KR20160043939A - Three-dimensional porous-structured electrode , and electrochemical device having the electrode - Google Patents

Abstract

The present invention relates to a three-dimensional structure electrode, a manufacturing method thereof, and an electrochemical device including the electrode. Specifically, the three-dimensional structure electrode includes: a porous non-woven fabric including a plurality of polymer fibers; a positive electrode active material particle including a lithium metal oxide, a derivative of the lithium metal oxide, or a mixture of the lithium metal oxide and the derivative, wherein a gap between the polymer fabrics included in the porous non-woven fabric is evenly filled with the positive electrode active material and the conductive material, and a gas hole is formed. The electrochemical device includes the three-dimensional structure electrode.

Description

TECHNICAL FIELD [0001] The present invention relates to a three-dimensional structure electrode, and an electrochemical device including the same. BACKGROUND OF THE INVENTION [0002]

Dimensional structure electrode, and an electrochemical device including the same.

Recently, market demand for IT electronic devices such as smart phones, tablet PCs and high-performance notebook PCs is increasing. In addition, as a measure against global warming and depletion of resources, demand for large-capacity power storage devices such as electric vehicles and smart grids has been greatly increased, and demand for electrochemical devices including secondary batteries has rapidly increased .

Particularly, lithium secondary batteries are considered to be the most popular secondary batteries due to their excellent cycle life and high energy density. However, in order to meet the demand for high power and high capacity, it is necessary to prepare an improvement measure for an electrochemical device that satisfies this requirement.

In this connection, the electrode contributing to the capacity of the electrochemical device is composed of the metal current collector and the mixture of the active material, the conductive agent, and the binder coated thereon, Only active materials contribute to energy density.

Therefore, when the additive materials such as the conductive material and the binder are minimized, the capacity per weight or volume of the electrode is increased, and ultimately the energy density of the electrochemical device can be increased.

In addition, it is preferable to use a lightweight current collector instead of a metal current collector. In the case of a metal current collector, it is one of the causes of reducing the capacity per volume and volume per electrode, because the weight and the volume in the electrode are large.

Further, by using a conductive material serving as a conductive material, the electrode can have a uniform electronic conduction network. This is because it is possible to improve the electronic conductivity by forming a uniform electronic conduction network between the active materials in the electrode, and as a result, to improve the output characteristics of the electrochemical device.

As described above, when an electrode material such as a conductive material and a binder is minimized, a collector made of a light material is used instead of a metal current collector, and an electrode having a good electronic conduction network is applied to an electrochemical device, Energy density, etc. However, research on the electrode considering all three aspects is still insufficient.

In order to solve the above-mentioned problems, the present inventors have developed a three-dimensional structure electrode considering all three aspects of the minimization of additive materials, a lightweight current collector, and a good electronic conduction network. The details of this are as follows.

According to an embodiment of the present invention, there is provided a three-dimensional structure electrode comprising a plurality of polymer fibers contained in a porous nonwoven fabric, wherein the active material particles and the conductive material are uniformly filled and pores are interconnected by the plurality of polymer fibers .

In another embodiment of the present invention, an electrochemical device including the three-dimensional structure electrode may be provided.

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

The three-dimensional structure electrode may include at least one selected from the group consisting of a lithium metal-based oxide, an oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), a derivative thereof, One active material particle is used.

On the other hand, the porosity of the three-dimensional structure electrode may be 5 to 95% by volume.

The content of each material contained in the three-dimensional structure electrode will be described as follows.

The content of the porous nonwoven fabric in the three-dimensional structure electrode may be 5 to 70% by weight based on the total weight of the three-dimensional structure electrode.

The content of the active material particles in the three-dimensional structure electrode may be 20 to 95% by weight based on the total weight of the three-dimensional structure electrode.

The ratio of the active material particles and the conductive material in the three-dimensional structure electrode may be 0.1: 100 to 50: 100 in terms of the weight ratio of the conductive material to the active material particles.

On the other hand, the average diameter of each material contained in the three-dimensional structure electrode will be described as follows.

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

The average diameter of the active material particles may be 0.001 to 30 탆.

The weight per unit area and the thickness of the three-dimensional structure electrode will be described as follows.

The thickness of the three-dimensional structure electrode may be 1 to 1000 탆.

The weight per area of the three-dimensional structure electrode 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, and the weight per area of the three-dimensional structure electrode having such a multi-layer structure may be 0.002 g / cm ² to 10 g / cm ² .

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

The polymer comprising the plurality of polymer fibers 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, polyvinylpyrrolidone, agarose, alginate, polyvinylidene hexafluoropropylene, polyurethane, nylon 6, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof, And mixtures thereof.

Independently, the polymer comprising the plurality of polymer fibers may be selected from the group consisting of carbon nanotubes, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, And derivatives thereof, and mixtures thereof, and may be at least one selected from the group consisting of carbon nanotubes.

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- Polyaniline, derivatives thereof, and mixtures thereof.

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

The three-dimensional structure electrode may be polar.

The three-dimensional structure electrode may be any one selected from a positive electrode and a negative electrode.

The three-dimensional structure electrode may include a step of dissolving the polymer in a solvent to prepare a polymer solution; Dispersing the active material particles and the conductive material in a dispersion medium to prepare a colloid 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 structure electrode, wherein the step of simultaneously spinning the polymer solution and the colloidal solution to produce a three-dimensional structural fiber comprises: A porous nonwoven fabric may be formed and a plurality of polymer fibers contained in the porous nonwoven fabric may be manufactured through a series of processes in which the active material particles and the conductive material are uniformly filled and pores are formed.

In the above series of processes, the active material particles may include a lithium metal oxide, an oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), derivatives thereof, At least one selected from the group is used.

Specifically, the step of simultaneously spinning the polymer solution and the colloidal solution to produce a three-dimensional structural fiber will be described as follows.

Electrospray, double spray, dual spray, electrospray, double spray, and combinations thereof.

The spinning speed of the polymer solution may be 2 to 15 μl / min, and the spinning speed of the colloid solution may be 30 to 100 μl / min.

On the other hand, the step of dissolving the polymer in a solvent to prepare a polymer solution will be described 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 solvent may be at least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, have.

The step of dispersing the active material particles and the conductive material in a dispersion medium to prepare a colloidal solution is described as follows.

The content of the active material particles in the colloidal solution may be 1 to 50% by weight based on the total weight of the colloidal solution.

Specifically, the method includes: pulverizing the active material particles; And dispersing the pulverized active material particles and the conductive material in the dispersion medium to prepare the colloidal solution.

Independently from each other, adding the conductive material to the active material particles to produce a mixed powder; Pulverizing the mixed powder to obtain an active material particle / conductive material composite; And dispersing the complex in the dispersion medium to prepare the colloidal solution.

The content ratio of the active material particles and the conductive material in the colloidal solution may be 0.1: 100 to 50: 100 in terms of the weight ratio of the conductive material to the active material particles.

The colloid solution may further comprise 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 colloid solution.

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

In another embodiment of the present invention, cathode; A separator disposed between the anode and the cathode; And an electrolyte impregnated into the positive electrode, the negative electrode and the separation membrane, wherein at least one of the positive electrode and the negative electrode is a three-dimensional structure electrode according to any one of the above-mentioned aspects.

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 one embodiment of the present invention, the three-dimensional densely packed structure described above minimizes the additive material and uses a lightweight current collector to form a uniform electronic conduction network while improving the capacity per weight and volume of the electrode Thereby contributing to the high output characteristics of the electrochemical device.

According to another embodiment of the present invention, it is possible to provide an electrochemical device having excellent weight per unit volume and volume, high energy density, and high output characteristics.

FIG. 1 schematically shows a method of manufacturing a three-dimensional structure electrode according to another embodiment of the present invention, together with a three-dimensional structure electrode according to an embodiment of the present invention.
2 is a schematic view of a lithium secondary battery module including a three-dimensional fiber structure electrode according to an embodiment of the present invention.
FIGS. 3A to 3C show results of observing the upper portion, the lower portion, and the cross-section of the electrode manufactured according to Example 1 of the present invention with a scanning electron microscope (SEM).
Figures 4a and 4b illustrate. 1 is an external view of an electrode manufactured according to Example 1 of the present invention.
Fig. 5 shows the results obtained by measuring the respective electronic conductivities of the three-dimensional structure electrode manufactured in Example 1 of the present invention and the electrode manufactured in Comparative Example 1. Fig.
6A is a graph showing the results of observing the discharge capacity per weight of active material particles for a lithium secondary battery fabricated by Example 1 of the present invention and a lithium secondary battery fabricated by Comparative Example 1. FIG.
FIG. 6B is a graph showing the results of observing the discharge capacity per electrode weight for 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 active material particles for a lithium secondary battery fabricated by Example 2 of the present invention and a lithium secondary battery fabricated by Comparative Example 2. FIG.
FIG. 7B is a graph showing the results of observing the discharge capacity per electrode weight for 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 electrode according to another embodiment of the present invention, together with a three-dimensional structure electrode 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; Active material particles; And a conductive material, wherein the active material particles and the conductive material are uniformly filled between the plurality of polymer fibers contained in the porous nonwoven fabric, and pores are formed.

The three-dimensional structure electrode may include at least one selected from the group consisting of a lithium metal-based oxide, an oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), a derivative thereof, One active material particle is used.

1, the three-dimensional structure electrode is a three-dimensional structure (super lattice), in which a plurality of polymer fibers 10 contained in the porous nonwoven fabric serve as a support, and between the plurality of polymer fibers 10 The anode active material particles 20 and the conductive material 30 are uniformly filled and an interconnected porous network is formed by the plurality of polymer fibers 10. [

This is a type of electrode in which all three aspects of minimizing additive materials, a lightweight current collector, and a good electronic conduction network are all considered.

Specifically, the weight of the electrode and the capacity per volume can be improved by minimizing the additive material by not including a separate binder and using the porous nonwoven fabric as a light material in place of the metal current collector.

In addition, by forming the active material particles in the three-dimensional filling structure surrounded by the conductive material, the electronic conduction network can be made uniform, contributing to high output characteristics of the electrochemical device, and the discharge characteristic can be improved Lt; / RTI > Especially, when the active material particles having poor electron conductivity are applied, the output characteristics can be maximized.

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

As described above, the three-dimensionally structured electrode forms a plurality of unevenly spaced spaces as a plurality of polymer fibers 10 contained in the porous nonwoven fabric are aggregated three-dimensionally irregularly and continuously.

Between the spaces thus formed, the active material particles and the conductive material are uniformly filled, and an interconnected porous network is formed by the plurality of polymer fibers 10.

Specifically, the porosity of the three-dimensional structure electrode 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, if it exceeds 95% by volume, there arises a problem that the loading value of the electrode is too small as compared with the volume, and the distance between the active material particles and the conductive material is distant, and the electronic conduction network may not be formed well. On the other hand, if the volume ratio is less than 5 vol%, the ion conductivity of the three-dimensional structure electrode may be deteriorated because the porosity is too small. Thus, the porosity is limited as described above.

More specifically, the porosity of the three-dimensional structure electrode may be 30 to 90% by volume. In this case, the ion conductivity of the three-dimensional structure electrode 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 content of the active material particles, which will be described later.

The content of each material contained in the three-dimensional structure electrode will be described as follows.

The content of the porous nonwoven fabric in the three-dimensional structure electrode may be 5 to 70% by weight based on the total weight of the three-dimensional structure electrode. By containing the porous nonwoven fabric in the above range instead of the metal current collector, the capacity per volume and volume of the electrode can be increased.

However, if it exceeds 70% by weight, the content of the active material particles and the conductive material may be excessively reduced as compared with the porous nonwoven fabric, resulting in a problem of deteriorated electron conductivity. On the other hand, if the content is less than 5% by weight, the porous nonwoven fabric does not sufficiently perform the role of the support, and the structure of the three-dimensional structure electrode can not be maintained. Therefore, the content of the porous nonwoven fabric in the three-dimensional structure electrode is limited as described above.

The content of the active material particles in the three-dimensional structure electrode may be 20 to 95% by weight based on the total weight of the three-dimensional structure electrode. When this range is satisfied, the capacity and the energy density of the electrochemical device can be improved, and the porosity of the three-dimensional structure electrode in the above range can be formed.

This is because the active material particles substantially contribute to the expression of the capacity and the energy density of the electrochemical device among the materials constituting the three-dimensional structure electrode, and the content of the active material particles in the three-dimensional structure electrode is the porosity of the three- This is one of the determining factors.

However, if it exceeds 95% by weight, the content of the active material particles in excess of the porous nonwoven fabric may not sufficiently perform the role of the support, and thus the structure of the three-dimensional structure electrode may not be maintained . On the other hand, if it is less than 20% by weight, it is difficult to form an electronic conduction network between the active material particles and the conductive material, and the output characteristics of the electrode may be deteriorated. Therefore, the content of the active material particles in the three-dimensional structure electrode is limited as described above.

The ratio of the active material particles and the conductive material in the three-dimensional structure electrode may be 0.1: 100 to 50: 100 in terms of the weight ratio of the conductive material to the active material particles. By containing the conductive material within the above range, it is possible to contribute to improving the output of the electrochemical device by providing an electronic conduction network in the electrode.

However, if the conductive material exceeds the above range, the dispersion state of the spinning solution for the production may not be maintained, which will be described in detail in another embodiment of the present invention to be described later. On the other hand, in the case of less than the above range, since the formation of the electronic conduction network by the conductive material is insufficient, the output characteristics of the electrode may be deteriorated, so that the content ratio of the active material particles and the conductive material is limited as described above.

On the other hand, the average diameter of each material contained in the three-dimensional structure electrode will be described as follows.

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 diameter of the active material particles may be 0.001 to 30 탆, specifically 0.001 to 10 탆. The active material particles having an average diameter in this range contribute to controlling the porosity of the three-dimensional structure electrode to the above-described range. In addition, in the method for producing a three-dimensional electrode to be described later, the dispersibility in the colloid solution containing the active material particles is improved, and the occurrence of problems in the double electrospinning method is minimized, whereby the pores of the finally obtained three- can do.

However, if it is more than 30 탆, there may arise a problem that the dispersion state of the spinning solution for the production thereof is not maintained. On the other hand, if it is less than 0.001 탆, the particle size is too small, The average diameter of the active material particles is limited.

The weight per unit area and the thickness of the three-dimensional structure electrode will be described as follows.

The weight per area of the three-dimensional structure electrode may be 0.001 mg / cm ² to 1 g / cm ² . This range corresponds to an increase in the weight per unit area of the electrode as the material added in the three-dimensional structure electrode is minimized and the porous nonwoven fabric is used in place of the metal current collector. That is, the capacity of the electrochemical device can be improved by the weight per area of the above range.

However, if it is less than 0.001 mg / cm ^2, the energy density of the electrode may be lowered. Therefore, the lower limit of the weight per unit area of the three-dimensional structure electrode is limited as described above.

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.

Specifically, the weight per area of the three-dimensional structure electrode may be 0.002 g / cm ² to 10 g / cm ² .

Independent thereto, the thickness of the three-dimensional structure electrode 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 three-dimensional structure electrode, there is an advantage that a smooth electronic 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.

Specifically, the polymer comprising the plurality of polymer fibers 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, polyvinylpyrrolidone, agarose, alginate, polyvinylidene hexafluoropropylene, polyurethane, nylon 6, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, derivatives thereof , And a mixture thereof.

Independently, the polymer comprising the plurality of polymer fibers may be selected from the group consisting of carbon nanotubes, graphene, graphene oxide, reduced graphene oxide, polypyrrole, poly 3,4-ethylenedioxythiophene, polyaniline, And derivatives thereof, and mixtures thereof, and may be at least one selected from the group consisting of carbon nanotubes. In this case, the strength and electron conductivity of the porous nonwoven fabric can be improved.

The active material particles may be at least one selected from the group consisting of the lithium metal oxide oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), derivatives thereof, Lt; / RTI > Specifically, the lithium metal oxide and the derivative thereof are known as a cathode active material, and the former can be a cathode. On the other hand, oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S) and derivatives thereof are known as negative active materials.

The active material particles may be coated with a carbon-based compound. Since this is generally known, a detailed description 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- bR _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 _{? Where} 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.

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

The three-dimensional structure electrode will be described as follows.

The three-dimensional structure electrode may be polar. In this case, excellent wettability with respect to the electrolyte can be realized.

The three-dimensional structure electrode may be any one selected from a positive electrode and a negative electrode.

The three-dimensional structure electrode may include a step of dissolving the polymer in a solvent to prepare a polymer solution; Dispersing the active material particles and the conductive material in a dispersion medium to prepare a colloid 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 structure electrode, wherein the step of simultaneously spinning the polymer solution and the colloidal solution to produce a three-dimensional structural fiber comprises: A porous nonwoven fabric may be formed and a plurality of polymer fibers contained in the porous nonwoven fabric may be manufactured through a series of processes in which the active material particles and the conductive material are uniformly filled and pores are formed.

This is a method for producing a three-dimensional structure electrode having excellent characteristics as described above by simultaneously spraying the two solutions of the polymer solution and the colloid solution.

In the above series of processes, the active material particles may include a lithium metal oxide, an oxide, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), derivatives thereof, At least one selected from the group is used.

Specifically, a colloidal solution containing the active material particles and 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, And forming a three-dimensional dense packing structure by the conductive material, thereby manufacturing a three-dimensional structure electrode.

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

And simultaneously spinning the polymer solution and the colloidal solution to produce a three-dimensional structural fiber, will be described as follows.

This is not particularly limited as long as the polymer solution and the colloidal solution can be simultaneously radiated. However, any method selected from the group including double electrospinning, electrospray, double spray, It may be one way.

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

Also. 50 minutes to 24 hours. The three-dimensional structure electrode can be formed within the range of the execution time, and the loading value of the active material particles in the three-dimensional structure electrode can be improved as the execution time increases.

The spinning speed of the polymer solution may be 2 to 15 μl / min, and the spinning speed of the colloid solution may be 30 to 100 μl / min. When the spinning speed range of each solution is satisfied, the three-dimensional structure electrode can be formed. Particularly, when the spinning speed of the colloid solution is increased within the above range, the loading value of the active material particles in the three-dimensional structure electrode can be improved.

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. In addition, if the colloidal solution spinning rate is not satisfied, the colloid solution may not be uniformly radiated and fall into a large droplet state. For this reason, the spinning speed of each solution is individually limited as described above.

On the other hand, the step of dissolving the polymer in a solvent to prepare a polymer solution will be described 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 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 &gt;

The step of dispersing the active material particles and the conductive material in a dispersion medium to prepare a colloidal solution is described as follows.

The content of the active material particles in the colloidal solution may be 1 to 50% by weight based on the total weight of the colloidal solution. By controlling the content of the active material particles in the colloidal solution to such a range, the porosity in the three-dimensional structure electrode can be controlled.

However, if it exceeds 50% by weight, dispersion of the active material particles may not be maintained, and if it is less than 1% by weight, the loading value of the three-dimensional electrode may become too small. Thereby limiting the content of the active material particles in the solution.

More specifically, the step of crushing the active material particles comprises: And dispersing the pulverized active material particles and the conductive material in the dispersion medium to prepare the colloidal solution.

This is for uniform dispersion of the active material particles in the colloidal solution and relates to limiting the average diameter of the active material particles. Specifically, when the active material particles having an average diameter in the unit of μm before the production of the colloid are pulverized to have an average diameter in the unit of nm, it is advantageous to uniformly disperse the particles in the colloid solution.

Of course, as described above, if the active material particles already have an average diameter of nm units (i.e., 0.001 mu m or more and less than 0.01 mu m), such a pulverization step may be unnecessary.

Independently from each other, adding the conductive material to the active material particles to produce a mixed powder; Pulverizing the mixed powder to obtain an active material particle / conductive material composite; And dispersing the complex in the dispersion medium to prepare the colloidal solution.

This is because, as described above, by uniformly dispersing the active material particles by pulverizing the active material particles and forming a complex with the conductive material, electron conductivity can further be imparted to the surface of the active material particles.

The content ratio of the active material particles and the conductive material in the colloidal solution may be 0.1: 100 to 50: 100 in terms of the weight ratio of the conductive material to the active material particles.

The inclusion of the conductive material in the above range can contribute to enhancement of the output of the electrochemical device by providing an electronic conductivity network in the electrode, and the reason for the limitation of the upper limit and the lower limit is as described above.

The colloid solution may further comprise 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 colloid solution.

When the dispersant is included in the above range, dispersion of the active material particles and conductive material in the colloid 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 polyvinylpyrrolidone, poly 3,4-ethylenedioxythiophene, and mixtures thereof.

The dispersion medium is not particularly limited as long as it can disperse the active material particles and 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.

In another embodiment of the present invention, cathode; A separator disposed between the anode and the cathode; And an electrolyte impregnated into the positive electrode, the negative electrode, and the separator, wherein at least one of the positive electrode and the negative electrode is the three-dimensional structure electrode described above.

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

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. 2 is a schematic view of a lithium secondary battery module including a three-dimensional fiber structure electrode 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 (oxalato) borate LiBOB) 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.

Preparation of electrode for lithium secondary battery and production of lithium secondary battery including the same

Example  One

Preparation of Polymer Solution First, polyacrylonitrile (PAN) is used as a polymer for producing a porous polymer, and N, N-dimethylformamide is used as a solvent for dissolving the polymer. Respectively.

After the polyacrylonitrile (PAN) is added to N, N-dimethylformamide, the content of polyacrylonitrile (PAN) in the solution is 10 wt% (wt%) So that a polymer solution was prepared.

In order to prepare a colloidal solution containing the produced addition, active material particles and a conductive material in a colloidal solution, with the active material particles and a lithium iron phosphate (LiFePO ₄₎ having an average diameter of 500 ㎚, the conductive material include a carbon nanotube ( carbonnanotube. Deionized water and iso-propylalcohol were used as co-solvent for the dispersion medium.

Specifically, the lithium iron phosphate (LiFePO ₄ ) was dispersed in the dispersion medium (weight ratio represented by deionized water: iso-propylalcohol = 3: 7), and lithium iron phosphate (LiFePO 4 ₄ ) was 5% by weight.

The active material particle solution to the addition of the carbon nanotubes (carbonnanotube) to 20% by weight relative to the weight of the lithium iron phosphate (LiFePO _4), wherein the lithium iron phosphate (LiFePO ₄₎ and the carbon nanotube dispersion with a colloidal solution . At this time, polyvinylpyrrolidone as a dispersant was added to the colloid solution so as to contain 1 wt%.

Preparation of Electrode by Dual Electrospinning The polymer solution and the colloid solution were introduced into an electrospinning apparatus (Nano , Inc. of the place of purchase), and the injection rate of the polymer solution was 6 l / min. At 65 l l / min, and simultaneously spinning (double electrospinning) for about 240 minutes to prepare a three-dimensional structural fiber.

The three-dimensional structural fiber was compressed using a roll press (purchased from Kibo & Co., Ltd.). As a result, a three-dimensional structure electrode having an active material loading of about 5 mg / cm ² and a thickness of about 30 탆 could be obtained.

Fabrication of Lithium Secondary Battery The lithium secondary battery was fabricated by applying the obtained three-dimensional structure electrode as a positive electrode.

Specifically, lithium metal was used as a cathode, and polyethylene (Tonen 20 μm) was used as a separation membrane.

The nonaqueous electrolytic solution was prepared by dissolving LiPF _{6 in} an organic solvent (EC: DEC = 1: 1 (v: v)) to a concentration of 1M.

A coin type lithium secondary battery was prepared by forming the coin type cells by inserting the prepared positive electrode, negative electrode and separator, and then injecting the non-aqueous electrolyte.

Example  2

By performing the same method as in Example 1 except that the double electrospinning was performed for about 480 minutes, a three-dimensional structure electrode having an active material loading of about 10 mg / cm ² and a thickness of about 55 탆 was obtained there was.

Comparative Example  One

Of manufacturing the positive electrode active material of an electrode of lithium iron phosphate (LiFePO ₄₎ 80% by weight of carbon black (Carbon Black) as a conductive material, 10% by weight, a binder of polyvinylidene fluoride (polyvinylidene fluoride, PVDF) 10% by weight solvent N -Methyl-2-pyrrolidone (NMP) to prepare a positive electrode mixture slurry.

After the after applying the positive electrode mixture slurry to the cathode current collector of an aluminum (Al) thin film having a thickness of 20㎛ drying to prepare a positive electrode, the press roll (press roll) carried by the active material loading of about 5mg / cm ² of electrode .

Preparation of lithium secondary battery A lithium secondary battery was prepared in the same manner as in Example 1, except that these electrodes were used as an anode.

Comparative Example  2

An electrode having an active material loading of about 10 mg / cm ² was prepared in the same manner as in Comparative Example 1 , except that the thickness of the slurry of the positive electrode mixture was applied on the current collector, and a lithium secondary battery was produced using the positive electrode And

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

Test Example  One: Example  Observation of electrode manufactured in 1

The upper portion, the lower portion, and the cross section of the electrode prepared in Example 1 were observed with a scanning electron microscope (SEM), and the results are shown in FIGS. 3A to 3C, respectively.

3A and 3B, in Example 1, large spaces existing between a plurality of polymer fibers included in the porous nonwoven fabric were completely filled with active material particles (lithium iron phosphate, LiFePO ₄ ) and carbon nanotubes, It can be seen that the active material particles are surrounded by the carbon nanotubes and a uniform electronic conduction network is formed.

3, it is confirmed that the active material particles and the carbon nanotubes are uniformly mixed even in the cross section of the electrode manufactured in Example 1, and the electronic conduction network is formed in the thickness direction of the electrode.

4 (a) and 4 (b) are photographs of the external appearance of the electrode manufactured in Example 1.

4A and 4B, it can be confirmed that the electrode structure is maintained well without desorbing the active material even when the electrode is bent even though no separate binder is used.

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

In order to compare the resistances of the surfaces of the electrodes prepared in Example 1 and Comparative Example 1, the electronic conductivity was measured.

Specifically, the electronic conductivity was measured by using a 4 probe tip manufactured by Dasol ENG Co., Ltd., and the surface resistance was measured. The results according to Example 1 and Comparative Example 1 are shown in FIG.

According to Fig. 5, in comparison with Comparative Example 1 in which the electronic conductivity of 0.561 S / cm was recorded, Example 1 showed an increase of about 6 times as 3.5 S / cm. As a result, it can be inferred that the electrode of Example 1 has high electron conductivity and can be used as an electrode without a separate current collector, and the output characteristics of the battery including the electrode can 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 discharge current rate was increased from 0.2 C to 20 C.

6A shows the result of observing the discharge capacity per weight of the active material particles of the lithium secondary battery fabricated in Example 1 and the lithium secondary battery fabricated in Comparative Example 1. FIG.

6B shows the result of observing the discharge capacity per electrode weight instead of the weight of the active material particles of FIG. 6A.

6A, the lithium secondary battery of Example 1 exhibits a higher discharge capacity than the lithium secondary battery of Comparative Example 1 as the discharge current rate increases. This is because, in Comparative Example 1, the electronic conductive network formed by carbon black was not formed uniformly and the adhesive polymer used as a binder interfered with the electronic conduction network. On the contrary, the electrode of Example 1, unlike Comparative Example 1, does not have a sticky polymer and forms a uniform electronic conduction network by the carbon nanotube. Therefore, when the lithium secondary battery is driven, .

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 to form an electronic conduction network Therefore, it can be seen that the discharge capacity per electrode weight is greatly increased as compared with Comparative Example 1 in accordance with the decrease of the additive material. 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

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, the coin cell discharge current rate was increased from 0.2 C to 20 C in the same manner as in Test Example 3, The discharge capacity per weight and the electrode weight were respectively observed, and the results according to each were shown in FIGS. 7A and 7B.

In general, as the loading value of the active material increases, the thickness of the electrode generally increases. In this case, it is difficult to form a uniform electronic conduction network in the electrode thickness direction, and as a result, the output characteristic of the battery tends to decrease.

However, in the case of the lithium secondary battery of Example 2 in which the loading value of the active material was increased, the discharge capacity was higher than that of the lithium secondary battery of Comparative Example 2 (Fig. 7A) 2 (Fig. 7B).

As a result, it can be deduced that Example 2 can form a uniform electronic network even in the thickness direction by including the carbon nanotubes in the electrode having the above-described structure, thereby suppressing the reduction of the output characteristics of the battery .

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.

The lithium secondary battery 200 anode 212,
Cathode 213 separator 100,
The sealing member 240 of the battery container 220,
Polymer fibers (10) Active particles (20)
Conductive materials (30)

Claims (16)

A porous nonwoven fabric comprising a plurality of polymer fibers;
Wherein the active material particles are at least one selected from the group consisting of lithium metal-based oxides, oxides, silicon (Si), tin (Sn), germanium (Ge), sulfur (S), derivatives thereof and mixtures thereof; And
Conductive material;
An interconnected porous network is formed by the plurality of polymer fibers,
Wherein the active material particles and the conductive material in the interconnected pore structure are uniformly filled to form a three-dimensional super lattice structure.
The method according to claim 1,
The porous non-
Wherein the plurality of polymer fibers are aggregated three-dimensionally irregularly and continuously,
Three dimensional structure electrode.
The method according to claim 1,
The porosity of the three-
5 to 95% by volume.
Three dimensional structure electrode.
The method according to claim 1,
The content of the porous nonwoven fabric in the three-
Dimensional structure electrode is 5 to 70% by weight based on the total weight of the three-dimensional structure electrode.
Three dimensional structure electrode.
The method according to claim 1,
The ratio of the active material particles and the conductive material in the three-
Wherein the weight ratio of the conductive material to the active material particles is 0.1: 100 to 50: 100.
Three dimensional structure electrode.
The method according to claim 1,
The average diameter of the plurality of polymer fibers may be,
0.001 to 1000 mu m.
Three dimensional structure electrode.
The method according to claim 1,
The average diameter of the active material particles,
0.001 to 30 탆.
Three dimensional structure electrode.
The method according to claim 1,
The thickness of the three-
1 to 1000 [mu] m.
Three dimensional structure electrode.
The method according to claim 1,
The weight per area of the three-
0.001 mg / cm ² to 1 g / cm ² .
Three dimensional structure electrode.
The method according to claim 1,
Wherein the three-dimensional structure electrode comprises:
Wherein a plurality of electrodes form a multilayer structure,
Three dimensional structure electrode.
11. The method of claim 10,
The weight per area of the three-
0.002 g / cm &lt; ² &gt; to 10 g / cm &lt; ² &
Three dimensional structure electrode.
The method according to claim 1,
The polymer constituting the plurality of polymer fibers may be,
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;
Three dimensional structure electrode.
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;
Three dimensional structure electrode.
The method according to claim 1,
Wherein the three-dimensional structure electrode comprises:
Lt; / RTI &gt;
Three dimensional structure electrode.
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 is a three-dimensional structure electrode according to any one of claims 1 to 14.
Electrochemical device.
16. The method of claim 15,
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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