capacity and a high output characteristic.

Hereinafter, the three-dimensional structure current collector provided in one embodiment of the present invention will be described in more detail.

The filled shape may be a form in which the conductive material covers the surface of the plurality of polymer fibers.

In this case, the electron conduction network in the three-dimensional structure current collector becomes more uniform, and the electron conductivity of the three-dimensional structure current collector can be improved, though the porous nonwoven fabric as the polymer material is used as the support.

Further, when the electrode includes the three-dimensional structure current collector, the output characteristic in the thickness direction of the electrode is excellent, and the discharge characteristic can be improved when compared with a generally known electrode. In particular, even when an active material having poor electron conductivity is applied to the three-dimensional current collector, the output characteristics of the battery can be improved. This fact is specifically supported by the following embodiments.

A detailed description of the three-dimensional structure current collector is as follows.

The ratio of the content of the porous nonwoven fabric and the conductive material in the three-dimensional structure current collector may be 5:95 to 95: 5, as a weight ratio of the conductive material to the porous nonwoven fabric.

By controlling the content ratio of the porous nonwoven fabric and the conductive material within the above range, the porosity of the three-dimensional structure current collector can be controlled and the above-described characteristics can be exhibited.

However, if the content of the conductive material is less than the above range, the electron conductivity may be deteriorated. Otherwise, if the content of the porous nonwoven fabric is less than the above range, the support may not be sufficiently performed, which may make it difficult to maintain the structure of the three-dimensional structure electrode.

The average diameter of the plurality of polymer fibers may be 0.001 to 1000 탆.

Since a plurality of polymer fibers having an average diameter in the above range form an aggregate three-dimensionally, it is possible to secure a space easily to fill the active material particles and the conductive material, and to have a uniform pore structure The absorption of the electrolyte in the electrode and the movement of ions can be smooth.

However, if the thickness exceeds 1000 μm, the thickness of the support formed by the plurality of polymer fibers becomes very thick, and the pores to be filled with the active material and the conductive material may be reduced. On the other hand, when the thickness is less than 0.001 탆, the support may have a poor physical property. Therefore, the average diameter of the plurality of polymer fibers is limited as described above.

Specifically, the average diameter of the plurality of polymer fibers may be about 0.01 to 1 탆, and in this case, the above effect can be maximized.

The average particle diameter of the conductive material may be 0.001 to 10 mu m.

The conductive material having an average diameter in this range can contribute to controlling the porosity of the three-dimensional structure current collector to a range described later. In addition, in the method for producing a three-dimensional structure current collector described later, the dispersibility of the colloidal solution containing the conductive material is improved, and the occurrence of problems in the double electrospinning method is minimized, The pores can be made uniform.

However, if it is more than 10 탆, the dispersibility of the colloidal solution may not be properly maintained. If the particle diameter is less than 0.001 탆, the particle size may be too small to handle, Limiting the average diameter of the conductive material.

The porosity of the three-dimensional structure current collector may be 5 to 95% by volume.

When the porosity is within the above range, the electrolyte can be easily absorbed and the mobility of ions can be appropriately controlled, thereby contributing to the improvement of the performance of the electrochemical device.

However, when it exceeds 95% by volume, the distance between the conductive materials may be distant and the electron conduction network may not be formed well. On the other hand, if it is less than 5% by volume, the porosity may be too small to cause a problem that the ion conductivity of the three-dimensional structure current collector is lowered. Thus, the porosity is limited as described above.

More specifically, the porosity of the three-dimensional structure current collector may be 30 to 90% by volume. In this case, the ion conductivity of the three-dimensional structure current collector may be further increased, and the mechanical strength may be improved.

In addition, the porosity of the three-dimensional structure electrode can be controlled by the diameter or the content of the active material particles.

The thickness of the three-dimensional structure current collector may be 1 to 1000 mu m.

Within this range, the thicker the thickness, the better the energy density of the electrode.

Generally, as the thickness of the electrode increases, the electron conductivity in the thickness direction decreases, and the output characteristic of the battery decreases. However, in the case of the electrode including the three-dimensional structure current collector, there is an advantage that a smooth electron conduction network is maintained in the thickness range and also in the thickness direction.

On the other hand, a detailed description of each material contained in the three-dimensional structure electrode is as follows.

The plurality of polymer fibers may be unevenly gathered to form the porous nonwoven fabric. However, if the polymer constituting the plurality of polymer fibers is a heat-resistant polymer, it is advantageous for securing thermal stability of the electrode.

For example, there may be mentioned polyolefins such as polyethylene terephthalate, polyimide, polyamide, polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene, polyetherimide, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, poly Polyvinylpyrrolidone, vinylpyrrolidone, agarose, alginate, polyvinylidene hexafluoropropylene, polyurethane, nylon 6, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof, and mixtures thereof . ≪ / RTI >

On the other hand, the conductive material is not particularly limited as long as it is a material capable of forming an electron conduction network.

For example, carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline , Derivatives thereof, and mixtures thereof.

In another embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: dissolving a polymer in a solvent to prepare a polymer solution; Dispersing a conductive material in a dispersion medium to produce a colloidal solution; Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber; And compressing the three-dimensional structural fibers to obtain a three-dimensional structural current collector, wherein the step of simultaneously spinning the polymer solution and the colloid solution to prepare a three-dimensional structural fiber comprises: Wherein the porous nonwoven fabric is filled with the conductive material between a plurality of polymer fibers contained in the porous nonwoven fabric.

This corresponds to a method of manufacturing a three-dimensional structure current collector having excellent characteristics as described above by a simple process of simultaneously spraying the polymer solution and the colloidal solution.

Specifically, a colloidal solution containing the conductive material is simultaneously radiated with the polymer solution to form an interconnected porous network by a plurality of polymer fibers serving as a support, A three-dimensional structure current collector can be manufactured.

Hereinafter, a method of manufacturing the three-dimensional structure current collector provided in one embodiment of the present invention will be described in detail, and a description overlapping with that described above will be omitted.

First, in the step of simultaneously spinning the polymer solution and the colloid solution to produce a three-dimensional structural fiber, the filled shape may be a form in which the conductive material covers the surface of the plurality of polymer fibers.

A detailed description thereof is as described above.

Meanwhile, the step of simultaneously spinning the polymer solution and the colloid solution to prepare a three-dimensional structural fiber will be described.

This can be any of the methods selected from the group including dual electrospinning, electrospray, double spray, and combinations thereof.

Specifically, a double electrospinning method can be used, which is advantageous for forming the three-dimensional dense filling structure and uniform pores.

The spinning speed of the polymer solution may be 2 to 10 μl / min, and the spinning speed of the colloid solution may be 30 to 80 μl / min.

When the spinning speed range of each of these solutions is all satisfied, the three-dimensional structure current collector can be formed.

However, if the range of the spinning rate of the polymer solution is not satisfied, the polymer solution may not be uniformly radiated to form a bead. Further, if the range of the colloidal solution spinning rate is not satisfied, the colloidal solution may not be uniformly radiated and may fall into a large droplet state. For this reason, the spinning speed of each solution is individually limited as described above.

Further, the step of dissolving the polymer in a solvent to prepare a polymer solution is explained as follows.

The content of the polymer in the polymer solution may be 5 to 30% by weight based on the total weight of the polymer solution.

When the above range is satisfied, a plurality of polymer fibers are formed by the injection of the polymer solution, whereby the porous nonwoven fabric can be formed.

However, if it exceeds 30% by weight, the polymer solution may not be radiated smoothly. In particular, the polymer solution may harden at the end of the nozzle through which the polymer solution is radiated. On the other hand, if it is less than 5% by weight, the polymer solution may not be uniformly radiated and a bead may be formed. In consideration of this, the content of the polymer in the polymer solution is limited as described above.

The polymer in the polymer solution is not particularly limited as long as it is capable of forming the porous nonwoven fabric, but may be selected from materials capable of improving the strength and electron conductivity of the porous nonwoven fabric.

For example, carbon nanotubes, carbon nanotubes, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof, Lt; / RTI >

The solvent is not particularly limited as long as it can dissolve the polymer.

At least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-methylpyrrolidone, Lt; / RTI >

A step of dispersing a conductive material in a dispersion medium to prepare a colloidal solution is explained as follows.

The content of the conductive material in the colloidal solution may be 0.1 to 50% by weight based on the total weight of the colloidal solution.

When the range is satisfied, the surface of the plurality of polymer fibers may be evenly covered with the conductive material by the injection of the colloidal solution.

However, if it exceeds 50% by weight, the conductive material in the colloidal solution may not be uniformly dispersed. When the content of the conductive material is less than 0.1% by weight, the content of the conductive material may be too small to form an electron conduction network. Considering this, the content of the conductive material in the colloidal solution is limited as described above.

The conductive material in the colloid solution is not particularly limited as long as it is a material capable of forming an electron conduction network as described above.

For example, carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline , Derivatives thereof, and mixtures thereof.

The dispersion medium is not particularly limited as long as it can disperse the conductive material.

For example, deionized water, iso-propylalcohol, buthalol, ethanol, hexanol, acetone, N, N-dimethylformamide, , N, N-dimethylacetamide, N, N-methylpyrrolidone, and combinations thereof.

The colloidal solution further comprises a dispersing agent, and the content of the dispersing agent in the colloid solution may be 0.001 to 10% by weight based on the total weight of the colloidal solution.

When the dispersant is included in the above range, dispersion of the conductive material in the colloidal solution can be assisted.

However, if the amount of the dispersing agent is more than 10% by weight, the amount of the dispersing agent may be excessively high, resulting in an excessively high viscosity of the colloid solution. If the amount is less than 0.001% by weight, The content is limited as described above.

Specifically, the dispersant may be at least one selected from the group consisting of polyvinyl pyrrolidone, poly 3,4-ethylenedioxythiophene, and mixtures thereof.

Compressing the three-dimensional structural fibers to obtain a three-dimensional structure current collector; And firing the three-dimensional structure current collector, wherein the plurality of polymer fibers contained in the pre-firing three-dimensional structure current collector may be converted into a plurality of carbon nanofibers by the firing.

Generally, when the polymer is fired in an inert gas atmosphere, only the carbon corresponding to the main chain of the polymer is left. In this regard, the plurality of polymer fibers is also a kind of polymer, which is changed into carbon by the firing, but the shape of the fiber is maintained as it is.

According to another embodiment of the present invention, there is provided a three dimensional structure collector; And an active material layer coated on a surface of the three-dimensional structure current collector, wherein the three-dimensional structure current collector comprises a plurality of polymer fibers; And a conductive material, wherein the conductive material is filled between a plurality of polymer fibers contained in the porous nonwoven fabric.

This corresponds to an electrode in which an active material layer is formed on the surface of the aforementioned three-dimensional structure current collector.

Specifically, by using the three-dimensional structure current collector, it is possible to provide an electrode having an improved capacity per weight and volume.

Hereinafter, the electrode provided in one embodiment of the present invention will be described in detail, and a description overlapping with that described above will be omitted.

The active material contained in the active material layer includes a lithium metal oxide, a carbonaceous material, an oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), derivatives thereof, At least one selected from the group consisting of < RTI ID = 0.0 >

The surface of the active material particles may be coated with a carbon-based compound. Since the surface of the active material particles is generally known, a detailed description thereof will be omitted.

Wherein the lithium metal oxide is at least one selected from the group consisting of lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, lithium titanium oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, And at least one selected from the group consisting of lithium iron phosphate-based oxide, lithium phosphate-based oxide, lithium manganese-based oxide, lithium manganese silicate-based oxide, lithium iron silicate-based oxide, and combinations thereof.

That is, at least one of cobalt, manganese, nickel, or a composite oxide of a metal and lithium in combination thereof may be used. As a specific example thereof, a compound represented by any one of the following formulas can be used.

Li _a A _{1 - b} R _b D ₂ wherein, in the formula, 0.90? A? 1.8 and 0? B? 0.5; Li _a E _{1 -b} R _b O _{2 -c} D _c wherein, in the formula, 0.90? A? 1.8, 0? B? 0.5, and 0? C? 0.05; LiE (in the above formula, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05) 2-b R b O 4-c D c; Li _a Ni _{1 -b- c} Co _b R _c D _{α where} 0.90 ≦ a ≦ 1.8, 0 ≦ b ≦ 0.5, 0 ≦ c ≦ 0.05, and 0 <α ≦ 2; Li _a Ni _{1 - b - c} Co _b R _c O _{2 - ?} Z _{? Wherein} 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05 and 0 <? LiaNi1-b-cCobRcO2-? Z2 wherein 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05 and 0 <? <2; Li _a Ni _{1 -b- c} Mn _b R _c D _? Wherein, in the formula, 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05, and 0 <? Li _a Ni _1-bc Mn _b R _c O _{2 -?} Z _{? Where} 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05 and 0 <? Li _a Ni _{1 -b- c} Mn _b R _c O _{2 - ?} Z ₂ wherein 0.90? A? 1.8, 0? B? 0.5, 0? C? 0.05 and 0 <? Li _a Ni _b E _c G _d O ₂ wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, and 0.001 ≤ d ≤ 0.1; Li _a Ni _b Co _c Mn _d GeO ₂ wherein 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.5, and 0.001 ≤ e ≤ 0.1; Li _a NiG _b O ₂ (in the above formula, 0.90? A? 1.8 and 0.001? B? 0.1); Li _a CoG _b O ₂ (in the above formula, 0.90? A? 1.8 and 0.001? B? 0.1); Li _a MnGbO ₂ (in the above formula, 0.90? A? 1.8 and 0.001? B? 0.1); Li _a Mn ₂ G _b O ₄ (in the above formula, 0.90? A? 1.8 and 0.001? B? 0.1); QO _2; QS ₂ ; LiQS ₂ ; V ₂ O ₅ ; LiV ₂ O ₅ ; LiTO ₂ ; LiNiVO _4; Li _(3-f) J ₂ (PO ₄ ) ₃ (0? F? 2); Li _(3-f) Fe ₂ (PO ₄ ) ₃ (0? F? 2); And _{LiFePO 4, LiMnPO 4, LiCoPO 4} , Li 3 V 2 (PO 4) 3, Li 4 Ti 5 O 12, LiMnSiO 4, LiFeSiO 4.

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

The oxide of the active material particle may be at least one selected from the group consisting of an iron-based oxide, a cobalt-based oxide, a tin-based oxide, a titanium-based oxide, a nickel-based oxide, a zinc-based oxide, a manganese-based oxide, a silicon-based oxide, a vanadium- And combinations thereof.

That _{is, Fe x O y, Co x} O y, S n O y, TiO y, NiO, Mn x O y, Si x O y, V x O y, Cu x O y is selected from the group comprising a combination thereof (Where 0.90? X? 2.2 and 0.9? Y? 6).

Specifically, lithium phosphate (LiFePO ₄ ) was selected as the active material particle in the following examples.

The weight per area of the electrode including the three-dimensional structure current collector may be 0.001 mg / cm ² to 1 g / cm ² .

This range corresponds to an improvement in the weight per unit area of the electrodes as the three-dimensional structure current collector is used in place of the metal current collector, thereby minimizing the added substance in the electrode. That is, the capacity of the electrochemical device can be improved by the weight per area of the above range.

On the other hand, when the three-dimensional structure electrode is formed as one layer, its weight per area can not exceed 1 g / cm ² .

In this regard, the three-dimensional structure electrode may have a plurality of electrodes formed in a multi-layered structure.

As a result, the loading value of the active material particles in the active material structure electrode can be maximized, and as a result, the capacity and the energy density of the electrochemical device can be improved.

In the multi-layer structure, the weight per area of the electrode including the three-dimensional structure current collector may be 0.002 mg / cm ² to 10 g / cm ² .

According to another embodiment of the present invention, there is provided a method for producing a polymer solution, comprising: dissolving a polymer in a solvent to prepare a polymer solution; Dispersing a conductive material in a dispersion medium to produce a colloidal solution; Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber; Compressing the three-dimensional structural fibers to obtain a three-dimensional structure current collector; And coating the active material slurry on the surface of the three-dimensional structure current collector to produce an electrode, wherein the step of simultaneously spinning the polymer solution and the colloid solution to prepare a three-dimensional structural fiber comprises: Wherein the porous nonwoven fabric is filled with the conductive material between a plurality of polymer fibers contained in the porous nonwoven fabric.

Forming an electrode by coating an active material slurry on the surface of the three-dimensional structure current collector; Thereafter, the electrode is compressed using a roll press; And drying the compressed electrode.

This is a method of manufacturing an electrode by manufacturing the three-dimensional structure current collector and coating the surface of the three-dimensional structure current collector with an active material slurry. With this simple method, it is possible to provide an electrode with improved capacity per weight and volume.

The method of manufacturing the three-dimensional structure current collector is as described above, and the method of coating the active material slurry on the surface of the three-dimensional structure current collector, the compressing method, and the drying method are well known and will not be described in detail.

According to another embodiment of the present invention, cathode; A separator disposed between the anode and the cathode; Wherein at least one of the anode and the cathode comprises a three-dimensional structure current collector according to any one of the above-mentioned embodiments, and an active material layer coated on the surface of the three-dimensional structure current collector, And an electrochemical device.

This corresponds to an electrochemical device having a high energy density and a high output characteristic, including a three-dimensional structure current collector having the above-described characteristics, by weight and capacity per unit volume.

The electrochemical device includes a group including a lithium secondary battery, a super capacitor, a lithium-sulfur battery, a sodium ion battery, a lithium-air battery, a zinc-air battery, an aluminum-air battery, and a magnesium ion battery It can be any one selected.

Specifically, it may be a lithium secondary battery, and an embodiment thereof is described below. FIG. 2 is a schematic view of a lithium secondary battery including a three-dimensional fiber structure current collector according to an embodiment of the present invention.

2, a lithium secondary battery 200 according to an embodiment of the present invention includes an anode 212, a cathode 213, a separation membrane 100 disposed between the anode 212 and the cathode 213, (Not shown) impregnated into the anode 212, the cathode 213 and the separator 100 and includes a battery container 220 and a sealing member 240 for sealing the battery container 220 The secondary battery module can be configured as a main part.

The lithium secondary battery 200 includes a separator 100 interposed between a positive electrode 212 including a positive electrode active material and a negative electrode 213 including a negative electrode active material and a positive electrode 212 and a negative electrode 213, And the separator 100 are accommodated in the battery container 220 and the electrolyte for the lithium secondary battery is injected into the pores of the separator 100 by sealing the battery container 220 after the electrolyte for the lithium secondary battery is injected. have. The battery container 220 may have various shapes such as a cylindrical shape, a square shape, a coin shape, and a pouch shape. In the case of a cylindrical lithium secondary battery, a lithium secondary battery can be constructed by stacking an anode 212, a cathode 213, and a separator 100 in this order and then winding them in a spiral wound state in a battery container 220 have.

Since the structure and manufacturing method of the lithium secondary battery are well known in the art, a detailed description thereof will be omitted in order to avoid an ambiguous interpretation of the present invention.

Also, as the electrolyte, a nonaqueous electrolyte in which a lithium salt is dissolved in an organic solvent, a polymer electrolyte, an inorganic solid electrolyte, a polymer electrolyte, and a composite material with an inorganic solid electrolyte may be used.

The non-aqueous organic solvent of the non-aqueous electrolyte serves as a medium through which ions involved in the electrochemical reaction of the battery can move. As the non-aqueous organic solvent, a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based or aprotic solvent may be used. The non-aqueous organic solvent may be used singly or in combination of one or more thereof. In the case of mixing one or more of them, the mixing ratio may be suitably adjusted in accordance with the performance of the desired battery, which is widely understood by those skilled in the art . The non-aqueous organic solvent of the non-aqueous electrolyte serves as a medium through which ions involved in the electrochemical reaction of the battery can move. As the non-aqueous organic solvent, a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based or aprotic solvent may be used. The non-aqueous organic solvent may be used singly or in combination of one or more thereof. In the case of mixing one or more of them, the mixing ratio may be suitably adjusted in accordance with the performance of the desired battery, which is widely understood by those skilled in the art .

The lithium salt is dissolved in a non-aqueous organic solvent to act as a source of lithium ions in the battery to enable the operation of a basic lithium secondary battery and to promote the movement of lithium ions between the positive and negative electrodes .

The lithium salt Representative examples are _{LiPF 6, LiBF 4, LiSbF 6} , LiAsF 6, LiC 4 F 9 SO 3, LiClO 4, LiAlO 2, LiAlCl 4, LiN (C x F 2x +1 SO 2) (C y F 2y ₊₁ SO ₂₎ (where, x and y are natural numbers), LiCl, LiI, LiB ( C 2 O 4) 2 ( lithium bis oxalate reyito borate (lithium bis (oxalato) borate; LiBOB) , or in a combination thereof The concentration of the lithium salt is preferably within the range of 0.1 to 2.0 M. When the concentration of the lithium salt is included in the range, the electrolyte has an appropriate conductivity and viscosity, so that an excellent electrolyte Performance, and lithium ions can move efficiently.

Hereinafter, preferred embodiments of the present invention and experimental examples therefor will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

For lithium secondary battery Whole-house  And manufacturing a lithium secondary battery comprising the same

Example  One

Preparation of Polymer Solution First, polyetherimide (PEI) is used as a polymer for producing a porous nonwoven fabric and dimethylacetamide (N, N-dimethylactamide) and N- Methyl-2-pyrrolidone in a weight ratio of 50:50 was used as a solvent.

The polymer was added to the solvent to prepare a polymer solution. At this time, the content of the polymer in the polymer solution was 25 wt% (wt%).

Preparation of colloidal solution In order to prepare a colloidal solution containing a conductive material, a carbon nanotube, which is a conductive material capable of maintaining a uniform spray state, was used. As the dispersion medium, deionized water and isopropyl alcohol -propylalcohol) in a weight ratio of 9: 1 was used.

The conductive material was added to the dispersion medium to prepare a colloidal solution. At this time, the content of the conductive material in the colloidal solution was 0.5 wt% (wt%). Further, in order to uniformly disperse the colloidal solution, polyvinylpyrrolidone as a dispersant was added to the colloid solution so as to contain 0.5% by weight.

Production of a current collector by double electrospinning The polymer solution and the colloid solution were introduced into an electrospinning apparatus (Nano Corporation). The injection rate of the polymer solution was 3 l / min, Was irradiated (dual electrospinning) at about 65 占 퐇 / min for about 240 minutes to prepare a three-dimensional structure current collector.

Applying the cathode mixture slurry to the surface of the entire manufacturing the three-dimensional structure house the electrode back, a roll press (Roll Press, point of purchase: ㈜ group Bay anti) is compressed using, and the loading of active material, from about ² ㎎ / cm 2, An electrode having a thickness of about 20 μm was prepared.

The negative electrode mixture slurry was prepared by mixing a mixture containing 70 wt% of silicon (Si) as a negative active material, 10 wt% of carbon black as a conductive material, and 20 wt% of polyacylic acid (PAA) H ₂ O) in the form of a slurry.

Preparation of Lithium Secondary Battery The above electrode was applied as a negative electrode to prepare a lithium secondary battery.

Specifically, lithium (Li) metal was used as a counter electrode, and polyethylene (Tonen 20 μm) was used as a separator.

Organic solvent (EC: DEC = 3: 7 (v: v)) after the addition of FEC 10% by weight, the concentration of LiPF ₆ was dissolved to prepare a nonaqueous electrolyte is 1.3M.

After forming the coin type cells by inserting the thus prepared positive electrode, negative electrode and separation membrane, the non-aqueous electrolyte was injected to prepare a coin type lithium secondary battery.

Example  2

A two-dimensional electrospinning was performed for about 480 minutes to prepare a three-dimensional structure current collector, and an electrode was manufactured so that the active material loading was about 5 mg / cm ² and the thickness was about 43 μm. A lithium secondary battery was fabricated.

Comparative Example  One

Preparation of Electrode An electrode having an active material loading of about 2 mg / cm ² was prepared in the same manner as in Example 1, except that a copper (Cu) thin film having a thickness of 20 탆 was used instead of the three-dimensional structure current collector.

Preparation of lithium secondary battery A lithium secondary battery was produced in the same manner as in Example 1, except that these electrodes were used as a cathode.

Comparative Example  2

An electrode having an active material loading of about 5 mg / cm &lt; ² &gt; was prepared in the same manner as in Comparative Example 1 , except that the anode mixture slurry was applied on the current collector to increase the thickness thereof. Manufactured

Evaluation of Electrode for Lithium Secondary Battery and Lithium Secondary Battery Containing It

Test Example  One: Example  Observation of electrode manufactured in 1

The surface and cross-section of the current collector manufactured by Example 1 were observed with a scanning electron microscope (SEM), and the results are shown in FIGS. 3A and 3B, respectively.

As a result of observing the surface through Fig. 3A, it was found that the current collector of Example 1 contained a plurality of polymer fibers, and the average diameter thereof was 1 mu m. Further, void spaces (pores) are present between the plurality of high-injection occupations, and the degree of porosity thereof is confirmed to be 70% by volume with respect to the total volume of the current collector.

The pores are filled with carbon nanotubes. Specifically, each surface of the plurality of polymer fibers is covered with the carbon nanotubes.

Meanwhile, as a result of observing a cross section through FIG. 3B, it can be seen that the carbon nanotubes uniformly cover each surface of the plurality of polymer fibers, thereby forming an electron conduction network in the thickness direction of the current collector.

Figs. 4A and 4B are photographs of the appearance before (Fig. 4A) and after (Fig. 4B) bending the current collector produced by Example 1. Fig.

Specifically, it was confirmed that the porous nonwoven fabric and the conductive material were not separated from each other in the bent state of the current collector (Fig. 4A) of Example 1 (Fig. 4B).

Accordingly, although the collector of Example 1 does not contain a separate material (for example, a binder), the three-dimensional super lattice structure of the porous nonwoven fabric and the conductive material is stably maintained .

Test Example  2: Example  Comparison of Surface Resistance of Each Electrode Made in 1

In order to examine the surface resistance characteristics of the electrode prepared in Example 1, the electronic conductivity was measured.

Specifically, the electronic conductivity was measured using a 4 probe tip manufactured by Dasol ENG Co., Ltd., and the results are shown in FIG.

According to Fig. 5, Example 1 shows a high electronic conductivity of 7 S / cm. As a result, it can be understood that the electron conduction network is uniformly formed inside the electrode (particularly, the current collector).

Furthermore, it can be inferred that the output characteristics of the battery including the electrode of Example 1 will also be improved.

Test Example  3: Example  1 and Comparative Example  Performance comparison of each cell manufactured in 1

In order to measure the performance of each cell manufactured in Example 1 and Comparative Example 1, the discharge capacity was observed while the coin cell charging current rate was fixed at 0.2C and the discharging current rate was increased from 0.2C to 5C.

Specifically, the results of observing the discharge capacity per weight of the active material are shown in FIG. 6A, and the results of observing the discharge capacity per electrode weight are shown in FIG. 6B. 6A and 6B, the lithium secondary battery manufactured in Example 1 of Comparative Example 1 shows a high discharge capacity.

First, according to FIG. 6A, as the discharge current rate increases, the lithium secondary battery of Example 1 exhibits a higher discharge capacity than the lithium secondary battery of Comparative Example 1. This is because the current collector of Comparative Example 1 had not only the structural characteristic that the electron conduction network was not uniformly formed by the carbon black but also the electronic conduction network was disturbed by the adhesive polymer used as the binder.

On the contrary, the current collector of Example 1 maintains a super lattice structure and forms a uniform electron conduction network by the carbon nanotubes in the three-dimensional super structure, It is evaluated that the performance is superior to that of Comparative Example 1.

Although a separate adhesive polymer was used as the binder in Example 1, the porous nonwoven fabric and the conductive material are not separated from each other without the binder, and the three-dimensional super lattice can be stably maintained Are as described above.

When the above results were observed in terms of the weight per electrode weight (FIG. 6B), unlike Comparative Example 1 in which a metal current collector was used, in Example 1, only the nonwoven fabric was used as a support and only carbon nanotubes were used for forming an electron conduction network Therefore, it can be seen that the discharge capacity per electrode weight is greatly increased as compared with Comparative Example 1. [ As a result, the lithium secondary battery of Example 1 is lighter than Comparative Example 1, and exhibits high output, high capacity, and high energy density.

Test Example  4: Example  2 and Comparative Example  Comparison of performance of each cell manufactured in 2

The charging current rate was fixed at 0.2 C and the coin cell discharging current rate was set at 0.2 C in the same manner as in Test Example 3 with respect to Example 2 and Comparative Example 2 in which the loading value of the active material was increased as compared with Example 1 and Comparative Example 1 To 5 C, and the discharge capacity was observed.

Specifically, the discharge capacity per weight of the active material was observed, and the discharge capacity per electrode weight was observed in FIG. 7B. 7A and 7B, the lithium secondary battery of Example 2 exhibits a higher discharge capacity than that of Comparative Example 2. FIG.

In general, the higher the loading value of the active material, the higher the thickness of the electrode. In this case, it is difficult to form a uniform electronic conduction network in the electrode thickness direction, and as a result, the output characteristics of the battery tend to decrease. Particularly, when a silicon active material is used, volume expansion and contraction occur during charging and discharging, and it is very difficult to maintain the electron conduction network uniformly in the thickness direction of the electrode including the silicon active material.

However, in the case of the lithium secondary battery of Example 2, the discharge capacity is higher than that of the lithium secondary battery of Comparative Example 2 (Fig. 7A) as the discharge current rate increases, despite the increase of the loading value of the active material It was confirmed that the discharge capacity also greatly increased in comparison with Comparative Example 2 (Fig. 7B).

Accordingly, since the electrode of Example 2 has a uniform electron conduction network in the thickness direction by the three-dimensional fiber structure current collector, it is possible to evaluate the phenomenon that the output characteristic of the battery is reduced effectively.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: three-dimensional structural current collector
10: Nonwoven fabric nanofiber 20: Conductive material
200: lithium secondary battery 212: positive electrode
213: cathode 220: battery container
240: sealing member

Claims (31)

A porous nonwoven fabric comprising a plurality of polymer fibers; And
Conductive material;
Pores are formed between the plurality of polymer fibers contained in the porous nonwoven fabric,
Wherein the pores are filled with the conductive material,
A three dimensional structure house.
The method according to claim 1,
The filled-
Wherein the conductive material is in the form of covering the surface of the plurality of polymer fibers.
A three dimensional structure house.
The method according to claim 1,
The ratio of the content of the porous nonwoven fabric and the conductive material in the three-
Wherein the weight ratio of the conductive material to the porous nonwoven fabric is from 5:95 to 95: 5.
A three dimensional structure house.
The method according to claim 1,
The average diameter of the plurality of polymer fibers may be,
0.001 to 1000 mu m.
A three dimensional structure house.
The method according to claim 1,
The average particle diameter of the conductive material is,
0.001 to 10 [mu] m.
A three dimensional structure house.
The method according to claim 1,
The porosity of the three-
5 to 95% by volume.
A three dimensional structure house.
The method according to claim 1,
The thickness of the three-
1 to 1000 [mu] m.
A three dimensional structure house.
The method according to claim 1,
The porous non-
Polyvinyl pyrrolidone, polyethylene terephthalate, polyimide, polyamide, polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene, polyetherimide, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone At least one selected from the group consisting of polyvinylidene fluoride, polyvinylidene hexafluoropropylene, polyurethane, nylon 6, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof, Lt; / RTI &gt;
A three dimensional structure house.
The method according to claim 1,
The conductive material may be,
Carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof And mixtures thereof. &Lt; RTI ID = 0.0 &gt;
A three dimensional structure house.
Dissolving the polymer in a solvent to prepare a polymer solution;
Dispersing a conductive material in a dispersion medium to produce a colloidal solution;
Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber; And
And compressing the three-dimensional structural fibers to obtain a three-dimensional structure current collector,
Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber,
Forming a porous nonwoven fabric including a plurality of polymer fibers and filling the plurality of polymer fibers contained in the porous nonwoven fabric with the conductive material,
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber,
Wherein the filled shape is a shape in which the conductive material covers the surface of the plurality of polymer fibers.
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber,
Wherein the method is any one selected from the group consisting of electrospray, electrospray, double spray, and combinations thereof.
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber,
The spinning speed of the polymer solution is 2 to 10 ㎕ / min,
Wherein the colloidal solution has a spinning rate of 30 to 80 占 퐇 / min.
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
In the step of dissolving the polymer in a solvent to prepare a polymer solution,
The content of the polymer in the polymer solution,
By weight, based on the total weight of the polymer solution, of 5 to 30%
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
In the step of dissolving the polymer in a solvent to prepare a polymer solution,
In the polymer solution,
At least one selected from the group consisting of carbon nanotubes, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof, One,
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
In the step of dissolving the polymer in a solvent to prepare a polymer solution,
The solvent may be,
At least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-methylpyrrolidone,
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Dispersing a conductive material in a dispersion medium to produce a colloidal solution,
The content of the conductive material in the colloidal solution may be,
By weight based on the total weight of the colloidal solution, 0.1 to 50%
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Dispersing a conductive material in a dispersion medium to produce a colloidal solution,
The conductive material may be,
Carbon nanotubes, silver nanowires, nickel nanowires, gold nanowires, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof And mixtures thereof. &Lt; RTI ID = 0.0 &gt;
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Dispersing a conductive material in a dispersion medium to produce a colloidal solution,
The dispersion medium,
But are not limited to, deionized water, iso-propylalcohol, buthalol, ethanol, hexanol, acetone, N, N-dimethylformamide, dimethylacetamide Is selected from the group consisting of N, N-dimethylacetamide, N, N-methylpyrrolidone, and combinations thereof.
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Dispersing a conductive material in a dispersion medium to produce a colloidal solution,
Wherein the colloidal solution further comprises a dispersing agent,
Wherein the content of the dispersing agent in the colloidal solution is 0.001 to 10% by weight based on the total weight of the colloidal solution.
A method for manufacturing a three-dimensional structure current collector.
21. The method of claim 20,
Preferably,
Is at least one selected from the group consisting of polyvinyl pyrrolidone, poly 3,4-ethylenedioxythiophene, and mixtures thereof.
A method for manufacturing a three-dimensional structure current collector.
11. The method of claim 10,
Compressing the three-dimensional structural fibers to obtain a three-dimensional structure current collector; Since the,
And firing the three-dimensional structure current collector,
Wherein the plurality of polymer fibers contained in the pre-firing three-dimensional structure current collector are converted into a plurality of carbon nanofibers by the firing.
A method for manufacturing a three-dimensional structure current collector.
A three dimensional structure collector; And
And an active material layer coated on a surface of the three-dimensional structure current collector,
Wherein the three-
A porous nonwoven fabric comprising a plurality of polymer fibers; And
Conductive material;
Wherein the conductive material is filled between a plurality of polymer fibers contained in the porous nonwoven fabric.
electrode.
24. The method of claim 23,
The active material contained in the active material layer may be,
At least one selected from the group consisting of lithium metal-based oxide, carbon-based material, oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), derivatives thereof, ,
electrode.
24. The method of claim 23,
The weight per area of the electrode including the three-
0.001 mg / cm ² to 1 g / cm ² .
electrode.
24. The method of claim 23,
Wherein the three-dimensional structure electrode comprises:
Wherein a plurality of electrodes form a multilayer structure,
electrode.
27. The method of claim 26,
The weight per area of the electrode including the three-
0.002 mg / cm ² to 10 g / cm ² .
electrode.
Dissolving the polymer in a solvent to prepare a polymer solution;
Dispersing a conductive material in a dispersion medium to produce a colloidal solution;
Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber;
Compressing the three-dimensional structural fibers to obtain a three-dimensional structure current collector;
And coating an active material slurry on the surface of the three-dimensional structure current collector to manufacture an electrode,
Simultaneously spinning the polymer solution and the colloidal solution to prepare a three-dimensional structural fiber,
Forming a porous nonwoven fabric including a plurality of polymer fibers and filling the plurality of polymer fibers contained in the porous nonwoven fabric with the conductive material,
Gt;
29. The method of claim 28,
Coating an active material slurry on the surface of the three-dimensional structure current collector to produce an electrode; Since the,
Compressing the electrode using a roll press; And
And drying the compressed electrode. &Lt; RTI ID = 0.0 &gt;
Gt;
anode;
cathode;
A separator disposed between the anode and the cathode;
And an electrolyte impregnated into the anode, the cathode, and the separator,
Wherein at least one of the positive electrode and the negative electrode comprises:
22. A three-dimensional structure comprising: a three-dimensional structure current collector according to any one of claims 1 to 22; and an active material layer coated on the surface of the three-
Electrochemical device.
31. The method of claim 30,
Wherein the electrochemical device comprises:
The battery is any one selected from the group consisting of a lithium secondary battery, a super capacitor, a lithium-sulfur battery, a sodium ion battery, a lithium-air battery, a zinc- ,
Electrochemical device.

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